EP0283114A2 - Alkalizer for fibre reactive dyes in cotton - Google Patents
Alkalizer for fibre reactive dyes in cotton Download PDFInfo
- Publication number
- EP0283114A2 EP0283114A2 EP88300516A EP88300516A EP0283114A2 EP 0283114 A2 EP0283114 A2 EP 0283114A2 EP 88300516 A EP88300516 A EP 88300516A EP 88300516 A EP88300516 A EP 88300516A EP 0283114 A2 EP0283114 A2 EP 0283114A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- potassium
- alkalizer
- bath
- tri
- carbonate
- 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
Links
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/58—Material containing hydroxyl groups
- D06P3/60—Natural or regenerated cellulose
- D06P3/66—Natural or regenerated cellulose using reactive dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- 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
- D06P1/673—Inorganic compounds
- D06P1/67333—Salts or hydroxides
- D06P1/6735—Salts or hydroxides of alkaline or alkaline-earth metals with anions different from those provided for in D06P1/67341
Definitions
- an alkaline material is added to promote a chemical reaction between the dye molecules and atoms of the cellulosic fibres.
- the dye combines chemically with the cellulosic material.
- the dye, so bonded, will not wash out of the cellulose. This is known as a “wash-fast” dyeing. Without the “salting out", which increases the substantivity of unreacted dye molecules with the fibre, much of the dye would not have reacted with the fibre and the colour would have been lost.
- a fibre-reactive dye molecule is made up of a colour portion and a chemically-reactive portion.
- the chemically-reactive portion reacts with an hydroxyl group on the cellulose macromolecule under alkaline conditions to form a chemical bond between the cullulosic material and the colour portion of the dye molecule.
- electrolytes in the form of neutral salts are added to the dyebath to enhance the substantivity of the dye molecules on to the cellulosic material fibres, before chemical reaction between the hydroxyl groups and the chemically-reactive portion of the dye takes place.
- a good yield in dyeing depends on causing a large proportion of the dye molecules to absorb, or "salt out", on to the cellulosic macromolecules, before chemical reaction occurs. This must then be followed by the addition of an alkaline material which promotes the chemical reaction between the cellulosic fibre and the dye molecule and minimizes the reaction between dye molecules and water molecules.
- sodium hydroxide alone or in combination with soda ash sodium carbonate
- sodium carbonate alone sodium carbonate alone
- tri-sodium phosphate sodium bicarbonate
- tri-potassium phosphate alone or in combination with a strong base such as potassium hydroxide and/or sodium hydroxide.
- K3PO4 tri-potassium phosphate
- KOH potassium hydroxide
- NaOH sodium hydroxide
- K2CO3 potassium carbonate
- Na2CO3 sodium caronate
- the combination of these ingredients can be made as a convenient direct textile bath additive in the form of an aqueous solution with the total solids ranging from about 10% up to approximately 50% by weight of the solution.
- the limit of lower percentage is dictated by the economics of having a more concentrated solution for transportation.
- the upper limit of concentration is determined by the temperature at which a mixture can be stored. For storage above 10°C, the concentration can even be higher.
- the liquid alkalizer of the present invention can be formulated over a wide range of concentration. It has been found that the combination of the ingredients of the present invention can be made in aqueous solutions with the total solids ranging from about 10%to up to approximately 50% by weight of the solution. The lower limit is dictated mainly by the economics of having a more concentrated solution for transportation, while the upper limit of concentration is determined by the temperature at which a mixture can be stored. For storage above 10°C, the concentration can be higher.
- K3PO4, KOH (or NaOH) plus K2CO3 (or Na2CO3) when used in combination as an alkalizer for dyeing a cellulosic material with fibre-reactive dyes, provides dyeings with less hydrolysis and therefore increased yield of colour on the cellulose.
- potassium hyroxide (or equivalent sodium hydroxide) is optional, it is a preferred component in that it functions in the dye-bath to neutralize acidity.
- NaOH may be substituted in equal amount for KOH and Na2CO3 may be substituted in equal amounts for the K2CO3.
- a typical method used for making the liquid alkalizers of the present invention is as follows: To prepare a formulation of the present invention, the appropriate amount of water is first added to a vessel. The K3PO4 can be added with stirring and, when dissolved, the desired amount of KOH is then added. Next, Na2CO3 or K2CO3 is added. The alkalizer mix is stirred and drained into drums after cooling below 40°C. The drummed material is the alkalizer ready for use or sale.
- the liquid alkalizer can be prepared using a phosphoric acid (H3PO4), a 45% solution of KOH and a 47% solution of K2CO3, all of which are commercially available.
- H3PO4 phosphoric acid
- KOH 45% solution of KOH
- K2CO3 47% solution of K2CO3
- the ingredients would be added in the same order as listed, using cooling as necessary to keep temperature below 70°C. Cool to 40°C and pack into drums.
- Formula (F) of TABLE II would be made as follows: 8.1% Water 61.8% KOH - 45% solution 21.6% H3PO4 - 75% solution 8.5% K2CO3 47% solution
- the alkalizer formulations of the present invention may be used for the dyeing of cellulosic materials with fibre-reactive dyes as follows, using an Ahiba Laboratory dyeing apparatus to carry out the dyeing: Into a suitable dyeing beaker of about 230 ml volume,. 100 ml of water at 80°F (27°C), 7 grams of sodium chloride, 0.05 grams of surfactant, Tanaterge LV (Sybron Chemicals, Inc), and 0.3 grams of Remazol REd F3B Fibre-Reactive Dye (American Hoechst) are added. Place the beaker in the water bath of the Ahiba device. Mount a swatch of 100% woven cotton on an agitator holder and insert it into the beaker.
- the agitator is capable of simultaneous vertical and rotational motion.
- the cotton swatch in held below the surface of the liquid at the lowest point of the agitator movement.
- the Ahiba bath is held at 80°F (27°C) while agitating for 10 minutes.
- about 0.5 gm of liquid alkalizer is added and the bath is agitated for 10 minutes.
- the bath is then heated to 140°F (60°C), and agitated for 45 minutes.
- the cotton swatch is then removed from the bath, washed with cold water, then hot water, then soap solution, then hot water and finally cold water.
- the swatch is then dried and the dyed colour evaluated.
- Formula (G) is a Sybron Chemicals, Inc. commercial alkalzier sold under the trademark ALKAFLO®. Using the ALKAFLO alkalizer as the reference standard alkalizer, the colours of 100% cotton swatches are compared and tested by means of the ACS Spectro Sensor (Applied Color Systems Inc.).
- the dry dyed cotton sample was folded over twice and then placed in the sample holder of the ACS Spectro Sensor. A scan of the sample is then run automatically and the spectro data automatically stored in the IBM PC computer which is connected to the ACS Sensor.
- the cotton sample which was dyed using ALKAFLO liquid alkalizer as the alkalizer is arbitrarily taken as the standard, with the strength reading set at 100.
- the spectro data of the other sampels are compared automatically by the IBM PC and strength results are printed out.
- Readings of 100 are equal to satandard. Readings above 100 show geater dye strength than standard. Readings below 100 show weaker type stength than standard.
- a small amount, such as 0.1%, of sodium gluconate or other suitable sequestering agent may be added to any of the above formulations, to prevent the formation of precipitates caused by impurities in the water or chemicals used.
Abstract
Description
- In the dyeing of cellulosic materials using fibre-reactive dyes, it is the practice to add the cellulosic material and dye to the dyebath first. Next a neutral salt (e.g. sodium sulfate or sodium chloride) is added and the bath is stirred and heated to a prescribed temperature for a prescribed period of time. During this period of time, the dye becomes absobed by the material as the result of the "salting out" effect of the salt which had been added. This "salting out" step is essential for placing dye molecules in very close proximity to the macromolecules of the cellulosic materials. At this point, the material has absorbed the dye, but the dye is not held fast to the fibre.
- After the salt addition and stirring as prescribed, an alkaline material is added to promote a chemical reaction between the dye molecules and atoms of the cellulosic fibres. As a result of this reaction, the dye combines chemically with the cellulosic material. The dye, so bonded, will not wash out of the cellulose. This is known as a "wash-fast" dyeing. Without the "salting out", which increases the substantivity of unreacted dye molecules with the fibre, much of the dye would not have reacted with the fibre and the colour would have been lost.
- A fibre-reactive dye molecule is made up of a colour portion and a chemically-reactive portion. When used to dye cellulosic materials, the chemically-reactive portion reacts with an hydroxyl group on the cellulose macromolecule under alkaline conditions to form a chemical bond between the cullulosic material and the colour portion of the dye molecule.
- In order to ensure a good yield of dyeing, electrolytes in the form of neutral salts are added to the dyebath to enhance the substantivity of the dye molecules on to the cellulosic material fibres, before chemical reaction between the hydroxyl groups and the chemically-reactive portion of the dye takes place.
- Addition of an alkaline material then, under proper conditions of time and temperature, casues the absorbed dye molecules to react with the hydroxyl groups of the cellulosic fibres to form chemical bonds between the dye molecule and the macromolecules of cellulose. There is also a tendency for the dye molecule to react with other hydroxyl groups, such as are present in water. This is known as hydrolysis. When this occurs, the water molecule becomes chemicaly bonded to the colour portion of the dye molecule, and hence, the dye molecule is lost for combining with the cellulose. The colour washes out of the cellulosic material. Hydrolysis thus results in a lower colour yield on the cellulosic material.
- A good yield in dyeing, then, depends on causing a large proportion of the dye molecules to absorb, or "salt out", on to the cellulosic macromolecules, before chemical reaction occurs. This must then be followed by the addition of an alkaline material which promotes the chemical reaction between the cellulosic fibre and the dye molecule and minimizes the reaction between dye molecules and water molecules.
- In the past, a number of chemicals have been used as the alkalizing material. For example, sodium hydroxide alone or in combination with soda ash (sodium carbonate); sodium carbonate alone; tri-sodium phosphate; sodium bicarbonate; tri-potassium phosphate alone or in combination with a strong base such as potassium hydroxide and/or sodium hydroxide.
- It has been discovered that a combination of tri-potassium phosphate (K₃PO₄), potassium hydroxide (KOH) [or sodium hydroxide (NaOH)] plus potassium carbonate (K₂CO₃) [or sodium caronate (Na₂CO₃)],when used as an alkalizer for dyeing cellulosic material with fibre-reactive dyes, yields dyeings with less hydrolysis and therefore increased yield of colour on the cellulose.
- It has been further discovered that the combination of these ingredients can be made as a convenient direct textile bath additive in the form of an aqueous solution with the total solids ranging from about 10% up to approximately 50% by weight of the solution. The limit of lower percentage is dictated by the economics of having a more concentrated solution for transportation. The upper limit of concentration is determined by the temperature at which a mixture can be stored. For storage above 10°C, the concentration can even be higher.
- The liquid alkalizer of the present invention can be formulated over a wide range of concentration. It has been found that the combination of the ingredients of the present invention can be made in aqueous solutions with the total solids ranging from about 10%to up to approximately 50% by weight of the solution. The lower limit is dictated mainly by the economics of having a more concentrated solution for transportation, while the upper limit of concentration is determined by the temperature at which a mixture can be stored. For storage above 10°C, the concentration can be higher. It has been found that a combination of K₃PO₄, KOH (or NaOH) plus K₂CO₃ (or Na₂CO₃), when used in combination as an alkalizer for dyeing a cellulosic material with fibre-reactive dyes, provides dyeings with less hydrolysis and therefore increased yield of colour on the cellulose.
-
- Although the potassium hyroxide (or equivalent sodium hydroxide) is optional, it is a preferred component in that it functions in the dye-bath to neutralize acidity.
- NaOH may be substituted in equal amount for KOH and Na₂CO₃ may be substituted in equal amounts for the K₂CO₃.
- A typical method used for making the liquid alkalizers of the present invention is as follows: To prepare a formulation of the present invention, the appropriate amount of water is first added to a vessel. The K₃PO₄ can be added with stirring and, when dissolved, the desired amount of KOH is then added. Next, Na₂CO₃ or K₂CO₃ is added. The alkalizer mix is stirred and drained into drums after cooling below 40°C. The drummed material is the alkalizer ready for use or sale.
- As an alternative to adding solids, the liquid alkalizer can be prepared using a phosphoric acid (H₃PO₄), a 45% solution of KOH and a 47% solution of K₂CO₃, all of which are commercially available.
-
- The ingredients would be added in the same order as listed, using cooling as necessary to keep temperature below 70°C. Cool to 40°C and pack into drums.
- Formula (F) of TABLE II would be made as follows:
8.1% Water
61.8% KOH - 45% solution
21.6% H₃PO₄ - 75% solution
8.5% K₂CO₃ 47% solution - Add ingredients in the order listed, using cooling to keep the temperature below 70°C. Cool finally to below 40°C and pack into drums.
- The alkalizer formulations of the present invention may be used for the dyeing of cellulosic materials with fibre-reactive dyes as follows, using an Ahiba Laboratory dyeing apparatus to carry out the dyeing:
Into a suitable dyeing beaker of about 230 ml volume,. 100 ml of water at 80°F (27°C), 7 grams of sodium chloride, 0.05 grams of surfactant, Tanaterge LV (Sybron Chemicals, Inc), and 0.3 grams of Remazol REd F3B Fibre-Reactive Dye (American Hoechst) are added. Place the beaker in the water bath of the Ahiba device. Mount a swatch of 100% woven cotton on an agitator holder and insert it into the beaker. The agitator is capable of simultaneous vertical and rotational motion. The cotton swatch in held below the surface of the liquid at the lowest point of the agitator movement. The Ahiba bath is held at 80°F (27°C) while agitating for 10 minutes. Then about 0.5 gm of liquid alkalizer is added and the bath is agitated for 10 minutes. The bath is then heated to 140°F (60°C), and agitated for 45 minutes. The cotton swatch is then removed from the bath, washed with cold water, then hot water, then soap solution, then hot water and finally cold water. The swatch is then dried and the dyed colour evaluated. - The above dyeing technique is used with three different alkalizers. These three alkalizers are formulas (A), (B), and (G) of TABLE II. Formula (G) is a Sybron Chemicals, Inc. commercial alkalzier sold under the trademark ALKAFLO®. Using the ALKAFLO alkalizer as the reference standard alkalizer, the colours of 100% cotton swatches are compared and tested by means of the ACS Spectro Sensor (Applied Color Systems Inc.).
- A specific description of the evaluation of the comparative test data obtained from the results is set forth in TABLE I.
- The dry dyed cotton sample was folded over twice and then placed in the sample holder of the ACS Spectro Sensor. A scan of the sample is then run automatically and the spectro data automatically stored in the IBM PC computer which is connected to the ACS Sensor.
- The cotton sample which was dyed using ALKAFLO liquid alkalizer as the alkalizer is arbitrarily taken as the standard, with the strength reading set at 100. The spectro data of the other sampels are compared automatically by the IBM PC and strength results are printed out.
- Readings of 100 are equal to satandard. Readings above 100 show geater dye strength than standard. Readings below 100 show weaker type stength than standard.
-
- It can be seen from the above TABLE I that the formulas of the present invention result in greater dye strength than the standard.
-
- A small amount, such as 0.1%, of sodium gluconate or other suitable sequestering agent may be added to any of the above formulations, to prevent the formation of precipitates caused by impurities in the water or chemicals used.
- Although particular embodiments of the present invention have been disclosed herein for purposes of explanation, further modifications or variations thereof will be apparent to those skilled in the art to which this invention pertains.
Claims (8)
Tri-potassium phosphate 5-45%
Potassium hydroxide and/or sodium hydroxide 0-10%
Potassium carbonate and/or sodium carbonate 2-10%
Water Balance
Tri-potassium phosphate 10-35%
Potassium hydrozide and/or sodium hydroxide 2-8%
Potassium carbonate and/or sodium carbonate 3-8%
Water Balance
Tri-potassium phosphate 10-35%
Potassium hydroxide and/or sodium hydroxide 2-8%
Potassium carbonate and/or sodium carbonate 3-8%
Water Balance.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT88300516T ATE93555T1 (en) | 1987-02-17 | 1988-01-22 | ALCALIZING AGENT FOR FIBER-REACTIVE DYES IN COTTON. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US1542887A | 1987-02-17 | 1987-02-17 | |
US15428 | 1987-02-17 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0283114A2 true EP0283114A2 (en) | 1988-09-21 |
EP0283114A3 EP0283114A3 (en) | 1991-09-11 |
EP0283114B1 EP0283114B1 (en) | 1993-08-25 |
Family
ID=21771355
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP88300516A Expired - Lifetime EP0283114B1 (en) | 1987-02-17 | 1988-01-22 | Alkalizer for fibre reactive dyes in cotton |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0283114B1 (en) |
AT (1) | ATE93555T1 (en) |
DE (1) | DE3883405T2 (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5242466A (en) * | 1991-03-12 | 1993-09-07 | Unilever Patent Holdings B.V. | Reactive dyebath additive:potassium silicate and potassium hydroxide |
EP0576865A1 (en) * | 1992-06-05 | 1994-01-05 | Hoechst Mitsubishi Kasei Co., Ltd. | Method and apparatus for dyeing cellulose fiber-containing materials |
US5382262A (en) * | 1992-04-27 | 1995-01-17 | Burlington Chemical Co. | Process for preparing a super saturated liquid alkali composition for reactive dyeing of textiles |
US5603736A (en) * | 1992-04-27 | 1997-02-18 | Burlington Chemical Co., Inc. | Liquid alkali for reactive dyeing of textiles |
US5609180A (en) * | 1992-04-27 | 1997-03-11 | Burlington Chemical Co., Inc. | Liquid alkali system for fiber reactive dyeing |
US5840084A (en) * | 1996-11-22 | 1998-11-24 | Sybron Chemicals, Inc. | Dye bath and method for reactive dyeing |
EP0940497A1 (en) * | 1998-03-04 | 1999-09-08 | DyStar Textilfarben GmbH & Co. Deutschland KG | Alkaline aqueous solutions and their use in a process for colouring cellulosic textiles |
US6530961B1 (en) | 1998-03-04 | 2003-03-11 | Dystar Textilfarben Gmbh & Co. Deutschland Kg | Alkaline aqueous solutions and use thereof in processes for dyeing cellulosic textile materials |
CN100427672C (en) * | 2006-03-10 | 2008-10-22 | 苏明辉 | Liquid dyeing base (SN) for active dye dying |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2148294A1 (en) * | 1971-08-05 | 1973-03-11 | Nippon Kayaku Kk | |
JPS5643490A (en) * | 1979-09-11 | 1981-04-22 | Toyo Boseki | Printing of polyester fiber product |
-
1988
- 1988-01-22 EP EP88300516A patent/EP0283114B1/en not_active Expired - Lifetime
- 1988-01-22 DE DE88300516T patent/DE3883405T2/en not_active Expired - Fee Related
- 1988-01-22 AT AT88300516T patent/ATE93555T1/en not_active IP Right Cessation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2148294A1 (en) * | 1971-08-05 | 1973-03-11 | Nippon Kayaku Kk | |
JPS5643490A (en) * | 1979-09-11 | 1981-04-22 | Toyo Boseki | Printing of polyester fiber product |
Non-Patent Citations (1)
Title |
---|
DATABASE WPIL, no 81-42770D Derwent Publications Ltd, London, GB, & JP-A-56 043 490 (TOYOBO KK)(22.04.1981) * |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5242466A (en) * | 1991-03-12 | 1993-09-07 | Unilever Patent Holdings B.V. | Reactive dyebath additive:potassium silicate and potassium hydroxide |
US5382262A (en) * | 1992-04-27 | 1995-01-17 | Burlington Chemical Co. | Process for preparing a super saturated liquid alkali composition for reactive dyeing of textiles |
US5603736A (en) * | 1992-04-27 | 1997-02-18 | Burlington Chemical Co., Inc. | Liquid alkali for reactive dyeing of textiles |
US5609180A (en) * | 1992-04-27 | 1997-03-11 | Burlington Chemical Co., Inc. | Liquid alkali system for fiber reactive dyeing |
US5772697A (en) * | 1992-04-27 | 1998-06-30 | Burlington Chemical Co., Inc. | Process for preparing a liquid caustic composition for use in reactive dyeing which has target total and active alkalinities |
US6214059B1 (en) * | 1992-04-27 | 2001-04-10 | Burlington Chemical Co., Inc. | Liquid alkali for reactive dyeing of textiles |
EP0576865A1 (en) * | 1992-06-05 | 1994-01-05 | Hoechst Mitsubishi Kasei Co., Ltd. | Method and apparatus for dyeing cellulose fiber-containing materials |
US5840084A (en) * | 1996-11-22 | 1998-11-24 | Sybron Chemicals, Inc. | Dye bath and method for reactive dyeing |
EP0940497A1 (en) * | 1998-03-04 | 1999-09-08 | DyStar Textilfarben GmbH & Co. Deutschland KG | Alkaline aqueous solutions and their use in a process for colouring cellulosic textiles |
US6530961B1 (en) | 1998-03-04 | 2003-03-11 | Dystar Textilfarben Gmbh & Co. Deutschland Kg | Alkaline aqueous solutions and use thereof in processes for dyeing cellulosic textile materials |
CN100427672C (en) * | 2006-03-10 | 2008-10-22 | 苏明辉 | Liquid dyeing base (SN) for active dye dying |
Also Published As
Publication number | Publication date |
---|---|
DE3883405D1 (en) | 1993-09-30 |
EP0283114A3 (en) | 1991-09-11 |
EP0283114B1 (en) | 1993-08-25 |
ATE93555T1 (en) | 1993-09-15 |
DE3883405T2 (en) | 1993-12-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4834771A (en) | Aqueous liquid dye composition of C.I. reactive blue ZI and caprolactam or N-methyl pyrrolidone | |
EP0978543B1 (en) | Reactive dye mixtures and their use for dyeing and printing fibrous materials containing hydroxyl and/or carbonamide groups | |
JPS588765A (en) | Reactive dye-liquid blend and use | |
EP0283114B1 (en) | Alkalizer for fibre reactive dyes in cotton | |
KR900005961B1 (en) | Liquid buffer composition and method of ph controlling by means of them | |
US4589885A (en) | Liquid reactive dyestuff formulations and their use | |
EP1645599B9 (en) | Disazo reactive dyestuffs containing a quaternary ammonium group and their use | |
US4078885A (en) | Stable liquid water-containing dyeing compositions containing disperse and reactive dyestuffs and their use for dyeing or printing mixed fibre materials | |
US4415333A (en) | Solid compositions of water-soluble fiber-reactive dyestuffs and dialkylnaphthalene sulfonic acid and formaldehye condensate | |
US4300900A (en) | Process and dye preparations for pad-dyeing | |
US5603736A (en) | Liquid alkali for reactive dyeing of textiles | |
US5382262A (en) | Process for preparing a super saturated liquid alkali composition for reactive dyeing of textiles | |
JPS5953952B2 (en) | Reactive dye composition for cellulose fibers | |
JPH0619046B2 (en) | Disazo compound and dye composition containing the same | |
JPH0655905B2 (en) | Disazo compound and dye composition containing the same | |
US5242467A (en) | Reactive dye mixtures and dyeing methods using them: c.i. reactive orange numbers 16 and 7 | |
EP0857762B1 (en) | Aqueous formulations of reactive dyes and processes for colouring and printing fibrous textile materials | |
JP2730200B2 (en) | Reactive dye composition and method for dyeing or printing cellulosic fiber material | |
EP0832940B1 (en) | Mixtures of dyes, process for their preparation and the use thereof | |
JP2565703B2 (en) | Reactive dye composition | |
JPH0354141B2 (en) | ||
US4280814A (en) | Dyeing process and compositions | |
JP2791263B2 (en) | Fiber reactive monoazo yellow dye | |
EP0087273B1 (en) | Reactive dye composition for cellulose fiber | |
US2675326A (en) | Aqueous solution of silk |
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 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AT BE CH DE FR GB IT LI LU NL SE |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): AT BE CH DE FR GB IT LI LU NL SE |
|
17P | Request for examination filed |
Effective date: 19911016 |
|
17Q | First examination report despatched |
Effective date: 19920227 |
|
ITF | It: translation for a ep patent filed |
Owner name: DE DOMINICIS & MAYER S.R.L. |
|
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 FR GB IT LI LU NL SE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Effective date: 19930825 Ref country code: LI Effective date: 19930825 Ref country code: CH Effective date: 19930825 Ref country code: BE Effective date: 19930825 Ref country code: AT Effective date: 19930825 |
|
REF | Corresponds to: |
Ref document number: 93555 Country of ref document: AT Date of ref document: 19930915 Kind code of ref document: T |
|
RAP2 | Party data changed (patent owner data changed or rights of a patent transferred) |
Owner name: SYBRON CHEMICAL HOLDINGS INC. |
|
REF | Corresponds to: |
Ref document number: 3883405 Country of ref document: DE Date of ref document: 19930930 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
ET | Fr: translation filed | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19940111 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19940112 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19940121 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19940131 Year of fee payment: 7 Ref country code: LU Payment date: 19940131 Year of fee payment: 7 |
|
EPTA | Lu: last paid annual fee | ||
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 |
|
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: 19950122 Ref country code: GB Effective date: 19950122 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Effective date: 19950801 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 19950122 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Effective date: 19950929 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 19950801 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Effective date: 19951003 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;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: 20050122 |