EP0585038A1 - Solution alcaline de silica - Google Patents
Solution alcaline de silica Download PDFInfo
- Publication number
- EP0585038A1 EP0585038A1 EP93306496A EP93306496A EP0585038A1 EP 0585038 A1 EP0585038 A1 EP 0585038A1 EP 93306496 A EP93306496 A EP 93306496A EP 93306496 A EP93306496 A EP 93306496A EP 0585038 A1 EP0585038 A1 EP 0585038A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- containing silica
- alkali containing
- silica solution
- bleaching
- 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
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/08—Silicates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3937—Stabilising agents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3937—Stabilising agents
- C11D3/394—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
- C11D7/14—Silicates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/265—Carboxylic acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3245—Aminoacids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/36—Organic compounds containing phosphorus
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
- D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
- D06L4/12—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen combined with specific additives
Definitions
- the invention relates to alkali containing silica solution containing organic calcium sequestrant, to a bleaching bath formulation containing said silica solution and to a process for the alkaline hydrogen peroxide bleaching of textiles.
- Silicates are well characterised in the literature, for example "The Chemistry of Silica” by R.K. Iler (published by Wiley Interscience 1979) and they have many forms depending on the cation associated with the silicate species, the ratio of metal oxide of this cation to the silicon dioxide content of the solution, and the total solids content.
- Silicate liquors find uses as sealants adhesives, protective coatings, binders and also stabilisation system in the hydrogen peroxide bleaching of textiles, for example cotton and polyester/cotton (see “The Encyclopedia of organic Chemistry", Kirk Othmer, 3rd Edition, Supplement Vol.3, 1979, pages 877 and 949).
- silicate containing either potassium or sodium oxide is recognised as being the best stabilising system for alkaline hydrogen peroxide bleaching of cotton and polyester/cotton (white goods), i.e. the reaction of the soluble silicate to prolong the active life of the hydrogen peroxide in the bleaching bath, the drawbacks of using silicate are well documented.
- the textile mill choosing the use of sodium silicate to stabilise an alkaline hydrogen peroxide bleaching process would dose conditioning chemicals to the bleaching bath to minimise these detrimental effects but adding to the complexity of the operation.
- conditioning chemicals are organic acid calcium sequestrants, fibre conditioning agents and anti-redeposition aids. Including the bleaching system, this can mean up to six streams of chemicals which need to be carefully metered to the bleaching bath, all of which having different reactivities, pH and concentrations.
- these chemicals can readily react with each other neutralising their conditioning action. This propensity to interact will increase if the mixing is poor and, in a bleaching bath, the only disturbance is the ribbon of cloth moving through the treatment zone.
- the textile mill uses higher concentrations of the conditioning chemicals, particularly organic acid sequestrants.
- the poor mixing regime in the bleaching bath can result in the silicate solution being destabilised by the acid stream of hydrogen peroxide.
- the metal oxide associated with the silicate is usually Na2O.
- potassium silicates can also be used and indeed benefits such as improved cloth handle and elimination of deposits are described.
- US 4,384,970 L'Air Liquide teaches improved performance in the stabilisation of peroxide bleaching systems by the use of colloidal magnesium silicate in conjunction with diethylenetriamine penta acetic acid (D.T.P.A.) and diethylenetriamine penta methylene phosphonic acid (D.T.P.M.P.).
- organic acids and calcium sequestrants including poly-alpha-hydroxy acid or alkoxy-acrylic acid, homopolymer of (meth)acrylic acid or copolymer of acrylic acid with methacrylic acid, (meth)acrylamide, (meth)acrylonitrile, (meth)acrylate esters or other ethylenically unsaturated mono or di-carboxylic acid, and/or copolymer of maleic acid with styrene are described in DE 3,423,452(Sandoz) as benefiting the alkaline hydrogen peroxide bleaching process. More particularly, it is disclosed that those organic acids avoid the use of alkaline silicates as stabilisers.
- alkali containing silica solutions can be made compatible with the neutralised form of organic acid calcium sequestrants even at high SiO2 concentration. It has been demonstrated that these alkali containing silica solutions can be used in the alkaline hydrogen peroxide bleaching of white goods, giving equivalent or better whiteness than that obtained with a normal silicate solution, with similar hydrogen peroxide consumption, and none of the detrimental effects usually associated with silicate. These are other benefits resulting from the use of the modified silicate as a stabiliser in the alkaline hydrogen peroxide bleaching of white goods. These are concerned with reducing the complexity of controlling the bleaching bath. For example, the addition of sodium hydroxide can be significantly reduced, if not eliminated in some cases, and there is no need to dose separately an organic acid calcium sequestrant to the bleaching bath.
- It is a first object of the present invention to provide an alkali containing silica solution comprising 15% to 30% by weight of silica, preferably 20% to 30% by weight of silica, 10% to 25% by weight of potassium or sodium oxide or mixtures thereof, 2 to 6% by weight of a compatible neutralised organic acid calcium sequestrant, preferably in the form of its sodium salt, the SiO2/Na2O weight ratio of the alkali containing silica solution being in the range 1.2 to 2.0, preferably 1.4 to 1.8.
- the alkali containing silica solution is not stable at SiO2/Na2O ratios outside the claimed range.
- SiO2/Na2O ratios outside the claimed range.
- metasilicate crystallises particularly with alkali containing silica solutions comprising Na2O as the alkaline metal oxide
- above ratio 2.0 the concentrated solutions of alkali containing silica solution and organic acid sequestrant in its sodium salt form instantaneously gel when brought into contact with each other, even where high shear dispersing apparatus is utilised.
- the alkali containing silica solution and the calcium sequestrant layer after their initial gelation.
- the organic acid calcium sequestrant is selected in the group constituted by, derivatives of amino (lower alkaline) acetic acids for example ethylene tetraacetic acid (EDTA), diethylene triamine penta methylene phosphonic acid (DTMP) and diethylene triamine pentaacetic acid (DTPA), or from homopolymer of (meth)acrylic acid or copolymer of acrylic acid with methacrylic acid (meth) acrylamide, (meth) acrylate esters and the copolymer of maleic acid with styrene or a vinyl ester of vinyl ether, or mixtures thereof.
- EDTA ethylene tetraacetic acid
- DTMP diethylene triamine penta methylene phosphonic acid
- DTPA diethylene triamine pentaacetic acid
- It is a second object of the present invention to provide for a bleaching bath formulation comprising 5 to 25 g/litre of hydrogen peroxide, 5 to 25 g/litre of sodium hydroxide, and 5 to 50 g/litre of a stabilising system
- the stabilising system is an alkali containing silica solution, comprising 15% to 30% by weight of silica, preferably 20% to 30% by weight of silica, 10% to 25% by weight of potassium or sodium oxide or mixtures thereof, 2% to 6% by weight of a compatible neutralised organic acid calcium sequestrant, preferably in the form of its sodium salt, the SiO2/Na2O weight ratio of the alkali containing silica solution being in the range 1.2 to 2.0, preferably 1.4 to 1.8.
- the whiteness values have been measured on the treated cloth, after bleaching for 20 minutes at 100°C in a Werner Mathis steamer. Listed below in Table 1 are the whiteness values obtained for the various silicate additions, the measurements being determined on an Elrepho spectrophotometer.
- the blends have been prepared by adding the candidate neutralised organic acid calcium sequestrant (40% solution as its sodium salt) to the stirred alkali containing silica solution. After aeration has settled, caused by the mixing action of the stirrer, the blends are transferred to a glass sample bottle and sealed to prevent moisture escaping. The blends have been stored for up to a period of 3-months at ambient temperature. The observations recorded in Table II are on the blends after standing for one month.
- the data demonstrates a range of stability for blends prepared from alkali containing silicate solutions with a weight ratio SiO2/M2O of 1.2 to 2.0 and organic acid calcium sequestrants up to a concentration of 10% as the 40% solution of their sodium salt, i.e. 4% as the anhydrous material.
- organic acid calcium sequestrants in form of a 40% solution of their sodium salt are compatible with alkali containing silica solutions, particularly in the SiO2/M2O ratio range of 1.2 to 2.0. It has also been shown that silicate solutions in this ratio range will stabilise alkaline hydrogen peroxide bleaching systems and there is no detrimental effect on the whiteness of the cloth obtained.
- the objective of this example is to show that the modified alkali containing silica solutions have a greater propensity to minimise the precipitation of calcium silicates than their parent silicate solutions.
- a test has been developed to monitor the extent of calcium precipitation. The test is based on measuring the increasing turbidity of a model bleaching system where a solution of calcium chloride is added to the diluted alkali containing silica solution at pH 11. The larger ⁇ CCPL the greater the extent of calcium ion suppression.
- the CCPL's for the range of modified alkali containing silica solutions containing 4% of the sequestrant in the form of its sodium salt, in the ratio range 1.6 to 2.0 are given in Table IV. TABLE IV Na Silicate Si02/Na20 weight ratio 2.0 1.6 Value of ⁇ CCPL for modifies silicates with 10% additions in ml. Alco 0.95 1.45 DTPA 0.6 0.75 DTPMP 0.80 1.20
- Example IV it has been demonstrated that the modified alkali containing silica solution in the ratio range 1.6 to 2.0 containing 4% organic acid calcium sequestrant, in the form of its sodium salt, suppresses the precipitation of calcium silicates.
- a silicate solution exhibiting this inhibitive behaviour would be as a stabiliser in the alkaline hydrogen peroxide bleaching system.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
- Silicon Compounds (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Saccharide Compounds (AREA)
- Cosmetics (AREA)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP93306496A EP0585038B1 (fr) | 1992-08-28 | 1993-08-18 | Solution alcaline de silica |
GR20000402124T GR3034433T3 (en) | 1992-08-28 | 2000-09-18 | Antifoaming agents. |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP92307886 | 1992-08-28 | ||
EP92307886 | 1992-08-28 | ||
EP93306496A EP0585038B1 (fr) | 1992-08-28 | 1993-08-18 | Solution alcaline de silica |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0585038A1 true EP0585038A1 (fr) | 1994-03-02 |
EP0585038B1 EP0585038B1 (fr) | 2000-07-26 |
Family
ID=8211472
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93306496A Expired - Lifetime EP0585038B1 (fr) | 1992-08-28 | 1993-08-18 | Solution alcaline de silica |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP0585038B1 (fr) |
AT (1) | ATE194998T1 (fr) |
BR (1) | BR9303474A (fr) |
DE (1) | DE69329089T2 (fr) |
DK (1) | DK0585038T3 (fr) |
ES (1) | ES2150436T3 (fr) |
GR (1) | GR3034433T3 (fr) |
PT (1) | PT585038E (fr) |
ZA (1) | ZA935690B (fr) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1995030791A1 (fr) * | 1994-05-07 | 1995-11-16 | Henkel Kommanditgesellschaft Auf Aktien | Utilisation de polymeres solubles dans l'eau et de polyhydroxymonocarboxylates ou polyhydroxybicarboxylates dans le blanchiment de textiles |
EP0750661A1 (fr) * | 1994-03-14 | 1997-01-02 | The Procter & Gamble Company | Compositions de blanchiment en granules |
WO2001046518A2 (fr) * | 1999-12-21 | 2001-06-28 | Clariant International Ltd. | Nouveau procede pour pretraiter les fibres de cellulose et les melanges de fibres de cellulose |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101545198B (zh) * | 2009-04-30 | 2011-02-09 | 祝洪哲 | 用于纤维素纤维织物漂白的纳米材料组合物 |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2838459A (en) * | 1955-02-01 | 1958-06-10 | Pennsalt Chemicals Corp | Stabilization of solutions containing peroxygen compounds |
GB923897A (en) * | 1959-08-28 | 1963-04-18 | Laporte Chemical | Improvements in or relating to the bleaching of cellulosic fibres |
US3150918A (en) * | 1962-03-29 | 1964-09-29 | Pittsburgh Plate Glass Co | Method of bleaching cotton piece goods |
GB1123071A (en) * | 1964-11-12 | 1968-08-14 | Bowmans Chemicals Ltd | Improvements in or relating to the treatment of natural or synthetic fibres |
US3449254A (en) * | 1966-06-14 | 1969-06-10 | Allied Chem | Borax-sodium silicate stabilizers for peroxide bleaching |
DE2147300A1 (de) * | 1970-09-24 | 1972-03-30 | The Procter & Gamble Co , Cincinna ti, Ohio (V St A) | Reinigungszusammensetzungen sowie Verfahren zu ihrer Herstellung |
EP0210952A1 (fr) * | 1985-07-19 | 1987-02-04 | Ciba-Geigy Ag | Composition aqueuse, alcaline contenant des silicates pour le blanchiment de matières fibreuses cellulosiques en présence de composés "per" |
FR2643093A1 (fr) * | 1989-02-15 | 1990-08-17 | Protex Manuf Prod Chimiq | Procedes ameliores de blanchiment oxydant de fibres cellulosiques |
EP0407626A1 (fr) * | 1989-07-10 | 1991-01-16 | Henkel Kommanditgesellschaft auf Aktien | Composition liquide détergente et nettoyante exempte de phosphate |
-
1993
- 1993-08-05 ZA ZA935690A patent/ZA935690B/xx unknown
- 1993-08-18 EP EP93306496A patent/EP0585038B1/fr not_active Expired - Lifetime
- 1993-08-18 DE DE69329089T patent/DE69329089T2/de not_active Expired - Lifetime
- 1993-08-18 AT AT93306496T patent/ATE194998T1/de active
- 1993-08-18 ES ES93306496T patent/ES2150436T3/es not_active Expired - Lifetime
- 1993-08-18 PT PT93306496T patent/PT585038E/pt unknown
- 1993-08-18 DK DK93306496T patent/DK0585038T3/da active
- 1993-08-25 BR BR9303474A patent/BR9303474A/pt not_active IP Right Cessation
-
2000
- 2000-09-18 GR GR20000402124T patent/GR3034433T3/el not_active IP Right Cessation
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2838459A (en) * | 1955-02-01 | 1958-06-10 | Pennsalt Chemicals Corp | Stabilization of solutions containing peroxygen compounds |
GB923897A (en) * | 1959-08-28 | 1963-04-18 | Laporte Chemical | Improvements in or relating to the bleaching of cellulosic fibres |
US3150918A (en) * | 1962-03-29 | 1964-09-29 | Pittsburgh Plate Glass Co | Method of bleaching cotton piece goods |
GB1123071A (en) * | 1964-11-12 | 1968-08-14 | Bowmans Chemicals Ltd | Improvements in or relating to the treatment of natural or synthetic fibres |
US3449254A (en) * | 1966-06-14 | 1969-06-10 | Allied Chem | Borax-sodium silicate stabilizers for peroxide bleaching |
DE2147300A1 (de) * | 1970-09-24 | 1972-03-30 | The Procter & Gamble Co , Cincinna ti, Ohio (V St A) | Reinigungszusammensetzungen sowie Verfahren zu ihrer Herstellung |
EP0210952A1 (fr) * | 1985-07-19 | 1987-02-04 | Ciba-Geigy Ag | Composition aqueuse, alcaline contenant des silicates pour le blanchiment de matières fibreuses cellulosiques en présence de composés "per" |
FR2643093A1 (fr) * | 1989-02-15 | 1990-08-17 | Protex Manuf Prod Chimiq | Procedes ameliores de blanchiment oxydant de fibres cellulosiques |
EP0407626A1 (fr) * | 1989-07-10 | 1991-01-16 | Henkel Kommanditgesellschaft auf Aktien | Composition liquide détergente et nettoyante exempte de phosphate |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0750661A1 (fr) * | 1994-03-14 | 1997-01-02 | The Procter & Gamble Company | Compositions de blanchiment en granules |
EP0750661A4 (fr) * | 1994-03-14 | 1998-10-07 | Procter & Gamble | Compositions de blanchiment en granules |
WO1995030791A1 (fr) * | 1994-05-07 | 1995-11-16 | Henkel Kommanditgesellschaft Auf Aktien | Utilisation de polymeres solubles dans l'eau et de polyhydroxymonocarboxylates ou polyhydroxybicarboxylates dans le blanchiment de textiles |
US5704947A (en) * | 1994-05-07 | 1998-01-06 | Kaiser; Heribert | Use of water-soluble polymers and polyhydroxymono- or dicarboxylates in the bleaching of textiles |
WO2001046518A2 (fr) * | 1999-12-21 | 2001-06-28 | Clariant International Ltd. | Nouveau procede pour pretraiter les fibres de cellulose et les melanges de fibres de cellulose |
WO2001046518A3 (fr) * | 1999-12-21 | 2002-03-14 | Clariant Int Ltd | Nouveau procede pour pretraiter les fibres de cellulose et les melanges de fibres de cellulose |
US7044985B2 (en) | 1999-12-21 | 2006-05-16 | Clariant Finance (Bvi) Limited | Process for pre-treating cellulosic fibers and cellulosic fiber blends |
Also Published As
Publication number | Publication date |
---|---|
ES2150436T3 (es) | 2000-12-01 |
PT585038E (pt) | 2000-11-30 |
DE69329089D1 (de) | 2000-08-31 |
DE69329089T2 (de) | 2000-12-21 |
DK0585038T3 (da) | 2000-12-18 |
ATE194998T1 (de) | 2000-08-15 |
BR9303474A (pt) | 1994-03-15 |
GR3034433T3 (en) | 2000-12-29 |
EP0585038B1 (fr) | 2000-07-26 |
ZA935690B (en) | 1995-02-06 |
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