EP0585038A1 - Solution alcaline de silica - Google Patents

Solution alcaline de silica Download PDF

Info

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
Application number
EP93306496A
Other languages
German (de)
English (en)
Other versions
EP0585038B1 (fr
Inventor
Derek Aldcroft
Charlotte Ruth Owen
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.)
Ineos Silicas Ltd
Original Assignee
Joseph Crosfield and Sons Ltd
Crosfield Ltd
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 Joseph Crosfield and Sons Ltd, Crosfield Ltd filed Critical Joseph Crosfield and Sons Ltd
Priority to EP93306496A priority Critical patent/EP0585038B1/fr
Publication of EP0585038A1 publication Critical patent/EP0585038A1/fr
Application granted granted Critical
Publication of EP0585038B1 publication Critical patent/EP0585038B1/fr
Priority to GR20000402124T priority patent/GR3034433T3/el
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/08Silicates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3902Organic or inorganic per-compounds combined with specific additives
    • C11D3/3937Stabilising agents
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3902Organic or inorganic per-compounds combined with specific additives
    • C11D3/3937Stabilising agents
    • C11D3/394Organic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02Inorganic compounds
    • C11D7/04Water-soluble compounds
    • C11D7/10Salts
    • C11D7/14Silicates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/26Organic compounds containing oxygen
    • C11D7/265Carboxylic acids or salts thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/32Organic compounds containing nitrogen
    • C11D7/3245Aminoacids
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/36Organic compounds containing phosphorus
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06LDRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/10Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
    • D06L4/12Bleaching 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)
EP93306496A 1992-08-28 1993-08-18 Solution alcaline de silica Expired - Lifetime EP0585038B1 (fr)

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)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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

Patent Citations (9)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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

Similar Documents

Publication Publication Date Title
EP0176124B1 (fr) Utilisation de suspensions contenant un acide péroxycarboxylique comme compositions de blanchiment, nouvelles compositions de blanchiment et compositions de blanchiment emballées
KR900005961B1 (ko) 액체 완충 조성물 및 이를 사용한 pH조절 방법
US4231890A (en) Bleaching composition causing no color change or fading of colored and figured cloths
CA2070556A1 (fr) Procede de blanchiment de la pate de bois
EP0814193A2 (fr) Agent stabilisateur pour le blanchiment au peroxyde et procédés pour le blanchiment d'un matériau fibreux l'utilisant
US3811833A (en) Stabilized hydrogen peroxide compositions containing ammonium ions,and process for bleaching therewith
EP0736049B1 (fr) Copolymeres d'acides carboxyliques insatures, leur procede de fabrication et leur utilisation
US5464563A (en) Bleaching composition
US3979312A (en) Detergent composition containing novel bleaching agent
US3061550A (en) Textile bleaching composition
US5616280A (en) Bleaching composition
EP0585038B1 (fr) Solution alcaline de silica
NO154343B (no) Stabiliseringsmiddel for peroksydforbindelser, samt en toeyvaske-pulverblanding inneholdende nevnte stabiliseringsmiddel.
US3687803A (en) Acid chloride activators for hydrogen peroxide bleaching
DE3211532A1 (de) Mittel zum waschen und faerbungsschonenden bleichen von textilien
US7156882B2 (en) Method for bleaching textile fibers
NO136417B (fr)
US6120555A (en) Hypochlorite bleaching compositions
SK19899A3 (en) Liquid bleaching composition, solid bleaching composition, use of a component having the ability to prevent the precipitation of the salts of buffering component and method of bleaching fabric
JPH0791557B2 (ja) 繊維製品用洗浄性向上剤
US5843191A (en) Process for bleaching fabrics
AU713983B2 (en) A process of bleaching fabrics
EP0781840B1 (fr) Compositions de blanchiment à base de hypochlorite
US3697217A (en) Bleaching and washing composition and process
CZ2021349A3 (cs) Hořečnaté sole derivátů asparagové kyseliny a jejich použití jako stabilizátorů peroxidu vodíku

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: A1

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

17P Request for examination filed

Effective date: 19940708

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: CROSFIELD LIMITED

17Q First examination report despatched

Effective date: 19970219

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

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 NL PT SE

REF Corresponds to:

Ref document number: 194998

Country of ref document: AT

Date of ref document: 20000815

Kind code of ref document: T

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: BOVARD AG PATENTANWAELTE

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: 69329089

Country of ref document: DE

Date of ref document: 20000831

ET Fr: translation filed
ITF It: translation for a ep patent filed

Owner name: ING. C. GREGORJ S.P.A.

REG Reference to a national code

Ref country code: PT

Ref legal event code: SC4A

Free format text: AVAILABILITY OF NATIONAL TRANSLATION

Effective date: 20000810

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2150436

Country of ref document: ES

Kind code of ref document: T3

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

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
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

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

Ref country code: DK

Payment date: 20020710

Year of fee payment: 10

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

Ref country code: IE

Payment date: 20020715

Year of fee payment: 10

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

Ref country code: PT

Payment date: 20020717

Year of fee payment: 10

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

Ref country code: CH

Payment date: 20020726

Year of fee payment: 10

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

Ref country code: IE

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

Effective date: 20030818

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

Ref country code: LI

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

Effective date: 20030831

Ref country code: CH

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

Effective date: 20030831

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

Ref country code: DK

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

Effective date: 20030901

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 NON-PAYMENT OF DUE FEES

Effective date: 20040229

REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: PT

Ref legal event code: MM4A

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

Effective date: 20040229

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

NLT1 Nl: modifications of names registered in virtue of documents presented to the patent office pursuant to art. 16 a, paragraph 1

Owner name: INEOS SILICAS LIMITED

REG Reference to a national code

Ref country code: FR

Ref legal event code: CD

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

Ref country code: ES

Payment date: 20080811

Year of fee payment: 16

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

Ref country code: IT

Payment date: 20080726

Year of fee payment: 16

Ref country code: FR

Payment date: 20080714

Year of fee payment: 16

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

Ref country code: GB

Payment date: 20080722

Year of fee payment: 16

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

Ref country code: SE

Payment date: 20080716

Year of fee payment: 16

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

Ref country code: GR

Payment date: 20080724

Year of fee payment: 16

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

Effective date: 20090818

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20100430

REG Reference to a national code

Ref country code: NL

Ref legal event code: SD

Effective date: 20100707

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

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20090819

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 NON-PAYMENT OF DUE FEES

Effective date: 20100303

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: 20090818

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

Effective date: 20090818

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

Ref country code: SE

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

Effective date: 20090819

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

Ref country code: ES

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

Effective date: 20090819

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

Ref country code: DE

Payment date: 20110823

Year of fee payment: 19

Ref country code: AT

Payment date: 20110812

Year of fee payment: 19

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 69329089

Country of ref document: DE

Representative=s name: PFENNING MEINIG & PARTNER GBR, DE

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

Ref country code: NL

Payment date: 20110825

Year of fee payment: 19

Ref country code: BE

Payment date: 20110811

Year of fee payment: 19

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 69329089

Country of ref document: DE

Representative=s name: PFENNING MEINIG & PARTNER GBR, DE

Effective date: 20111214

Ref country code: DE

Ref legal event code: R081

Ref document number: 69329089

Country of ref document: DE

Owner name: PQ SILICAS UK LTD., GB

Free format text: FORMER OWNER: INEOS SILICAS LTD., WARRINGTON, GB

Effective date: 20111214

BERE Be: lapsed

Owner name: PQ SILICAS UK LTD

Effective date: 20120831

REG Reference to a national code

Ref country code: NL

Ref legal event code: V1

Effective date: 20130301

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 194998

Country of ref document: AT

Kind code of ref document: T

Effective date: 20120818

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

Ref country code: NL

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

Effective date: 20130301

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: 20120831

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

Ref country code: AT

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

Effective date: 20120818

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: 20130301

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 69329089

Country of ref document: DE

Effective date: 20130301