EP0997523A1 - Solutions aqueuses d'acides phosphoniques - Google Patents
Solutions aqueuses d'acides phosphoniques Download PDFInfo
- Publication number
- EP0997523A1 EP0997523A1 EP99121341A EP99121341A EP0997523A1 EP 0997523 A1 EP0997523 A1 EP 0997523A1 EP 99121341 A EP99121341 A EP 99121341A EP 99121341 A EP99121341 A EP 99121341A EP 0997523 A1 EP0997523 A1 EP 0997523A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- acids
- phosphonic acids
- aqueous solutions
- phosphonic
- 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
- 150000003009 phosphonic acids Chemical class 0.000 title claims abstract description 31
- 239000007864 aqueous solution Substances 0.000 title claims abstract description 25
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 6
- 239000008139 complexing agent Substances 0.000 claims description 22
- 150000002978 peroxides Chemical class 0.000 claims description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 15
- 238000004061 bleaching Methods 0.000 claims description 15
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000002657 fibrous material Substances 0.000 claims description 9
- 239000004480 active ingredient Substances 0.000 claims description 8
- 230000002328 demineralizing effect Effects 0.000 claims description 7
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 6
- 238000005115 demineralization Methods 0.000 claims description 6
- 239000002655 kraft paper Substances 0.000 claims description 5
- 239000004753 textile Substances 0.000 claims description 5
- 239000007844 bleaching agent Substances 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical class NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 claims description 4
- -1 amine ion Chemical class 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 239000012190 activator Substances 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 229910001425 magnesium ion Inorganic materials 0.000 claims 1
- 239000000725 suspension Substances 0.000 claims 1
- 239000013543 active substance Substances 0.000 abstract description 14
- 150000007513 acids Chemical class 0.000 abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 11
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 6
- 229920000742 Cotton Polymers 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 4
- 229940120146 EDTMP Drugs 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000009897 hydrogen peroxide bleaching Methods 0.000 description 1
- JRFKIOFLCXKVOT-UHFFFAOYSA-N hydroxymethylnicotinamide Chemical compound OCNC(=O)C1=CC=CN=C1 JRFKIOFLCXKVOT-UHFFFAOYSA-N 0.000 description 1
- 229950005422 hydroxymethylnicotinamide Drugs 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004076 pulp bleaching Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 238000009988 textile finishing Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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
- C11D3/16—Organic compounds
- C11D3/36—Organic compounds containing phosphorus
- C11D3/364—Organic compounds containing phosphorus containing nitrogen
-
- 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
Definitions
- the invention relates to aqueous solutions of phosphonic acids and / or their salts and in particular their use as complexing agents for the treatment of cellulosic fiber materials used in demineralization processes and used to stabilize bleaching solutions containing peroxide become.
- Complexing agents are used in the refinement of cellulosic fiber material, remove the interfering metal ions during a treatment or something mask that impairment of the process during treatment is reduced.
- complexing agents are also used, whereby in textile bleaching processes mainly DTPMP and in the bleaching of non-digested Wood pulp DTPA is used (ibid., P. 426-428).
- the described Use concentration is 0.1 - 0.2 wt .-%, based on the respective anhydrous complexing agent.
- amino carboxylic acids are assessed unfavorably. With the exception of the technically ineffective NTA, EDTA and DTPA are not biodegradable and are also not eliminated in sewage treatment plants by adsorption. Since all amino carboxylic acids are suspected of remobilizing toxic heavy metals - SCH ⁇ BERL and HUBER, Tenside Surfactants Detergents 25 2 (1988) 105-106 - they are checked in surface waters that are used for drinking water production. Maximum quantity restrictions for NTA in household detergents up to restrictive prohibitions of any use of EDTA or DTPA already apply today in textile finishing, wood and pulp industry depending on national and regional laws and regulations.
- Phosphonates which are better at the risk of remobilization of heavy metals be assessed, see GLEDHILL and FEIJTEL, The Handbook of Environmental Chemistry, Vol 3, Part F, pp. 261-285 (1992) are also considered not to be harmless classified because they are also not biodegradable and according to OECD 302B investigations can only be inadequately eliminated through adsoption.
- Phosphorus levels in wastewater whether it is a textile plant or a pulp mill, have strict limits may be subject to any improvement in this elimination data from great interest.
- the object of the invention is to provide aqueous solutions of phosphonic acids and / or to produce their salts which have an active substance content of at least 25% by weight, at least based on free phosphonic acid or the complexing agent Make liquids stable for 6 months at room temperature. Furthermore is the object of the invention to provide a new, effective and environmentally friendly process for demineralizing cellulose-containing Fiber material and for the stabilization of hydrogen peroxide Bleaching solutions for native textile fiber materials and kraft pulps.
- aqueous solutions of the phosphonic acid mentioned and / or their Salts with an active ingredient content of at least 30% by weight, in particular To produce 40 wt .-% with the desired storage stability.
- the mentioned partially neutralized or free phosphonic acids as complexing agents are used, it is special in the sense of the present invention preferred, this in an amount of 0.002 to 0.20 wt .-%, in particular in an amount of 0.005 to 0.05% by weight, based on the active substance To use acids and the dry amount of fiber.
- peroxide bleaches in the event that hydrogen peroxide used as peroxide use, preferably in an amount from 0.1 to 15% by weight, in particular from 0.2 to 5% by weight, based on the dry amount of fiber used.
- the bleach is particularly preferred at a pH in the range from 7 to 14, in particular in the range from 9 to 13.
- the temperature can in this case, for example, in the range from 20 to 140 ° C., in particular 70 to 120 ° C. can be set. If necessary, it is also possible to suspend the magnesium salts add, the amount of magnesium by up to 0.5 wt .-%, in particular 0.01 to 0.2 wt .-% is increased.
- Another embodiment of the present invention is its use of the above-mentioned aqueous solutions for demineralizing cellulosic fiber material, with aminophosphonic acids as complexing agents with at least 6 phosphonate groups.
- demineralization of cellulosic fiber material is also possible directly with the above-mentioned phosphonic acids of the general formula I and / or II use as a complexing agent.
- salts of To use phosphonic acid of the general formula I is to be understood as meaning that preferably at least one hydrogen atom of phosphonic acid is replaced by an alkali metal, alkaline earth metal, ammonium or amine ion.
- alkali metal alkaline earth metal
- ammonium or amine ion for the purposes of the present invention, they are particularly preferred the aqueous solutions around those of triethylenetetramine hexa (methylenephosphonic acid).
- phosphonic acids of the general formula I particularly preferred, mixtures of diethylenetriaminepenta (methylenephosphonic acid) and to use triethylenetetramine hexa (methylenephosphonic acid).
- the weight ratio of diethylenediaminepentamethylenephosphonic acid is particularly preferably to triethylenetetramine hexa (methylenephosphonic acid) 1 to 1 to 5 to 1.
- the final product contained 32% by weight of TTHMP. This value is usually based on the amine used related, since technical aminopolyphosphonates beginning with the ATMP consist of mixtures which, in addition to the highly phosphonomethylated and eponymous component also less phosphonomethylated Homologues and other by-products included.
- amines especially those that are technically available in large quantities, e.g. Tetraethylene pentamine, pentaethylene hexamine, but also polyethylene imines with weight averages up to 50000.
- Mathis-Labomat TM 100 ° C (internal temperature measurement), 90 min, 10% by weight consistency, 1.0% by weight NaOH, 1.5% by weight hydrogen peroxide.
- the complexing agents were each adjusted to 30% by weight of active substance, based on free acid.
- Table 3 shows that 0.05% by weight of TTHMP used as 30% by weight Active substance solution, even when reducing hydrogen peroxide 0.2% better whiteness than comparison tests without TTHMP.
- a non-pretreated cotton jersey was treated with a solution of 0.2 g / l Epsom salt, 40 ml / l hydrogen peroxide 35% by weight, 15 g / l sodium hydroxide 50% by weight, 5 g / l Felosan JET ® and 2 g / l TTHMP solution from Example 1 padded (90% by weight liquor pickup) and held for 20 hours at room temperature.
- the Berger whiteness rose from 15 to 68, the residual peroxide was 27% by weight. Without the addition of TTHMP, the whiteness was only 63 and the residual peroxide was 2% by weight.
- An untreated cotton jersey was made with a solution of 30 g / l sodium hydroxide solution 50% by weight, 2 g / l Cotoblanc® TAA and 4 g / l TTHMP solution from example 1 treated for 30 minutes at 98 ° C and a liquor ratio of 1:10. Calcium decreased from 530 to 270 ppm, magnesium from 220 to 130 ppm and iron from 38 to 26 ppm. The comparison test without adding TTHMP gave 480 ppm calcium, 190 ppm magnesium and 35 ppm iron.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paper (AREA)
- Detergent Compositions (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19849379 | 1998-10-27 | ||
| DE19849379A DE19849379A1 (de) | 1998-10-27 | 1998-10-27 | Wäßrige Lösungen von Phosphonsäuren |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0997523A1 true EP0997523A1 (fr) | 2000-05-03 |
| EP0997523B1 EP0997523B1 (fr) | 2002-12-04 |
Family
ID=7885717
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP99121341A Expired - Lifetime EP0997523B1 (fr) | 1998-10-27 | 1999-10-26 | Solutions aqueuses d'acides phosphoniques |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0997523B1 (fr) |
| AT (1) | ATE229065T1 (fr) |
| DE (2) | DE19849379A1 (fr) |
| ES (1) | ES2188086T3 (fr) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005073130A1 (fr) * | 2004-02-02 | 2005-08-11 | Giovanni Bozzetto S.P.A. | Utilisation de polyaminomethylenephosphonates en tant qu'agents dispersants |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0009839A1 (fr) * | 1978-09-27 | 1980-04-16 | Unilever N.V. | Solutions aqueuses alcalines de peroxyde d'hydrogène stabilisées contre la décomposition |
| EP0125766A1 (fr) * | 1983-03-23 | 1984-11-21 | Albright & Wilson Limited | Phosphonates |
| EP0369711A2 (fr) * | 1988-11-11 | 1990-05-23 | Albright & Wilson Limited | Composition de phosphate et son utilisation |
| WO1996002624A1 (fr) * | 1994-07-13 | 1996-02-01 | So-Safe Specialty Products Pty. Ltd. | Kit, composition et procedes de nettoyage |
| EP0700874A1 (fr) * | 1994-09-01 | 1996-03-13 | Monsanto Europe S.A./N.V. | Concentré de phosphonate d'hexaméthylène |
| DE19528843A1 (de) * | 1995-08-04 | 1997-02-06 | Cht R Beitlich Gmbh | Verfahren zur Stabilisierung von alkalischen peroxidenthaltenden Bleichflotten für die Bleiche von Zellstoffen und anderen Faserstoffen |
-
1998
- 1998-10-27 DE DE19849379A patent/DE19849379A1/de not_active Withdrawn
-
1999
- 1999-10-26 DE DE59903638T patent/DE59903638D1/de not_active Expired - Lifetime
- 1999-10-26 ES ES99121341T patent/ES2188086T3/es not_active Expired - Lifetime
- 1999-10-26 EP EP99121341A patent/EP0997523B1/fr not_active Expired - Lifetime
- 1999-10-26 AT AT99121341T patent/ATE229065T1/de active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0009839A1 (fr) * | 1978-09-27 | 1980-04-16 | Unilever N.V. | Solutions aqueuses alcalines de peroxyde d'hydrogène stabilisées contre la décomposition |
| EP0125766A1 (fr) * | 1983-03-23 | 1984-11-21 | Albright & Wilson Limited | Phosphonates |
| EP0369711A2 (fr) * | 1988-11-11 | 1990-05-23 | Albright & Wilson Limited | Composition de phosphate et son utilisation |
| WO1996002624A1 (fr) * | 1994-07-13 | 1996-02-01 | So-Safe Specialty Products Pty. Ltd. | Kit, composition et procedes de nettoyage |
| EP0700874A1 (fr) * | 1994-09-01 | 1996-03-13 | Monsanto Europe S.A./N.V. | Concentré de phosphonate d'hexaméthylène |
| DE19528843A1 (de) * | 1995-08-04 | 1997-02-06 | Cht R Beitlich Gmbh | Verfahren zur Stabilisierung von alkalischen peroxidenthaltenden Bleichflotten für die Bleiche von Zellstoffen und anderen Faserstoffen |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005073130A1 (fr) * | 2004-02-02 | 2005-08-11 | Giovanni Bozzetto S.P.A. | Utilisation de polyaminomethylenephosphonates en tant qu'agents dispersants |
| US7659315B2 (en) | 2004-02-02 | 2010-02-09 | Giovanni Bozzetto S.P.A. | Use of polyaminomethylenephosphonates as dispersing agents |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2188086T3 (es) | 2003-06-16 |
| DE19849379A1 (de) | 2000-05-04 |
| EP0997523B1 (fr) | 2002-12-04 |
| ATE229065T1 (de) | 2002-12-15 |
| DE59903638D1 (de) | 2003-01-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE2226784A1 (fr) | ||
| EP0713882B1 (fr) | Chitosanes phosphonométhylées | |
| DE2161727C2 (de) | Verwendung von Poly-α-hydroxyacrylaten oder deren Derivaten zur Sequestrierung von Metallionen | |
| DE3720806C2 (de) | Verwendung eines Stabilisators in Peroxydbleichverfahren | |
| EP0233350B1 (fr) | Stabilisateurs pour peroxydes exempts de silicates et de magnésium | |
| DE1617161A1 (de) | Verstaerkungsmittel fuer synthetische Detergentien | |
| EP0842321B1 (fr) | Procede de stabilisation de bains de blanchiment alcalins contenant des peroxydes pour le blanchiment de pates de cellulose et d'autres substances fibreuses | |
| EP0997523B1 (fr) | Solutions aqueuses d'acides phosphoniques | |
| US4384970A (en) | Stabilizing compositions for peroxide products | |
| DE3820160C2 (de) | Konzentriertes Präparat und dessen Verwendung als Stabilisator für alkalische peroxydhaltige Flotten | |
| DE69022515T3 (de) | Bei niedrigen Temperaturen wirksame Bleichmittelzusammensetzungen für Textilien. | |
| DE69824279T2 (de) | Stabilisiertes Natriumcarbonat-Peroxyhydrat | |
| EP0557730A1 (fr) | Composition de régulation de blanchiment et procédé d'applications | |
| DE2544242A1 (de) | Verfahren zum waschen von textilien, sowie mittel zur durchfuehrung des verfahrens | |
| DE2903980C2 (de) | Aktivchlorhaltige Mittel | |
| DE19638569A1 (de) | Bleichregulatoren und Bleichverfahren damit | |
| EP0315848B1 (fr) | Procédé pour le prétraitement de matériaux textiles | |
| DE3925727A1 (de) | Verwendung von 2-hydroxy-3-aminopropionsaeure-derivaten als komplexbildner, bleichmittelstabilisatoren und gerueststoffe in wasch- und reinigungsmitteln | |
| DE2401062A1 (de) | Phosphatfreie waschmittelmischungen | |
| DD220328A1 (de) | Waschhilfsmittel zur weissgradverstaerkung | |
| GB2226341A (en) | Stabilising hydrogen peroxide bleach | |
| DE3335011A1 (de) | Peroxysaeure enthaltendes bleich- und waschmittel | |
| EP0759103A1 (fr) | Utilisation de polymeres solubles dans l'eau et de polyhydroxymonocarboxylates ou polyhydroxybicarboxylates dans le blanchiment de textiles | |
| EP0775226B2 (fr) | Utilisation d'un concentre d'agents stabilisants pour solutions aqueuses de blanchiment et de traitement a base de peroxyde d'hydrogene et/ou d'autres composes peroxo organiques et/ou inorganiques | |
| DD144073A1 (de) | Verfahren zur herstellung von stabilisierten peroxid enthaltenden loesungen |
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 DE ES FI SE |
|
| AX | Request for extension of the european patent |
Free format text: AL;LT;LV;MK;RO;SI |
|
| 17P | Request for examination filed |
Effective date: 20001012 |
|
| AKX | Designation fees paid |
Free format text: AT DE ES FI SE |
|
| 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 |
|
| 17Q | First examination report despatched |
Effective date: 20020409 |
|
| 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 DE ES FI SE |
|
| REF | Corresponds to: |
Ref document number: 229065 Country of ref document: AT Date of ref document: 20021215 Kind code of ref document: T |
|
| REF | Corresponds to: |
Ref document number: 59903638 Country of ref document: DE Date of ref document: 20030116 |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2188086 Country of ref document: ES Kind code of ref document: 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 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20031029 Year of fee payment: 5 |
|
| 26N | No opposition filed |
Effective date: 20030905 |
|
| 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: 20041027 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FI Payment date: 20051021 Year of fee payment: 7 |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20041027 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20061026 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20071220 Year of fee payment: 9 |
|
| EUG | Se: european patent has lapsed | ||
| 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: 20081027 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20141204 Year of fee payment: 16 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 20141022 Year of fee payment: 16 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 59903638 Country of ref document: DE |
|
| REG | Reference to a national code |
Ref country code: AT Ref legal event code: MM01 Ref document number: 229065 Country of ref document: AT Kind code of ref document: T Effective date: 20151026 |
|
| 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: 20160503 |
|
| 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: 20151026 |