EP1513916A1 - Verwendung von alkylenoxideinheiten enthaltenden copolymeren als zusatz in wasch- und reinigungsmitteln - Google Patents
Verwendung von alkylenoxideinheiten enthaltenden copolymeren als zusatz in wasch- und reinigungsmittelnInfo
- Publication number
- EP1513916A1 EP1513916A1 EP03740181A EP03740181A EP1513916A1 EP 1513916 A1 EP1513916 A1 EP 1513916A1 EP 03740181 A EP03740181 A EP 03740181A EP 03740181 A EP03740181 A EP 03740181A EP 1513916 A1 EP1513916 A1 EP 1513916A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- copolymers
- mol
- component
- detergents
- alkylene
- 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
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
Definitions
- copolymers containing alkylene oxide units as additives in detergents and cleaning agents
- the present invention relates to the use of copolymers containing alkylene oxide units which
- R 1 is hydrogen or methyl
- R 2 is a chemical bond or unbranched or branched Ci-C ⁇ -alkylene
- R 3 are identical or different unbranched or branched C 2 -C alkylene radicals
- R 4 unbranched or branched C 1 -C 6 alkyl
- the invention relates to detergents and cleaning agents which contain these copolymers as a deposit-inhibiting additive.
- the dishes In automatic dishwashing, the dishes should be cleaned in a residue-free state with an immaculately shiny surface, for which a cleaner, rinse aid and regeneration salt usually have to be used to soften the water.
- the so-called "2inl" dishwashing detergents introduced on the market contain, in addition to the detergent for removing the soiling on the wash ware, integrated rinse aid surfactants, which ensure that water flows off the wash ware during the rinse and drying cycle and thus prevent limescale and water stains. Refilling a rinse aid is no longer necessary when using these products.
- Modern machine dishwashers "3inl" cleaners, are to combine the three functions of cleaning, rinsing and water softening in a single detergent formulation, so that the refill of salt with water hardness levels of 1 to 3 is also superfluous for the consumer.
- Sodium tripolyphosphate is usually added to these cleaners to bind the hardness-forming calcium and magnesium ions. This in turn results in calcium and magnesium phosphate deposits on the wash ware.
- EP-A-324 568 describes water-soluble copolymers for detergents and cleaning agents which are obtained by polymerizing acrylic acid, methacrylic acid and alkoxypolyethylene glycol methacrylates, which have a long-chain alkoxy radical and / or a long-chain polyethylene glycol block, in the presence of isopropanol be preserved.
- the alkoxypolyethylene glycol methacrylate content of these copolymers is ⁇ 1 mol%.
- copolymers based on at least one monomer from the group of maleic acid, acrylic acid and methacrylic acid and an optionally methoxy- or ethoxylated polyethylene glycol (meth) acrylate as a further monomer which have an average molecular weight M w of 1,000 to 10,000, are used for desizing, cleaning, bleaching and dyeing natural and synthetic bevels.
- Copolymers of acrylic acid and methoxypolyethylene glycol methacrylate are disclosed in detail.
- JP-A-2000/24691 describes copolymers of monomers containing unsaturated carboxylic acids and polyalkylene oxide units with average molecular weights M w of> 50,000 to 3,000,000 as agents against scale based in particular on silicates in water circuits, for example cooling systems. In one only copolymers of acrylic acid and methoxypolyethylene glycol methacrylate are disclosed individually.
- the object of the invention was to remedy the problems outlined above and to provide an additive which can also be used advantageously, in particular, in multifunctional cleaners and in particular has a deposit-inhibiting effect.
- R 1 is hydrogen or methyl
- R 2 is a chemical bond or unbranched or branched Ci-C ß alkylene
- R 3 are identical or different unbranched or branched C 2 -C alkylene radicals
- R 4 unbranched or branched Ci-C ß alkyl
- copolymerized randomly or in blocks found as an additive to detergents and cleaning agents. Furthermore, detergents and cleaning agents have been found which contain the copolymers containing alkylene oxide units as a coating-inhibiting additive.
- the copolymers containing alkylene oxide units contain as copolymerized components (a) and (b) acrylic acid or methacrylic acid and / or water-soluble salts of these acids, in particular the alkali metal salts, such as potassium and especially sodium salts, and ammonium salts.
- the proportion of acrylic acid (a) in the copolymers to be used according to the invention is 50 to 93 mol%, preferably 65 to 85 mol% and particularly preferably 65 to 75 mol%.
- Methacrylic acid (b) is present in the copolymers to be used according to the invention in an amount of 5 to 30 mol%, preferably 10 to 25 mol% and especially 15 to 25 mol%.
- the copolymers contain, as component (c), nonionic monomers of the formula I.
- R 1 is hydrogen or preferably methyl
- R 2 unbranched or branched Ci-C ⁇ alkylene or preferably a chemical bond
- R 3 same or different unbranched or branched
- R 4 unbranched or branched Ci-C ⁇ -alkyl, preferably dC 2 alkyl;
- n 3 to 50 preferably 5 to 40, particularly preferably 10 to 30.
- methoxypolyethylene glycol (meth) acrylate methoxypolypropylene glycol (meth) acrylate, methoxypolybutylene glycol (meth) acrylate, methoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate, ethoxy polyethylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, ethoxypolybutylene glycol (meth) acrylate and Ethoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate, methoxypolyethylene glycol (meth) acrylate and methoxypolypropylene glycol (meth) acrylate being preferred and methoxypolyethylene glycol methacrylate being particularly preferred.
- the polyalkylene glycols contain 3 to 50, especially 5 to 40 and especially 10 to 30 alkylene oxide units.
- the proportion of nonionic monomers (c) in the copolymers to be used according to the invention is 2 to 20 mol%, preferably 5 to 15 mol% and especially 5 to 10 mol%.
- the copolymers to be used according to the invention generally have an average molecular weight M w of 3,000 to 50,000, preferably 10,000 to 30,000 and particularly preferably 15,000 to 25,000.
- the K value of the copolymers is usually 15 to 40, in particular 20 to 35, especially 27 to 30 (measured in 1% by weight aqueous solution at 25 ° C., according to H. Fikentscher, Cellulose- Chemie, vol. 13, pp. 58-64 and 71-74 (1932)).
- copolymers to be used according to the invention can be produced by radical polymerization of the monomers. All known radical polymerization processes can be used. In addition to bulk polymerization, the methods of solution polymerization and emulsion polymerization should be mentioned in particular, with solution polymerization being preferred.
- the polymerization is preferably carried out in water as a solvent.
- alcoholic solvents in particular C 1 -C 4 alcohols, such as methanol, ethanol and isopropanol, or mixtures of these solvents with water.
- thermally activatable polymerization initiators include initiators with a decomposition temperature in the range from 20 to 180 ° C., in particular from 50 to 90 ° C., are preferred.
- suitable thermal initiators are inorganic peroxo compounds, such as peroxodisulfates (ammonium and preferably sodium peroxoxdisulfate), peroxosulfates, percarbonates and hydrogen peroxide; organic peroxo compounds, such as diacetyl peroxide, di tert.-butyl peroxide, diamyl peroxide, dioctanoyl peroxide, didecanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, bis (o-toloyl) peroxide, succinyl peroxide, tert.-butyl peracetate, tert , tert-butyl peroctoate, tert.
- inorganic peroxo compounds such as peroxo
- Butyl perneodecanoate tert. -Butylperbenzoa, tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxy-2-ethylhexanoate and diisopropyl peroxidicarbamate; Azo compounds such as 2, 2 '-azobisisobutyronitrile, 2,2' -azo-bis (2-methylbutyronitrile) and azobis (2-amidopropane) dihydrochloride.
- initiators can be used in combination with reducing compounds as starter / controller systems.
- reducing compounds include phosphorus-containing compounds, such as phosphorous acid, hypophosphites and phosphinates, sulfur-containing compounds, such as sodium bisulfite, sodium sulfite and sodium formaldehyde sulfoxilate, and hydrazine.
- photoinitiators examples include benzophenone, aceto-phenone, benzoin ether, benzyl dialkyl ketones and their derivatives.
- Thermal initiators are preferably used, inorganic peroxo compounds, in particular sodium peroxodisulfate (sodium persulfate), being preferred.
- the peroxo compounds are used particularly advantageously in combination with sulfur-containing reducing agents, in particular sodium bisulfite, as the redox initiator system.
- sulfur-containing reducing agents in particular sodium bisulfite
- copolymers are obtained which contain -S0 ⁇ Na + and / or -S0 ⁇ Na + as end groups and are notable for particular cleaning power and deposit-inhibiting action.
- starter / regulator systems containing phosphorus can also be used, e.g. Hypophosphites / phosphinates.
- the quantities of photoinitiator and starter / regulator system must be matched to the substances used. If, for example, the preferred system peroxodisulfate / hydrogen sulfite is used, 2 to 6% by weight, preferably 3 to 5% by weight, peroxodisulfate and usually 5 to 30% by weight, preferably 5 to 10% by weight, are usually used. %, Hydrogen sulfite, based in each case on the monomers (a), (b) and (c).
- polymerization regulators can also be used.
- the compounds known to those skilled in the art are suitable, for example sulfur compounds, such as mercaptoethanol, 2-ethylhexylthioglycolate, thioglycolic acid and dodecyl mercaptan. If polymerisa- tion controller are used, their amount is in the
- the polymerization temperature is generally 30 to 200 ° C, preferably 50 to 150 ° C and particularly preferably 80 to
- the polymerization can be carried out under atmospheric pressure, but is preferably carried out in a closed system under the self-developing pressure.
- the monomers (a), (b) and (c) can be used as such in the preparation of the copolymers to be used according to the invention, but reaction mixtures which are obtained in the preparation of the monomers (c) can also be used.
- reaction mixtures which are obtained in the preparation of the monomers (c) can also be used.
- methoxypolyethylene glycol methacrylate the monomer mixture obtained in the esterification of polyethylene glycol monomethyl ether with an excess of methacrylic acid can be used.
- the esterification can advantageously also be carried out in situ in the polymerization mixture by combining (1) acrylic acid, (2) a mixture of methacrylic acid and polyethylene glycol monomethyl ether and (3) radical initiators in parallel.
- a catalyst required for the esterification such as methanesulfonic acid or p-toluenesulfonic acid, can additionally be used.
- copolymers to be used according to the invention can also be obtained by a polymer-analogous reaction, e.g. by reacting an acrylic acid / methacrylic acid copolymer with polyalkylene glycol onoalkyl ether.
- a polymer-analogous reaction e.g. by reacting an acrylic acid / methacrylic acid copolymer with polyalkylene glycol onoalkyl ether.
- the radical copolymerization of the monomers is preferred.
- the aqueous solutions obtained in the preparation of the copolymers containing carboxylic acid groups to be used according to the invention can be neutralized or partially neutralized, i.e., by adding base, in particular sodium hydroxide solution. adjusted to a pH in the range 4-8, preferably 4.5-7.5.
- copolymers used according to the invention are outstandingly suitable as additives for detergents and cleaning agents.
- the copolymers used according to the invention thereby also increase the cleaning power of the dishwashing detergent. In addition, they promote the drainage of the water from the wash items even in low concentrations, so that the proportion of rinse aid surfactants in the dishwashing detergent can be reduced.
- copolymers containing sulfonic acid groups are used, in particular also when the dishwasher is operated without water regeneration salt for water softening.
- the copolymers containing sulfonic acid groups can therefore be used advantageously not only in 2inl cleaners but also in 3inl cleaners.
- copolymers used according to the invention can be used directly in the form of the aqueous solutions obtained in the preparation and also in dried, e.g. form obtained by spray drying, fluidized spray drying, roller drying or freeze drying. Accordingly, the detergents and cleaning agents according to the invention can be in solid or liquid form, e.g. be provided as powders, granules, extrudates, tablets, liquids or gels.
- reaction mixture After stirring for two hours at 100 ° C., the reaction mixture was cooled to room temperature and adjusted to a pH of 7.2 by adding 190 g of 50% strength by weight sodium hydroxide solution. A slightly yellowish, clear solution of a copolymer with a solids content of 25.7% by weight and a K value of 27.2 (1% by weight aqueous solution, 25 ° C.) was obtained.
- Dishwasher Miele G 686 SC rinses: 2 rinses 55 ° C normal (without pre-rinsing) dishes: knife (WMF table knife Berlin, monoblock) 10 and barrel-shaped glass beaker (Matador, Ruhr Kristall)
- Dishwashing liquid 21 g copolymer: 4.2 g rinse aid temperature: 65 ° C 15 water hardness: 25 ° dH
- the items to be washed were assessed 18 hours after cleaning by visual inspection in a black-painted light box with halogen spotlight and pinhole using a grading scale from 20 10 (very good) to 1 (very bad).
- the highest grade 10 corresponds to surfaces free of deposits and drips, from scores ⁇ 5 deposits and drops are already recognizable with normal room lighting, so they are perceived as disturbing.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10225594 | 2002-06-07 | ||
DE10225594A DE10225594A1 (de) | 2002-06-07 | 2002-06-07 | Verwendung von Alkylenoxideinheiten enthaltenden Copolymeren als Zusatz in Wasch- und Reinigungsmitteln |
PCT/EP2003/005823 WO2003104373A1 (de) | 2002-06-07 | 2003-06-04 | Verwendung von alkylenoxideinheiten enthaltenden copolymeren als zusatz in wasch- und reinigungsmitteln |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1513916A1 true EP1513916A1 (de) | 2005-03-16 |
EP1513916B1 EP1513916B1 (de) | 2006-10-11 |
Family
ID=29557707
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP03740181A Expired - Lifetime EP1513916B1 (de) | 2002-06-07 | 2003-06-04 | Verwendung von alkylenoxideinheiten enthaltenden copolymeren als zusatz in geschirrspülmitteln |
Country Status (11)
Country | Link |
---|---|
US (1) | US20050245427A1 (de) |
EP (1) | EP1513916B1 (de) |
JP (1) | JP2005531653A (de) |
CN (1) | CN1273577C (de) |
AT (1) | ATE342332T1 (de) |
AU (1) | AU2003274115A1 (de) |
BR (1) | BR0311490B1 (de) |
CA (1) | CA2488032C (de) |
DE (2) | DE10225594A1 (de) |
MX (1) | MXPA04011456A (de) |
WO (1) | WO2003104373A1 (de) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10350420A1 (de) * | 2003-10-28 | 2005-06-02 | Basf Ag | Verwendung von Alkylenoxideinheiten enthaltenden Copolymeren als belagsinhibierende Additive im Klarspülgang des maschinellen Geschirrspülers |
DE102005028460A1 (de) | 2005-06-17 | 2006-12-28 | Basf Ag | Verwendung von Alkylenoxideinheiten enthaltenden Copolymeren als Zusatz zu wäßrigen Systemen |
DE102005041347A1 (de) * | 2005-08-31 | 2007-03-01 | Basf Ag | Reinigungsformulierungen für die maschinelle Geschirrreinigung enthaltend hydrophil modifizierte Polycarboxylate |
DE102005041349A1 (de) | 2005-08-31 | 2007-03-01 | Basf Ag | Reinigungsformulierungen für die maschinelle Geschirrreinigung enthaltend hydrophil modifizierte Polycarboxylate |
DE102008028229A1 (de) * | 2008-06-16 | 2009-12-17 | Fit Gmbh | Zusammensetzung zur Herstellung von Reinigungsmitteln, Tablettiermischung, Polymerkombination, Reinigunsmittel-Formkörper und Verfahren zur deren Herstellung |
US8685911B2 (en) * | 2009-11-30 | 2014-04-01 | The Procter & Gamble Company | Rinse aid compositions |
JP5668936B2 (ja) * | 2011-09-06 | 2015-02-12 | 三浦工業株式会社 | 全窒素の定量方法 |
JPWO2020027310A1 (ja) * | 2018-08-03 | 2021-08-02 | 株式会社日本触媒 | ポリカルボン酸系共重合体 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3719647A (en) * | 1971-01-25 | 1973-03-06 | Procter & Gamble | New polymers and detergent compositions containing them |
JP2901294B2 (ja) * | 1989-12-12 | 1999-06-07 | 日華化学株式会社 | 繊維製品用洗浄性向上剤 |
JP2000024691A (ja) * | 1998-07-09 | 2000-01-25 | Jsr Corp | 水溶性共重合体(塩)およびスケール防止剤 |
US6998453B2 (en) * | 2001-10-03 | 2006-02-14 | Nippon Shokubai Co., Ltd. | (Meth)acrylic acid type polymer and unsaturated polyalkylene glycol type copolymer, and methods for production thereof |
-
2002
- 2002-06-07 DE DE10225594A patent/DE10225594A1/de not_active Withdrawn
-
2003
- 2003-06-04 WO PCT/EP2003/005823 patent/WO2003104373A1/de active IP Right Grant
- 2003-06-04 US US10/516,201 patent/US20050245427A1/en not_active Abandoned
- 2003-06-04 AU AU2003274115A patent/AU2003274115A1/en not_active Abandoned
- 2003-06-04 EP EP03740181A patent/EP1513916B1/de not_active Expired - Lifetime
- 2003-06-04 CA CA2488032A patent/CA2488032C/en not_active Expired - Fee Related
- 2003-06-04 JP JP2004511434A patent/JP2005531653A/ja active Pending
- 2003-06-04 CN CNB038131765A patent/CN1273577C/zh not_active Expired - Fee Related
- 2003-06-04 MX MXPA04011456A patent/MXPA04011456A/es active IP Right Grant
- 2003-06-04 BR BRPI0311490-2A patent/BR0311490B1/pt not_active IP Right Cessation
- 2003-06-04 DE DE50305365T patent/DE50305365D1/de not_active Expired - Lifetime
- 2003-06-04 AT AT03740181T patent/ATE342332T1/de not_active IP Right Cessation
Non-Patent Citations (1)
Title |
---|
See references of WO03104373A1 * |
Also Published As
Publication number | Publication date |
---|---|
ATE342332T1 (de) | 2006-11-15 |
DE10225594A1 (de) | 2003-12-18 |
CA2488032A1 (en) | 2003-12-18 |
BR0311490A (pt) | 2005-03-15 |
BR0311490B1 (pt) | 2013-04-09 |
WO2003104373A1 (de) | 2003-12-18 |
CN1659264A (zh) | 2005-08-24 |
AU2003274115A1 (en) | 2003-12-22 |
EP1513916B1 (de) | 2006-10-11 |
CN1273577C (zh) | 2006-09-06 |
CA2488032C (en) | 2010-09-14 |
MXPA04011456A (es) | 2005-02-14 |
DE50305365D1 (de) | 2006-11-23 |
JP2005531653A (ja) | 2005-10-20 |
US20050245427A1 (en) | 2005-11-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1516040B1 (de) | Verwendung von sulfons uregruppenhaltigen copolymeren als zusatz in wasch- und reinigungsmitteln | |
EP0451508B1 (de) | Verfahren zur Herstellung von Homo- und Copolymerisaten monoethylenisch ungesättigter Dicarbonsäuren und ihre Verwendung | |
EP0471710B1 (de) | Copolymerisate, die polyalkylenoxid-blöcke enthaltende monomere einpolymerisiert enthalten, ihre herstellung und ihre verwendung | |
DE19516957C2 (de) | Wasserlösliche Copolymere und Verfahren zu ihrer Herstellung und ihre Verwendung | |
DE4303320C2 (de) | Waschmittelzusammensetzung mit verbessertem Schmutztragevermögen, Verfahren zu dessen Herstellung und Verwendung eines geeigneten Polycarboxylats hierfür | |
DE69026908T2 (de) | Biologisch abbaubare, wasserlösliche Pfropfcopolymere, Zusammensetzungen solcher Copolymere und Verfahren für die Anwendung solcher Copolymere | |
EP1682645B1 (de) | Verwendung von alkylenoxideinheiten enthaltenden copolymeren als belagsinhibierende additive in klarspülmitteln für maschinelle geschirrspüler | |
EP1687348B1 (de) | Polyalkylenoxidgruppen und quartäre stickstoffatome enthaltende copolymere | |
DE10243661A1 (de) | Flüssige Wasch-und Reinigungsmittel mit Konsistenz-gebenden Polymeren | |
EP1513916B1 (de) | Verwendung von alkylenoxideinheiten enthaltenden copolymeren als zusatz in geschirrspülmitteln | |
DE4209923A1 (de) | Flüssige Reinigungsmittel für harte Oberflächen | |
DE3711299C2 (de) | Verwendung von Pfropfpolymerisaten auf Basis von Polyvinylpyrrolidon als Vergrauungsinhibitoren beim Waschen und Nachbehandeln von Synthesefasern enthaltendem Textilgut | |
DE10062355A1 (de) | Verwendung eines ampholytischen, amphiphilen Copolymers als Oberflächenbehandlungsmittel und Oberflächenbehandlungszusammensetzung, die das Copolymer enthält | |
EP0637627B1 (de) | Waschmittelformulierungen | |
EP0622449B1 (de) | Wasserenthärtende Formulierungen | |
EP1660547B1 (de) | Sulfonsäuregruppen- und carboxylgruppenhaltige copolymere | |
DE4316744A1 (de) | Klarspülmittel mit biologisch abbaubaren Polymeren | |
EP2992075B1 (de) | Kammpolymere als waschkraftverstärker für waschmittel | |
EP0625567B1 (de) | Maschinengeschirreinigungsmittel | |
DE4316743A1 (de) | Klarspülmittel mit biologisch abbaubaren Polymeren |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20050107 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL LT LV MK |
|
DAX | Request for extension of the european patent (deleted) | ||
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
RTI1 | Title (correction) |
Free format text: USE OF COPOLYMERS CONTAINING ALKYLENE OXIDE UNITS, AS AN ADDITIVE IN DISHWASHING COMPOSITIONS |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR |
|
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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20061011 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20061011 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20061011 Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20061011 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20061011 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20061011 Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20061011 Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20061011 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: GERMAN |
|
REF | Corresponds to: |
Ref document number: 50305365 Country of ref document: DE Date of ref document: 20061123 Kind code of ref document: P |
|
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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070111 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070111 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070111 |
|
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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070122 |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 20070117 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070319 |
|
NLV1 | Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act | ||
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FD4D |
|
ET | Fr: translation filed | ||
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 |
Effective date: 20070712 |
|
BERE | Be: lapsed |
Owner name: BASF A.G. Effective date: 20070630 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070630 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
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: 20070630 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070630 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070112 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070630 |
|
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: 20070604 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20061011 |
|
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: 20070604 Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20061011 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070412 Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20061011 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 13 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 14 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 15 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 16 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20210628 Year of fee payment: 19 Ref country code: FR Payment date: 20210625 Year of fee payment: 19 Ref country code: IT Payment date: 20210622 Year of fee payment: 19 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20210625 Year of fee payment: 19 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 50305365 Country of ref document: DE |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20220604 |
|
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: 20220630 |
|
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: 20220604 Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230103 |
|
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: 20220604 |