EP0555258A1 - Enzymatisches flüssigwaschmittel. - Google Patents
Enzymatisches flüssigwaschmittel.Info
- Publication number
- EP0555258A1 EP0555258A1 EP91918230A EP91918230A EP0555258A1 EP 0555258 A1 EP0555258 A1 EP 0555258A1 EP 91918230 A EP91918230 A EP 91918230A EP 91918230 A EP91918230 A EP 91918230A EP 0555258 A1 EP0555258 A1 EP 0555258A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- fatty
- mixture
- saturated
- composition according
- 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
- C11D10/00—Compositions of detergents, not provided for by one single preceding group
- C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
- C11D10/042—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on anionic surface-active compounds and soap
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/662—Carbohydrates or derivatives
-
- 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
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38663—Stabilised liquid enzyme compositions
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
Definitions
- the invention relates to a liquid detergent which contains enzymes and is largely composed of surfactants which are obtained from native raw materials.
- liquid detergents which contain alkyl polyglycosides as nonionic surfactants, enzymes and as solvents water and lower monofunctional alcohols with 1 to 3 carbon atoms or glycols such as 1,2-propanediol.
- the alcoholic solvent component acts as an enzyme stabilizer.
- Liquid detergents with enzymes are known from German patent application 31 25 533, polyols and boric acid or their boron equivalent being used as enzyme stabilizers.
- Suitable polyols are diols, such as 1,2-propanediol or ethylene glycol, and glycerin.
- German patent application 3910947 describes an enzymatic liquid detergent which contains anionic surfactants such as fatty alkyl sulfate and soap and, as a solvent, water and a mixture of mono- and polyfunctional alcohols.
- the monofunctional alcohol consists of ethanol, while 1,2-propanediol is used as the polyfunctional alcohol.
- the invention accordingly relates to an enzymatic liquid detergent, the anionic surfactants and water and as a solvent contains a mixture of mono- and polyfunctional alcohols and is characterized in that it contains fatty alkyl sulfates as anionic surfactants in the form of the sodium salts and soaps, consisting of salts of ethylenically unsaturated C12 to Cig fatty acids and saturated (2- to Cj ⁇ fatty acids in the Weight ratio of 3: 1 to 1: 3, as an organic solvent contains a mixture of ethanol and glycerol and enzymes from the group of proteases, aylases, lipases and mixtures of these.
- Suitable fatty alkyl sulfates are the sulfuric acid monoesters of (42- to Ci8-fatty alcohols such as lauryl, myristyl or cetyl alcohol) and the fatty alcohol mixtures obtained from coconut oil, palm and palm kernel oil and tallow, which also contain proportions of unsaturated alcohols, e.g. Mixtures in which the proportions of the alkyl radicals are 50 to 70% by weight up to (42, 18 to 30% by weight up to (44, 5 to 15% by weight). -% on (46, less than 3% by weight on (40 and less than 10% by weight on CQ.
- the proportion of fatty alkyl sulfates in the compositions is preferably 3 to 20% by weight and in particular 5 to 16% by weight. - 5 -
- the soaps are the salts of saturated and unsaturated fatty acids with ( 42 to Ci ⁇ chain lengths in the form of their mixtures.
- a preferred soap mixture is formed from sodium oleate and the sodium salts of the saturated Ci2-Ci5 fatty acid mixtures.
- the proportion of Ci2-i4 Fatty acids in the saturated soap component is expediently at least 60% by weight, preferably at least 75% by weight (calculated as fatty acid) .
- Coconut fatty acids of which the proportions of 10 and Fewer carbon atoms are largely separated off
- oleic acid and coconut fatty acid can still contain certain proportions of stearic acid, but their proportion, based on soap-forming fatty acids, should not exceed 25% by weight preferably less than 20% by weight, and a mixture of sodium oleate and the sodium salt of lauric acid is also preferred
- the ratio of unsaturated soaps to saturated soaps is preferably 2: 1 to 1: 2 and in particular 1: 1 to 1: 1.5.
- the arrival part of the soaps in the compositions is preferably 10 to 25% by weight and in particular 12 to 20% by weight.
- the preferably builder-free agents contain water and a mixture of ethanol and glycerol as solvents.
- the proportion of organic solvents is preferably 5 to 20% by weight and in particular 7 to 17% by weight.
- the weight ratio of ethanol to glycerol is preferably 3: 1 to 1: 3 and in particular 2: 1 to 1: 1.5.
- a mixture of ethanol and glycerin with a given weight ratio ethanol: glycerin has a higher enzyme stability than equal amounts of a mixture of ethanol and 1,2-propanediol with the same, given weight ratio ethanol: 1,2-propanediol.
- glycerin is obtained from native and not from petrochemical raw materials.
- glycerin in the liquid detergent according to the invention therefore also appears to be particularly advantageous from an ecological point of view.
- the proportion of water is chosen so that non-gelling solutions are formed which are stable against segregation, for which 45-55% by weight of water are generally sufficient.
- a greater dilution of the agents with water has no advantages because of the greater packaging requirement.
- Preferred enzymes are proteases, in particular mixtures of protease and amylase, the weight ratio protease: amylase advantageously being between 15: 1 and 5: 1.
- the total proportion of the enzymes is preferably 0.2 to 1% by weight and in particular 0.2 to 0.8% by weight.
- the liquid detergents according to the invention can contain nonionic surfactants as further constituents.
- Particularly preferred embodiments contain 1 to 10% by weight of alkyl glucosides of the general formula R0 (G) x , where R is a fatty alkyl radical, G is a glucose unit and x is a number between 1 and 10.
- Suitable fatty alkyl glucosides are glucosides with a Cg to C22 alkyl radical.
- the higher fatty alcohols are preferably obtained by reducing natural fats, so that within the scope of this disclosure the term alkyl in alkyl glucoside includes saturated and ethylenically unsaturated residues and their mixtures, including those with different chain lengths in the mixture.
- a preferred alkyl radical is an im essentially from (42 to Cjg existing alkyl radical, which is derived from lauryl, myristyl, cetyl and stearyl alcohol and from technical fractions, which preferably contain saturated alcohols.
- Particularly preferred is the use of alkyl glucosides, the alkyl radical of 50-70 wt % (42 and 18-30% by weight (44.
- the index number x is any number between 1 and 10; it indicates the degree of oligo erization, ie the distribution of monoglucosides and oligoglucosides.
- the average degree of oligomerization is preferred x has a value of 1.1-3.0 and in particular of significantly less than 1.5. A degree of oligomerization between 1.1 and 1.4 is particularly preferred.
- the clear liquid agents can contain further non-ionic surfactants of the type of the adducts of 1-10 mol ethylene oxide with primary (42 to cig fatty alcohols and their mixtures such as coconut, tallow or oleyl alcohols.
- Oxo alcohols according to The alcohols produced by the oxosynthesis or hydroformylation method are likewise suitable, but are less preferred on account of their origin from fossil raw materials, and the proportion of the fatty alcohol ethoxylates in the compositions can be 0-17% by weight, preferably up to 14% by weight .
- the pH of the agents according to the invention is generally 7 to 10.5, preferably 7 to 9.5.
- the agents can contain small amounts of free sodium hydroxide solution, which are required to set higher pH values between 8.5 and 10.5.
- the detergents can contain known additives commonly used in detergents, for example salts of citric acid in amounts of 0.1-2, preferably 0.3-1% by weight (calculated as free acid), salts of polyphosphonic acids, optical brighteners, further enzyme stabilizers, filler salts and colorants and fragrances.
- the salts of optionally present polyphosphonic acids are preferably the neutral reacting sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate and diethylenetriamine pentamethylene phosphonate in amounts of 0.1-1.5% by weight.
- the total phosphorus content in the compositions is preferably less than 0.5%.
- the agents can contain further enzyme stabilizers.
- enzyme stabilizers for example, 0.5 to 1% by weight sodium formate can be used.
- proteases which are stabilized with soluble calcium salts and a calcium content of preferably 1.2% by weight, based on the enzyme.
- boron compounds for example boric acid, boron oxide, borax and other alkali metal borates, such as the salts of orthoboric acid (H3BO3), metaboric acid (HBO2) and pyroboric acid (tetraboric acid H2B4O7), is particularly advantageous.
- Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica. Mixtures of different foam inhibitors can also advantageously be used, eg. B. from silicone, paraffins or waxes.
- the compositions contain 5 to 15% by weight of fatty alkyl sulfate, 10 to 20% by weight of soaps, consisting of the salt of 01-acid and the salt of saturated C42- bis (45-fatty acids or mixtures thereof in the weight ratio of oleate to saturated soap such as 2: 1 to 1: 2, 1 to 5% by weight of fatty alkyl glucoside, 12 to 17% by weight of ethanol and glycerol, 0.5 to 1% by weight of protease and 0.2 to 1% by weight. -% salt of citric acid (based on free acid).
- Liquid detergents which contain 3 to 8% by weight of fatty alkyl sulfate, 12 to 20% by weight of soaps and consist of sodium oleate and the sodium salt of saturated (42- to (46-fatty acids or mixtures thereof) are particularly advantageous in the weight ratio of oleate to saturated soap such as 2: 1 to 1: 2, 0 to 3 wt .-% fatty alkyl glucoside, 8 to 14 wt .-% fatty alcohol with 1 to 10 moles of ethylene oxide per mole of fatty alcohol, 8 to 12 wt .-% ethanol and glycerol in a weight ratio of 2: 1 to 1: 1.5, 0.5 to 1% by weight of protease or a mixture of protease and amylase and 0 to 1% by weight of salt of citric acid (based on free acid) contain.
- oleate to saturated soap such as 2: 1 to 1: 2, 0 to 3 wt .-% fatty alkyl glucoside
- soaps consisting of sodium oleate and the sodium salt of saturated (42 to Cjo fatty acids or their mixtures in the weight ratio of oleate to saturated soap such as 2: 1 to 1: 1, 1 to 4% by weight of fatty alkyl glucoside, 2 to 5% by
- the agents are notable for easy assembly, storage stability, especially at low temperatures between + 5 ° C. and -5 ° C., and easy miscibility with water. When used in mechanical washing processes, they also show good washing-in behavior.
- the liquid detergents can be produced in a manner known per se.
- the oleic acid and the C42 bis (46 fatty acid or the Ci2-Ci6 fatty acid mixture and optionally citric acid are first dissolved in a preheated mixture to 50-80 ° C., which contains water, sodium hydroxide and glycerol, and stirred in
- the remaining constituents of the liquid detergent can be added in any order.
- alkyl sulfate is added before the addition of alkyl glucoside and fatty alcohol ethoxylate.
- the enzyme or the enzyme mixture is added as the last component, preferably at room temperature Liquid detergent stirred in. Examples
- Liquid detergents according to the invention can be composed of the components listed in Table 1, where in particular means:
- the fatty acid mixture (B1 + B2) contained a total of 10% by weight of stearic acid, based on the fatty acid mixture; Industrial oleic acid consisted of 12% by weight of palmitic acid.
- the agents were prepared by first heating a mixture of water, sodium hydroxide (D) and glycerol (F2) to 70 ° C.
- the fatty acids (B1) and (B2) and optionally citric acid (G) were stirred into the warm solution.
- Fatty alkyl sulfate (A), alkyl glucoside (C) and fatty alcohol ethoxylate (E) were added in the order given with constant stirring.
- ethanol (Fl) was added to the clear solution.
- the enzyme and colorants and fragrances which belong to the remaining constituents, were added. 9
- fatty alkyl sulfate in the above composition is partly or wholly by lauryl, myristyl or cetyl sulfate, by the sulfation product of oleyl alcohol or by the sulfation products of fatty alcohol mixtures obtained from palm and palm kernel oil and tallow, and by mixtures is replaced by these.
- soap-forming saturated fatty acids (B2) specified in the above composition are partially or completely replaced by lauric, myristic or palmitic acid or by natural fatty acid mixtures such as hydrogenated tallow and by mixtures of these.
- fatty alcohol ethoxylate used in the above agents is wholly or partly by pure C ⁇ 2 ⁇ C14, Ci6, saturated and unsaturated C ⁇ g fatty alcohol with 1-10 ethylene oxide groups (E0) or other native fatty alcohol - 3 mixtures, which are obtained, for example, from palm oil, palm kernel oil or dough fat, by means of Ci2-Ci4 fatty alcohol with 3 EO, Ci2-Ci4 fatty alcohol with 4 EO, Ci2-Ci8 fatty alcohol with 3 EO, Ci2-Ci8 fatty alcohol with 5 EO, by a mixture of Ci2-C ⁇ 8 fatty alcohol with 5 EO and Ci2-Ci4-fatty alcohol with 3 EO, by cetyloleyl alcohol (iodine number 50 - 55) with 2 EO, cetyloleyl alcohol (iodine number 50 - 55) with 7 EO, cetyloleyl alcohol (Iodine number 50-55) with 50% E0, by a mixture
- the agents according to the invention are distinguished by a skin-friendly surfactant combination which is very readily biodegradable.
- the protease activity of agents 1 to 4 was determined after 1 hour at 50 ° C. by absorbance measurement (Cenco autoanalyzer) at 420 nm relative to a known standard.
- the absolute activity of the standard was determined by a second method ("For determining the proteolytic activity in enzyme concentrates and detergents, detergents and cleaning agents containing enzymes", HG van Raay, H. Saran, H. Verbeek, Tenside Detergents , 7th year, pages 125 to 132, 1 * 970).
- the protease activity of agents i to 4_ was between 79 and 83% after 1 hour, in each case based on the initial value.
- agents VI to V4 were measured, which differed from I to 1 only in that they contained (F2) 1,2-propanediol instead of glycerol.
- the protease activity in means VI to V4 after 1 hour was between 68 and 73%, in each case based on the initial value.
- the enzyme stability in the agents i to 1 according to the invention is therefore significantly higher than in the comparison agents VI to V4.
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)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Detergent Compositions (AREA)
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4034840A DE4034840A1 (de) | 1990-11-02 | 1990-11-02 | Enzymatisches fluessigwaschmittel |
DE4034840 | 1990-11-02 | ||
PCT/EP1991/002022 WO1992007930A1 (de) | 1990-11-02 | 1991-10-25 | Enzymatisches flüssigwaschmittel |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0555258A1 true EP0555258A1 (de) | 1993-08-18 |
EP0555258B1 EP0555258B1 (de) | 1996-04-24 |
Family
ID=6417505
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP91918230A Expired - Lifetime EP0555258B1 (de) | 1990-11-02 | 1991-10-25 | Enzymatisches flüssigwaschmittel |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0555258B1 (de) |
JP (1) | JPH06502197A (de) |
AT (1) | ATE137261T1 (de) |
DE (2) | DE4034840A1 (de) |
ES (1) | ES2085488T3 (de) |
WO (1) | WO1992007930A1 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102008061686A1 (de) | 2008-12-11 | 2010-06-17 | Bayer Materialscience Ag | Verfahren zur Herstellung von Isocyanaten in der Gasphase |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4315854A1 (de) * | 1993-05-12 | 1994-11-17 | Henkel Kgaa | Lipasehaltige Wasch- und Reinigungsmittel |
EP0798371A1 (de) * | 1996-03-29 | 1997-10-01 | The Procter & Gamble Company | Reinigungsmittelzusammensetzungen enthaltend eine spezifische Amylase und Alkylpolyglukosidtenside |
DE19626620A1 (de) * | 1996-07-03 | 1998-01-08 | Clariant Gmbh | Enzymhaltige Waschmittelformulierung |
WO2014056743A1 (en) * | 2012-10-12 | 2014-04-17 | Henkel Ag & Co. Kgaa | Liquid detergent compositions with soap, sulfo-estolide surfactant and cellulase |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT1129814B (it) * | 1980-07-02 | 1986-06-11 | Unilever Nv | Composizione detergente enzimatica liquida |
EP0162033B1 (de) * | 1984-05-14 | 1989-12-13 | The Procter & Gamble Company | Borsäure enthaltende flüssige Reinigungsmittel zur Stabilisierung von Enzymen |
EP0214278A1 (de) * | 1985-03-07 | 1987-03-18 | A.E. Staley Manufacturing Company | Waschmittel mit enzym und glykosidoberflächenaktivem mittel |
DE3910974A1 (de) * | 1989-04-05 | 1990-10-11 | Henkel Kgaa | Fluessigwaschmittel |
DE3920480A1 (de) * | 1989-06-22 | 1991-01-03 | Henkel Kgaa | Fluessigwaschmittel |
JPH04500385A (ja) * | 1989-06-26 | 1992-01-23 | ユニリーバー・ナームローゼ・ベンノートシヤープ | 酵素洗剤組成物 |
-
1990
- 1990-11-02 DE DE4034840A patent/DE4034840A1/de not_active Withdrawn
-
1991
- 1991-10-25 AT AT91918230T patent/ATE137261T1/de not_active IP Right Cessation
- 1991-10-25 DE DE59107741T patent/DE59107741D1/de not_active Expired - Fee Related
- 1991-10-25 EP EP91918230A patent/EP0555258B1/de not_active Expired - Lifetime
- 1991-10-25 ES ES91918230T patent/ES2085488T3/es not_active Expired - Lifetime
- 1991-10-25 WO PCT/EP1991/002022 patent/WO1992007930A1/de active IP Right Grant
- 1991-10-25 JP JP3516889A patent/JPH06502197A/ja active Pending
Non-Patent Citations (1)
Title |
---|
See references of WO9207930A1 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102008061686A1 (de) | 2008-12-11 | 2010-06-17 | Bayer Materialscience Ag | Verfahren zur Herstellung von Isocyanaten in der Gasphase |
Also Published As
Publication number | Publication date |
---|---|
EP0555258B1 (de) | 1996-04-24 |
DE59107741D1 (de) | 1996-05-30 |
WO1992007930A1 (de) | 1992-05-14 |
ES2085488T3 (es) | 1996-06-01 |
JPH06502197A (ja) | 1994-03-10 |
ATE137261T1 (de) | 1996-05-15 |
DE4034840A1 (de) | 1992-05-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
AT396110B (de) | Klares, waessriges waschmittel | |
DE4331297A1 (de) | Stückseifen | |
DE4023893A1 (de) | Bleichendes fluessigwaschmittel | |
DE1080250B (de) | Waschmittel | |
DE4337031C2 (de) | Stückseifen | |
EP0513138B2 (de) | Wässriges flüssiges reinigungsmittel | |
WO1994010279A1 (de) | VERFAHREN ZUR HERSTELLUNG WÄssRIGER LÖSUNGEN ANIONISCHER TENSIDE MIT VERBESSERTER KÄLTESTABILITÄT | |
EP0582608B1 (de) | Flüssigwaschmittel | |
DE69209381T2 (de) | Flüssige Detergenszusammensetzungen | |
DE2628976A1 (de) | Klares, stabiles, einphasiges und fluessiges wasch- und reinigungsmittel | |
DE19511571A1 (de) | Perlglanzkonzentrat mit newton'schem Viskositätsverhalten | |
EP0555258A1 (de) | Enzymatisches flüssigwaschmittel. | |
DE69202807T2 (de) | Flüssiges Geschirrspülmittel. | |
WO1995014073A1 (de) | Glycerinoctylether in tensidmischungen | |
DE602004000307T2 (de) | Seifenzusammensetzung in Schmelzblockform | |
EP0403948A1 (de) | Flüssigwaschmittel | |
DE4307186A1 (de) | Wäßrige Textilweichmacher-Zusammensetzung | |
EP0848746B1 (de) | Wässriges reinigungsmittel | |
CH635614A5 (en) | Liquid detergent and process for its preparation | |
DE19527596A1 (de) | Wäßrige Tensidmischung | |
DE4041172A1 (de) | Fluessige seifenzubereitung | |
DE4328355A1 (de) | Milde wäßrige Rasierpräparate | |
WO1994010274A1 (de) | Flüssiges waschmittel | |
EP0897973A1 (de) | Wasch-und Reinigungsmittel | |
DE4420515A1 (de) | Milde wäßrige Rasierpräparate |
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: 19930424 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE ES FR IT LI NL |
|
17Q | First examination report despatched |
Effective date: 19940929 |
|
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 ES FR IT LI NL |
|
REF | Corresponds to: |
Ref document number: 137261 Country of ref document: AT Date of ref document: 19960515 Kind code of ref document: T |
|
ET | Fr: translation filed | ||
REF | Corresponds to: |
Ref document number: 59107741 Country of ref document: DE Date of ref document: 19960530 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2085488 Country of ref document: ES Kind code of ref document: T3 |
|
ITF | It: translation for a ep patent filed |
Owner name: STUDIO JAUMANN |
|
NLT2 | Nl: modifications (of names), taken from the european patent patent bulletin |
Owner name: HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN |
|
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 | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20001010 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 20001011 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20001016 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20001025 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20001026 Year of fee payment: 10 Ref country code: CH Payment date: 20001026 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20001215 Year of fee payment: 10 |
|
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: 20011025 |
|
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: 20011026 |
|
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: 20011031 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20011031 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20011031 |
|
BERE | Be: lapsed |
Owner name: HENKEL K.G.A.A. Effective date: 20011031 |
|
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: 20020501 |
|
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: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020628 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20020501 |
|
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: 20020702 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20021113 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20051025 |