EP0670364B1 - Flüssige bleichmittelzusammensetzung - Google Patents

Flüssige bleichmittelzusammensetzung Download PDF

Info

Publication number
EP0670364B1
EP0670364B1 EP92923981A EP92923981A EP0670364B1 EP 0670364 B1 EP0670364 B1 EP 0670364B1 EP 92923981 A EP92923981 A EP 92923981A EP 92923981 A EP92923981 A EP 92923981A EP 0670364 B1 EP0670364 B1 EP 0670364B1
Authority
EP
European Patent Office
Prior art keywords
surfactant
bleaching agent
agent composition
bleach activator
group
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.)
Expired - Lifetime
Application number
EP92923981A
Other languages
English (en)
French (fr)
Other versions
EP0670364A1 (de
EP0670364A4 (de
Inventor
Yoshinori 2606 Akabane Tamura
Hiroyuki 649-19 Kamitomatsuricho Yamada
Muneo 217-13 Tsurutacho Aoyagi
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.)
Kao Corp
Original Assignee
Kao Corp
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=20429223&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0670364(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Kao Corp filed Critical Kao Corp
Priority claimed from PCT/JP1992/001508 external-priority patent/WO1994011484A1/ja
Publication of EP0670364A1 publication Critical patent/EP0670364A1/de
Publication of EP0670364A4 publication Critical patent/EP0670364A4/de
Application granted granted Critical
Publication of EP0670364B1 publication Critical patent/EP0670364B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions

Definitions

  • the present invention relates to a liquid bleaching agent composition, more particularly to a liquid bleaching agent composition having not only an excellent storage stability but also a good bleaching power.
  • Bleaching agent is chemically classified into chlorine-base bleaching agent and oxygen-base bleaching agent. Further, it is physically classified into solid (powdery) bleaching agent and liquid bleaching agent.
  • the chlorine-base bleaching agent is limited in the kind of fibers to which it can be applied, cannot be used for colored or patterned fabrics, and has a peculiar odor. For this reason, in recent years, an oxygen-base bleaching agent free from these drawbacks has come to widely spread in the art.
  • Sodium percarbonate and sodium perborate are particularly utilized as the solid oxygen-base bleaching agent from the viewpoint of bleaching performance, stability, etc.
  • a liquid oxygen-base bleaching agent wherein use is made of hydrogen peroxide has also considerably spread by virtue of its handleability.
  • a bleaching agent composition comprising a combination of the oxygen-base bleaching agent with various bleach activators are utilized in the art.
  • the activator include nitriles represented by acetonitrile, 0-acetylated compounds represented by glucose pentaacetate (GPAC), N-acylated compounds represented by tetraacetylethylenediamine (TAED) and acid anhydrides represented by maleic anhydride.
  • Patent Nos. 4,412,934 (assignee: Procter & Gamble Co.; date of grant: November 1, 1983) and 4,681,592 (assignee: Procter & Gamble Co.; date of grant: November 1, 1987).
  • the bleaching agent composition comprises a mixture of solid substances
  • a good storage stability can generally be attained when the composition comprises a mixture of a solid peracid salt with the above-described solid bleach activator as a dried particle capable of yielding the above-described organic peracid.
  • a good storage stability can generally be attained when the composition comprises a mixture of a solid peracid salt with the above-described solid bleach activator as a dried particle capable of yielding the above-described organic peracid.
  • the composition is exposed to a highly humid environment, for example, in a bathroom, the dry bleaching agent (solid peracid salt) becomes humid, whereby its activity is lowered.
  • hydrogen peroxide which is liquid at an ordinary temperature is used as a peroxide source, it is impossible to provide a bleaching agent composition in a dried particle form.
  • U.S. Patent No. 3,970,575 discloses a bleaching agent composition comprising hydrogen peroxide which is stable under an acidic condition and is colored blue with a phthalocyanine pigment.
  • U.S. Patent No. 3,956,159 discloses a liquid bleaching agent composition comprising an organic peracid and its salt dissolved in an anhydrous organic ternary solvent (a three-component solvent). Further, U.S. Patent No.
  • 4,238,192 discloses a liquid bleaching agent composition based on hydrogen peroxide. This composition contains an acid for adjusting the pH value thereof to 1.8 to 5.5 and a nitrogen compound (particularly an amino acid) for imparting a stability thereto.
  • U.S. Patent No. 4,130,501 discloses a stable, viscous, liquid bleaching agent composition comprising hydrogen peroxide which contains a surfactant and a thickener being added thereto.
  • a detergent composition comprising an alkylphenolic nonionic surfactant, hydrogen peroxide and a stabilizer (phosphoric acid or the like), and an aqueous concentrate for bleaching having an excellent storage stability and a pH value of 10 or less and containing hydrogen peroxide, a nonionic tenside and a specified amine oxide as a stabilizer are also known in the art.
  • All of these inventions are ones made for the purpose of stabilizing a liquid bleaching agent composition comprising hydrogen peroxide, and no consideration is given to an improvement in the bleaching power. Further, since no bleach activator is incorporated in all of them, the bleaching power cannot be said to be satisfactory.
  • a liquid bleaching agent composition which utilizes a bleach activator capable of yielding an organic peracid is also known in the art.
  • U.S. Patent No. 4,772,290 (assignee: Clorox, date of patent: September 20, 1988) discloses a composition having an excellent storage stability and a low temperature activity and comprising an acidic aqueous solution containing hydrogen peroxide and a solid bleach activator dispersed therein. Since, however, this composition is not transparent and a bleach activator is dispersed therein, it has a drawback that the activator precipitates and separates during storage, so that the object of the use of the composition is remarkably spoiled.
  • this composition also has a drawback that no satisfactory bleaching power can be attained during use because the bleach activator is stored in an aqueous solution and therefore it gradually undergoes hydrolysis.
  • any liquid bleaching agent composition which is transparent and excellent in storage stability and contains, dissolved therein, a bleach activator capable of yielding an organic peracid.
  • U.S. Patent No. 5,160,655 discloses an aqueous structured liquid detergent composition comprising detergents active materials and a peroxygen bleach compound, said detergent composition showing less than 25% volume increase while stored at a temperature between 20° and 37°C for three months after preparation.
  • a transparent liquid oxygen-base bleaching agent composition having an improved storage stability and a higher bleaching power and containing a bleach activator dissolved therein is required in the art, and an'object of the present invention is to provide such a liquid oxygen-base bleaching agent composition.
  • the present inventors have made extensive studies with a view to developing a liquid oxygen-base bleaching agent composition which is excellent in storage stability and transparent and has a higher bleaching power. As a result, they have found that the ⁇ value as an index for the magnitude of interaction between a surfactant and a bleach activator correlates to the storage stability.
  • the present invention provides a liquid bleaching agent composition
  • a liquid bleaching agent composition comprising hydrogen peroxide (a), a surfactant (b) and a bleach activator (c) capable of yielding an organic peracid when reacted with hydrogen peroxide characterized in that the liquid bleaching agent composition is transparent and has a value of an interaction parameter, ⁇ , of a mixed system consisting of the surfactant (b) and the bleach activator (c) as calculated according to the following equation of smaller than -2:
  • the interaction parameter ⁇ used herein is defined in "Advances in Colloid and Interface Science", Vol. 26, pp. 111-129 (1986).
  • hydrogen peroxide (a) is incorporated in an amount of 0.3 to 30% by weight, preferably 0.5 to 10% by weight, particularly preferably 2 to 7% by weight, into the composition.
  • the composition of the present invention preferably contains at least one surfactant selected from the group consisting of nonionic surfactants, anionic surfactants and amphoteric surfactants, or at least one surfactant selected from the group consisting of nonionic surfactants and amphoteric surfactants.
  • anionic surfactants to be used in the present invention include the following compounds.
  • a nonionic surfactant consisting of the alkyl glycoside(s) represented by the above general formula wherein x (average value) is 0 to 5 and y (average value) is 1 to 10 is preferable.
  • amphoteric surfactant to be used in the present invention examples include a sulfobetaine and a carbobetaine each having a straight-chain or branched alkyl or alkenyl group having 1 to 22 carbon atoms.
  • Still preferred examples of the amphoteric surfactant include sulfobetaines and carbobetaines represented by the following general formula (B): wherein R 13 represents an alkyl group having 8 to 22 carbon atoms, R 14 and R 15 , which may be the same or different from each other, represent an alkyl group having 1 to 3 carbon atoms, R 16 represents an alkylene group having 1 to 5 carbon atoms which may have a hydroxyl group, D represents a group or a group, E represents an alkylene group having 1 to 5 carbon atoms, a and b are either both 0 or both 1, and Y - represents -SO 3 - , -OSO 3 - , -COO - or -OCOO -
  • R 13 represents an alkyl group having 8 to 22 carbon atoms, particularly preferably an alkyl group having 12 to 18 carbon atoms.
  • R 14 and R 15 represent an alkyl group having 1 to 3 carbon atoms, particularly preferably a group having one carbon atom, i.e., methyl group.
  • R 16 preferably represents a propylene or hydroxypropylene group having 3 carbon atoms.
  • R 16 preferably represents an alkylene group having 1 to 5 carbon atoms.
  • the bleach activator (c) to be used in the present invention which yields an organic peracid when reacted with hydrogen peroxide, is not particularly limited so far as it can be solubilized by a surfactant used for the preparation of the liquid bleaching agent composition of the present invention, and examples thereof include triacetin, a fatty acid anhydride having 2 to 18 carbon atoms, and sodium alkanoyloxybenzenesulfonate.
  • bleach activator include compounds represented by the following general formula (I), including compounds capable of yielding an organic peracid having a quaternary ammonium group: wherein R represents an alkyl, alkenyl, aryl or alkylsubstituted aryl group which may have a group, n is 0 or 1, and L represents an eliminable group having an anionic group.
  • general formula (I) including compounds capable of yielding an organic peracid having a quaternary ammonium group: wherein R represents an alkyl, alkenyl, aryl or alkylsubstituted aryl group which may have a group, n is 0 or 1, and L represents an eliminable group having an anionic group.
  • the total number of carbon atoms in the R is preferably 1 to about 20.
  • L examples include -O-R 17 -(O) p -SO 3 - and -O-R 17 -(O) p -SO 3 M (wherein R 17 represents an alkylene group, p is 0 or 1 and M represents H or an alkali metal).
  • R 17 represents an alkylene group, p is 0 or 1 and M represents H or an alkali metal.
  • the alkylene group R 17 preferably has 1 to 5 carbon atoms.
  • Preferred examples of the bleach activator include also compounds represented by the following general formula (II): wherein R' represents an alkyl, alkenyl, aryl or alkylsubstituted aryl group having 1 to 20 carbon atoms in total and n is 0 or 1.
  • bleach activator include one capable of yielding an organic peracid having a quaternary ammonium group, and specific examples thereof include compounds represented by the following general formula (III):
  • R 1 represents an alkyl group having 1 to 18 carbon atoms, preferably 1 to 14 carbon atoms
  • A represents represents -(CH 2 ) n -, -(OCH 2 CH 2 ) n - or (wherein n is 1 to 12, particularly preferably 1 to 5).
  • R 2 and R 3 which may be the same or different from each other, represent an alkyl group having 1 or 2 carbon atoms.
  • the linking group is a divalent group and not particularly limited, and examples thereof include a straight-chain or branched alkylene group, a cycloalkylene group, a phenylene group, an alkylene-phenylene group and an oxyalkylene group (-CH 2 CH 2 O-).
  • examples of the eliminable group include the following groups, it is not limited to these examples only: -O-R 17 -(O) p -SO 3 - and -O-R 17 -(O) p -SO 3 M (wherein R 17 represents an alkylene group, preferably an alkylene group having 1 to 5 carbon atoms, p is 0 or 1 and M represents H or an alkali metal).
  • X - represents an inorganic or organic counter ion. However, X - is absent when the eliminable group is or -O-R 17 -(O) p -SO 3 - .
  • Specific examples of the compound represented by the general formula (III) include the following compounds.
  • the surfactant (b) and the bleach activator (c), which yields an organic peracid when reacted with hydrogen peroxide are incorporated in a total amount ((b) plus (c)) of 0.1 to 50% by weight, preferably 6 to 45% by weight, particularly preferably 8 to 25% by weight, into the liquid bleaching agent composition.
  • the weight ratio of the component (b) to the component (c) is 50/1 to 1/5, preferably 15/1 to 1/1, particularly preferably 10/1 to 3/1.
  • the bleach activator (c) and the surfactant (b) are selected in such a combination that the ⁇ value is smaller than -2, it becomes possible to produce a transparent liquid oxygen-base bleaching composition wherein the bleach activator (c) is in a very stabilized state in the aqueous hydrogen peroxide solution.
  • the surfactant (b) and the bleach activator (c) it is important to select the surfactant (b) and the bleach activator (c) in such a combination that the ⁇ value is smaller than -2.
  • the value of the interaction parameter ⁇ does not depend upon the relative molar ratio such as the molar fractions (X 1 , X 2 ) of the surfactant and bleach activator in the mixed micelle and the molar fractions ( ⁇ 1 , ⁇ 2 ) of the surfactant and bleach activator in the whole mixed solute but is uniquely determined by the kind and combination of the surfactant and bleach activator used. Therefore, an aqueous mixed solution comprising equimolar amounts of the surfactant and the bleach activator is selected in the measurement of the ⁇ value.
  • the parameter of interaction ( ⁇ ) between the surfactant and the bleach activator is determined from the above ⁇ 1 , C 1 and C* as a function of the molar fraction X 1 , an unknown quantity, of the surfactant in the mixed micelle.
  • the parameter of interaction ( ⁇ ) between the surfactant and the bleach activator is similarly determined from the above ⁇ 2 , C 2 and C* as a function of the molar fraction X 2 , an unknown quantity, of the bleach activator in the mixed micelle.
  • the measurement of the interaction parameter ⁇ can be extended to a multi-component system comprising three or more components.
  • the interaction parameter ⁇ can be determined by regarding the mixture of surfactants A 1 and A 2 as one surfactant and determining the critical micelle concentration of the surfactant and that of the bleach activator. This is also true of the case where the bleaching agent comprises a multi-component system or the surfactant and the bleach activator each comprise a multi-component system.
  • the present inventors have studied on the relationship between the interaction parameter ⁇ and the stability of the liquid bleaching agent composition with respect to a system where various surfactants and bleach agents are present together and, as a result, have found that a transparent liquid oxygen-base bleaching agent composition, wherein a bleach activator is in a very stable state in an aqueous hydrogen peroxide solution, can be produced only when a combination of the bleach activator with the surfactant is selected in such a manner that the ⁇ value is smaller than -2.
  • the solubilization of the bleach activator in a micelle of the surfactant serves to prevent the occurrence of a reaction of the bleach activator with a bulk solution and contributes to the stabilization of the bleach activator.
  • the system wherein the bleach activator can be more stabilized include a system wherein the rate of exchange of the bleach activator in the micelle with one in a monodisperse state in the bulk solution is lower, a system wherein the probability of the presence of the bleach activator in the micelle is higher, and a system wherein the bleach activator is less liable to react with hydrogen peroxide in the bulk.
  • the bleaching agent composition has a good storage stability in a system wherein the bleach activator difficultly migrates from the mixed micelle to the bulk. It is conceivable that when the bleaching agent composition is diluted during washing or bleaching, the mixed micelle is broken, thus inducing an intended reaction for yielding an organic peracid.
  • a chelating agent (d) can be incorporated into the liquid bleaching agent composition of the present invention.
  • the chelating agent (d) to be used in the present invention include scavengers for a divalent metal ion, for example, the following compounds:
  • the chelating agent (d) enhances the bleaching detergency of the bleaching agent composition and, at the same time, can improve the storage stability. For this reason, the amount of incorporation of the chelating agent in the composition is preferably 0.0005 to 5% by weight, particularly preferably 0.01 to 1% by weight.
  • the liquid bleaching agent composition of the present invention usually contains the above components (a) to (c) or the above components (a) to (d), and water.
  • the pH value of the composition is preferably in a neutral range, or in weakly acidic to acidic range (pH 6 or less, preferably 3.5 or less). If necessary, besides the above components, pH regulators, dispersants, thickeners, perfumes, dyes, fluorescent dyes and enzymes, such as protease, lipase, amylase and cellulase, may be incorporated into the liquid bleaching agent composition of the present invention.
  • the formation of a mixed micelle comprising the two components serves to stabilize the bleach activator.
  • the bleach activator is dissolved in a homogeneous and transparent state in an aqueous solution of hydrogen peroxide by the formation of the above-described mixed micelle. This provides a transparent liquid oxygen-base bleaching agent composition wherein a bleach activator is in a very stabilized state in an aqueous solution of hydrogen peroxide.
  • Nitto black tea (yellow package) was boiled in 3 l of deionized water for about 15 min and filtered through a previously desized bleached cotton.
  • a cotton shirting #2003 cloth was immersed in the filtrate and boiled for about 15 min.
  • the container containing the black tea and the cotton shirting was removed away from the heat source and allowed to stand for 2 hrs.
  • the cotton shirting was spontaneously dried, washed with water until the washing had no color, dehydrated and pressed.
  • the pressed cloth was cut into a test piece having a size of 8 ⁇ 8 cm and applied to the experiment.
  • the surface tension of each solution was measured with a Surface Tensiometer CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (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)

Claims (12)

  1. Flüssige Bleichmittelzusammensetzung, umfassend Wasserstoffperoxid (a), ein Tensid (b) und einen Bleichaktivator (c), der in der Lage ist, eine organische Persäure zu ergeben, wenn er mit Wasserstoffperoxid reagiert hat, dadurch gekennzeichnet, daß die flüssige Bleichmittelzusammensetzung transparent ist und einen Wert eines Wechselwirkungsparameters β eines gemischten Systems, bestehend aus dem Tensid (b) und dem Bleichaktivator (c), von kleiner als -2 hat, berechnet entsprechend der folgenden Gleichung: β = In[α1C*/(x1C1)](1 - x1)2 = In[α2C*/(x2C2)](1 - x2)2 worin bedeuten:
    C1 : die kritische Micellenkonzentration des Tensides, gemessen bei 25°C;
    C2: die kritische Micellenkonzentration des Bleichaktivators, gemessen bei 25°C;
    α1: die molare Fraktion des Tensides in der gesamten gemischten Lösung (molare Fraktion des zugegebenen Tensides);
    α2: die molare Fraktion des Bleichaktivators in der gesamten gemischten Lösung (molare Fraktion an zugegebenem Aktivator);
    C*: die kritische Mizellenkonzentration des gemischten Systems, gemessen bei 25°C;
    X1: die molare Fraktion des Tensides in der gemischten Micelle; und
    X2: die molare Fraktion des Bleichaktivators in der gemischten Micelle.
  2. Flüssige Bleichmittelzusammensetzung nach Anspruch 1, worin das Tensid (b) zumindest eine Verbindung ist, ausgewählt aus der Gruppe bestehend aus nicht-ionischen Tensiden, anionischen Tensiden und amphoteren Tensiden.
  3. Flüssige Bleichmittelzusammensetzung nach Anspruch 2, worin das Tensid (b) ein amphoteres Sulfobetaintensid umfaßt.
  4. Flüssige Bleichmittelzusammensetzung nach Anspruch 1, worin das Tensid (b) zumindest eine Verbindung ist, ausgewählt aus der Gruppe, bestehend aus nicht-ionischen und amphoteren Tensiden.
  5. Flüssige Bleichmittelzusammensetzung nach Anspruch 4, worin das Tensid (b) ein amphoteres Sulfobetaintensid umfaßt.
  6. Flüssige Bleichmittelzusammensetzung nach Anspruch 1, worin der Bleichaktivator (c) zumindest eine Verbindung ist, ausgewählt aus der Gruppe, bestehend aus Verbindungen, dargestellt durch die folgende allgemeine Formel (I):
    Figure 00480001
    worin R eine alkyl-, alkenyl-, aryl- oder alkylsubstituierte Arylgruppe ist, die eine
    Figure 00490001
    - Gruppe haben kann, n 0 oder 1 ist und L eine eliminierbare Gruppe mit einer anionischen Gruppe ist.
  7. Flüssige Bleichmittelzusammensetzung nach Anspruch 1, die weiterhin ein Chelatisierungsmittel (d) enthält.
  8. Transparente flüssige Bleichmittelzusammensetzung nach Anspruch 1, worin der Gehalt des Wasserstoffperoxides (a) 0,3 bis 30 Gew.% ist, bezogen auf die Gesamtmenge der Zusammensetzung, der Gesamtgehalt des Tensides (b) und des Bleichaktivators (c) 0,1 bis 50 Gew.% ist, bezogen auf die Gesamtmenge der Zusammensetzung, das Gewichtsverhältnis des Tensides (b) zu dem Bleichaktivator (c) 50/1 bis 1/5 ist.
  9. Flüssige Bleichmittelzusammensetzung nach Anspruch 8, worin das Tensid (b) zumindest eine Verbindung ist, ausgewählt aus der Gruppe, bestehend aus nicht-ionischen Tensiden, anionischen Tensiden und amphoteren Tensiden.
  10. Flüssige Bleichmittelzusammensetzung nach Anspruch 9, worin das Tensid (b) ein amphoteres Sulfobetaintensid umfaßt.
  11. Flüssige Bleichmittelzusammensetzung nach Anspruch 8, worin das Tensid (b) zumindest eine Verbindung ist, ausgewählt aus der Gruppe, bestehend aus nicht-ionischen und amphoteren Tensiden.
  12. Flüssige Bleichmittelzusammensetzung nach Anspruch 11, worin das Tensid (b) ein amphoteres Sulfobetaintensid umfaßt.
EP92923981A 1992-11-18 1992-11-18 Flüssige bleichmittelzusammensetzung Expired - Lifetime EP0670364B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PCT/JP1992/001508 WO1994011484A1 (en) 1992-11-18 1992-11-18 Liquid bleach composition
SG1996001492A SG52260A1 (en) 1992-11-18 1992-11-18 Liquid bleaching agent composition

Publications (3)

Publication Number Publication Date
EP0670364A1 EP0670364A1 (de) 1995-09-06
EP0670364A4 EP0670364A4 (de) 1996-07-03
EP0670364B1 true EP0670364B1 (de) 1998-04-22

Family

ID=20429223

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92923981A Expired - Lifetime EP0670364B1 (de) 1992-11-18 1992-11-18 Flüssige bleichmittelzusammensetzung

Country Status (3)

Country Link
EP (1) EP0670364B1 (de)
DE (1) DE69225246T2 (de)
SG (1) SG52260A1 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9600159D0 (en) * 1996-01-05 1996-03-06 Warwick Int Group Process for bleaching or disinfecting a substrate
DE19824356A1 (de) * 1998-05-30 1999-12-02 Henkel Ecolab Gmbh & Co Ohg Verfahren zur Reinigung von Geschirr

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2945162B2 (ja) * 1991-05-15 1999-09-06 花王株式会社 液体漂白剤助剤及び２剤型液体漂白剤組成物
JPH04337399A (ja) * 1991-05-15 1992-11-25 Kao Corp 液体漂白剤組成物

Also Published As

Publication number Publication date
DE69225246T2 (de) 1998-09-17
DE69225246D1 (de) 1998-05-28
SG52260A1 (en) 1998-09-28
EP0670364A1 (de) 1995-09-06
EP0670364A4 (de) 1996-07-03

Similar Documents

Publication Publication Date Title
EP0552812B1 (de) Aminosäurederivate als Amphotere
EP1967579B1 (de) Flüssiges reinigungsmittel
US5827447A (en) Liquid bleaching agent composition
CA2018868A1 (en) Bleaching composition
JP3766746B2 (ja) 液体漂白剤組成物
JP3330200B2 (ja) 液体漂白剤組成物
EP0670364B1 (de) Flüssige bleichmittelzusammensetzung
JP2638410B2 (ja) 液体漂白剤助剤及び２剤型漂白剤組成物
JP2669590B2 (ja) 液体漂白剤組成物及びその製法
JP3874832B2 (ja) 液体漂白剤組成物
JPH1072598A (ja) 液体酸素系漂白性組成物
EP0512533A2 (de) Bleichmittel oder bleichende Waschmittelzusammensetzung
JPH08100196A (ja) 液体漂白剤組成物
JPH0734094A (ja) 液体漂白剤組成物
JP4498475B2 (ja) 液体漂白剤組成物
JP2801054B2 (ja) 漂白洗浄剤組成物
WO1994011484A1 (en) Liquid bleach composition
JP3583547B2 (ja) 液体漂白剤組成物
JP3425227B2 (ja) 液体漂白剤組成物
IE904574A1 (en) Concentrated aqueous liquid bleach composition
JPH08120295A (ja) 液体漂白剤組成物
JP3330226B2 (ja) 液体漂白剤組成物
JP3352206B2 (ja) 液体漂白剤組成物
JP3382338B2 (ja) 液体漂白剤組成物
JP2635178B2 (ja) 漂白洗浄剤組成物

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: 19950426

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE FR GB

A4 Supplementary search report drawn up and despatched
AK Designated contracting states

Kind code of ref document: A4

Designated state(s): DE FR GB

RHK1 Main classification (correction)

Ipc: C11D 3/39

17Q First examination report despatched

Effective date: 19961126

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): DE FR GB

REF Corresponds to:

Ref document number: 69225246

Country of ref document: DE

Date of ref document: 19980528

ET Fr: translation filed
PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

26 Opposition filed

Opponent name: THE PROCTER & GAMBLE COMPANY

Effective date: 19990122

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PLCK Communication despatched that opposition was rejected

Free format text: ORIGINAL CODE: EPIDOSNREJ1

PLBN Opposition rejected

Free format text: ORIGINAL CODE: 0009273

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: OPPOSITION REJECTED

27O Opposition rejected

Effective date: 20060202

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

Ref country code: FR

Payment date: 20101123

Year of fee payment: 19

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

Ref country code: DE

Payment date: 20101110

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: 20101117

Year of fee payment: 19

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

Effective date: 20111118

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20120731

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 69225246

Country of ref document: DE

Effective date: 20120601

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: 20111118

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: 20111130

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: 20120601