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WO1994012607A1 - Hard-surface cleaning compositions comprising solvent, surfactant and lipase - Google Patents

Hard-surface cleaning compositions comprising solvent, surfactant and lipase Download PDF

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Publication number
WO1994012607A1
WO1994012607A1 PCT/EP1993/002736 EP9302736W WO9412607A1 WO 1994012607 A1 WO1994012607 A1 WO 1994012607A1 EP 9302736 W EP9302736 W EP 9302736W WO 9412607 A1 WO9412607 A1 WO 9412607A1
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WO
WIPO (PCT)
Prior art keywords
surfactant
solvent
cleaning
composition according
enzyme
Prior art date
Application number
PCT/EP1993/002736
Other languages
French (fr)
Inventor
Alexander Martin
David Roscoe
Original Assignee
Unilever Plc
Unilever Nv
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
Priority claimed from GB929221256A external-priority patent/GB9221256D0/en
Priority claimed from GB929221255A external-priority patent/GB9221255D0/en
Application filed by Unilever Plc, Unilever Nv filed Critical Unilever Plc
Priority to AU51758/93A priority Critical patent/AU5175893A/en
Publication of WO1994012607A1 publication Critical patent/WO1994012607A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43Solvents
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38627Preparations containing enzymes, e.g. protease or amylase containing lipase

Definitions

  • the most preferred solvent is n-butoxy propan-2-ol which has one alcoholic hydroxyl group and a single ether linkage: i.e the ether formed by linking the linear n- butyl group to the primary hydroxyl of propan-1,2-diol.
  • Preferred levels of solvent lie between 0.2-20%wt, preferably 2-10%, most preferably 3-5%wt.
  • This material is commercially available as ' DOWANOL PnB' . It is envisaged that the alkane could equally well be branched or that free hydroxyl group on a primary rather than a secondary position.
  • the preferred primary alcohol sulphate comprises a mixture of materials of the general formulation:
  • R is a C 8 to C 18 primary alkyl group and M is an equivalent cation.
  • This class of surfactant is not only particularly efficient in cleaning hard surfaces but is also readily broken down in the environment and can be obtained from natural sources.

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  • 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)

Abstract

Selected combinations of particular solvents and surfactant are compatible with lipolytic enzymes in that after a first application of the compositions of the present invention the cleaning effort required to remove soils in subsequent cleaning cycles is reduced. The invention provides a cleaning composition for hard surfaces which comprises: a) a solvent having at least one alcoholic hydroxyl group and at most one ether linkage, b) a surfactant, and, c) a lipolytic enzyme. It is believed that the selected solvents interact with the enzyme to somehow prevent the surfactant from interfering with the activity of the enzyme, in a synergistic interaction in that the addition of either enzyme or solvent to a surfactant increases cleaning effort as compared with surfactant alone whereas the addition of both solvent and surfactant reduces cleaning effort as compared with surfactant alone.

Description

Hard-surface cleaning compositions comprising solvent, surfactant and Hpase
Technical Field
The present invention relates to improvements relating to cleaning compositions and in particular to hard surface cleaning compositions comprising solvents and enzymes.
Background of the Invention
A wide range of surfactants are used in cleaning compositions. Typical surfactant systems include alkyl benzene sulphonates (anionic) , alcohol ethoxylates (nonionic) , mixtures thereof and optionally small amounts of fatty soaps. Further examples of surfactants can be found' in Schwartz-Perry "Surface Active Agents and Detergents", Vol. I (1949) and Vol. II (1958).
Many cleaning compositions for use in cleaning of household and industrial hard surfaces comprise solvent components, in addition to surfactants. These solvents are generally selected from a wide range including terpenes, acetone, ethanol (often in the form of industrial methylated spirits) , isopropyl alcohol and ethers such as butoxy propanol, and dipropylene and diethylene glycol butyl ethers.
In particular applications one or more of these solvents has been preferred. Typical compositions for cleaning glass are described in EP 261874 (The Procter and Gamble Company: 1986/87) . In that document are described cleaning compositions which comprise a specific isomer of butoxy propanol: n-butoxy propan-2-ol, available commercially as 'DOWANOL PnB' (RTM, from the DOW Chemical Company) chosen due to the low odour of this isomer. n- butoxy propan-2-ol is miscible with water up to a level of around 6% dependent on temperature and levels of isomers.
For may years it has been known to use lipolytic enzymes in fabric washing. In this specification the term lipolytic enzymes embraces all enzymes which split fats. These enzymes have been used to a lesser extent in both machine and hand dishwashing compositions (EP 171007) . Other published documents show that lipolytic enzymes have been used for cleaning baths, ovens (GB 1273545), lab equipment, floors, cattle stalls (JP 02245129) or as components of a general purpose cleaner (JP 01225700, EP 352244).
Solvents and enzymes have been combined in fabric washing formulations. EP 352244 (Novo-Nordisk, 1988) discloses formulations comprising various enzymes active against fats, proteins and carbohydrates and, optionally, ethanol or diethylene glycol monoethylether as a solven . EP 352244 is concerned with the use of certain amphoteric surfactants to replace anionic surfactants and thus obtain compositions in which the enzyme stability is improved.
It is generally believed, in the art of fabric washing, that the effect of lipolytic enzymes is not, as was originally supposed, merely to facilitate the cleaning process, but rather to assist the cleaning action in the subsequent wash cycle by activity occurring between wash cycles, i.e. the use of lipolytic enzymes in one fabric washing cycle improves the efficiency of cleaning in subsequent washing cycles. However, it has been found that certain lipolytic enzymes have an activity during the wash. For the avoidance of doubt it should be noted that the term lipolytic enzymes as used in this specification embraces both enzymes which function during the actual cleaning operation and between cleaning operations.
It is desirable that the beneficial effect of lipolytic enzymes, should be made to occur in hard surface cleaning compositions and operations. While some similarities exist between fabric washing and hard surface cleaning there are also major differences, especially as regards dilute use (in fabrics washing) versus neat use (in hards surface cleaning) . Experiment has shown that it is difficult to formulate effective products which comprise surfactant, solvent and lipolytic enzyme. As will be shown by way of example hereafter simple combinations of enzymes and surfactants often behave no better, or even behave less efficiently as regards cleaning than the surfactant taken alone.
Brief Description of the Invention
We have now determined that selected combinations of particular solvents and surfactant are compatible with lipolytic enzymes in that after a first application of the compositions of the present invention the cleaning effort required to remove soils in subsequent cleaning cycles is reduced.
Detailed Description of the Invention
Accordingly the present invention provides a cleaning composition for hard surfaces which comprises:
a) a solvent having at least one alcoholic hydroxyl group and one ether linkage, b) a surfactant, and,
c) a lipolytic enzyme.
While we do not wish to limit the invention by reference to any theory of operation, it is believed that the selected solvents interact with both the lipolytic enzyme and the surfactant to somehow prevent the surfactant from interfering with the activity of the enzyme while at least maintaining the initial cleaning performance of the composition. This is believed to be particularly important in those compositions which comprise anionic surfactants as these surfactants are believed to be particularly inhibiting to enzymes. Experimental evidence presented below demonstrates that there is a synergistic interaction in that the addition of either enzyme or solvent to a surfactant increases cleaning effort as compared with surfactant alone whereas the addition of both selected solvent and enzyme to a surfactant reduces cleaning effort as compared with the cleaning effort required with surfactant alone.
Solvents
The presence of a specific type of solvent is essential for the performance of the present invention. The specific class is the class of solvents having at least one alcoholic hydroxyl group and one ether linkage.
Typically the solvent comprises a 1-5 carbon alcohol- alkane ether, preferably with an ether linked 1-5 carbon alkane.
The most preferred solvent is n-butoxy propan-2-ol which has one alcoholic hydroxyl group and a single ether linkage: i.e the ether formed by linking the linear n- butyl group to the primary hydroxyl of propan-1,2-diol. Preferred levels of solvent lie between 0.2-20%wt, preferably 2-10%, most preferably 3-5%wt. This material is commercially available as ' DOWANOL PnB' . It is envisaged that the alkane could equally well be branched or that free hydroxyl group on a primary rather than a secondary position.
As will be shown hereinafter by way of example the selection of solvents outside of this class produces compositions which have a worse cleaning performance than those from which solvent and enzyme are completely omitted.
Surfactants
The presence of surfactant is essential for the performance of the present invention.
The preferred surfactants comprise anionic surfactants, nonionic surfactants or mixtures thereof.
Preferably the anionic surfactant is a primary alcohol sulphate (PAS) .
The preferred primary alcohol sulphate comprises a mixture of materials of the general formulation:
;ROSO3),M
wherein R is a C8 to C18 primary alkyl group and M is an equivalent cation. This class of surfactant is not only particularly efficient in cleaning hard surfaces but is also readily broken down in the environment and can be obtained from natural sources.
The cation M is preferably an alkaline metal or an alkaline earth equivalent, ammonium or substituted ammonium. Magnesium and sodium are preferred as cations.
The nonionic surfactants and preferably alkoxylated surfactant, more preferably ethoxylated surfactants.
The preferred ethoxylated surfactants are nonionic alcohol ethoxylates. Preferably these comprise a mixture of materials of the general formulation:
R-(OCH2CH2)m-OH
wherein R is straight or branched C8 to C18 alkyl, and wherein the average degree of ethoxylation m is 2-10, more preferably 3-5.
Alternative ethoxylated surfactants include, ethoxylated alkanolamides of the general formula:
R-CO-N-(Rx) (OCH2CH20) -H
wherein R-_ is an ethyleneoxy or propyleneoxy group, Y is hydrogen or -R_ (CH2CH20)qH, p is 1 or more, q is 0, 1 or more, and R is alkyl, preferably lauryl or coconut alkyl.
Ethoxylated alklyphenols and ethoxylated fatty acids are also known and it is envisaged that these can be employed as alternatives to the surfactants mentioned above. Typically, the level of surfactant will lie between 0.5- 30% with higher concentrations being used for concentrates. In use, typical levels of surfactant would be 2-10%, most preferably about 3-7%wt. Compositions comprising both nonionic surfactant and anionic surfactant are particularly preferred, in which compositions it is preferable that the ratio of anionic to nonionic will lie in the range 5:1-1:5. Compositions which comprise an excess of nonionic surfactant over anionic surfactant are preferred to those in which anionic surfactant predominates.
Enzyme
The presence of lipolytic enzyme is essential for the performance of the present invention.
Preferably, the enzyme concentration is equivalent to 0.01-1% of a solution having 100 Novo Lipase Units/mg.
While the invention is described with particular reference to Novo Lipolase (TM) it is envisaged that other lipolytic enzymes can be employed.
It is believed that the reduction in cleaning effort obtained in embodiments of the present invention is due to the lipolytic activity of the enzyme rather than by the absorbtion of the enzyme onto the surface as a protein and any effects associated therewith. As will be shown by experimental evidence presented hereinafter, substitution of active enzyme by denatured enzyme or with other proteins did not attain the effects obtained in embodiments of the invention.
It should be noted that the pH of the formulation will modify the enzyme activity. While the present invention is described in terms of embodiments which employ near neutral pH this is not intended to restrict the scope of the invention. Reference to the literature will provide details of the optimum pH for any particular enzyme.
The presence of proteases in compositions according to the invention should generally be avoided as this class of enzyme is known to be able to digest lipolytic enzymes. Very preferably, compositions according to the present invention are free of protease enzymes.
Minors
The compositions of the invention can further comprise other components selected from the group comprising: surfactants, perfumes, electrolytes, colours and dyes, abrasives, hygiene agents compatible with the enzyme, further solvent components, foam-control agents, viscosity modifying agents, hydrotropes and mixtures thereof.
Whether or not the presence of a particular component interferes with the activity of the enzyme can be determined by methods similar to or derived from those provided hereafter in the examples.
As will be elaborated upon hereafter by way of example the advantages of the present invention are most readily apparent during repeated cleaning cycles, accordingly a further aspect of the present invention resides in a process for cleaning of hard surfaces which comprises the repeated application of a composition embodying the present invention.
In order that the present invention may be further understood it will be described hereafter by way of example and with reference to the accompanying figure which shows a graph of the cleaning performance of the embodiments and comparative examples as described below,
EXAMPLES
Cleaning compositions were prepared as in Tables 1 and 2 below, all figures being given in wt% on product and being made up to 100% with water by simple mixing. The following abbreviations are used to identify the components:
P: Dowanol PnB [RTM ex DOW] : n-butoxy propan-2-ol: monoether solvent.
B: Butyl Digol [RTM ex.UNION CARBIDE] : diethylene glycol mono butyl ether: diether solvent.
A: Empicol ML-26-f [RTM ex. Shell] : Magnesium salt of Cιo~C18 primary alcohol sulphate: anionic surfactant.
N: Imbentin 91-35 OFA. [RTM] : nonionic surfactant having
C9-C11 alkyl chain and 3-5 EO.
E: Lipolase 100L solution [RTM ex NOVO] : lipolytic enzyme.
The cleaning efficiency of the compositions was evaluated by "the following procedure.
a) Relatively new Decamel [RTM] tiles were cleaned and rinsed thoroughly with water. The surface of the tiles was soiled with fat/particulate soil at 0.25mg/cm.cm. The soil comprised 1% glycerol tripalmitate, 0.5% glycerol trioleate, 0.5% china clay, 0.2% liquid paraffin, 0.1% palmitic acid, 0.02% carbon black in industrial methylated spirits. The tiles were allowed to dry overnight at room temperature.
b) 2-4ml of products 1-6 were applied to the soiled tile, laid flat, and the tile was wiped with a sponge using reciprocal rubbing cycles. The effort required to clean the tiles was determined mechanically. Six duplicates were performed with each sample and the results averaged to obtain a value for the effort required in a first cleaning cycle.
c) For repeat cleaning, the tiles were re-soiled with an identical soil at the same concentration as in the first cycle, allowed to dry overnight and cleaned in the same manner. Six duplicates were performed with each sample and the results averaged to obtain a value for the effort required in a second cleaning cycle.
EXAMPLES 1-5: anionic surfactants
TABLE 1
Figure imgf000013_0001
In Table 1, example 1 is an embodiment of the present invention, whereas examples 2-5 are comparative trials. The figures given at 'Day 1' and 'Day 2' represent the total cleaning effort required to remove fatty soil from a surface to a visibly clean limit. The total cleaning effort over the two day period is also given. These results are also presented in the upper portion of the graph provided as figure 1, wherein the darker shaded portion of the bar represents the cleaning effort on the first day and the lighter shaded portion of the bar is the cleaning effort required on the second day. The total length of the bar represents the total effort required on the first and second days.
The results presented in Table 1 show that the formulation according to the present invention is superior or at least equivalent to all the comparative formulations in terms of initial cleaning performance (day 1 figures, Example 1: AEP on the graph) : there being only a slight improvement over compositions which comprise anionic only (Example 4: A on the graph) . It is noted that addition of enzyme only (Example 3: AE on the graph) or the preferred solvent only (Example 5: AP on the graph) both show poorer performance that than the combination of enzyme surfactant and solvent indicating the synergistic interaction which is believed to occur between the three components. It should also be noted that the wrong choice of solvent (Example 2: AEB on the graph) gives poor initial cleaning even when enzyme is present (compare AEB and AEP) .
From an examination of the results of the secondary cleaning (DAY 2) it can be seen that much the same benefits accrue with the combination of anionic enzyme and the selected solvent now clearly requiring less energy for cleaning than anionic alone whereas the other combination all require more energy to be used.
Similar results were obtained with other anionic surfactants, including Empicol LX (TM) and DOBS 102 (TM) . With the Empicol LX (sodium PAS rather than magnesium PAS) the addition of Butyl Digol diether solvent was again found to reduce the effectiveness of the compositions.
EXAMPLES: 6-11: Nonionic surfactants
13
TABLE 2
Figure imgf000015_0001
Results for nonionic surfactants as shown in Table 2 and the lower portion of the graph are presented in the same manner as for anionics.' These are shown in Table 2, wherein Example 6 is an embodiment of the invention and the other examples are comparative examples.
The results presented in Table 2 show that the formulation according to the present invention is again superior to all the comparative formulations in terms of initial cleaning performance (day 1 figures, Example 6: NEP on the graph) : there being a clear improvement over compositions which comprise nonionic only (Example 11: N on the graph) . It is noted that compositions which comprise nonionic plus enzyme only (Example 10: NE on the graph) or nonionic plus the preferred solvent only (Example 8: NP on the graph) show an improvement over nonionic alone. It should again be noted that the wrong choice of solvent gives poorer initial cleaning than nonionic alone even when enzyme is present (Example 7 and 9: NEB and NB on the graph) . From an examination of the results of the secondary cleaning (DAY 2) it can be seen that much the same benefits accrue with the combination of nonionic enzyme and the selected solvent clearly requiring less energy for cleaning than other combinations. Taking into account the overall energy use, it can be seen that the combination of nonionic, enzyme and the selected solvent outperforms all other combinations.
Similar results were obtained with the alkyl phenyl ethoxylate Triton X-114 (TM) and the C12-14 amine oxide E pigen OB (TM) . With the Triton X-114 the addition of Dowanol PnB as solvent was found to markedly improve the cleaning performance as assessed by the percentage of soil removed whereas when Butyl Digol was used no significant improvement in cleaning performance was noted.
With mixed surfactant systems it was found that the addition of Butyl Digol (diether solvent) to a 1:1 mixture of Imbentin and either NaPAS or MgPAS reduced the cleaning effectiveness of the compositions whereas the addition of Dowanol PnB (monoether solvent) improved the effectiveness of the compositions in terms of % soil removal.
EXAMPLES: 12-16: Effect of other proteins
In order to demonstrate that the technical effect of the present invention is due to the presence of enzyme rather than the mere presence of protein cleaning experiments were performed to provide comparisons between lipase and other proteins, including the protease Savinase (TM) and bovine serum albumen. Results were obtained as follows: TABLE 3
Figure imgf000017_0001
From the results given in Table 3 it can be seen that the technical effect of the present invention is due to the presence of lipolytic enzyme rather than the presence of proteins including proteases such as Savinase.
EXAMPLES 17-21: Further Solvent Effects
To further demonstrate the effect of solvent type, the compositions listed below in Table 4 were prepared. All five compositions contained 1% IMBENTIN as described above. Compositions of examples 18-21 comprised 0.05% Lipolase 100L solution and 5%wt of the specified solvent. These examples show the effect of non-ether solvents
(ethanol) , two different mono ether solvents (DOWANOL PnB and BUTYL CELLOSOLVE (RTM) ) and the diether solvent (BUTYL DIGOL) . TABLE 4
Figure imgf000018_0001
The following procedure was employed in examples 17-21. Clean DECAMEL tiles were sub-divided into four equal test areas (15cm by 15cm) with masking tape and the tile was soiled with fat/particulate soil at 0.5mg/cm.cm. as described above. The tiles were stored overnight and the reflectance from each quarter of the tile measured before cleaning. Each test area was cleaned with a folded non- woven cloth ('J-Cloth' [RTM]) to which 2gm water per gm cloth followed by 0.5ml of the composition had been applied. The tiles were wiped manually with a circular motion for 30 sees, at which point the cloth was refolded to expose a clean area of cloth used for a final wipe. The reflectance of each test area was then measured so as to enable the percentage soil removal to be determined. The initial percentage of soil removed is given in the table as the percentage 'primary cleaning' . Although some test areas were still soiled, the tiles were resoiled and the procedure repeated to obtain the 'secondary cleaning' figures given in the table. All examples were performed in duplicate and showed good consistency, except for examples 18a and 18b where both results are given separately. Examples 20 and 21 were duplicated twice (i.e. four experiments were averaged).
From the results it can be seen that the most effective primary and secondary cleaning is found with the monoether solvents (Examples 20 and 21) . With the diether solvent (Example 19) and the simple alcohol (Example 18) less effective removal of the soil is seen.

Claims

CLAIMS :
1. A cleaning composition for hard surfaces which comprises :
a) a solvent having at least one alcoholic hydroxyl group and one ether linkage,
b) a surfactant, and,
c) a lipolytic enzyme.
2. Composition according to claim 1 wherein the solvent is a 1-5 carbon alcohol-alkane ether.
3. Composition according to claim 2 wherein the solvent has an ether linked 1-5 carbon alkane.
4. Composition according to claim 3 wherein the solvent is n-butoxy propan-2-ol.
5. Composition according to claim 1 comprising 0.2-20%wt solvent.
6. Composition according to claim 1 wherein the surfactant comprises anionic surfactant, nonionic surfactant or mixtures thereof.
7. Composition according to claim 6 wherein the surfactant comprises a mixture of materials of the general formulation:
(ROS03)2M
wherein R is a C8 to C18 primary alkyl group and M is an equivalent cation.
8. Composition according to claim 6 wherein the surfactant comprises a mixture of materials of the general formulation:
R-(OCH2CH2)m-OH
wherein R is straight or branched C8 to C18 alkyl, and wherein the average degree of ethoxylation m is 2-10.
-
9. Composition according to claim 1 wherein the level of surfactant lies between 0.5-30%.
10. Composition according to claim 6 wherein the ratio of anionic to nonionic falls in the range 5:1-1:5.
11. Composition according to claim 1 wherein the enzyme concentration is equivalent to 0.01-1% of a solution having 100 Novo Lipase Units/mg.
12. A process for cleaning of hard surfaces which comprises the repeated application of a composition according to claim 1.
PCT/EP1993/002736 1992-10-09 1993-10-05 Hard-surface cleaning compositions comprising solvent, surfactant and lipase WO1994012607A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU51758/93A AU5175893A (en) 1992-10-09 1993-10-05 Hard-surface cleaning compositions comprising solvent, surfactant and lipase

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB929221256A GB9221256D0 (en) 1992-10-09 1992-10-09 Improvements relating to cleaning compositions comprising solvent,surfactant and enzymes
GB9221255.4 1992-10-09
GB9221256.2 1992-10-09
GB929221255A GB9221255D0 (en) 1992-10-09 1992-10-09 Improvements relating to cleaning compositions comprising solvent,surfactant and enzymes

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997032480A1 (en) * 1996-03-06 1997-09-12 Novo Nordisk A/S A method of killing or inhibiting microbial cells
EP0893489A1 (en) * 1997-07-22 1999-01-27 Calgon Corporation Composition and method for cleaning surfaces
US10947480B2 (en) 2016-05-17 2021-03-16 Conopeo, Inc. Liquid laundry detergent compositions

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1930636A1 (en) * 1968-06-24 1970-07-09 Albright & Wilson cleaning supplies
FR2087745A5 (en) * 1969-01-02 1971-12-31 Witco Chemical Corp
EP0352244A2 (en) * 1988-07-20 1990-01-24 Novo Nordisk A/S Stabilized enzymatic liquid detergent
WO1991009929A1 (en) * 1989-12-22 1991-07-11 Henkel Kommanditgesellschaft Auf Aktien Stabilizers for aqueous cleaning fluids

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1930636A1 (en) * 1968-06-24 1970-07-09 Albright & Wilson cleaning supplies
FR2087745A5 (en) * 1969-01-02 1971-12-31 Witco Chemical Corp
EP0352244A2 (en) * 1988-07-20 1990-01-24 Novo Nordisk A/S Stabilized enzymatic liquid detergent
WO1991009929A1 (en) * 1989-12-22 1991-07-11 Henkel Kommanditgesellschaft Auf Aktien Stabilizers for aqueous cleaning fluids

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997032480A1 (en) * 1996-03-06 1997-09-12 Novo Nordisk A/S A method of killing or inhibiting microbial cells
US6287585B1 (en) 1996-03-06 2001-09-11 Novozymes A/S Methods for laundry using polycations and enzymes
EP0893489A1 (en) * 1997-07-22 1999-01-27 Calgon Corporation Composition and method for cleaning surfaces
US6080244A (en) * 1997-07-22 2000-06-27 Calgon Corporation Composition and methods for cleaning surfaces
US10947480B2 (en) 2016-05-17 2021-03-16 Conopeo, Inc. Liquid laundry detergent compositions
US11572529B2 (en) 2016-05-17 2023-02-07 Conopeo, Inc. Liquid laundry detergent compositions

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