CA2162021A1

CA2162021A1 - Cleaning gel

Info

Publication number: CA2162021A1
Application number: CA002162021A
Authority: CA
Inventors: POUL NõRGAARD CHRISTENSEN; Bo Kalum; Otto Andresen
Original assignee: Individual
Current assignee: Novo Nordisk AS
Priority date: 1993-05-05
Filing date: 1994-05-04
Publication date: 1994-11-10
Also published as: US5965503A; NO954401D0; EP0697037A1; NO954401L; JPH08509759A; US5998344A; WO1994025561A1; AU6720294A; MX9403289A

Abstract

An enzymatic detergent composition for cleaning hard surfaces which is capable of forming a gel when water is added. The composition comprises one surfactant together with an electrolyte or more than one surfactant, optionally together with an electrolyte.

Description

WO94125561 2 1 6 2 0 2 1 PCT~K94/00176 CLEANING GEL

FIELD OF lN V ~ r, ~ lON

This invention relates to a detergent composition for cleaning hard surfaces with superior cleaning qualities.

5 R~.OUND OF THE lNv~N.lON

In food industry hard surface cleaning has traditional-ly been carried out by high pressure foam cleaning. There are some severe safety problems by using high pressure foam cleaning: High pH, aggressive cleaning agents, aerosol for-o mation and mechanical noise and damage are the most importantones, but there are also environmental problems connected to high pressure foam cleaning due to a large water consumption and thereby effluent treatment.
It has also been excluded to add enzymes to the detergents in the normal hard surface cleaning. The risk of inhaling enzymes (allergy potential) due to aerosol formation is so obvious that it rules out the use of enzymes in the traditional high pressure foam cleaning.
To overcome these difficulties in recent years much 20 effort has been put into developing different hard surface cleaners in the form of gels. The gel cleaners have the advantages of giving a safe application, they do not or only insignificantly create aerosols, they have a low water con-sumption, so if the cleaning capacity of the gel is satis-z5 factory, the gel application method is a safe and gentle way ofcleaning hard surfaces.

UMM~Y OF THE lN V ~ N ~ lON

In this invention it is surprisingly found that a special gel cleaning composition with enzyme(s), which contains 30 no thickeners, has extraordinary good cleaning capacities on hard surfaces.

WO94/25561 PCT~X~4/00176 21 62021 ~

Accordingly, the present invention relates to a detergent composition for cleaning hard surfaces, the com-position comprising one surfactant together with an electrolyte or more than one surfactant, optionally together with an 5 electrolyte, which composition is capable of forming a gel when water is added, the composition further comprising one or more enzymes.

The present invention is further illustrated by 10 reference to the accompanying drawings, in which Fig. l shows the cleaning result of the C14 dimethyl amine oxide/sodium oleate/protease gel, pH 12 (top), pH 10.1 -(bottom), half the lid with enzyme, the other half without enzyme, the gel produced as described in Example 1.
Fig. 2 shows the cleaning result of the C1214 alkyl dimethyl betaine/sodium oleate/protease gel, pH 12, half the lid with enzyme, the other half without enzyme, the gel produced as described in Example 1.
Fig. 3 shows the cleaning result of the 6-O-dodecanoyl 20 glycoside/sodium dodecyl ether sulfate/protease gel, pH 4 (bottom), pH 8 (top), half the lid with enzyme, the other half without enzyme, the gel produced as described in Example 1.
Fig. 4 shows the cleaning result of the 6-O-dodecanoyl glycoside/sodium dodecyl sulfate/amylase gel, pH 7, half the Z5 lid with enzyme, the other half without enzyme, the gel produced as described in Example 2.

DET~TT~n DISC~08~RE OF T~ lNv~s.~lON

Gel Compositions Gel cleaning agents containing one or more enzymes for 30 use as industrial hard surface cleaners have been described before (see Research Disclosure, August 1992, p.619, No.34045).

WO94/25561 ~- PCT~K94/00176 These gels are characterized by containing at least one or more surfactants, builders, thickeners and one or more enzymes.
According to the invention, it is preferred to add enzyme(s) to a special gel cleaning composition which contains 5 no thickeners. (Gels containing thickeners are described in Research Disclosure, August 1992, p.619, No.34045). Basically these gels are made of one surfactant together with an electro-lyte or more than one surfactant, optionally together with an electrolyte, which composition is capable of forming a gel when 10 water is added. Some surfactants have this special capacity; in the present invention it has been found that there may be two surfactants, the first surfactant may be an amine oxide or a betaine or a tetraalkylammoniumchloride and the second surfact-ant an alkali metal salt of a fatty acid, or the first surfact-15 ant may be a nonionic glycolipid and the second surfactant acharged surfactant, preferably an anionic surfactant, prefer-ably sodium lauryl sulfate or sodium lauryl ether sulfate.
The amine oxide may be one of the general formula R - N ~ O, where R = C12-C18, and R1 is the same or different and selected 25 from alkyl, substituted alkyl, aryl or substituted aryl. An example of a suitable amine oxide is C~4 dimethyl amine oxide.
The betaine may be one of the general formula I

30 R - N+ - CH2-COO., I

where R = C12-C18, and R1 is the same or different and selected from alkyl, substituted alkyl, aryl or substituted aryl. An 35 example of a suitable betaine is C1214 alkyl dimethyl betaine, in which C1214 alkyl is derived from coconut.

W094/25561 2 1 6 2 0 2 ~ PCT~Kg4/00176 The tetraalkylammoniumchloride may be one of the general formula R
I

s R - N+ - R, Cl I
R

where R is the same or different and selected from alkyl or substituted alkyl.
The alkali metal salt of a fatty acid may be one of the general formula o Il R--CH2 - C--O M~, R = C8--C16-An example of a suitable alkali metal salt of a fatty acid is sodium oleate.
The glycolipid may be a sugar or sugar alcohol fatty acid ester (as described in JP 63-112,993) or a derivative thereof or a fatty acid monoester or a mixture of fatty acid 20 monoesters of alkylglycoside (as described in US 5,191,071 and in US 5,200,328) or a derivative thereof.
The ratio of the first surfactant (the amine oxide or the betaine or the tetraalkylammoniumchloride or the glyco-lipid) and the second surfactant (the alkali metal salt of a 25 fatty acid or the charged surfactant) is suitably 1:10 - 10:1, preferably 1:1 - 10:1.
The gel composition may optionally also contain other detergent ingredients such as solvents and sequestrants.
The gel composition may also contain an electrolyte 30 (e.g. sodium chloride) to induce gel formation or increase gel strength. When all the components except the enzyme(s) are added, the pH is adjusted to less than 12.5. This detergent composition is admixed with water to a total water con-centration of 10-80%, preferably 20-70%, more preferably 40-WO94125~61 2 1 6 2 0 2 1 PCT~h94/00176 ~ . ..... ~

60%. At this concentrated form the detergent composition is aneasily pumpable liquid.
Then one or more enzymes are added to the surfactant composition of the present invention. The enzymes are in 5 particular proteases (for instance Savinase 16.0 L, Alcalase 2.5 L, Esperase- 8.0 L or Durazym~ 16.0 L, all available from Novo Nordisk A/S), amylases (for instance Termamyl~ 300 L
available from Novo Nordisk A/S), lipases (for instance Lipolase lO0 L available from Novo Nordisk A/S) or cellulases 10 (for instance Celluzyme~ l.0 L available from Novo Nordisk A/S). The amount of techn;cal enzyme may be dosed so that the percentage of enzyme in the finished gel will be of 0.001-10%, preferably 0.01-1%, in particular about O.Ol-0.1%.
The above mentioned surfactant combination forms a gel 15 when water is added. The gel formation may be promoted by an electrolyte which may be present in the concentrated detergent composition or in the water added to generate the gel. This reflects the well known fact that in a triangular phase diagram describing a ternary system (first surfactant, second surf-20 actant, water) changes in the mole fractions often lead tophase transition, e.g. the transition from a liquid phase to a gel phase. It is also known that this phase transition may be reversed by changing the mole fraction.
lt has surprisingly been found that the enzymes perform 25 extremely well in the surfactant system of the present inven-tion despite the impaired diffusion possibility of the macro-molecular enzymes in the gel network. This can be explained by the gel being in a dynamic state of constant micelle refor-mation generating a stirring action in situ.

30 Gel Making in situ The gel is made in situ. The detergent composition comprising the surfactants, the enzyme(s) and optionally the electrolyte are diluted with water and applied to the soiled surfaces by using some kind of application system (e.g. diluted 35 through a venturi and applied via a special lance). The detergent composition is best applied using gel generation WO94/25~61 2 1 6 2 ~ 2 ~ PCT~Kg4/00176 equipment which automatically draws in the required percentage.
Application equipment is available from for instance Scanio A/S, Blytaekkervej 4-6, DK-9000 Aalborg, Denmark.
In order to make the proper gel, the water used for 5 mixing should be added in an amount so as to generate a final surfactant concentration in the range of 0.1-25%, preferably in the range of 0.5-10%.

Cleaninq Hard Surfaces The gel is applied to the soiled surfaces as described 10 above. The gel will set on the surfaces within a few seconds.
The enzymes will participate in the degradation of protein (proteases), starch (amylases), lipid (lipases) and cellulose (cellulases) residues. The gel will remain in its form even on complicated ~hAp~ equipment, vertical surfaces and ceilings 15 and will therefore give very long contact times. Dwell times are difficult to estimate beforehand and should be determined by trial. A dwell time of 5-30 minutes may often be required.
After a sufficient dwell time to allow for enzyme and surfactant action the gel composition is rinsed off using a 20 washing system. In some cases it may be necessary to use a pressure washing system to rinse off the gel composition, but often removal by gentle flushing with water is easy and all that is needed.

~valuation of the Cleaninq Results In the present invention the efficiency of the deter-gent formulations on hard surfaces is evaluated visually. This is of course a primitive method, but for the skilled eye the best there is today.

Potential Applications The enzyme gel detergent described in this invention may be used in all kinds of food industries: in dairies, in slaughterhouses, in breweries, in sea food production units etc. It may also be used in the transport sector, for instance as a cleaning agent in car washing and for general vessel wash.

WO94/25561 PCT~K94/00176 ~ -` 21 6~02~

It may also work as a general purpose cleaner in households, for instance as an efficient oven cleaner.
The invention is further illustrated in the following example which is not intended to be in any way limiting to the 5 scope of the invention as claimed.

Test of an Enzyme Gel Detergont on Hard 8urf~ceQ with Protein ~oils Protein Soils 3 whole eggs and 50 ml of skimmed milk were blended together at lowest speed in a Braun UK20 for 1 min. This mixture was poured over the curved side of a stainless steel lid. The lid was left to dry for at least 4 hours at room temperature in a drying rack where excess soil drained off.
Before use the soiled lid was dipped in boiling water for 30 sec. In this way the soil was made more difficult to remove.

Treatment with Protease Gel Deterqent (Amine Oxide and Sodium Oleate) A detergent composition made of zo 10.0% dipropylene glycol monomethyl ether 16.0% C14 dimethyl amine oxide 5.3% oleic acid ~.2% NaOH (47%) 11.0% NaCl 10.0% triethanolamine (85%) 8.0% Dequest 2000 37.5% water was prepared. After addition of each of the components the mixture was blended. After addition of the last component pH
30 was 10.1. In a sample pH was adjusted to 12Ø A gel was made of the detergent composition, protease (Savinase 16.0 L) and water in such a way that the water content of the ready-to-use gel was 96.5%, and the enzyme content was 0.5%.

WO94/25561 PCT~K94/00176 ~: 2 ~ 6202 1 ~

The gel was smeared evenly over the top surface of the lid with a pastry brush. After a dwell time of 10 min. water (35-40C) was rinsed over the lid. Then the lid was left to dry. In order to see the effect of the enzyme one half of the 5 lid was treated with gel plus enzyme and the other half of the lid was treated with gel without the enzyme.
Fig. 1 shows the result when pH of the gel is 12.0 (top) and when pH of the gel is 10.1 (bottom). It goes without saying that the effect of the enzyme is remarkable.

10 Treatment with Protease Gel Detergent (Betaine and Sodium Oleate) A detergent composition made of 10.0% dipropylene glycol monomethyl ether 16.0% C1214 alkyl dimethyl betaine 5.3% oleic acid 2.2% NaOH (47%) 13.0% NaCl 10.0% triethanolamine (85%) 8.0% Dequest 2000 35.S% water was prepared. After addition of each of the components the mixture was blended. After addition of the last component pH
was 7Ø In a sample pH was adjusted to 12Ø A gel was made of the detergent composition, protease (Savinase 16.0 L), and 25 water in such a way that the content of detergent composition was 15% and the enzyme content was 0.5%.
The gel was smeared evenly over the top surface of the lid with a pastry brush. After a dwell time of 10 min. water (35-40-C) was rinsed over the lid. Then the lid was left to 30 dry. In order to see the effect of the enzyme one half of the lid was treated with gel plus enzyme and the other half of the lid was treated with gel without the enzyme.
Fig. 2 shows the result. The effect of the enzyme is remarkable.

wo 94/25561 2 1 6 2 ~2 1 PCT~K94/00176 Treatment with Protease Gel Detergent (6-O-dodecanoyl GlYcoside and Sodium DodecYl Ether Sulfate) A detergent composition made of 47.98% water 3% sodium dodecyl ether sulfate 0.02% citric acid 15% propyleneglycol 7% dipropylene glycol monomethyl ether 25% 6-O-dodecanoyl glycoside 2% oleic acid was prepared. Components were added in the order stated, starting with water, with thorough mixing after each addition.
After addition of the last component, pH was approximately 4.
In one sample of detergent, pH was adjusted to 8.0 with NaOH.
A gel was made of the detergent composition, protease (Savinase 16.0 L) and water in such a way that the water content of the final gel was 82.7%, and the enzyme content was 0.5%.
The gel was smeared evenly over the top surface of the 20 lid with a pastry brush. After a dwell time of 10 min. water (handwarm) was rinsed over the lid ac~omr~nied by a gentle mechanical manual treatment. Then the lid was left to dry. In order to see the effect of the enzyme, one half of the lid was treated with gel plus enzyme, and the other half of the lid was 25 treated with gel without enzyme.
Fig. 3 shows the result when pH of the gel is 4 (bottom) and when pH of the gel is 8 (top). The effect of the enzyme is remarkable.

30 Test of an Enzyme Gel Detergent on Hard 8urfaces with 8tarch 80ils Starch Soils 60 g of corn starch were dissolved in 1.5 litres of water and blended for lO minutes. Then 1.5 litres of water were W~94/25561 PCT~X94/00176 2~6202~ ~

.

added, and the mixture was cooked for 10 minutes, whereafter it was left to cool to 60 C.
Stainless steel lids were one by one pulled through the solution in a tray.
The lids were left to dry until next day.

Treatment with Amylase Gel Detergent f6-0-dodecanoyl GlYcoside and Sodium Dodecyl Sulfate) A detergent composition made of 49.7% water 5% sodium dodecyl sulfate 0.3% Na2SO4 10% propyleneglycol 25% 6-0-dodecanoyl glycoside 5% oleic acid 5% dipropylene glycol monomethyl ether was prepared. Components were added in the order stated, starting with water, with thorough mixing after each addition.
After addition of the last component, pH was adjusted to 7 with NaOH.
A gel was made of the detergent composition, amylase (Termamyl 60 L) and water in such a way that the water content of the final gel was 83.3%, and the enzyme content was 0.1%.
The gel was smeared evenly over the top surface of the lid with a pastry brush. After a dwell time of 15 min. water 25 (handwarm) was rinsed over the lid. A Iodine solution was sprayed over the lid to develop remaining starch. In order to see the effect of the enzyme, one half of the lid was treated with gel plus enzyme, and the other half of the lid was treated with gel without enzyme.
Fig. 4 shows the result when pH of the gel is 7. The effect of the enzyme is remarkable.

Claims

1. A detergent composition for cleaning hard surfaces, the composition comprising one surfactant together with an electrolyte or more than one surfactant, optionally together with an electrolyte, which composition is capable of forming a gel when water is added, the composition further comprising one or more enzymes.

2. A detergent composition according to claim 1, wherein the said detergent composition comprises two surf-actants, optionally containing an electrolyte, which are capable of forming a gel when water is added.

3. A detergent composition according to claims 1-2, wherein the first surfactant is an amine oxide or a betaine or a tetraalkylammoniumchloride and the second surfactant is an alkali metal salt of a fatty acid.

4. A detergent composition according to claim 3, wherein the amine oxide has the formula , where R = C12-C18, and R1 is the same or different and selected from alkyl, substituted alkyl, aryl or substituted aryl.

5. A detergent composition according to claim 4, wherein the amine oxide is C14 dimethyl amine oxide.

6. A detergent composition according to claim 3, wherein the betaine has the formula , where R = C12-C18, and R1 is the same or different and selected from alkyl, substituted alkyl, aryl or substituted aryl.

7. A detergent composition according to claim 6, wherein the betaine is C12-14 alkyl dimethyl betaine.

8. A detergent composition according to claim 3, wherein the tetraalkylammoniumchloride has the formula where R is the same or different and selected from alkyl or substituted alkyl.

9. A detergent composition according to claim 3, wherein the alkali metal salt of the fatty acid is the sodium or potassium salt of a fatty acid containing 10-18 carbon atoms.

10. A detergent composition according to claim 9, wherein the alkali metal salt of a fatty acid is sodium oleate.

11. A detergent composition according to claims 1-2, wherein the first surfactant is a nonionic glycolipid and the second surfactant is a charged surfactant.

12. A detergent composition according to claim 11, wherein the glycolipid is a sugar or sugar alcohol fatty acid ester or a derivative thereof or a fatty acid monoester or a mixture of fatty acid monoesters of alkylglycoside or a derivative thereof.

13. A detergent composition according to claim 12, wherein the glycolipid is a fatty acid monoester or a mixture of fatty acid monoesters of ethylglycoside, the fatty acid containing 8-22 carbon atoms.

14. A detergent composition according to claims 12-13, wherein the glycolipid is ethyl 6-0-dodecanoyl glycoside.

15. A detergent composition according to claim 11, wherein the charged surfactant is an anionic surfactant.

16. A detergent composition according to claim 15, wherein the anionic surfactant is sodium dodecyl sulfate or sodium dodecyl ether sulfate.

17. A detergent composition according to claims 1-16, wherein the ratio of the first surfactant and the second surfactant is 1:10 - 10:1, preferably wherein the ratio of the first surfactant and the second surfactant is 1:1 - 10:1.

18. A detergent composition according to any of claims 1-17, wherein the enzyme(s) are chosen from proteases, amylas-es, cellulases and lipases.

19. A detergent composition according to any of claims 1-18, wherein the pH is less than 12.5.

20. A detergent composition according to claim 1, wherein the electrolyte is a cation, e.g. Na+ from NaCl.

21. A detergent composition according to any of claims 1-7 and 17-20, wherein the first surfactant is C14 dimethyl amine oxide, the second surfactant is sodium oleate, the electrolyte is NaCl, and the enzyme is a protease.

22. A detergent composition according to any of claims 1-3 and 6-7 and 17-20, wherein the first surfactant is C12-14 alkyl dimethyl betaine, the second surfactant is sodium oleate, the electrolyte is NaCl, and the enzyme is a protease.

23. A detergent composition according to any of claims 1-2 and 11-20, wherein the first surfactant is ethyl 6-0-dodecanoyl glycoside, the second surfactant is sodium dodecyl ether sulfate, the electrolyte is NaCl, and the enzyme is a protease.

24. A detergent composition according to any of claims 1-2 and 11-20, wherein the first surfactant is ethyl 6-0-dodecanoyl glycoside, the second surfactant is sodium dodecyl sulfate, the electrolyte is NaCl, and the enzyme is an amylase.

25. A detergent composition according to any of claims 1-24 admixed with water to a total water concentration of 10-80%, preferably 20-70%, more preferably 40-60%.

26. A method of preparing a detergent composition for cleaning hard surfaces, the method comprising mixing im-mediately prior to use water with a detergent composition comprising one surfactant together with an electrolyte or more than one surfactant, optionally together with an electrolyte, which composition is capable of forming a gel when water is added, the composition further comprising one or more enzymes.

27. A method according to claim 26, wherein the surfactant(s), the electrolyte, the enzyme(s), the pH, and the mixing ratio of the two surfactants are as described in claims 1-25.

28. A method according to claims 26 and 27, wherein the final concentration of surfactant(s) in the gel after admixing with water is in the range of 0.1-25%, preferably in the range of 0.5-10%.

29. A method of cleaning hard surfaces, wherein a detergent composition produced by the method according to any of claims 26-28 is applied on a hard surface and is then rinsed off after a period of time sufficient to permit action of the surfactant(s) and enzyme(s) applied on the surface.