CA2204507C - Thickened bleaching compositions, method of use and process for making them - Google Patents
Thickened bleaching compositions, method of use and process for making them Download PDFInfo
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- CA2204507C CA2204507C CA002204507A CA2204507A CA2204507C CA 2204507 C CA2204507 C CA 2204507C CA 002204507 A CA002204507 A CA 002204507A CA 2204507 A CA2204507 A CA 2204507A CA 2204507 C CA2204507 C CA 2204507C
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- 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
- C11D1/835—Mixtures of non-ionic with cationic compounds
-
- 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
-
- 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
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium compounds
-
- 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
- C11D1/75—Amino oxides
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention relates to stable thickened acidic aqueous compositions comprising a source of active oxygen or mixtures thereof as well as a quaternary ammonium compound together with a short chain amine oxide, i.e. an amine oxide having the following formula R1R2R3NO, wherein R2 and R3 are independently C1-C4 alkyl groups and wherein R1 is a C6 to C10 alkyl group. Said compositions are particularly suitable for the cleaning of non-horizontal surfaces.
Description
CA 02204~07 1997-0~-0~
WO 96/17044 PCI'lUS9S/lS49S
THICKENED BLEACHING COMPOSITIONS, METHOD OF USE AND
20Technical field The present invention relates to aqueous bleaching compositions, more particularly to stable acidic thickened aqueous compositions comprising a 25 source of active oxygen. Said compositions find particular application in the cleaning of hard-surfaces, especially inclined hard-surfaces, such as toilet bowls and the like.
3 oBackground A great variety of bleaching and cleaning compositions have been described in the art. Bleaching/cleaning compositions comprising a source - 35 of active oxygen and formulated at low pH are particularly interesting for the cleaning of hard-surfaces, especially for the hygienic cleaning of sanitary fittings such as toilet bowls and the like.
CA 02204~07 1997-0~-0~
WO 96/17W4 PCI/US95/lS495 Representative of this technical field is, for instancei EP-A-598 694 which discloses acidic aqueous compositions comprising persulfate salts which are preferably in the form of an emulsion of nonionic surfactants.
5 However, such compositions have not been found satisfactory as regards their residence time on the surface to be cleaned in particular if the surface is wet. Indeed, it is desired to formulate compositions having greater residence time on non-horizontal surfaces such as inclined wall of a toilet bowl when applied thereto, allowing thereby that said compositions 10 perform their cleaning action for longer periods of time. There are many such compositions known in the art that have the requisite viscosity characteristics. However, most of the thickeners known in the art, whilst allowing to effectively increase the viscosity of aqueous acidic compositions, do have some disadvantages in use. Indeed, thickeners like 15 nonionic surfactants (nonyl phenol ethoxylates) or quaternary ammonium compounds have the disadvantage that they require to be used at high levels to achieve satisfactory viscosity, thus making them expensive to use. Also, some thickeners show significant instability in acidic medium, especially in acidic medium with hydrogen peroxide, or a source thereof,
WO 96/17044 PCI'lUS9S/lS49S
THICKENED BLEACHING COMPOSITIONS, METHOD OF USE AND
20Technical field The present invention relates to aqueous bleaching compositions, more particularly to stable acidic thickened aqueous compositions comprising a 25 source of active oxygen. Said compositions find particular application in the cleaning of hard-surfaces, especially inclined hard-surfaces, such as toilet bowls and the like.
3 oBackground A great variety of bleaching and cleaning compositions have been described in the art. Bleaching/cleaning compositions comprising a source - 35 of active oxygen and formulated at low pH are particularly interesting for the cleaning of hard-surfaces, especially for the hygienic cleaning of sanitary fittings such as toilet bowls and the like.
CA 02204~07 1997-0~-0~
WO 96/17W4 PCI/US95/lS495 Representative of this technical field is, for instancei EP-A-598 694 which discloses acidic aqueous compositions comprising persulfate salts which are preferably in the form of an emulsion of nonionic surfactants.
5 However, such compositions have not been found satisfactory as regards their residence time on the surface to be cleaned in particular if the surface is wet. Indeed, it is desired to formulate compositions having greater residence time on non-horizontal surfaces such as inclined wall of a toilet bowl when applied thereto, allowing thereby that said compositions 10 perform their cleaning action for longer periods of time. There are many such compositions known in the art that have the requisite viscosity characteristics. However, most of the thickeners known in the art, whilst allowing to effectively increase the viscosity of aqueous acidic compositions, do have some disadvantages in use. Indeed, thickeners like 15 nonionic surfactants (nonyl phenol ethoxylates) or quaternary ammonium compounds have the disadvantage that they require to be used at high levels to achieve satisfactory viscosity, thus making them expensive to use. Also, some thickeners show significant instability in acidic medium, especially in acidic medium with hydrogen peroxide, or a source thereof,
2 0 like monopersulfate. Indeed, some thickeners are easily oxidizable by sources of active oxygen, like monopersulfate, in aqueous acidic compositions, leading thereby to a loss of the total amount of active oxygen which would otherwise be available to perform bleaching action on the surface to be cleaned. In other words, some thickeners do not allow 25 to formulate acidic aqueous compositions comprising a source of active oxygen with salisfactory chemical stability for long storage periods.
It is thus an object of the present invention to formulate acidic aqueous compositions comprising a source of active oxygen having improved 30 thickening properties.
It is a further object of the present invention to formulate acidic aqueous compositions comprising a source of active oxygen with high thickening at low total thickening surfactant level.
CA 02204~07 1997-0~-0~
WO 96/17044 PCI'/US9S/lS495 It is another object of the present invention to formulate thickened aqueous acidic compositions comprising a source of active oxygen which are chemically stable for long storage periods.
5 It has now been found that the above mentioned objects could be met by formulating an acidic aqueous composition comprising a source of active oxygen and, as the thickening system, a quaternary ammonium compound together with a short chain amine oxide (C6-C10). More particularly, it has unexpectedly been found that the addition of a small amount of a short 10 chain amine oxide to a quaternary ammonium compound, as the thickening system, in an acidic aqueous composition comprising a source of active oxygen allows to formulate highly thickened aqueous acidic compositions as compared to the use of only said quaternary ammonium compound, as the thickening system, i.e. a thickening system being free of any short 15 chain amine oxide. Allernali~ely, the present invention allows to use low level of total thickening surfactant to achieve a given viscosity for an acidic aqueous composition comprising a source of active oxygen. In other words, to obtain a desired thickening effect for a given acidic aqueous composition, a lower level of total thickening surfactants ~quaternary 20 ammonium compounds and short chain amine oxides) is sufficient in the present invention, as compared to the level of quaternary ammonium compound which would otherwise be required to obtain the same thickening effect when used alone, in absence of any short chain amine oxide. This thickening effect is even more noliceable in the preferred 2 5 compositions of the present invention wherein said source of active oxygen is a persulfate salt such as monopersulfate salt. Indeed, it has been found that said persulfate salt together with said quaternary ammonium compound act as a thickening system.
It is thus an object of the present invention to formulate acidic aqueous compositions comprising a source of active oxygen having improved 30 thickening properties.
It is a further object of the present invention to formulate acidic aqueous compositions comprising a source of active oxygen with high thickening at low total thickening surfactant level.
CA 02204~07 1997-0~-0~
WO 96/17044 PCI'/US9S/lS495 It is another object of the present invention to formulate thickened aqueous acidic compositions comprising a source of active oxygen which are chemically stable for long storage periods.
5 It has now been found that the above mentioned objects could be met by formulating an acidic aqueous composition comprising a source of active oxygen and, as the thickening system, a quaternary ammonium compound together with a short chain amine oxide (C6-C10). More particularly, it has unexpectedly been found that the addition of a small amount of a short 10 chain amine oxide to a quaternary ammonium compound, as the thickening system, in an acidic aqueous composition comprising a source of active oxygen allows to formulate highly thickened aqueous acidic compositions as compared to the use of only said quaternary ammonium compound, as the thickening system, i.e. a thickening system being free of any short 15 chain amine oxide. Allernali~ely, the present invention allows to use low level of total thickening surfactant to achieve a given viscosity for an acidic aqueous composition comprising a source of active oxygen. In other words, to obtain a desired thickening effect for a given acidic aqueous composition, a lower level of total thickening surfactants ~quaternary 20 ammonium compounds and short chain amine oxides) is sufficient in the present invention, as compared to the level of quaternary ammonium compound which would otherwise be required to obtain the same thickening effect when used alone, in absence of any short chain amine oxide. This thickening effect is even more noliceable in the preferred 2 5 compositions of the present invention wherein said source of active oxygen is a persulfate salt such as monopersulfate salt. Indeed, it has been found that said persulfate salt together with said quaternary ammonium compound act as a thickening system.
3 0 It has further been found that the thickening system of the present invention exhibits good stability in acidic medium and in presence of strong oxidants like sources of active oxygen. Indeed, the decomposition of said source of active oxygen, e.g. persulfate salt, is reduced with the thickening system of the present invention as compared to other surfactant blends 35 like for instance alkylethoxylated alcohols. In other words, sources of active oxygen in thickened aqueous acidic compositions of the present invention are chemically stable for longer periods of storage.
CA 02204~07 1997-0~-0~
CA 02204~07 1997-0~-0~
4 PCT/US9S/lS49S
An advantage of the present invention is that the stable thickened aqueous acidic compositions comprising a source of active oxygen according to the present invention are less sensitive to the presence of perfumes. Indeed,
An advantage of the present invention is that the stable thickened aqueous acidic compositions comprising a source of active oxygen according to the present invention are less sensitive to the presence of perfumes. Indeed,
5 the thickening system of the present invention allows to formulate stable acidic aqueous compositions comprising a source of active oxygen and still having high viscosity, despite the presence of perfumes, even at high levels. In fact, high levels of perfume are known to have a general tendency to significantly decrease composition viscosity by changing 10 micellar aggregation.
Another advantage of the present invention is that said stable thickened aqueous acidic compositions are efficient on various surfaces to clean 15 various soils and stains. Additionally, said compositions when used to treat hard surfaces, especially toilet bowls, exhibit outstanding soil discoloration, soil solubilization and emulsification properties together with a germicidal action, this when used both neat or diluted.
2 0 A further advantage is that the present invention allows to formulate compositions which are clear, as opposite to clouded, and thus well accepted from a consumer view point. Also the present invention allows to formulate cG.nposilions that are Newtonian. By "Newtonian" it is meant herein a composition which has the same viscosity within a very wide 25 range of applied shear stresses.
In the field of thickened aqueous acidic compositions the following patent applications are representative of the prior art.
EP-A-275 043 discloses an acidic cleaner for aluminium surfaces containing a peroxide, acids, a C12-C22 alkyl dimethylamine oxide. Said cleaner has a pH at most 2. EP-A-275 043 discloses cationic surfactants as optional ingredients but no specific compounds of this class of surfactants are mentioned, let alone quaternary ammonium compounds.
EP-A-265 979 discloses acidic thickened aqueous cleaning composition comprising a disinfecting and/or oxidizing agent, an organic anionic CA 02204~07 1997-0~-0~
sulphonate and a surfactant selected from the group of ( 1 ) quaternary ammonium compounds wherein at least one of the hydrocarbon groups linked to the nitrogen is a linear or branched alkyl group containing at least 12 carbon atoms and of (2) tertiary amine oxides wherein at least one of 5 the hydrocarbon groups linked to the nitrogen is a linear or branched alkyl group containing at least 16 carbon atoms. In contrast, the present invention uses quaternary ammonium compounds together with short chain amine oxides ~C6-C10) as the thickening system. Also, nowhere in EP-A-265 979 a source of active oxygen is disclosed.
EP-A-188 025 discloses aqueous stable thickened low-pH bleaching compositions comprising an inorganic peroxy compound, a strong acid and a thickening surfactant. In EP-A-188 025 the thickening surfactant is selected from (1) amine oxides wherein at least one of the hydrocarbon 15 groups linked to the nitrogen is a linear or branched alkyl group of C6 to C18 carbon atoms, preferably C12 to C18, ~2) amines and (3) quaternary ammonium salts wherein at least one of the hydrocarbon groups linked to the nitrogen is a linear or branched alkyl group of C8 to C18 carbon atoms.
Indeed, EP-A-188 025 teaches to use as a thickening surfactant one of 20 these surfactants. And as rega~s-the amine oxides, this patent application teaches to preferably use long chain amine oxides. Also none of the compositions exemplified comprises, as the thickening system, a quater"ar~/ ammonium compound together with an amine oxide, let alone a quaternary ~-"."onium cG"")ound together with a short chain amine oxide.
Summarv of the invention 30 The present invention encorr~passes a stable thickened aqueous acidic bleaching composition comprising a source of active oxygen and, as a thickening system, a quaternary ammonium compound and an amine oxide according to the formula R1R2R3N0 wherein R2 and R3 are independently C1-C4 alkyl groups and wherein R1 is a C6 to C10 alkyl group.
In a preferred embodiment the stable thickened aqueous acidic compositions of the present invention further comprise a perfume.
CA 02204~07 1997-0~-0~
WO 96/17044 PCT/US9S/lS495 The present invention also encompasses a process of treating hard-surfaces wherein a stable thickened aqueous acidic composition, according to the present invention, is used.
The present invention also encompasses a process for the manufacture of a composition according to the present invention wherein:
- an acidic matrix is prepared which comprises at least water, a source of active oxygen and an acid, - then a quaternary ammonium compound is added to said matrix, - then a perfume, if present, is further added and finally a short chain amine oxide is added, - the resulting composition is then stirred over at least three hours.
The present invention further encompasses the use of persulfate salt together with a quaternary ammonium compound in an aqueous acidic composition to increase the viscosity of said composition.
Detailed de--scriDtion of the invention The compositions according to the present invention are stable. By "stable~ it is meant herein that a composition comprising a source of active 25 oxygen or mixtures thereof, such as persulfate salt, preferably does not undergo more than 30 % persulfate loss, in six months at room te""~eral.lre (20~C-25~C). Persulfate concentration can be measured by titration with potassium permanganate after reduction with a solution containing ammonium ferrous sulphate. Said stability test method is well 30 known in the art and is reported, for example, on the technical information sheet of Curox~ commercially available from Interox. Alternatively persulfate concentration can a~so be measured using a chromatography method described in the literature for peracids (F. Di Furia et al., Gas-liquid Chromatography Method for Determination of Peracids, Analyst, Vol 113, 35 May 1988, p 793-795~.
CA 02204~07 1997-0~-0~
WO 96/17044 PCT/US95/lS495 The compositions according to the present invention comprise, as an essential element, a source of active oxygen or mixtures thereof. The source of active oxygen according to the present invention acts as an oxidizing agent, it increases the ability of the compositions to remove 5 colored stains and organic stains in general, to destroy malodorous molecules and to kill germs. Suitable sources of active oxygen are hydrogen peroxide or sources thereof. As used herein a hydrogen peroxide source refers to any compound which produces hydrogen peroxide when said compound is in contact with water. Suitable water-soluble inorganic 10 sources of hydrogen peroxide for use herein include persulfate, persulfuric acid, percarbonates, metal peroxides, perborates and persilicate salts.
In addition, other cl~sses of peroxides can be used as an alternative to hydrogen peroxide and sources thereof or in combination with hydrogen peroxide and sources thereof. Suitable classes include dialkylperoxides, 15 diacylperoxide, performed percarboxylic acids, organic and inorganic peroxides and/or hydroperoxides. Suitable organic peroxides/hydroperoxides include diacyl and dialkyl peroxides/hydroperoxides such as dibenzoyl peroxide, t-butyl hydroperoxide, dilauroyl peroxide, dicumyl peroxide, and mixtures thereof.
20 Suitable preformed peroxyacids for use in the compositions according to the present invention include diperoxydodecandioic acid DPDA, magnesium perphthalic acid, perlauric acid, perbenzoic acid, diperoxyazelaic acid and mixtures thereof.
Persulfate salts or mixtures thereof are the preferred sources of active 25 oxygen to be used in the compositions according to the present invention.
Plefer.~d persulfate salt to be used herein is the monopersulfate triple salt.
One example of monopersulfate salt commercially available is potassium monopersulfate commercialized by Peroxide Chemie GMBH under the trade name Curox@). Other persulfate salts such as dipersulfate salts 30 commercially available from Peroxide Chemie GMBH can be used in the compositions according to the present invention.
The compositions according to the present invention comprise from 0.1%
to 30% by weight of the total composition of said source of active oxygen, or mixtures thereof, preferably from 0.1% to 20%, and more preferably 35 fromO.1%to 15%.
CA 02204~07 1997-0~-0 WO 96/17044 PCT/US95/lS495 Persulfate salts are preferred to be used herein, as-it has been found that they allow when used together with a quaternary ammonium compound to increase the viscosity of an aqueous acidic composition. This is especially noticeable in said aqueous acidic compositions in absence of perfumes.
5 Indeed, it has now been found that the addition of a persulfate salt such as a monopersulfate salt, as the source of active oxygen, to an aqueous acidic composition comprising a quaternary ammonium compound such as C16 trimethyl ammonium methylsulfate improves the viscosity of said composition as compared to the viscosity of the same composition but 10 without said persulfate salt. It is believed that (HS05-) anion coming from persulfate salt like monopersulfate salt strongly interacts with the cation head group of the quaternary ammonium compound displacing its own counterion (e.g., methylsulfate). It is bclicvcd that the interaction of persulfate salt like monopersulfate salt with a quaternary ammonium 15 compound plays a significant role in thickening the compositions of the present invention, together with the thickening effect related to the addition of short chain amine oxide to said quaternary ammonium compound.
20 Thus in another aspect, the present invention further encorrpasses the use of persulfate salt together with a quaternary ammonium compound in an aqueous acidic composition to increase the viscosity of said composition.
The compositions of the present invention comprise as a further essential 25 01e.,.ent a thickening system. Said thickening system comprises a quaternary ammonium co" Ipound, or mixtures thereof, together with a short chain amine oxide, or mixtures thereof.
Suitable qualer"ary ammonium compounds to be used according to the 3 0 present invention are quaternary ammonium compounds wherein one or two of the hydrocarbon groups linked to nitrogen are a linear or branched alkyl group of 6 to 30 carbon atoms, preferably of 10 to 25 carbon atoms and more preferably 12 to 20 carbon atoms, saturated or unsaturated, and wherein the other hydrocarbon groups (i.e. three when one hydrocarbon 35 group is a long chain hydrocarbon group as mentioned hereinbefore or two when two hydrocarbon groups are long chain hydrocarbon groups as mentioned hereinbefore) linked to the nitrogen are independently CA 02204~07 1997-0~-0~
WO 96/17044 PCI/US95/lS495 substituted or unsubstituted, linear or branched, alkyl chain of from 1 to 4 carbon atoms, preferably of from 1 to 3 carbon atoms and more preferably are methyl groups. In the embodiment of the present invention where persulfate salts or mixtures thereof are used as sources of active oxygen the quaternary ammonium compound is preferably a non-chloride quaternary ammonium compound. The counterion used in said quaternary ammonium compounds are compatible with any source of active oxygen and are selected from the group of fluoride or methyl sulfate, or methylsulfonate, or hydroxide and the like.
Particularly preferred to be used in the compositions of the present invention are trimethyl quaternary ammonium compounds like myristyl t-i-"t:lt-ylsulfate, cetyl trimethylsulfate a-nd/or tallow trimethylsulfate. Such trimethyl quaternary ammonium compounds are commercially available from Hoechst, or from Albright & Wilson under the trade name EMPIGEN
CM~.
The compositions according to the present invention comprise from 0.1%
to 20% by weight of a quaternary ammonium compound, or mixtures thereof, preferably of from 0.1% to 15%, more preferably of from 0.1% to 10% and most preferably of from 1% to 5%.
Suitable short chain amine oxides to be used according to the present invention are amine oxides having the following formula R1 R2R3N0 wherein R1 is a C6 to C10 alkyl group, preferably a C8 to C10 alkyl group and wherein R2 and R3 are independently substituted or unsubstituted, linear or branched alkyl groups of from 1 to 4 carbon atoms, preferably of from 1 to 3 carbon atoms and more preferably are methyl groups. R1 may be a linear or branched alkyl group, being saturated or unsaturated.
Suitable short chain amine oxides for use herein are preferably compatible with any source of active oxygen. Preferred short chain amine oxides for use herein are for instance natural blend C8/C10 amine oxide available from Hoechst.
The compositions according to the present invention comprise from 0.01%
to 15 % by weight of a short chain amine oxide, or mixtures thereof, -CA 02204~07 1997-0~-0~
WO 96/17W4 PCT/USgS/lS49S
preferably of from 0.1% to 10% more preferably of from 0.1% to 5% and most preferably of from 0.1 % to 3%.
The total level of thickening system, i.e. of quaternary ammonium compound and of short chain amine oxide, to be used in a given aqueous acidic composition comprising a source of active oxygen depends on the thickening desired for said composition, said level being lower than 20%, preferably between 1% and 15%, more preferably between 1% and 10%
and most preferably between 1 % and 6%.
The compositions of the present invention have a viscosity of more than 250 cps at 20~C, preferably of from 250 cps to 1500 cps and more preferably of from 250 cps to 900 cps, when measured with a Brookfield viscometer at 60 rpm with a spindle n~ 2 or with the Carri-med rheometer at 50 dyne/cm2.
Furthermore, the stable thickened aqueous acidic compositions of the present invention comprise a quaternary ammonium compound and a short chain amine oxide, as the thickening system, the weight ratio of said short chain amine oxide to said quaternary ammonium compound being from 1 :2 to 1:100, preferably from 1:4 to 1:30 and more preferably from 1:10 to 1:20.
In an embodiment of the present invention the compositions as described hereinbefore further comprise a perfume or mixtures thereof . It is well known that perfumes have a general tendency to significantly decrease the viscosil~ of cG,~posilions in which they are introduced. An advantage of the thickened acidic compositions of the present invention is, that they are less sensitive to the presence of perfume, even the presence of high levels of perfumes. Suitable perfumes to be used herein are all the perfumes well known in the field per se or blend of such perfumes.
The compositions according to the present invention comprise up to 3% by weight of the total composition of a perfume or mixtures thereof, preferably of from 0.1 % to 2% and more preferably of from 0.2% to 1 %.
CA 02204~07 1997-0~-0~
WO 96/17044 PCI/US95/lS495 The compositions of the present invention are acidic compositions. In order to obtain appropriate stability of the source of active oxygen in the compositions according to the present invention, said compositions are formulated at a pH between 0 to 6, more preferably at a pH between 0 and 5 4 and most preferably at a pH between 0 and 2. Acidity further contributes to formulate compositions according to the present invention which exhibit good limesc~le removing performance while having also good disinfecting properties. Accordingly, the compositions of the present invention further comprise organic and/or inorganic acids. Particularly suitable organic acids 10 to be used herein are aryl and/or alkyl sulfonate, such as methane sulfonic acids, citric acid, succinic acid, sulphamic acid and the like. Particularly suitable inorganic acids are sulfuric, phosphoric, nitric acids and the like.
15 The compositions according to the present invention are aqueous. The compositions according to the present invention comprise from 40% to 99% by weight of the total composition of water, preferably from 60% to 95%, most preferably from 70% to 90%. Deionized water is preferably used.
As an optional but highly preferred ingredient the co,-"~ositions according to the present invention further comprise an alkali metal sulphate or mixtures thereof. Plefer,ed alkali metal sulphates to be used herein include ~,olassium sulphate, sodium sulphate or mixtures thereof. We have now 25 found that the addition of an alkali metal sulphate in the compositions of the present invention comprising persulfate salt such as monopersulfate salt, as the source of active oxygen, improves the chemical stability of said compositions. Indeed the percentage of monopersulfate lost upon storage time in a liquid composition according to the present invention comprising 30 a given amount of monopersulfate and an alkali metal salt of sulphate is reduced as compared to the percentage of monopersulfate lost upon storage time in the same composition but without said alkali metal sulphate. Monopersulfate concentration can be measured as already defined herein before. It is believed that the addition of an alkali metal 35 sulphate stabilises monopersulfate salts by shifting the following equilibrium to the left hand side:
CA 02204~07 1997-0~-0~
WO g6/17044 PCT/US9S115495 H20+KHS04+KHS05 - K2S04+H2S04+H202 Accordingly the compositions according to the present invention comprise up to 10% by weight of the total composition of said alkali metal sulphate 5 or mixtures thereof, preferably from 1% to 10% and more preferably from 2% to 7%.
In another aspect, the present invention further encorr~passes the use of an alkali metal sulphate in an aqueous composition comprising a persulfate 10 salt, preferably monopersulfate salt to improve the chemical stability of said composition.
Depending on the end use envisioned, the compositions according to the present invention may further comprise a variety of other ingredients 15 including other surfactants of all types to boost the performance over a wider range of soils/encrustations, organic or inorganic alkalis, dyes, optical brighteners, builders, chelants, pigments, enzymes, dye transfer inhibitors, solvents, buffering agents, stabilizers and the like.
2 0 The present invention further encompasses a process of treating hard-surfaces, especially non-horizontal surfaces, wherein a composition according to the present invention is used in its neat or diluted form.
By "in its diluted form" it is meant herein that said compositions may be 25 diluted with water up to 99% of water. Said dilution may occur either before, after or while said composition is applied to a hard-surface.
The co"-posiliGns herein find a preferred application in the cleaning of toilet bowls and bath tubs. While cleaning toilet bowls compositions according 30 to the present invention may be diluted while or after they are applied to the surface to be cleaned. For example, said compositions may be dispensed from a container onto said hard-surface, then diluted in water and left to act onto said surfaces, then removed by rinsing or flushing.
35 As used in the foregoing paragraphs, the expression "treating" includes washing as the compositions used in the process according to the present CA 02204~07 1997-0~-0~
WO 96/17044 PCT/US95/lS495 invention comprise surfactants and bleaching agents as said compositions also comprise a source of active oxygen, preferably persulfate salts.
The compositions according to the present invention may be manufactured 5 by adding the different ingredients in any order. However, the desired initial viscosity of an aqueous composition Df the present invention is obtained immediately, when following a preferred mixing order for the incorporation of the different ingredients in said composition. Accordingly, the present invention further encompasses a process for the manufacture 10 of the compositions of the present invention, wherein said process comprises the steps of:
- preparing an acidic matrix comprising at least water, a source of active oxygen and an acid, - adding to said matrix the quaternary ammonium compound, 15 - then adding the perfume if present and finally the short chain amine oxide, - and as a final step the resulting composition is stirred over at least three hours.
20 The present invention is further illusl(ated by the following examples.
Example I
Compositions are made which comprise the listed ingredients in the listed 25 proportions (weight %).
C~ osili~.. s #1 #2 #3 #4 #5 C16 t,imell,yl ammonium 4.0 4.2 5.0 0.0 0.0 methylsulfate C16/18 I,i",ell,yl 0.0 0.0 0.0 4.0 4.0 ammonium methylsulfate C8/C10 amine oxide 0.2 0.0 0.0 0.2 0.0 Curox~9 ~ 6.0 6.0 6.0 6.0 6.0 Methane sulfonic acid 5.0 5.0 5.0 S.0 5.0 Perfume 0.7 0.7 0.7 0.7 0.7 Water and mlnors up to 100 CA 02204~07 1997-0~-0~
WO 96/17044 PCI/US95/lS495 pH
Initial viscosity~ (cps) 300 20 300 960 30 Appearance clearnot clear clearnot clear clear Rheological Behaviour Newt.Pseud. Newt. PseudNewt.
Curox~9 is one of the commercial names of monopersulfate salts ~Viscosity grows with time; therefore, those are the lowest achievable viscosities with the above indicated compositions.
The initial viscosity of the above compositions were measured by a Carri-Med Rheomoter at fixed shear stress (50 dyne/cm2) at 20~C. It has been chosen a standard value of the shear stress to compare the viscosity of the above mentioned compositions, some of which showing a pseudoplastic 10 behaviour. 50 dyne/cm2 as shear stress value is representative of a fluid flow occurring on a inclined surface when the product thickness is around 1mm and the only external force is due to the gravity field as per toilet cleaning application.
Compositions #1 and #4 are representative of the stable thickened aqueous acidic compositions according to the present invention, i.e. they comprise a quaternary ammonium compound and a short chain amine oxide as the thickening system. Compositions #2, #3 and #5 are taken as 20 reference, they are free of short chain amine oxides.
The above data surprisingly show that the addition of a small amount of a short chain amine oxide (0.2% by weight) to a quaternary ammonium 25 compound (4% by weight) in an acidic composition comprising a source of active oxygen, like monopersulfate, allows to formulate a composition having a higher viscosity as compared to the same composition wherein the thickening system used is only a quaternary ammonium compound.
(See composition #1 with a viscosity of 300 cps versus composition #2 30 with a viscosity of 20 cps as well as composition #4 with a viscosity of 960 cps as compared to composition #5 with a viscosity of 30 cps).
CA 02204~07 1997-0~-0~
WO g6/17044 PCT/US9S/lS49S
Also the above data show that the addition of a small amount of short chain amine oxide (0.2% by weight) to quaternary ammonium compound (4% by weight) in an acidic composition comprising a source of active 5 oxygen, like monopersulfate, allows to decrease the level of total thickening surfactant needed to formulate an aqueous acidic composition with a desired viscosity as compared to the use, as a thickening system, of a quaternary ammonium compound alone without any short chain amine oxide (see composition #1 with a level of 4.2% of thickening system 10 according to the present invention versus composition #3 with a level of 5% of thickening system in order to obtain compositions having the same viscosity, i.e. 300 cps). In other words, the present invention allows to formulate thickened aqueous acidic compositions at low total level of thickening surfactants, i.e. to achieve the same viscosity, the thickening 15 system of the present invention used in composition #1 allows a reduction of 16% by weight of the total level of thickening surfactant needed as compared to the level required with composition #3 .
2 0 The data also show that the compositions according to the present invention were clear compositions, as opposite to clouded (i.e. not clear) compositions and Newtonian compositions.
ExamDle ll Compositions are made which further illustrate the present invention and 30 which comprise the listed ingredients in the listed proportions (weight %).
ComDositions #1 #2 #3 #4 #S
C16 trimethyl ammonium 4.00 4.00 4.00 4.00 4.00 methylsulfate C8/C10 amine oxide 0.00 0.00 0.30 0.30 0.30 CA 02204~07 1997-0~-0~
WO 96/17044 PCT/US9S/lS495 Curox~) } 6.00 6.00 0.00 6.00 4.00 Sulfuric acid 6.00 6.00 4.00 6.00 6.00 Perfume 0.00 0.70 0.70 0.70 0 70 Water and minors Jp to 10 ~
pH < 2 < 2 < 2 < 2 < 2 Initial viscosity~' ~cps) 5000 <50 50 300 250 Appearance clear cloud clear clear clear Rheological Behaviour Newt. Pseud. Newt. Newt. Newt.
~ Curox~) is one of the commercial names of monopersulfate salts *~Viscosity grows with time; therefore, those are the lowest achievable 5 viscosities with the above indicated compositions.
The initial viscosity of the above compositions were measured by a Carri-Med Rheomoter at fixed shear stress ~50 dyne/cm2) at 20~C. It has been 10 chosen a standard value of the shear stress to compare the viscosity of the above mentioned compositions, some of which showing a pseudoplastic behaviour. 50 dyne/cm2 as shear stress value is representative of a fluid flow occurring on a inclined surface when the product thickness is around 1mm and the only external force is due to the gravity field as per toilet 15 cleaning application.
Co,-")ositions #1 and #2 are taken as reference, they are free of short chain amine oxides. Composition #3 is taken as reference, it is free of 20 monopersulfate salt. Compositions #4 and #5 are representative of the stable thickened aqueous acidic compositions according to the present invention, i.e. they comprise a quaternary ammonium compound, a short chain amine oxide and monopersulfate salt.
The above data surprisingly show that the addition of a monopersulfate salt to a acidic aqueous composition comprising a short chain amine oxide and a quaternary ammonium compound allows to formulate a composition CA 02204~07 1997-0~-0~
WO 96/17044 PCT/US9S/lS49S
having a higher viscosity as compared to the same composition but without said monopersulfate salt. (See compositions #4 and #5 comprising respectively 6% and 4% by weight of the total composition of monopersulfate salt with a viscosity of respectively 300 cps and 250 cps 5 as compared to composition #3 without monopersulfate salt and with a viscosity of 50 cps). Also the aboYe data show the correlation between the increase of the concentration of monopersulfate salt and the increase of viscosity in said matrix.
The above results further show that the present invention allows to formulate thickened aqueous acidic compositions at low total level of thickening surfactants, even if perfume is present, by combining monopersulfate, quaternary ammonium compound and short chain amine 15 oxide.
ExamDle 111 Compositions are made which further illustrate the present invention and which comprise the listed ingredients in the listed proportions (weight %).
ComDositions #1 #2 #3 #4 C16 ~ hyl ammonium 4.70 5.00 5.70 7.00 methylsulfate C81C10 amine oxide 0.36 0.38 0.44 0.54 Curox~ ~ 6.00 6.00 6.00 6.00 Methane sulfonic acid 5.00 5.00 5.00 5.00 Perfume 0.7 0.7 0.7 0.7 Sodium sulphate 5.00 5.00 5.00 5.00 Water and minors up to up to up to up to pH ~ 2 < 2 < 2 ~ 2 Initial viscosity (cps) 370 400 800 1400 Appearance clear clear clear clear -CA 02204~07 1997-0~-0 WO 96/17044 PCT/US9S1154g5 ¦ Rheological Behaviour ¦ Newt. ¦ Newt. ¦ Newt. ¦ Newt. ¦
ExamDle IV
ComDositions #1 #2 #3 #4 #5 #6 C16 trimethyl ammonium 4.00 4.00 4.00 4.004.00 4.00 methylsulfate C8/C10 amine oxide 0.30 0.10 0.30 0.300.30 0.30 Curox~ * 6.00 6.00 6.00 6.006.00 6.00 Methanesulfonic acid 10.00 15.00 0.00 0.005.00 0.00 Sulfuric acid 0.00 0.00 3.00 6.006.00 0.00 Phosphoric acid 0.00 0.00 0.00 0.000.00 12.00 Perfume 0.70 0.70 0.70 0.700.70 0.70 Water and minors up to 100 pH 0.66 0.35 1.00 0.78 0.50 1.00 Initial viscosity ~cps) 270 330 380 400 300 320 Appearance clear clear clear clear clear clear Rheological Behaviour Newt. Newt. Newt. Newt. Newt. Newt.
5 * Curox~ is one of the commercial names of monopersulfate salts.
All the above mentioned acidic aqueous compositions comprising monopersulfate provide significant benefits in toilet soils cleaning both when used neat or diluted. Said compositions were found to be stable 10 over lon~ periods of time. Indeed, these compositions had not more than ~ 10% loss after 1 month at room temperature.
Another advantage of the present invention is that said stable thickened aqueous acidic compositions are efficient on various surfaces to clean 15 various soils and stains. Additionally, said compositions when used to treat hard surfaces, especially toilet bowls, exhibit outstanding soil discoloration, soil solubilization and emulsification properties together with a germicidal action, this when used both neat or diluted.
2 0 A further advantage is that the present invention allows to formulate compositions which are clear, as opposite to clouded, and thus well accepted from a consumer view point. Also the present invention allows to formulate cG.nposilions that are Newtonian. By "Newtonian" it is meant herein a composition which has the same viscosity within a very wide 25 range of applied shear stresses.
In the field of thickened aqueous acidic compositions the following patent applications are representative of the prior art.
EP-A-275 043 discloses an acidic cleaner for aluminium surfaces containing a peroxide, acids, a C12-C22 alkyl dimethylamine oxide. Said cleaner has a pH at most 2. EP-A-275 043 discloses cationic surfactants as optional ingredients but no specific compounds of this class of surfactants are mentioned, let alone quaternary ammonium compounds.
EP-A-265 979 discloses acidic thickened aqueous cleaning composition comprising a disinfecting and/or oxidizing agent, an organic anionic CA 02204~07 1997-0~-0~
sulphonate and a surfactant selected from the group of ( 1 ) quaternary ammonium compounds wherein at least one of the hydrocarbon groups linked to the nitrogen is a linear or branched alkyl group containing at least 12 carbon atoms and of (2) tertiary amine oxides wherein at least one of 5 the hydrocarbon groups linked to the nitrogen is a linear or branched alkyl group containing at least 16 carbon atoms. In contrast, the present invention uses quaternary ammonium compounds together with short chain amine oxides ~C6-C10) as the thickening system. Also, nowhere in EP-A-265 979 a source of active oxygen is disclosed.
EP-A-188 025 discloses aqueous stable thickened low-pH bleaching compositions comprising an inorganic peroxy compound, a strong acid and a thickening surfactant. In EP-A-188 025 the thickening surfactant is selected from (1) amine oxides wherein at least one of the hydrocarbon 15 groups linked to the nitrogen is a linear or branched alkyl group of C6 to C18 carbon atoms, preferably C12 to C18, ~2) amines and (3) quaternary ammonium salts wherein at least one of the hydrocarbon groups linked to the nitrogen is a linear or branched alkyl group of C8 to C18 carbon atoms.
Indeed, EP-A-188 025 teaches to use as a thickening surfactant one of 20 these surfactants. And as rega~s-the amine oxides, this patent application teaches to preferably use long chain amine oxides. Also none of the compositions exemplified comprises, as the thickening system, a quater"ar~/ ammonium compound together with an amine oxide, let alone a quaternary ~-"."onium cG"")ound together with a short chain amine oxide.
Summarv of the invention 30 The present invention encorr~passes a stable thickened aqueous acidic bleaching composition comprising a source of active oxygen and, as a thickening system, a quaternary ammonium compound and an amine oxide according to the formula R1R2R3N0 wherein R2 and R3 are independently C1-C4 alkyl groups and wherein R1 is a C6 to C10 alkyl group.
In a preferred embodiment the stable thickened aqueous acidic compositions of the present invention further comprise a perfume.
CA 02204~07 1997-0~-0~
WO 96/17044 PCT/US9S/lS495 The present invention also encompasses a process of treating hard-surfaces wherein a stable thickened aqueous acidic composition, according to the present invention, is used.
The present invention also encompasses a process for the manufacture of a composition according to the present invention wherein:
- an acidic matrix is prepared which comprises at least water, a source of active oxygen and an acid, - then a quaternary ammonium compound is added to said matrix, - then a perfume, if present, is further added and finally a short chain amine oxide is added, - the resulting composition is then stirred over at least three hours.
The present invention further encompasses the use of persulfate salt together with a quaternary ammonium compound in an aqueous acidic composition to increase the viscosity of said composition.
Detailed de--scriDtion of the invention The compositions according to the present invention are stable. By "stable~ it is meant herein that a composition comprising a source of active 25 oxygen or mixtures thereof, such as persulfate salt, preferably does not undergo more than 30 % persulfate loss, in six months at room te""~eral.lre (20~C-25~C). Persulfate concentration can be measured by titration with potassium permanganate after reduction with a solution containing ammonium ferrous sulphate. Said stability test method is well 30 known in the art and is reported, for example, on the technical information sheet of Curox~ commercially available from Interox. Alternatively persulfate concentration can a~so be measured using a chromatography method described in the literature for peracids (F. Di Furia et al., Gas-liquid Chromatography Method for Determination of Peracids, Analyst, Vol 113, 35 May 1988, p 793-795~.
CA 02204~07 1997-0~-0~
WO 96/17044 PCT/US95/lS495 The compositions according to the present invention comprise, as an essential element, a source of active oxygen or mixtures thereof. The source of active oxygen according to the present invention acts as an oxidizing agent, it increases the ability of the compositions to remove 5 colored stains and organic stains in general, to destroy malodorous molecules and to kill germs. Suitable sources of active oxygen are hydrogen peroxide or sources thereof. As used herein a hydrogen peroxide source refers to any compound which produces hydrogen peroxide when said compound is in contact with water. Suitable water-soluble inorganic 10 sources of hydrogen peroxide for use herein include persulfate, persulfuric acid, percarbonates, metal peroxides, perborates and persilicate salts.
In addition, other cl~sses of peroxides can be used as an alternative to hydrogen peroxide and sources thereof or in combination with hydrogen peroxide and sources thereof. Suitable classes include dialkylperoxides, 15 diacylperoxide, performed percarboxylic acids, organic and inorganic peroxides and/or hydroperoxides. Suitable organic peroxides/hydroperoxides include diacyl and dialkyl peroxides/hydroperoxides such as dibenzoyl peroxide, t-butyl hydroperoxide, dilauroyl peroxide, dicumyl peroxide, and mixtures thereof.
20 Suitable preformed peroxyacids for use in the compositions according to the present invention include diperoxydodecandioic acid DPDA, magnesium perphthalic acid, perlauric acid, perbenzoic acid, diperoxyazelaic acid and mixtures thereof.
Persulfate salts or mixtures thereof are the preferred sources of active 25 oxygen to be used in the compositions according to the present invention.
Plefer.~d persulfate salt to be used herein is the monopersulfate triple salt.
One example of monopersulfate salt commercially available is potassium monopersulfate commercialized by Peroxide Chemie GMBH under the trade name Curox@). Other persulfate salts such as dipersulfate salts 30 commercially available from Peroxide Chemie GMBH can be used in the compositions according to the present invention.
The compositions according to the present invention comprise from 0.1%
to 30% by weight of the total composition of said source of active oxygen, or mixtures thereof, preferably from 0.1% to 20%, and more preferably 35 fromO.1%to 15%.
CA 02204~07 1997-0~-0 WO 96/17044 PCT/US95/lS495 Persulfate salts are preferred to be used herein, as-it has been found that they allow when used together with a quaternary ammonium compound to increase the viscosity of an aqueous acidic composition. This is especially noticeable in said aqueous acidic compositions in absence of perfumes.
5 Indeed, it has now been found that the addition of a persulfate salt such as a monopersulfate salt, as the source of active oxygen, to an aqueous acidic composition comprising a quaternary ammonium compound such as C16 trimethyl ammonium methylsulfate improves the viscosity of said composition as compared to the viscosity of the same composition but 10 without said persulfate salt. It is believed that (HS05-) anion coming from persulfate salt like monopersulfate salt strongly interacts with the cation head group of the quaternary ammonium compound displacing its own counterion (e.g., methylsulfate). It is bclicvcd that the interaction of persulfate salt like monopersulfate salt with a quaternary ammonium 15 compound plays a significant role in thickening the compositions of the present invention, together with the thickening effect related to the addition of short chain amine oxide to said quaternary ammonium compound.
20 Thus in another aspect, the present invention further encorrpasses the use of persulfate salt together with a quaternary ammonium compound in an aqueous acidic composition to increase the viscosity of said composition.
The compositions of the present invention comprise as a further essential 25 01e.,.ent a thickening system. Said thickening system comprises a quaternary ammonium co" Ipound, or mixtures thereof, together with a short chain amine oxide, or mixtures thereof.
Suitable qualer"ary ammonium compounds to be used according to the 3 0 present invention are quaternary ammonium compounds wherein one or two of the hydrocarbon groups linked to nitrogen are a linear or branched alkyl group of 6 to 30 carbon atoms, preferably of 10 to 25 carbon atoms and more preferably 12 to 20 carbon atoms, saturated or unsaturated, and wherein the other hydrocarbon groups (i.e. three when one hydrocarbon 35 group is a long chain hydrocarbon group as mentioned hereinbefore or two when two hydrocarbon groups are long chain hydrocarbon groups as mentioned hereinbefore) linked to the nitrogen are independently CA 02204~07 1997-0~-0~
WO 96/17044 PCI/US95/lS495 substituted or unsubstituted, linear or branched, alkyl chain of from 1 to 4 carbon atoms, preferably of from 1 to 3 carbon atoms and more preferably are methyl groups. In the embodiment of the present invention where persulfate salts or mixtures thereof are used as sources of active oxygen the quaternary ammonium compound is preferably a non-chloride quaternary ammonium compound. The counterion used in said quaternary ammonium compounds are compatible with any source of active oxygen and are selected from the group of fluoride or methyl sulfate, or methylsulfonate, or hydroxide and the like.
Particularly preferred to be used in the compositions of the present invention are trimethyl quaternary ammonium compounds like myristyl t-i-"t:lt-ylsulfate, cetyl trimethylsulfate a-nd/or tallow trimethylsulfate. Such trimethyl quaternary ammonium compounds are commercially available from Hoechst, or from Albright & Wilson under the trade name EMPIGEN
CM~.
The compositions according to the present invention comprise from 0.1%
to 20% by weight of a quaternary ammonium compound, or mixtures thereof, preferably of from 0.1% to 15%, more preferably of from 0.1% to 10% and most preferably of from 1% to 5%.
Suitable short chain amine oxides to be used according to the present invention are amine oxides having the following formula R1 R2R3N0 wherein R1 is a C6 to C10 alkyl group, preferably a C8 to C10 alkyl group and wherein R2 and R3 are independently substituted or unsubstituted, linear or branched alkyl groups of from 1 to 4 carbon atoms, preferably of from 1 to 3 carbon atoms and more preferably are methyl groups. R1 may be a linear or branched alkyl group, being saturated or unsaturated.
Suitable short chain amine oxides for use herein are preferably compatible with any source of active oxygen. Preferred short chain amine oxides for use herein are for instance natural blend C8/C10 amine oxide available from Hoechst.
The compositions according to the present invention comprise from 0.01%
to 15 % by weight of a short chain amine oxide, or mixtures thereof, -CA 02204~07 1997-0~-0~
WO 96/17W4 PCT/USgS/lS49S
preferably of from 0.1% to 10% more preferably of from 0.1% to 5% and most preferably of from 0.1 % to 3%.
The total level of thickening system, i.e. of quaternary ammonium compound and of short chain amine oxide, to be used in a given aqueous acidic composition comprising a source of active oxygen depends on the thickening desired for said composition, said level being lower than 20%, preferably between 1% and 15%, more preferably between 1% and 10%
and most preferably between 1 % and 6%.
The compositions of the present invention have a viscosity of more than 250 cps at 20~C, preferably of from 250 cps to 1500 cps and more preferably of from 250 cps to 900 cps, when measured with a Brookfield viscometer at 60 rpm with a spindle n~ 2 or with the Carri-med rheometer at 50 dyne/cm2.
Furthermore, the stable thickened aqueous acidic compositions of the present invention comprise a quaternary ammonium compound and a short chain amine oxide, as the thickening system, the weight ratio of said short chain amine oxide to said quaternary ammonium compound being from 1 :2 to 1:100, preferably from 1:4 to 1:30 and more preferably from 1:10 to 1:20.
In an embodiment of the present invention the compositions as described hereinbefore further comprise a perfume or mixtures thereof . It is well known that perfumes have a general tendency to significantly decrease the viscosil~ of cG,~posilions in which they are introduced. An advantage of the thickened acidic compositions of the present invention is, that they are less sensitive to the presence of perfume, even the presence of high levels of perfumes. Suitable perfumes to be used herein are all the perfumes well known in the field per se or blend of such perfumes.
The compositions according to the present invention comprise up to 3% by weight of the total composition of a perfume or mixtures thereof, preferably of from 0.1 % to 2% and more preferably of from 0.2% to 1 %.
CA 02204~07 1997-0~-0~
WO 96/17044 PCI/US95/lS495 The compositions of the present invention are acidic compositions. In order to obtain appropriate stability of the source of active oxygen in the compositions according to the present invention, said compositions are formulated at a pH between 0 to 6, more preferably at a pH between 0 and 5 4 and most preferably at a pH between 0 and 2. Acidity further contributes to formulate compositions according to the present invention which exhibit good limesc~le removing performance while having also good disinfecting properties. Accordingly, the compositions of the present invention further comprise organic and/or inorganic acids. Particularly suitable organic acids 10 to be used herein are aryl and/or alkyl sulfonate, such as methane sulfonic acids, citric acid, succinic acid, sulphamic acid and the like. Particularly suitable inorganic acids are sulfuric, phosphoric, nitric acids and the like.
15 The compositions according to the present invention are aqueous. The compositions according to the present invention comprise from 40% to 99% by weight of the total composition of water, preferably from 60% to 95%, most preferably from 70% to 90%. Deionized water is preferably used.
As an optional but highly preferred ingredient the co,-"~ositions according to the present invention further comprise an alkali metal sulphate or mixtures thereof. Plefer,ed alkali metal sulphates to be used herein include ~,olassium sulphate, sodium sulphate or mixtures thereof. We have now 25 found that the addition of an alkali metal sulphate in the compositions of the present invention comprising persulfate salt such as monopersulfate salt, as the source of active oxygen, improves the chemical stability of said compositions. Indeed the percentage of monopersulfate lost upon storage time in a liquid composition according to the present invention comprising 30 a given amount of monopersulfate and an alkali metal salt of sulphate is reduced as compared to the percentage of monopersulfate lost upon storage time in the same composition but without said alkali metal sulphate. Monopersulfate concentration can be measured as already defined herein before. It is believed that the addition of an alkali metal 35 sulphate stabilises monopersulfate salts by shifting the following equilibrium to the left hand side:
CA 02204~07 1997-0~-0~
WO g6/17044 PCT/US9S115495 H20+KHS04+KHS05 - K2S04+H2S04+H202 Accordingly the compositions according to the present invention comprise up to 10% by weight of the total composition of said alkali metal sulphate 5 or mixtures thereof, preferably from 1% to 10% and more preferably from 2% to 7%.
In another aspect, the present invention further encorr~passes the use of an alkali metal sulphate in an aqueous composition comprising a persulfate 10 salt, preferably monopersulfate salt to improve the chemical stability of said composition.
Depending on the end use envisioned, the compositions according to the present invention may further comprise a variety of other ingredients 15 including other surfactants of all types to boost the performance over a wider range of soils/encrustations, organic or inorganic alkalis, dyes, optical brighteners, builders, chelants, pigments, enzymes, dye transfer inhibitors, solvents, buffering agents, stabilizers and the like.
2 0 The present invention further encompasses a process of treating hard-surfaces, especially non-horizontal surfaces, wherein a composition according to the present invention is used in its neat or diluted form.
By "in its diluted form" it is meant herein that said compositions may be 25 diluted with water up to 99% of water. Said dilution may occur either before, after or while said composition is applied to a hard-surface.
The co"-posiliGns herein find a preferred application in the cleaning of toilet bowls and bath tubs. While cleaning toilet bowls compositions according 30 to the present invention may be diluted while or after they are applied to the surface to be cleaned. For example, said compositions may be dispensed from a container onto said hard-surface, then diluted in water and left to act onto said surfaces, then removed by rinsing or flushing.
35 As used in the foregoing paragraphs, the expression "treating" includes washing as the compositions used in the process according to the present CA 02204~07 1997-0~-0~
WO 96/17044 PCT/US95/lS495 invention comprise surfactants and bleaching agents as said compositions also comprise a source of active oxygen, preferably persulfate salts.
The compositions according to the present invention may be manufactured 5 by adding the different ingredients in any order. However, the desired initial viscosity of an aqueous composition Df the present invention is obtained immediately, when following a preferred mixing order for the incorporation of the different ingredients in said composition. Accordingly, the present invention further encompasses a process for the manufacture 10 of the compositions of the present invention, wherein said process comprises the steps of:
- preparing an acidic matrix comprising at least water, a source of active oxygen and an acid, - adding to said matrix the quaternary ammonium compound, 15 - then adding the perfume if present and finally the short chain amine oxide, - and as a final step the resulting composition is stirred over at least three hours.
20 The present invention is further illusl(ated by the following examples.
Example I
Compositions are made which comprise the listed ingredients in the listed 25 proportions (weight %).
C~ osili~.. s #1 #2 #3 #4 #5 C16 t,imell,yl ammonium 4.0 4.2 5.0 0.0 0.0 methylsulfate C16/18 I,i",ell,yl 0.0 0.0 0.0 4.0 4.0 ammonium methylsulfate C8/C10 amine oxide 0.2 0.0 0.0 0.2 0.0 Curox~9 ~ 6.0 6.0 6.0 6.0 6.0 Methane sulfonic acid 5.0 5.0 5.0 S.0 5.0 Perfume 0.7 0.7 0.7 0.7 0.7 Water and mlnors up to 100 CA 02204~07 1997-0~-0~
WO 96/17044 PCI/US95/lS495 pH
Initial viscosity~ (cps) 300 20 300 960 30 Appearance clearnot clear clearnot clear clear Rheological Behaviour Newt.Pseud. Newt. PseudNewt.
Curox~9 is one of the commercial names of monopersulfate salts ~Viscosity grows with time; therefore, those are the lowest achievable viscosities with the above indicated compositions.
The initial viscosity of the above compositions were measured by a Carri-Med Rheomoter at fixed shear stress (50 dyne/cm2) at 20~C. It has been chosen a standard value of the shear stress to compare the viscosity of the above mentioned compositions, some of which showing a pseudoplastic 10 behaviour. 50 dyne/cm2 as shear stress value is representative of a fluid flow occurring on a inclined surface when the product thickness is around 1mm and the only external force is due to the gravity field as per toilet cleaning application.
Compositions #1 and #4 are representative of the stable thickened aqueous acidic compositions according to the present invention, i.e. they comprise a quaternary ammonium compound and a short chain amine oxide as the thickening system. Compositions #2, #3 and #5 are taken as 20 reference, they are free of short chain amine oxides.
The above data surprisingly show that the addition of a small amount of a short chain amine oxide (0.2% by weight) to a quaternary ammonium 25 compound (4% by weight) in an acidic composition comprising a source of active oxygen, like monopersulfate, allows to formulate a composition having a higher viscosity as compared to the same composition wherein the thickening system used is only a quaternary ammonium compound.
(See composition #1 with a viscosity of 300 cps versus composition #2 30 with a viscosity of 20 cps as well as composition #4 with a viscosity of 960 cps as compared to composition #5 with a viscosity of 30 cps).
CA 02204~07 1997-0~-0~
WO g6/17044 PCT/US9S/lS49S
Also the above data show that the addition of a small amount of short chain amine oxide (0.2% by weight) to quaternary ammonium compound (4% by weight) in an acidic composition comprising a source of active 5 oxygen, like monopersulfate, allows to decrease the level of total thickening surfactant needed to formulate an aqueous acidic composition with a desired viscosity as compared to the use, as a thickening system, of a quaternary ammonium compound alone without any short chain amine oxide (see composition #1 with a level of 4.2% of thickening system 10 according to the present invention versus composition #3 with a level of 5% of thickening system in order to obtain compositions having the same viscosity, i.e. 300 cps). In other words, the present invention allows to formulate thickened aqueous acidic compositions at low total level of thickening surfactants, i.e. to achieve the same viscosity, the thickening 15 system of the present invention used in composition #1 allows a reduction of 16% by weight of the total level of thickening surfactant needed as compared to the level required with composition #3 .
2 0 The data also show that the compositions according to the present invention were clear compositions, as opposite to clouded (i.e. not clear) compositions and Newtonian compositions.
ExamDle ll Compositions are made which further illustrate the present invention and 30 which comprise the listed ingredients in the listed proportions (weight %).
ComDositions #1 #2 #3 #4 #S
C16 trimethyl ammonium 4.00 4.00 4.00 4.00 4.00 methylsulfate C8/C10 amine oxide 0.00 0.00 0.30 0.30 0.30 CA 02204~07 1997-0~-0~
WO 96/17044 PCT/US9S/lS495 Curox~) } 6.00 6.00 0.00 6.00 4.00 Sulfuric acid 6.00 6.00 4.00 6.00 6.00 Perfume 0.00 0.70 0.70 0.70 0 70 Water and minors Jp to 10 ~
pH < 2 < 2 < 2 < 2 < 2 Initial viscosity~' ~cps) 5000 <50 50 300 250 Appearance clear cloud clear clear clear Rheological Behaviour Newt. Pseud. Newt. Newt. Newt.
~ Curox~) is one of the commercial names of monopersulfate salts *~Viscosity grows with time; therefore, those are the lowest achievable 5 viscosities with the above indicated compositions.
The initial viscosity of the above compositions were measured by a Carri-Med Rheomoter at fixed shear stress ~50 dyne/cm2) at 20~C. It has been 10 chosen a standard value of the shear stress to compare the viscosity of the above mentioned compositions, some of which showing a pseudoplastic behaviour. 50 dyne/cm2 as shear stress value is representative of a fluid flow occurring on a inclined surface when the product thickness is around 1mm and the only external force is due to the gravity field as per toilet 15 cleaning application.
Co,-")ositions #1 and #2 are taken as reference, they are free of short chain amine oxides. Composition #3 is taken as reference, it is free of 20 monopersulfate salt. Compositions #4 and #5 are representative of the stable thickened aqueous acidic compositions according to the present invention, i.e. they comprise a quaternary ammonium compound, a short chain amine oxide and monopersulfate salt.
The above data surprisingly show that the addition of a monopersulfate salt to a acidic aqueous composition comprising a short chain amine oxide and a quaternary ammonium compound allows to formulate a composition CA 02204~07 1997-0~-0~
WO 96/17044 PCT/US9S/lS49S
having a higher viscosity as compared to the same composition but without said monopersulfate salt. (See compositions #4 and #5 comprising respectively 6% and 4% by weight of the total composition of monopersulfate salt with a viscosity of respectively 300 cps and 250 cps 5 as compared to composition #3 without monopersulfate salt and with a viscosity of 50 cps). Also the aboYe data show the correlation between the increase of the concentration of monopersulfate salt and the increase of viscosity in said matrix.
The above results further show that the present invention allows to formulate thickened aqueous acidic compositions at low total level of thickening surfactants, even if perfume is present, by combining monopersulfate, quaternary ammonium compound and short chain amine 15 oxide.
ExamDle 111 Compositions are made which further illustrate the present invention and which comprise the listed ingredients in the listed proportions (weight %).
ComDositions #1 #2 #3 #4 C16 ~ hyl ammonium 4.70 5.00 5.70 7.00 methylsulfate C81C10 amine oxide 0.36 0.38 0.44 0.54 Curox~ ~ 6.00 6.00 6.00 6.00 Methane sulfonic acid 5.00 5.00 5.00 5.00 Perfume 0.7 0.7 0.7 0.7 Sodium sulphate 5.00 5.00 5.00 5.00 Water and minors up to up to up to up to pH ~ 2 < 2 < 2 ~ 2 Initial viscosity (cps) 370 400 800 1400 Appearance clear clear clear clear -CA 02204~07 1997-0~-0 WO 96/17044 PCT/US9S1154g5 ¦ Rheological Behaviour ¦ Newt. ¦ Newt. ¦ Newt. ¦ Newt. ¦
ExamDle IV
ComDositions #1 #2 #3 #4 #5 #6 C16 trimethyl ammonium 4.00 4.00 4.00 4.004.00 4.00 methylsulfate C8/C10 amine oxide 0.30 0.10 0.30 0.300.30 0.30 Curox~ * 6.00 6.00 6.00 6.006.00 6.00 Methanesulfonic acid 10.00 15.00 0.00 0.005.00 0.00 Sulfuric acid 0.00 0.00 3.00 6.006.00 0.00 Phosphoric acid 0.00 0.00 0.00 0.000.00 12.00 Perfume 0.70 0.70 0.70 0.700.70 0.70 Water and minors up to 100 pH 0.66 0.35 1.00 0.78 0.50 1.00 Initial viscosity ~cps) 270 330 380 400 300 320 Appearance clear clear clear clear clear clear Rheological Behaviour Newt. Newt. Newt. Newt. Newt. Newt.
5 * Curox~ is one of the commercial names of monopersulfate salts.
All the above mentioned acidic aqueous compositions comprising monopersulfate provide significant benefits in toilet soils cleaning both when used neat or diluted. Said compositions were found to be stable 10 over lon~ periods of time. Indeed, these compositions had not more than ~ 10% loss after 1 month at room temperature.
Claims (23)
1. A stable thickened aqueous acidic composition comprising from about 0.1% to about 30% by weight of the composition of a source of active oxygen, from about 0.1% to about 20% by weight of the composition of a quaternary ammonium compound and from about 0.01% to about 15% by weight of the composition of an amine oxide having the following formula R1R2R3NO wherein R2 and R3 are independently C1-C4 alkyl groups and wherein R1 is a C6 to C10 alkyl group.
2. A composition according to claim 1 wherein said quaternary ammonium compound is a quaternary ammonium compound wherein one or two of the hydrocarbon groups linked to nitrogen are a linear or branched alkyl group of about 6 to about 30 carbon atoms, saturated or unsaturated, and wherein the other hydrocarbon groups linked to the nitrogen are independently substituted or unsubstituted, linear or branched alkyl chain of from about 1 to about 4 carbon atoms, and wherein the counterion used in said quaternary ammonium compound is preferably selected from the group of fluoride, or methyl sulfate, or methylsulfonate or hydroxide.
3. A composition according to claim 2 wherein said quaternary ammonium compound is a quaternary ammonium compound wherein one or two of the hydrocarbon groups linked to nitrogen are a linear or branched alkyl group of about 10 to about 25 carbon atoms, saturated or unsaturated, and wherein the other hydrocarbon groups linked to the nitrogen are independently substituted or unsubstituted, linear or branched alkyl chain of from about 1 to about 3 carbon atoms.
4. A composition according to claim 1 wherein in said amine oxide having the formula R1R2R3NO, R1 is a C8 to C10 alkyl group, and R2 and R3 are independently alkyl groups of from about 1 to about 3 carbon atoms, and preferably are methyl groups.
5. A composition according to claims 1, 2 or 4 wherein said composition comprises from about 0.1% to about 10% by weight of the total composition of said amine oxide, or mixtures thereof.
6. A composition according to claims 1, 2 or 4 wherein said composition comprises from about 0.1% to about 15% by weight of the total composition of said quaternary ammonium compound, or mixtures thereof.
7. A composition according to claims 1, 2 or 4 wherein in said composition the weight ratio of said amine oxide to said quaternary ammonium compounds is from about 1:2 to about 1:100.
8. A composition according to claims 1, 2 or 4 wherein in said composition the weight ratio of said amine oxide to said quaternary ammonium compounds is from about 1:4 to about 1:30.
9. A composition according to claims 1, 2 or 4 wherein in said composition the weight ratio of said amine oxide to said quaternary ammonium compounds is from about 1:10 to about 1:20.
10. A composition according to claims 1, 2 or 4 wherein the total level of said quaternary ammonium compound and said amine oxide is no more than about 20%.
11. A composition according to claims 1, 2 or 4 wherein the total level of said quaternary ammonium compound and said amine oxide is between about 1% to about 15%.
12. A composition according to claims 1, 2 or 4 wherein the total level of said quaternary ammonium compound and said amine oxide is between about 1% to about 10%.
13. A composition according to claims 1, 2 or 4 wherein said composition has a viscosity of more than about 250 cps.
14. A composition according to claims 1, 2 or 4 wherein said composition has a viscosity of from about 250 cps to about 1500 cps.
15. A composition according to claims 1, 2 or 4 wherein the pH of said composition is from about 0 to about 6.
16. A composition according to claims 1, 2 or 4 wherein the pH of said composition is from about 0 to about 4.
17. A composition according to claims 1, 2 or 4 wherein said composition further comprises a perfume, preferably at a level of from about 0%
to about 3% by weight of the total composition.
to about 3% by weight of the total composition.
18. A composition according to claims 1, 2 or 4 wherein said source of active oxygen is a persulfate salt, and is present at a level of from about 0.1% to about 30% by weight of the total composition.
19. A composition according to claims 1, 2 or 4 wherein said source of active oxygen is monopersulfate, and is present at a level of from about 0.1% to about 20% by weight of the total composition.
20. A composition according to claims 1, 2 or 4 wherein said composition further comprises an alkali metal sulphate, in an amount up to about 10% by weight of the total composition.
21. A process of treating hard-surfaces wherein a composition according to claims 1, 2 or 4 is used.
22. A process for the manufacture of a composition according to any of claims 1, 2 or 4 wherein in said process :
- an acidic matrix is prepared which comprises at least said water, said source of active oxygen and said acid, - then said quaternary ammonium compound is added to said matrix, - then said perfume, if present, is further added and finally said amine oxide is added, - the resulting composition is then stirred over at least three hours.
- an acidic matrix is prepared which comprises at least said water, said source of active oxygen and said acid, - then said quaternary ammonium compound is added to said matrix, - then said perfume, if present, is further added and finally said amine oxide is added, - the resulting composition is then stirred over at least three hours.
23. The use of a persulfate salt together with a quaternary ammonium compound in an aqueous acidic composition to increase the viscosity of said composition.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP94870184.2 | 1994-11-25 | ||
| EP94870184 | 1994-11-25 | ||
| PCT/US1995/015495 WO1996017044A1 (en) | 1994-11-25 | 1995-11-14 | Thickened bleaching compositions, method of use and process for making them |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2204507A1 CA2204507A1 (en) | 1996-06-06 |
| CA2204507C true CA2204507C (en) | 2002-02-19 |
Family
ID=8218683
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002204507A Expired - Fee Related CA2204507C (en) | 1994-11-25 | 1995-11-14 | Thickened bleaching compositions, method of use and process for making them |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0793707B1 (en) |
| JP (1) | JPH10509992A (en) |
| AR (1) | AR000201A1 (en) |
| AT (1) | ATE231910T1 (en) |
| AU (1) | AU4370896A (en) |
| BR (1) | BR9509822A (en) |
| CA (1) | CA2204507C (en) |
| DE (1) | DE69529533T2 (en) |
| ES (1) | ES2189834T3 (en) |
| MX (1) | MX9703841A (en) |
| WO (1) | WO1996017044A1 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0779357A1 (en) * | 1995-12-16 | 1997-06-18 | The Procter & Gamble Company | Stable emulsions comprising a hydrophobic liquid ingredient |
| GB2325471A (en) * | 1997-05-24 | 1998-11-25 | Procter & Gamble | A detergent composition |
| FR2761080B1 (en) * | 1997-03-21 | 2002-07-19 | Quadrimex | COMPOSITION BASED ON PERACIDS FOR THE CLEANING, DISINFECTION AND DECONTAMINATION OF SURFACES STAINED BY TOXIC AGENTS |
| EP1065262A1 (en) * | 1999-06-29 | 2001-01-03 | The Procter & Gamble Company | Bleaching compositions |
| JP4732064B2 (en) * | 2005-08-05 | 2011-07-27 | 花王株式会社 | Cleaning composition for hard surface |
| JP4732115B2 (en) * | 2005-10-14 | 2011-07-27 | 花王株式会社 | Acid detergent composition for hard surfaces |
| WO2008043638A1 (en) * | 2006-10-13 | 2008-04-17 | Unilever N.V. | Aqueous liquid bleach compositions |
| JP5467788B2 (en) * | 2009-03-31 | 2014-04-09 | 花王株式会社 | Liquid bleach composition |
| GB201103964D0 (en) * | 2011-03-09 | 2011-04-20 | Reckitt Benckiser Nv | Composition |
| WO2013059970A1 (en) * | 2011-10-28 | 2013-05-02 | Kimberly-Clark Worldwide, Inc. | Sporicidal formulation including amine oxide surfactant and a mixture of oxidants |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4166794A (en) * | 1978-05-25 | 1979-09-04 | Colgate-Palmolive Company | Liquid bleach-softener compositions |
| GB8500116D0 (en) * | 1985-01-03 | 1985-02-13 | Unilever Plc | Liquid bleaching compositions |
| ATE103970T1 (en) * | 1986-09-29 | 1994-04-15 | Akzo Nv | THICKENED WATER CLEANING AGENTS. |
| JPS63172799A (en) * | 1987-01-12 | 1988-07-16 | 日本パ−カライジング株式会社 | Surface cleaning agent of aluminum |
| US5149463A (en) * | 1989-04-21 | 1992-09-22 | The Clorox Company | Thickened acidic liquid composition with sulfonate fwa useful as a bleaching agent vehicle |
| ATE163037T1 (en) * | 1992-11-16 | 1998-02-15 | Procter & Gamble | CLEANING AND BLEACHING COMPOSITIONS |
| GB9225333D0 (en) * | 1992-12-03 | 1993-01-27 | Jeyes Group Plc | Lavatory cleansing compositions |
| EP0621335B1 (en) * | 1993-04-19 | 1999-12-15 | Reckitt & Colman Inc. | All purpose cleaning composition |
-
1995
- 1995-11-14 AU AU43708/96A patent/AU4370896A/en not_active Abandoned
- 1995-11-14 ES ES95942503T patent/ES2189834T3/en not_active Expired - Lifetime
- 1995-11-14 JP JP8517891A patent/JPH10509992A/en active Pending
- 1995-11-14 AT AT95942503T patent/ATE231910T1/en not_active IP Right Cessation
- 1995-11-14 DE DE69529533T patent/DE69529533T2/en not_active Expired - Fee Related
- 1995-11-14 MX MX9703841A patent/MX9703841A/en not_active Application Discontinuation
- 1995-11-14 CA CA002204507A patent/CA2204507C/en not_active Expired - Fee Related
- 1995-11-14 EP EP95942503A patent/EP0793707B1/en not_active Expired - Lifetime
- 1995-11-14 BR BR9509822A patent/BR9509822A/en not_active Application Discontinuation
- 1995-11-14 WO PCT/US1995/015495 patent/WO1996017044A1/en active IP Right Grant
- 1995-11-24 AR AR33438095A patent/AR000201A1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JPH10509992A (en) | 1998-09-29 |
| EP0793707A1 (en) | 1997-09-10 |
| DE69529533T2 (en) | 2003-12-04 |
| DE69529533D1 (en) | 2003-03-06 |
| AR000201A1 (en) | 1997-05-21 |
| CA2204507A1 (en) | 1996-06-06 |
| MX9703841A (en) | 1997-08-30 |
| ES2189834T3 (en) | 2003-07-16 |
| EP0793707B1 (en) | 2003-01-29 |
| WO1996017044A1 (en) | 1996-06-06 |
| BR9509822A (en) | 1997-10-21 |
| ATE231910T1 (en) | 2003-02-15 |
| AU4370896A (en) | 1996-06-19 |
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