EP0129980B1 - Bleaching compositions - Google Patents
Bleaching compositions Download PDFInfo
- Publication number
- EP0129980B1 EP0129980B1 EP84303453A EP84303453A EP0129980B1 EP 0129980 B1 EP0129980 B1 EP 0129980B1 EP 84303453 A EP84303453 A EP 84303453A EP 84303453 A EP84303453 A EP 84303453A EP 0129980 B1 EP0129980 B1 EP 0129980B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- alkyl
- composition
- composition according
- amount
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial 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
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/162—Organic compounds containing Si
-
- 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
- C11D3/395—Bleaching agents
- C11D3/3953—Inorganic bleaching agents
-
- 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
- C11D3/395—Bleaching agents
- C11D3/3956—Liquid compositions
Definitions
- This invention relates to hypochlorite bleach compositions and in particular to aqueous hypochlorite bleaches containing a bactericidal material.
- Quaternary ammonium compounds in general, are known to have bactericidal characteristics, and certain water soluble quaternary ammonium surfactants such as cetyl pyridinium bromide are very effective antibacterial agents.
- Polymeric dialkyl siloxane and silane structures are well known as having a high affinity for siliceous surfaces and thus a combination of a quaternary ammonium function and a siloxane or silane grouping might be expected to provide a long lasting antibacterial effect on siliceous surfaces of the type mentioned above.
- Detergent compositions containing quaternary organosilanes are known, examples of such disclosures being provided by the commonly assigned US Patent Nos. US-A-4005028 and US-A-4005030.
- US-A-4005028 discloses mixtures of organo silanes and organic detergents selected from nonionic zwitterionic and ampholytic surfactants, while US-A-4005030 discloses similar mixtures with anionic surfactants.
- a variety of detergent compositions incorporating such mixtures are also disclosed in each patent.
- Aqueous cleaning and bleaching compositions are also well known in the art, examples of such compositions being provided by European Published Patent Application No. 0079697.
- the materials display physical stability in aqueous alkalis and commercial aqueous hypochlorite and also display surface substantive properties.
- surface substantivity is markedly impaired due to solubilisation into surfactant micelles.
- these shorter chain alkyl quaternised alkoxy silanes do not display broad range antibacterial efficacy.
- Quaternary alkoxy silanes containing an alkyl chain longer than C 14 are less water soluble and do not even display long term stability in aqueous alkaline solutions but precipitate therefrom, probably in polymerised, and hence antibacterially ineffective, form.
- Aqueous hypochlorite bleach compositions forming suitable vehicles for the delivery of the quaternised alkoxy silanes should be free or substantially free of anionic surfactants and preferably should have a low ionic strength.
- the present invention provides a chlorine bleach-containing composition
- a chlorine bleach-containing composition comprising
- the composition contains from 0.005% to 0.05% and most preferably from 0.01 % to 0.03% of the organosilicon quaternary ammonium compound.
- R 1 is a C 18 alkyl group.
- the viscosity of the composition is at least 2.10 -1 Pa ⁇ s at 20°C and comprises alkali metal hypochlorite in an amount of from 8% to 10% by weight, a C 14 ⁇ C 14 alkyl dimethyl amine oxide as the only surfactant in an amount of from 1.0 to 1.5% by weight together with at least 400 ppm of a secondary or tertiary alcohol as hereinafter defined or the ester thereof with a C 2 ⁇ C 3 alkanoic acid, and the composition has an ionic strength of less than 4.0 g moles/dm 3 .
- Compositions in accordance with the present invention have a density in the range from 1.10 to 1.25 g/cm 3 , typically approximately 1.15 g/cm 3 , so that the numerical value of the kinematic viscosity in mm 2 /s is slightly less than that of the dynamic viscosity in mPa ⁇ s.
- Organosilicon quaternary ammonium compounds having the desired combination of broad spectrum antibacterial activity and physico chemical stability in compositions in accordance with the invention have the general structure: wherein R 1 is C 16 ⁇ C 20 alkyl, R 2 is C 1 -C 4 alkyl, R 3 is C 1 ⁇ C 4 alkyl, y is an integer from 0 to 2, and X - is a water soluble anion.
- a preferred chain length for R 1 is C 18 for antibacterial efficacy reasons, and for reasons of cost and ease of preparation R 2 and R 3 are usually methyl.
- references herein to the organic silicon quaternary ammonium compound include the silanol derivative thereof.
- X - is normally halide, particularly chloride, but can also include methosulphate, acetate or phosphate.
- the level of incorporation of the organosilicon compound is from 0.001 % to 0.25% based on the total weight of the composition but is more usually in the range of from 0.005% to 0.05% and most preferably from 0.01% to 0.03% by weight.
- hypochlorite bleach and the alkali metal chloride and chlorate salts which accompany it in commercially available material, provide the majority and preferably substantially all of the ionic strength requirement. This will normally result in an ionic strength of at least 3.0 g moles/dm 3 . lonic strength values in excess of 5.0 g moles/dm 3 are not desirable because of their adverse influence on the stability of both the hypochlorite and organosilicon quaternary ammonium compound components.
- the ionic strength is less than 4.0 g moles/dm 3 and values in the region of 3.4-3.8 g moles/dm 3 are considered to be optimum where a stable product of viscosity ⁇ 2 x 10 -1 Pa.s is desired.
- the alkali metal hypochlorite may be a lithium, potassium or sodium hypochlorite and the level of hypochlorite in the composition is arranged to lie in the range 1-12%, preferably 5-10% by weight.
- Customarily hypochlorite bleach compositions contain approximately 6% or 9% hypochlorite by weight.
- the activity of chlorine bleaching compositions is conventionally expressed in terms of the weight percentage of available chlorine in the composition, and the actual weight percentage of bleaching species is arranged to provide the desired level of'available chlorine'.
- the preferred hypochlorite species is sodium hypochlorite which contains 95.3% available chlorine.
- Alkali metal hypochlorites are commercially available as aqueous solutions containing 10-15% by weight 'available chlorine' and the bulk suppliers normally produce material having available chlorine contents towards the upper end of this range viz. 12-14% by weight.
- These commercially available hypochlorite solutions contain other salts as byproducts or contaminants, more specifically free alkalinity in the form of alkali metal hydroxide and alkali metal carbonate, and alkali metal chloride.
- Low levels of other species such as sodium chlorate are also believed to be forming during hypochlorite manufacture but their chemical stability is sufficiently low that they have largely decomposed by the time the hypochlorite is employed in product formulations.
- the levels of the byproduct materials depend on the processing conditions employed in the manufacture of the hypochlorite but in general they fall within the ranges
- Amine oxides useful in the present invention have the formula R 4 R 5 R 6 N ⁇ O wherein R 4 is a C 10 ⁇ C 18 alkyl group and R 5 and R 6 are C l -C 4 alkyl groups.
- the amine oxide is present in an amount of from 0.1 % to 5%, more preferably from 0.5% to 2.5% and, in preferred embodiments of the invention in which the R 4 average chain length ⁇ 14 carbon atoms, from 1 % to 1.5% by weight of the composition.
- the Regroup may be linear or branched and may be derived from natural or synthetic hydrocarbon sources. For the purposes of the present invention linear groups are defined as including moieties incorporating up to 25% methyl branching, predominantly in the 2-position relative to the nitrogen atom of the amine oxide.
- Methyl branching on the alkyl chain also predominates in those amine oxides useful in the present invention in which the R 4 group is branched, rather than linear in nature.
- amine oxides are normally a mixture of where R 7 is methyl, and which mixture arises as a result of the processing route used to form the precursor alcohol or aldehyde.
- This route involves carbonylating or hydroformylating an olefin, preferably a linear a-olefin and leads to a mixture of the desired branched chain aldehyde or alcohol of the same carbon number.
- the resultant alcohol or aldehyde mixture contains compounds of different carbon number and isomers containing straight chain and 2-alkyl branched chain alkyl groups.
- a typical commercially available mixture comprises 65 to 75% by weight C 13 and 35 to 25% by weight C 15 amine oxides with approximately 50% by weight straight chain and 50% by weight 2-alkyl branched chain where the 2-alkyl group is predominantly methyl. These are available from ICI under the trade name Synprolam 35 DMO (RTM) as a 30% aqueous solution.
- RTM Synprolam 35 DMO
- the branched chain amine oxides and mixtures thereof with linear chain amine oxides are used at levels towards the upper end of the range viz. ⁇ 2% by weight of the composition and typically from 2.0% to 2.5% by weight.
- the preferred amine oxide structure for'thickened' products having a viscosity of ⁇ 2 x 10 -1 Pa.s is one in which R 4 is a linear group which has an average chain length in the range 6 14 ⁇ C 15 .
- Compositions containing these preferred amine oxides require a lower amine oxide level viz. ⁇ 2.0%, more typically 1.0-1.5% and also a lower ionic strength viz. 3.0 g moles/dm' minimum in order to achieve target viscosity. Both of these reductions in ingredient level lead to improved storage stability and also lower the cost of the product.
- Another hypochlorite-stable surfactant suitable for the purposes of the present invention is a substituted betaine of formula. wherein R 7 is a C 8 ⁇ C 18 alkyl group, preferably a C 10 ⁇ C 14 alkyl group, R s and R. are C 1 ⁇ C 4 alkyl groups, more preferably methyl groups, and R 10 is a C l -C 4 alkylene group, more preferably a C 2 -C 3 alkylene group. Specific examples include octyl, decyl, dodecyl, tetradecyl and hexadecyl betaines in which R 10 is an ethylene or propylene group and R 3 and Rg are methyl groups.
- hypochlorite-stable surfactants are also known in the art particularly where it is desired to increase the viscosity of the system and examples of other hypochlorite-stable surfactants include saturated fatty acid soaps, alkyl sulphates, alkane sulphonates, sarcosinates and taurides.
- These surfactants which are anionic in type should be employed at levels which do not interfere with the efficacy of the quaternised alkoxy silane. Because of the tendency of cationic and anionic surfactant species to react to form high molecular weight, relatively water-insoluble complexes, anionic surfactants should be present at less than the amount necessary to complex the quaternised alkoxy silane completely.
- quaternised alkoxy silane deposited on a siliceous surface from compositions in accordance with the invention provides 80% to 90% reduction in bacteria (E. Coli) count on exposed surfaces when the treated surfaces are subsequently exposed to an inoculum of fresh bacteria in a distilled water environment.
- bacteria E. Coli
- anionic surfactants in excess of the amount necessary to complex the quaternised alkoxy silane leads to a significant diminution of the bacteria count reduction under the same conditions.
- composition should be substantially free of anionic surfactants, substantially free being defined as less than the amount of surfactant necessary to completely complex the quaternised alkoxy silane, and preferably should be completely free of such surfactants.
- a highly preferred optional component for hypochlorite bleach compositions suitable for incorporating the quaternised alkoxy silanes, particularly those utilising from 1.0 to 2.0% of an amine oxide wherein R, has an average chain length of about 14 carbon atoms, is at least 400 ppm based on the weight of the composition, of at least one secondary or tertiary alcohol selected from cedrol, tetra hydro linalool, tetra hydro muguol (a 50:50 mixture of tetra hydro linalool and a positional isomer, tetra hydromyrcenol), verdol, dihydro terpineol, isoborneol, 4-tertiary butyl cyclo hexanol and methanol and mixtures of any of these or of their hydrolysable C 2 -C 3 carboxylic acid esters.
- These alcohols and their C 2 -C 3 carboxylic acid esters are known and used as ingredients in fragrances, including those
- the incorporation of at least one of the above mentioned secondary or tertiary alcohols or an ester thereof with C 2 -C 3 alkanoic acid provides an enhancement of the viscosity of the bleach solution and facilitates the generation of viscosities of 200 mPa.s and greater at 20°C.
- the secondary or tertiary alcohol or ester is present in an amount of more than 600 ppm and, where the amine oxide level is ⁇ 1.5% by weight is more preferably present in an amount of at least 800 ppm.
- a mixture of the alcohols or their C 2 ⁇ C 3 alkanoic acid esters is used in a total amount of from 600 to 1600 ppm although it is preferred that one of the components of the mixture should be present in an amount of at least 500 ppm by weight of the composition.
- the most preferred materials are cedrol, tetrahydro linalool, tetrahydro myrcenol and dihydro terpineol and their acetate esters. These materials have tertiary alcohol functionality and are relatively immune to breakdown in hypochlorite-containing solutions, resulting in viscosity-enhancement effects which are stable with time.
- Thickened aqueous hypochlorite bleach compositions including the above mentioned alcohol derivatives are particularly preferred for the incorporation of the quaternised alkoxy silane antibacterial component as such compositions utilise the minimum amounts of amine oxide surfactant and ionic salts necessary to generate the desired product viscosity and hence enhance the stability of the quaternised alkoxy silanes.
- the salts accompanying the hypochlorite bleach provide most if not all of the ionisable species necessary for the ionic strength requirement.
- other non surface active organic or inorganic compounds can be added where necessary to provide an ionic strength in the desired range.
- the ionisable compound(s) can be inorganic in nature e.g. hydroxide, sulphate, halide, (particularly chloride), carbonate, nitrate, or orthophosphate, pyrophosphate, or polyphosphate, or organic such as formate, acetate or succinate.
- inorganic compounds such as silicates and organic compounds incorporating oxidisable groups are avoided because of their tendency to have adverse effects on physical and/or chemical stability of the compositions on storage.
- Certain organic sequestrants such as the amino poly (alkylene phosphonates) salts can, however, be incorporated in an oxidised form in which they are not susceptible to attack by the hypochlorite bleach. Such sequestrants are normally present in amounts of from 0.1% to 0.5% by weight of the composition.
- the ionic strength of the composition is calculated by means of the expression.
- the function C ; Z ; Z is calculated for each of the ionic species in solution, these functions are summed and divided by two to give the composition ionic strength.
- the ionisable alkali metal compound normally comprises a caustic alkali such as sodium or potassium hydroxide either alone or in admixture with alkali metal salts.
- a caustic alkali such as sodium or potassium hydroxide either alone or in admixture with alkali metal salts.
- the amount of caustic alkali is normally limited to a valve in the range of from 0.5% to 2%, more usually from 0.75% to 1.5% by weight of the composition.
- a desirable optional component of compositions in accordance with the invention is a perfume which is present at a level of from 0.01 % to 0.5%, preferably from 0.05% to 0.25% by weight of the composition.
- the alcohol component(s) can conveniently be incorporated in the perfume mixture.
- a further desirable optional component in compositions in accordance with the invention is an agent for siliceous glaze protection such as zinc oxide, or aluminium oxide and water soluble bismuth salts. This can be added in an amount of from 0.01% to 0.1% by weight of the composition, more preferably from 0.02% to 0.06% by weight.
- compositions are made by conventional mixing techniques. Because of the relatively low aqueous solubility of the organo silicon compound which is normally supplied as a solution in methanol, a premix of the amine oxide, perfume, added caustic alkali and water is normally prepared and the organo silicon compound is then added with vigorous agitation.
- This mixture is then added to the hypochlorite solution to make the final product.
- Other orders of addition can be used but unless the amine oxide is present in the solution to which the organo silicon compound solution is added, problems of incomplete solution or precipitation can arise.
- This composition had the following analysis, in percent by weight and had a density of 1.15 g/cm 2 .
- This product was a single phase solution having a dynamic viscosity of 2.7 x 10 -1 Pa.s as measured at 20°C with a Brookfield viscometer using the No. 3 spindle at 100 rpm on product that was 24 hours old.
- the ionic strength of this composition was calculated to be 3.66.
- the density of each of these compositions is 1.15 g/ml and the ionic strength for each composition is calculated to be 3.5 g moles/dm 3 .
- the product viscosity was measured at 20°C using the technique of
- compositions were prepared according to the technique of Example 1.
- the alcohol and ester levels are given in ppm.
- Brookfield viscosity measurements were made after 24 and 72 hours and were as follows; values are in Pa.s x 10 -1 :
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
- This invention relates to hypochlorite bleach compositions and in particular to aqueous hypochlorite bleaches containing a bactericidal material.
- Aqueous bleach compositions containing alkali metal hypohalites, particularly sodium hypochlorite, have been known for many years. Because of their powerful oxidizing action they have also been acknowledged to be powerful germicides and have been used extensively where this property is beneficial, e.g. in the cleaning of baths, wash basis, flush toilets, drains and ceramic tile floors. However, it has long been recognised that the germicidal effectiveness of surface treatments using such materials is limited by the relatively short period of time during which the aqueous composition containing the hypohalite is in contact with the surface concerned. Recent developments in the formulation of hypochlorite bleach products have shown a trend towards the use of higher viscosities, viz. 10-4 M 2 S-1 or greater, and this will increase the retention of such products on non horizontal surfaces.
- Nevertheless, the increase in retention time introduced by such a thickened formulation will not be particularly significant, being measured in seconds or at most minutes, and a need exists for a bactericidal and germicidal material that is capable of retention on a target surface for much longer periods.
- Quaternary ammonium compounds, in general, are known to have bactericidal characteristics, and certain water soluble quaternary ammonium surfactants such as cetyl pyridinium bromide are very effective antibacterial agents. Polymeric dialkyl siloxane and silane structures are well known as having a high affinity for siliceous surfaces and thus a combination of a quaternary ammonium function and a siloxane or silane grouping might be expected to provide a long lasting antibacterial effect on siliceous surfaces of the type mentioned above. Such is indeed the case and the antimicrobial effectiveness of a represenative alkoxy silane (3(trimethoxy silyl) propyl dimethyl octadecyl ammonium chloride) on a variety of surfaces, siliceous, metallic, synthetic, plastic and natural textile in nature, has been reported by A. J. Isquith et al in J. Applied Microbiology, 24 (6), 1972, pp 859-863.
- Detergent compositions containing quaternary organosilanes are known, examples of such disclosures being provided by the commonly assigned US Patent Nos. US-A-4005028 and US-A-4005030. US-A-4005028 discloses mixtures of organo silanes and organic detergents selected from nonionic zwitterionic and ampholytic surfactants, while US-A-4005030 discloses similar mixtures with anionic surfactants. A variety of detergent compositions incorporating such mixtures are also disclosed in each patent.
- Aqueous cleaning and bleaching compositions are also well known in the art, examples of such compositions being provided by European Published Patent Application No. 0079697.
- However, the incorporation of quaternised alkoxy silanes into aqueous cleaning or bleaching compositions poses considerable difficulty. All alkoxy silanes of this type will hydrolyse in contact with water, to produce the corresponding silanol derivatives which themselves are prone to polymerisation via condensation of the silanol groups. The polymerised materials are less surface substantive than the parent silanols.
- In the case of the more water soluble alkoxy silanes, containing a C12-C14 alkyl group in the quaternary ammonium portion of the molecule, the materials display physical stability in aqueous alkalis and commercial aqueous hypochlorite and also display surface substantive properties. However, in the presence of hypochlorite-stable surfactants, surface substantivity is markedly impaired due to solubilisation into surfactant micelles. Furthermore, these shorter chain alkyl quaternised alkoxy silanes do not display broad range antibacterial efficacy.
- Quaternary alkoxy silanes containing an alkyl chain longer than C14 are less water soluble and do not even display long term stability in aqueous alkaline solutions but precipitate therefrom, probably in polymerised, and hence antibacterially ineffective, form.
- However, it has surprisingly been found that those quaternised alkoxy silanes containing a Cl6-C20 alkyl group can be incorporated into certain aqueous hypochlorite bleach compositions to produce a physically stale product capable of delivering hydrophobic properties and a long lasting antibacterial effect to siliceous surfaces treated therewith.
- Aqueous hypochlorite bleach compositions forming suitable vehicles for the delivery of the quaternised alkoxy silanes should be free or substantially free of anionic surfactants and preferably should have a low ionic strength.
- Accordingly the present invention provides a chlorine bleach-containing composition comprising
- i) a surfactant,
- ii) a chlorine bleach,
- iii) non-bleach inorganic compounds,
- iv) an organosilicon mono-long chain alkyl quaternary ammonium compound of formula
- v) compatible optional ingredients, wherein
- a) the composition is aqueous, the percentage weight of water present together with that of components i) to v) totalling 100% by weight,
- b) the chlorine bleach is an alkali metal hypochlorite comprised in the amount of from 1% to 12% by weight,
- c) the surfactant is selected from amine oxides of formula R4R5R5N→O wherein R4 is a C10―C18 alkyl group and R5 and R6 are C1-C4 alkyl groups, substituted betaines of formula R7R8R9N+― R10COO- where R7 is a C8―C18 alkyl group, R8 and R9 are C1-C4 alkyl groups and R10 is a C1―C4 alkylene group and mixtures thereof, and is comprised in the amount of from 0.1% to 5% by weight,
- d) the ionic strength of the composition is less than 5.0 g moles/dm3 and the pH of the composition is in the range from 10 to 13,
- e) the alkyl group R1 of the organosilicon compound contains from 16 to 20 carbon atoms, this organosilicon compound being comprised in the amount of from 0.001% to 0.25% by weight,
- f) the composition is substantially free of anionic surfactant species and,
- g) the non-bleach inorganic compounds are comprised in the amount of from 1% to 15% by weight.
- Preferably the composition contains from 0.005% to 0.05% and most preferably from 0.01 % to 0.03% of the organosilicon quaternary ammonium compound. Preferably R1 is a C18 alkyl group.
- In highly preferred compositions in accordance with the invention, the viscosity of the composition is at least 2.10-1 Pa·s at 20°C and comprises alkali metal hypochlorite in an amount of from 8% to 10% by weight, a C14―C14 alkyl dimethyl amine oxide as the only surfactant in an amount of from 1.0 to 1.5% by weight together with at least 400 ppm of a secondary or tertiary alcohol as hereinafter defined or the ester thereof with a C2―C3 alkanoic acid, and the composition has an ionic strength of less than 4.0 g moles/dm3.
- The above mentioned reference to viscosity is to the dynamic viscosity η which is mesured by a Brookfield RVT viscometer and for the purposes of this specification measurements are made with Spindle No. 3 at 100 rpm and a liquid temperature of 20°C. Fluid viscosity can also be expressed as the kinematic viscosity v in mm2/s (centistokes) as measured by an Ostwald viscometer and is characterised by the expression v = η/ρ where η is the dynamic viscosity in mPa·s (centipoises) and p is the density in g/cm3. Compositions in accordance with the present invention have a density in the range from 1.10 to 1.25 g/cm3, typically approximately 1.15 g/cm3, so that the numerical value of the kinematic viscosity in mm2/s is slightly less than that of the dynamic viscosity in mPa·s.
- Organosilicon quaternary ammonium compounds having the desired combination of broad spectrum antibacterial activity and physico chemical stability in compositions in accordance with the invention have the general structure:
- The level of incorporation of the organosilicon compound is from 0.001 % to 0.25% based on the total weight of the composition but is more usually in the range of from 0.005% to 0.05% and most preferably from 0.01% to 0.03% by weight.
- In compositions in accordance with the invention, the hypochlorite bleach, and the alkali metal chloride and chlorate salts which accompany it in commercially available material, provide the majority and preferably substantially all of the ionic strength requirement. This will normally result in an ionic strength of at least 3.0 g moles/dm3. lonic strength values in excess of 5.0 g moles/dm3 are not desirable because of their adverse influence on the stability of both the hypochlorite and organosilicon quaternary ammonium compound components. Preferably the ionic strength is less than 4.0 g moles/dm3 and values in the region of 3.4-3.8 g moles/dm3 are considered to be optimum where a stable product of viscosity ≥ 2 x 10-1 Pa.s is desired.
- The alkali metal hypochlorite may be a lithium, potassium or sodium hypochlorite and the level of hypochlorite in the composition is arranged to lie in the range 1-12%, preferably 5-10% by weight. Customarily hypochlorite bleach compositions contain approximately 6% or 9% hypochlorite by weight. However, the activity of chlorine bleaching compositions is conventionally expressed in terms of the weight percentage of available chlorine in the composition, and the actual weight percentage of bleaching species is arranged to provide the desired level of'available chlorine'. The preferred hypochlorite species is sodium hypochlorite which contains 95.3% available chlorine.
- Alkali metal hypochlorites are commercially available as aqueous solutions containing 10-15% by weight 'available chlorine' and the bulk suppliers normally produce material having available chlorine contents towards the upper end of this range viz. 12-14% by weight. These commercially available hypochlorite solutions contain other salts as byproducts or contaminants, more specifically free alkalinity in the form of alkali metal hydroxide and alkali metal carbonate, and alkali metal chloride. Low levels of other species such as sodium chlorate are also believed to be forming during hypochlorite manufacture but their chemical stability is sufficiently low that they have largely decomposed by the time the hypochlorite is employed in product formulations. The levels of the byproduct materials depend on the processing conditions employed in the manufacture of the hypochlorite but in general they fall within the ranges
- 0.2-1.0% alkali metal hydroxide
- 0.01-0.1% alkali metal carbonate
- 10.0-18.0% alkali metal chloride
expressed as a weight percentage of the hypochlorite solution as supplied. - Amine oxides useful in the present invention have the formula R4R5R6N→O wherein R4 is a C10―C18 alkyl group and R5 and R6 are Cl-C4 alkyl groups. The amine oxide is present in an amount of from 0.1 % to 5%, more preferably from 0.5% to 2.5% and, in preferred embodiments of the invention in which the R4 average chain length ≈14 carbon atoms, from 1 % to 1.5% by weight of the composition. The Regroup may be linear or branched and may be derived from natural or synthetic hydrocarbon sources. For the purposes of the present invention linear groups are defined as including moieties incorporating up to 25% methyl branching, predominantly in the 2-position relative to the nitrogen atom of the amine oxide.
- Methyl branching on the alkyl chain also predominates in those amine oxides useful in the present invention in which the R4 group is branched, rather than linear in nature.
- Commercially available sources of these amine oxides are normally a mixture of
- Although the above-described mixture of straight chain and branched chain alkyl dimethyl amine oxides has been found suitable for the purposes of the invention, their use does not constitute the most preferred execution of the invention. This is because a bleaching composition containing 8-10% hypochlorite and an amine oxide in which the long chain alkyl group has a carbon number of about 13.3 requires an ionic strength of at least 4.7 g moles/dm3 to achieve the preferred product viscosity of at least 200 mPa.s. This level of ionic strength is believed to make the storage stability of the hypochlorite bleach less than that which is considered desirable for the expected shelf life of the product. The preferred amine oxide structure for'thickened' products having a viscosity of ≥2 x 10-1 Pa.s is one in which R4 is a linear group which has an average chain length in the range 614―C15. Compositions containing these preferred amine oxides require a lower amine oxide level viz. <2.0%, more typically 1.0-1.5% and also a lower ionic strength viz. 3.0 g moles/dm' minimum in order to achieve target viscosity. Both of these reductions in ingredient level lead to improved storage stability and also lower the cost of the product.
- Another hypochlorite-stable surfactant suitable for the purposes of the present invention is a substituted betaine of formula.
- Mixtures of hypochlorite-stable surfactants are also known in the art particularly where it is desired to increase the viscosity of the system and examples of other hypochlorite-stable surfactants include saturated fatty acid soaps, alkyl sulphates, alkane sulphonates, sarcosinates and taurides. These surfactants which are anionic in type should be employed at levels which do not interfere with the efficacy of the quaternised alkoxy silane. Because of the tendency of cationic and anionic surfactant species to react to form high molecular weight, relatively water-insoluble complexes, anionic surfactants should be present at less than the amount necessary to complex the quaternised alkoxy silane completely. It has been found that quaternised alkoxy silane deposited on a siliceous surface from compositions in accordance with the invention provides 80% to 90% reduction in bacteria (E. Coli) count on exposed surfaces when the treated surfaces are subsequently exposed to an inoculum of fresh bacteria in a distilled water environment. However the presence in the composition of anionic surfactants in excess of the amount necessary to complex the quaternised alkoxy silane leads to a significant diminution of the bacteria count reduction under the same conditions.
- Accordingly, the composition should be substantially free of anionic surfactants, substantially free being defined as less than the amount of surfactant necessary to completely complex the quaternised alkoxy silane, and preferably should be completely free of such surfactants.
- A highly preferred optional component for hypochlorite bleach compositions suitable for incorporating the quaternised alkoxy silanes, particularly those utilising from 1.0 to 2.0% of an amine oxide wherein R, has an average chain length of about 14 carbon atoms, is at least 400 ppm based on the weight of the composition, of at least one secondary or tertiary alcohol selected from cedrol, tetra hydro linalool, tetra hydro muguol (a 50:50 mixture of tetra hydro linalool and a positional isomer, tetra hydromyrcenol), verdol, dihydro terpineol, isoborneol, 4-tertiary butyl cyclo hexanol and methanol and mixtures of any of these or of their hydrolysable C2-C3 carboxylic acid esters. These alcohols and their C2-C3 carboxylic acid esters are known and used as ingredients in fragrances, including those employed in detergent compositions. As such their level of incorporation conventionally lies between 10 ppm and 600 ppm of the composition.
- It has now surprisingly been found that in aqueous hypochlorite bleach solutions containing from 1.0% to 2.0% of a C14―C16 amine oxide as the only surfactant, the incorporation of at least one of the above mentioned secondary or tertiary alcohols or an ester thereof with C2-C3 alkanoic acid provides an enhancement of the viscosity of the bleach solution and facilitates the generation of viscosities of 200 mPa.s and greater at 20°C. Preferably the secondary or tertiary alcohol or ester is present in an amount of more than 600 ppm and, where the amine oxide level is ≤1.5% by weight is more preferably present in an amount of at least 800 ppm. Advantageously a mixture of the alcohols or their C2―C3 alkanoic acid esters is used in a total amount of from 600 to 1600 ppm although it is preferred that one of the components of the mixture should be present in an amount of at least 500 ppm by weight of the composition.
- The most preferred materials are cedrol, tetrahydro linalool, tetrahydro myrcenol and dihydro terpineol and their acetate esters. These materials have tertiary alcohol functionality and are relatively immune to breakdown in hypochlorite-containing solutions, resulting in viscosity-enhancement effects which are stable with time.
- The mode of operation of these materials in this system is not fully understood but it is hypothesised that in the absence of anionic surfactants, hydrogen bonding occurs between adjacent alcohol functions of the relatively water insoluble alcohols held in the amine oxide micelles. This is believed to lead to the formation of an extended micellar structure in the solution which provides an increased viscosity. The maximum viscosity of the system is not reached immediately upon mixing, but develops over a period of time and accordingly viscosity is measured 24 hours after the product has been made.
- Thickened aqueous hypochlorite bleach compositions including the above mentioned alcohol derivatives are particularly preferred for the incorporation of the quaternised alkoxy silane antibacterial component as such compositions utilise the minimum amounts of amine oxide surfactant and ionic salts necessary to generate the desired product viscosity and hence enhance the stability of the quaternised alkoxy silanes.
- As stated hereinbefore, the salts accompanying the hypochlorite bleach provide most if not all of the ionisable species necessary for the ionic strength requirement. However, other non surface active organic or inorganic compounds can be added where necessary to provide an ionic strength in the desired range.
- The ionisable compound(s) can be inorganic in nature e.g. hydroxide, sulphate, halide, (particularly chloride), carbonate, nitrate, or orthophosphate, pyrophosphate, or polyphosphate, or organic such as formate, acetate or succinate.
- In the preferred embodiments of the invention, inorganic compounds such as silicates and organic compounds incorporating oxidisable groups are avoided because of their tendency to have adverse effects on physical and/or chemical stability of the compositions on storage. Certain organic sequestrants such as the amino poly (alkylene phosphonates) salts can, however, be incorporated in an oxidised form in which they are not susceptible to attack by the hypochlorite bleach. Such sequestrants are normally present in amounts of from 0.1% to 0.5% by weight of the composition.
-
- C, is the molar concentration of the ionic species in g moles/dm3
- Z is the valency of the species.
- The function C;Z; Z is calculated for each of the ionic species in solution, these functions are summed and divided by two to give the composition ionic strength.
- The ionisable alkali metal compound normally comprises a caustic alkali such as sodium or potassium hydroxide either alone or in admixture with alkali metal salts. This gives a composition pH (as is) of 10 to 13, although in-use the pH of the bleaching solution normally has a value in the range from 11 to 12.
- For product safety reasons the amount of caustic alkali is normally limited to a valve in the range of from 0.5% to 2%, more usually from 0.75% to 1.5% by weight of the composition.
- A desirable optional component of compositions in accordance with the invention is a perfume which is present at a level of from 0.01 % to 0.5%, preferably from 0.05% to 0.25% by weight of the composition. In the preferred thickened bleach compositions incorporating one or more of the above described secondary or tertiary alcohol components the alcohol component(s) can conveniently be incorporated in the perfume mixture.
- A further desirable optional component in compositions in accordance with the invention is an agent for siliceous glaze protection such as zinc oxide, or aluminium oxide and water soluble bismuth salts. This can be added in an amount of from 0.01% to 0.1% by weight of the composition, more preferably from 0.02% to 0.06% by weight.
- The compositions are made by conventional mixing techniques. Because of the relatively low aqueous solubility of the organo silicon compound which is normally supplied as a solution in methanol, a premix of the amine oxide, perfume, added caustic alkali and water is normally prepared and the organo silicon compound is then added with vigorous agitation.
- This mixture is then added to the hypochlorite solution to make the final product. Other orders of addition can be used but unless the amine oxide is present in the solution to which the organo silicon compound solution is added, problems of incomplete solution or precipitation can arise.
- The invention is illustrated in the following examples in which percentages are expressed by weight of the composition unless otherwise stated.
-
- 420 g of a 30% solution of C14 alkyl dimethyl amine oxide was added to 3555.6 g of demineralised water and 12.5 g of a perfume material containing 6.4 g of isobornyl acetate was dispersed therein.-To this solution was slowly added, with vigorous agitation, 11.9 g of a 42% solution in methanol of 3(trimethoxy silyl) propyl dimethyl octadecyl ammonium chloride (available from Dow Corning Ltd as DC 5700) to form a premix solution. 125 g of solid sodium hydroxide was dissolved in 5875 g of sodium hypochlorite solution (15.3% AvCl2 solution supplied by ICI Ltd) and 4000 g of the premix was then blended with high shear agitation into this solution.
-
- This product was a single phase solution having a dynamic viscosity of 2.7 x 10-1 Pa.s as measured at 20°C with a Brookfield viscometer using the No. 3 spindle at 100 rpm on product that was 24 hours old.
- The ionic strength of this composition was calculated to be 3.66.
-
- The density of each of these compositions is 1.15 g/ml and the ionic strength for each composition is calculated to be 3.5 g moles/dm3. The product viscosity was measured at 20°C using the technique of
-
-
Claims (10)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT84303453T ATE40151T1 (en) | 1983-05-25 | 1984-05-22 | BLEACH COMPOSITIONS. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8314500 | 1983-05-25 | ||
GB838314500A GB8314500D0 (en) | 1983-05-25 | 1983-05-25 | Cleaning compositions |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0129980A2 EP0129980A2 (en) | 1985-01-02 |
EP0129980A3 EP0129980A3 (en) | 1986-06-11 |
EP0129980B1 true EP0129980B1 (en) | 1989-01-18 |
Family
ID=10543354
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP84303453A Expired EP0129980B1 (en) | 1983-05-25 | 1984-05-22 | Bleaching compositions |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP0129980B1 (en) |
JP (1) | JPS6063300A (en) |
AT (1) | ATE40151T1 (en) |
CA (1) | CA1217004A (en) |
DE (1) | DE3476220D1 (en) |
ES (1) | ES532754A0 (en) |
GB (1) | GB8314500D0 (en) |
GR (1) | GR81613B (en) |
IE (1) | IE57534B1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9637708B2 (en) | 2014-02-14 | 2017-05-02 | Ecolab Usa Inc. | Reduced misting and clinging chlorine-based hard surface cleaner |
US10750748B2 (en) | 2017-06-28 | 2020-08-25 | Collidion, Inc. | Compositions, methods and uses for cleaning, disinfecting and/or sterilizing |
US11272710B2 (en) | 2018-01-14 | 2022-03-15 | Collidion, Inc. | Compositions, kits, methods and uses for cleaning, disinfecting, sterilizing and/or treating |
US12048307B2 (en) | 2020-08-17 | 2024-07-30 | Collidion, Inc. | Compositions, methods and uses for cleaning, disinfecting and/or sterilizing |
Families Citing this family (49)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6257494A (en) * | 1985-09-05 | 1987-03-13 | サンポ−ル株式会社 | Liquid detergent composition for fungal contamination |
US5833764A (en) * | 1987-11-17 | 1998-11-10 | Rader; James E. | Method for opening drains using phase stable viscoelastic cleaning compositions |
US5011538A (en) * | 1987-11-17 | 1991-04-30 | The Clorox Company | Viscoelastic cleaning compositions and methods of use therefor |
US5055219A (en) * | 1987-11-17 | 1991-10-08 | The Clorox Company | Viscoelastic cleaning compositions and methods of use therefor |
US4898957A (en) * | 1988-04-18 | 1990-02-06 | Dow Corning Corporation | Organosilicon diamine antimicrobial compound |
US4900467A (en) * | 1988-05-20 | 1990-02-13 | The Clorox Company | Viscoelastic cleaning compositions with long relaxation times |
US5073298A (en) * | 1988-07-20 | 1991-12-17 | Dow Corning Corporation | Antimicrobial antifoam compositions and methods |
US5034150A (en) * | 1989-05-03 | 1991-07-23 | The Clorox Company | Thickened hypochlorite bleach solution and method of use |
US5145596A (en) * | 1989-08-07 | 1992-09-08 | Dow Corning Corporation | Antimicrobial rinse cycle additive |
US5064613A (en) * | 1989-11-03 | 1991-11-12 | Dow Corning Corporation | Solid antimicrobial |
US5013459A (en) * | 1989-11-09 | 1991-05-07 | Dow Corning Corporation | Opthalmic fluid dispensing method |
US5705467A (en) * | 1991-10-22 | 1998-01-06 | Choy; Clement K. | Thickened aqueous cleaning compositions and methods of use |
US5279758A (en) * | 1991-10-22 | 1994-01-18 | The Clorox Company | Thickened aqueous cleaning compositions |
ZA935882B (en) * | 1992-10-19 | 1994-03-11 | Clorox Co | Composition and method for developing extensional viscosity in cleaning compositions. |
AU676066B2 (en) | 1993-06-01 | 1997-02-27 | Ecolab Inc. | Thickened hard surface cleaner |
CA2127936C (en) * | 1993-07-27 | 2006-09-12 | Aram Garabedian Jr. | Gelled hypochlorite-based cleaner |
EP0649898A3 (en) * | 1993-10-22 | 1996-02-28 | Clorox Co | Phase stable, thickened aqueous abrasive bleaching cleanser. |
EP0651051A3 (en) * | 1993-10-29 | 1996-02-28 | Clorox Co | Gelled hypochlorite-based cleaner. |
ES2153900T3 (en) * | 1994-07-21 | 2001-03-16 | Minnesota Mining & Mfg | CONCENTRATED CLEANING COMPOSITIONS ABLE TO INCREASE VISCOSITY WITH DISSOLUTION. |
US6027668A (en) * | 1995-12-19 | 2000-02-22 | Firmenich S.A. | Use of 4-tert-butyl-1-cyclohexanol as an antioxidant |
JPH11501081A (en) * | 1995-12-19 | 1999-01-26 | フイルメニツヒ ソシエテ アノニム | Use of 4-tert-butyl-1-cyclohexanol as an antioxidant |
GB9622176D0 (en) * | 1996-10-24 | 1996-12-18 | Reckitt & Colman Inc | Improvements in compositions containing organic compounds |
GB9713255D0 (en) * | 1997-06-23 | 1997-08-27 | Unilever Plc | Process for treatment of surfaces |
CN1299405A (en) * | 1998-05-08 | 2001-06-13 | 汉高两合股份公司 | Bleaching and disinfecting agent |
GB2340502B (en) | 1998-08-11 | 2002-08-07 | Reckitt & Colman Inc | Alkaline aqueous hard surface treatment compositions |
GB2340501B (en) * | 1998-08-11 | 2002-07-03 | Reckitt & Colman Inc | Improvements in or relating to organic compositions |
WO2000054587A1 (en) | 1999-03-16 | 2000-09-21 | Coating Systems Laboratories, Inc. | Antimicrobial skin preparations containing organosilane quaternaries |
JP4790130B2 (en) * | 2001-01-12 | 2011-10-12 | 花王株式会社 | Liquid bleach detergent composition |
US9764264B2 (en) | 2003-05-22 | 2017-09-19 | Coating Systems Laboratories, Inc. | Ballast water treatment systems |
US9364572B2 (en) | 2003-05-22 | 2016-06-14 | Coating Systems Laboratories, Inc. | Static fluid disinfecting systems and related methods |
US8257780B2 (en) | 2003-10-31 | 2012-09-04 | Resource Development L.L.C. | Therapeutic composition containing an organosilane quaternary compound and hydrogen peroxide for treating skin disorders and methods of using |
US6994890B2 (en) * | 2003-10-31 | 2006-02-07 | Resource Development L.L.C. | Cleaning and multifunctional coating composition containing an organosilane quaternary compound and hydrogen peroxide |
US7754004B2 (en) | 2005-07-06 | 2010-07-13 | Resource Development, L.L.C. | Thickened surfactant-free cleansing and multifunctional liquid coating compositions containing nonreactive abrasive solid particles and an organosilane quaternary compound and methods of using |
JP2007211080A (en) * | 2006-02-08 | 2007-08-23 | Kawaken Fine Chem Co Ltd | Chlorine-removing agent, method for removing chlorine using the same, and composition containing the same |
JP2007302736A (en) * | 2006-05-09 | 2007-11-22 | Kawaken Fine Chem Co Ltd | Chlorine scavenger and chemical agent containing the same |
US7589054B2 (en) | 2007-01-02 | 2009-09-15 | Resource Development L.L.C. | Clathrates of an organosilane quaternary ammonium compound and urea and methods of use |
WO2010073825A1 (en) | 2008-12-25 | 2010-07-01 | 国立大学法人広島大学 | Antibacterial composition and antiviral composition each containing silicon-containing compound, antibacterializing method, cleaning/mouth cleaning method, and method for immobilizing antibacterial agent or antiviral agent |
US8735618B2 (en) | 2010-05-07 | 2014-05-27 | Resource Development L.L.C. | Solvent-free organosilane quaternary ammonium compositions, method of making and use |
US9133417B2 (en) * | 2012-03-23 | 2015-09-15 | The Procter & Gamble Company | Liquid cleaning and disinfecting compositions comprising an assymetrically branched amine oxide |
US8470755B1 (en) | 2012-03-23 | 2013-06-25 | The Procter & Gamble Company | Liquid cleaning and disinfecting compositions comprising a zinc inorganic salt |
US10208273B2 (en) | 2012-09-10 | 2019-02-19 | The Clorox Company | Drain formulation for enhanced hair dissolution |
US9487742B2 (en) | 2012-09-10 | 2016-11-08 | The Clorox Company | Drain formulation for enhanced hair dissolution |
US9624384B2 (en) | 2015-04-07 | 2017-04-18 | IndusCo, Ltd. | Water stable antimicrobial silanol quaternary ammonium compounds |
US9744120B2 (en) | 2015-05-28 | 2017-08-29 | IndusCo, Ltd. | Durable skin sanitizers containing water stable antimicrobial silanol quaternary ammonium compounds |
US10010080B2 (en) | 2015-09-14 | 2018-07-03 | IndusCo, Ltd. | Process for the production of partially polymerized antimicrobial silanol quaternary ammonium compounds |
US10752785B2 (en) | 2016-09-09 | 2020-08-25 | IndusCo, Ltd. | Anti-slip botanical antimicrobial microemulsions |
US10967082B2 (en) | 2017-11-08 | 2021-04-06 | Parasol Medical, Llc | Method of limiting the spread of norovirus within a cruise ship |
US10864058B2 (en) | 2018-03-28 | 2020-12-15 | Parasol Medical, Llc | Antimicrobial treatment for a surgical headlamp system |
IT202100022721A1 (en) * | 2021-09-01 | 2023-03-01 | Viraschutz Europe Srl | ANTIMICROBIAL COMPOSITION FOR HARD SURFACES |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4005030A (en) * | 1975-04-22 | 1977-01-25 | The Procter & Gamble Company | Organosilane-containing anionic detergent composition |
US4005028A (en) * | 1975-04-22 | 1977-01-25 | The Procter & Gamble Company | Organosilane-containing detergent composition |
-
1983
- 1983-05-25 GB GB838314500A patent/GB8314500D0/en active Pending
-
1984
- 1984-05-16 GR GR74730A patent/GR81613B/el unknown
- 1984-05-22 EP EP84303453A patent/EP0129980B1/en not_active Expired
- 1984-05-22 DE DE8484303453T patent/DE3476220D1/en not_active Expired
- 1984-05-22 AT AT84303453T patent/ATE40151T1/en not_active IP Right Cessation
- 1984-05-23 CA CA000454934A patent/CA1217004A/en not_active Expired
- 1984-05-24 IE IE1296/84A patent/IE57534B1/en not_active IP Right Cessation
- 1984-05-24 ES ES532754A patent/ES532754A0/en active Granted
- 1984-05-24 JP JP59105639A patent/JPS6063300A/en active Granted
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9637708B2 (en) | 2014-02-14 | 2017-05-02 | Ecolab Usa Inc. | Reduced misting and clinging chlorine-based hard surface cleaner |
US10220421B2 (en) | 2014-02-14 | 2019-03-05 | Ecolab Usa Inc. | Reduced misting and clinging chlorine-based hard surface cleaner |
US10750748B2 (en) | 2017-06-28 | 2020-08-25 | Collidion, Inc. | Compositions, methods and uses for cleaning, disinfecting and/or sterilizing |
US10750747B2 (en) | 2017-06-28 | 2020-08-25 | Collidion, Inc. | Compositions, methods and uses for cleaning, disinfecting and/or sterilizing |
US11974573B2 (en) | 2017-06-28 | 2024-05-07 | Collidion, Inc. | Compositions, methods and uses for cleaning, disinfecting and/or sterilizing |
US11272710B2 (en) | 2018-01-14 | 2022-03-15 | Collidion, Inc. | Compositions, kits, methods and uses for cleaning, disinfecting, sterilizing and/or treating |
US11910797B2 (en) | 2018-01-14 | 2024-02-27 | Collidion, Inc. | Compositions, kits, methods and uses for cleaning, disinfecting, sterilizing and/or treating |
US12048307B2 (en) | 2020-08-17 | 2024-07-30 | Collidion, Inc. | Compositions, methods and uses for cleaning, disinfecting and/or sterilizing |
Also Published As
Publication number | Publication date |
---|---|
CA1217004A (en) | 1987-01-27 |
EP0129980A3 (en) | 1986-06-11 |
JPH0455480B2 (en) | 1992-09-03 |
ES8603944A1 (en) | 1986-01-01 |
GB8314500D0 (en) | 1983-06-29 |
IE57534B1 (en) | 1992-11-04 |
GR81613B (en) | 1984-12-11 |
DE3476220D1 (en) | 1989-02-23 |
ATE40151T1 (en) | 1989-02-15 |
ES532754A0 (en) | 1986-01-01 |
JPS6063300A (en) | 1985-04-11 |
IE841296L (en) | 1984-11-25 |
EP0129980A2 (en) | 1985-01-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0129980B1 (en) | Bleaching compositions | |
US4576728A (en) | Cleaning compositions | |
EP0188025B1 (en) | Liquid bleaching compositions | |
EP0204472B1 (en) | Cleaning compositions | |
US4752409A (en) | Thixotropic clay aqueous suspensions | |
EP0199385B1 (en) | Liquid bleaching compositions | |
CA1305641C (en) | Thixotropic clay aqueous suspensions containing long chain saturated fatty acid stabilizers | |
EP0376704B1 (en) | Bleaching composition | |
CA2179409C (en) | Thickened alkali metal hypochlorite compositions | |
US6255270B1 (en) | Cleaning and disinfecting compositions with electrolytic disinfecting booster | |
EP0144160B1 (en) | Movement sensor | |
JP2648739B2 (en) | Concentrated hypochlorite bleaching compositions and their use | |
CZ368598A3 (en) | Process for preparing basic bleaching substance containing compounds of chlorine and bromine | |
US3050467A (en) | Antiseptic cleaner | |
GB1586067A (en) | Detergent composition | |
EP0079697B2 (en) | Cleaning compositions | |
EP3565879B1 (en) | A hard surface cleaning composition | |
EP0784091A1 (en) | Stable perfumed bleaching composition | |
AU9411998A (en) | Detergents, cleaning compositions and disinfectants comprising chlorine-active substances and fattyacid alkyl ester ethoxylates | |
EP0345611B1 (en) | High alkalinity liquid automatic dishwasher detergent compositions | |
US20080261839A1 (en) | Odor reduction for agents containing hypochlorite | |
EP0010822B1 (en) | Alkaline dishwasher detergent | |
EP4155373A1 (en) | Disinfectant and protective composition for textiles or similar | |
JPS58222195A (en) | Mild homogeneously aqueous alkaline built detergent composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Designated state(s): AT BE CH DE FR GB IT LI NL SE |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): AT BE CH DE FR GB IT LI NL SE |
|
17P | Request for examination filed |
Effective date: 19861202 |
|
17Q | First examination report despatched |
Effective date: 19870611 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE FR GB IT LI NL SE |
|
REF | Corresponds to: |
Ref document number: 40151 Country of ref document: AT Date of ref document: 19890215 Kind code of ref document: T |
|
ITF | It: translation for a ep patent filed |
Owner name: ING. C. GREGORJ S.P.A. |
|
REF | Corresponds to: |
Ref document number: 3476220 Country of ref document: DE Date of ref document: 19890223 |
|
ET | Fr: translation filed | ||
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
ITTA | It: last paid annual fee | ||
EAL | Se: european patent in force in sweden |
Ref document number: 84303453.9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20000320 Year of fee payment: 17 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20000404 Year of fee payment: 17 Ref country code: AT Payment date: 20000404 Year of fee payment: 17 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20000504 Year of fee payment: 17 Ref country code: FR Payment date: 20000504 Year of fee payment: 17 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20000531 Year of fee payment: 17 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20000620 Year of fee payment: 17 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 20000621 Year of fee payment: 17 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20010522 Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20010522 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20010523 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20010531 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20010621 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20010621 |
|
BERE | Be: lapsed |
Owner name: THE PROCTER & GAMBLE CY Effective date: 20010531 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20011201 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20010522 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020131 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20011201 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020301 |