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.
• 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 si lanes 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 an aqueous bleaching composition
• a surfactant selected from amine oxides of 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 1 -C 4 alkyl groups, substituted betaines of formula R 7 R 8 R 9 N + -R 10 COO - wherein R 7 is a C 8 -C 18 alkyl group and R 8 , and R 9 are C l -C 4 alkyl groups, and R 10 is a C l -C 4 alkylene group and mixtures thereof, from 1.0% to 12.0% by weight of an alkali metal hypochlorite and from 1.0% to 15% by weight of inorganic compounds other than hypochlorite, said composition having a pH in the range from 10 to 13, wherein the composition also contains from 0.001-0.25% by weight of an organosilicon quaternary ammonium compound of formula
• 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 200 centipoises at 20°C and comprises alkali metal hypochlorite in an amount of from 8% to 10% by weight, a C 14 -C 15 alkyl dimethyl amine oxide as the only surfactant in an amount of from 1.0 to 1.5% by weight together with at least 400ppm 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 , typically approximately 1.15 g/cm 3 , so that the numerical value of the kinematic viscosity in centistokes is slightly less than that of the dynamic viscosity in centipoises.
• 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 l - C 4 alkyl, R 3 is C l -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 R2 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 . Ionic strength values in excess of 5.0 g moles/dm 3 are not desirable beacuse 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 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 ⁇ 200 centipoises is desired.
• the alkali metal hypochlorite may be a lithium, potassium or sodium hypochlorite and the level of hypochlorite in the composition is normally 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 formed 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 0.5% 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 R 4 group may be linear or branched and may be derived from natural or synthetic hydrocarbon sources.
• 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 lineard-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 as a 30% aqueous solution.
• 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 ⁇ 200 cp is one in which R 4 is a linear group which has an average chain length in the range C 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/dm3 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.
• R 7 is a C 8 -C 18 alxyl group, preferably a C 10 -C 14 alkyl group
• R 8 and R 9 are C l -C 4 alkyl groups, more preferably methyl groups
• 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 prcpylene group and R 8 and R 9 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 ccmplex 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 innoculum 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 l 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 menthol and mixtures of any of these or of their hydrolysable C 2 -C 3 carboxylic acid esters.
• fragrances including those employed in detergent compositions.
• level of incorporation conventionally lies between 10 ppm and 600 ppm of the composition depending on the perfume formulation and the nature of the detergent composition.
• aqueous hypochlorite bleach solutions containing from 1.0% to 2.0% of a C 14 -C 16 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 .
• C 2 -C 3 alkanoic acid provides an enhancement of the viscosity of the bleach solution and facilitates the . generation of viscosities of 200 centipoises 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 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 m y rcenol 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 eg. hydroxide, sulphate, halide, (particularly chloride), carbonate, nitrate, or orthaphosphate, pyrqphosphate, 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 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 value 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 canposition 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 270 centipoises 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.
• compositions are prepared according to the technique of Exanple 1:
• 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 Example 1.
• compositions were prepared according to the technique of Example 1.
• the alcohol and ester levels are given in ppm.
• Brookfield viscosity measurements in centipoises were made after 24 and 72 hours and were as folows: * The solution was cloudy and appeared to display non homogeneity. This disappeared after further storage.

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Cited By (33)

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Citations (2)

• 1983
  • 1983-05-25 GB GB838314500A patent/GB8314500D0/en active Pending
• 1984
  • 1984-05-16 GR GR74730A patent/GR81613B/el unknown
  • 1984-05-22 AT AT84303453T patent/ATE40151T1/de not_active IP Right Cessation
  • 1984-05-22 EP EP84303453A patent/EP0129980B1/fr not_active Expired
  • 1984-05-22 DE DE8484303453T patent/DE3476220D1/de not_active Expired
  • 1984-05-23 CA CA000454934A patent/CA1217004A/fr not_active Expired
  • 1984-05-24 JP JP59105639A patent/JPS6063300A/ja active Granted
  • 1984-05-24 ES ES532754A patent/ES8603944A1/es not_active Expired
  • 1984-05-24 IE IE1296/84A patent/IE57534B1/en not_active IP Right Cessation

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