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
  • C11D3/395—Bleaching agents
  • C11D3/3956—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
  • C11D1/66—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
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
  • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
• • 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
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/12—Water-insoluble compounds
  • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
  • C11D3/1246—Silicates, e.g. diatomaceous earth
  • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
  • C11D3/1266—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in 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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
  • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in 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
  • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
  • C11D2111/10—Objects to be cleaned
  • C11D2111/14—Hard surfaces

Definitions

• the present invention relates to aqueous thickened bleaching compositions comprising hypochlorite, surfactant, polymeric thickeners and colloidal inorganic thickeners.
• the invention also relates to methods of use for said compositions and an application device for said compositions.
• Aqueous liquid hypochlorite bleach compositions are well known in the art. On the one hand they are used for bleaching and stain removal on laundry, on the other hand they are used for cleaning and disinfecting hard surfaces such as kitchen surfaces, floors and toilets. To increase contact time between the surface and the bleach, on inclined and vertical surfaces bleach compositions intended for cleaning hard surfaces preferably have a relatively high viscosity and such compositions are generally known as "thick bleach".
• thickening systems for hypochlorite have been described in the prior art involving a variety of combinations of surfactants.
• these GB 1,466,560 describes thickening systems comprising an alkali metal sarcosinate or tauride surfactant and another surfactant chosen from amine oxides, quaternary ammonium compounds, betaines, alkanolamides and fatty acid soaps.
• Thickened liquids and gels designed for hard surface cleaning are generally delivered from pouring packs, for example to the toilet bowl and under the toilet rim.
• trigger spray packs can offer greater convenience for product application to some surfaces, for example in removing mould or mildew from walls and grouting, the insides of bins.
• EP0694061 B1 discloses the use of a hypochlorite stable surfactant and foaming trigger head as a method of delivering a low irritancy spray bleach cleaner. Delivery of thickened or gelled liquids through a trigger head is much more difficult, as most products are too viscous to be readily drawn up the dip-tube and through the trigger head without blocking the trigger mechanism.
• US6194372 B1 discloses use of clays to provide a sprayable gel cleaning composition based on a montmorillonite clay in conjunction with surfactants and a solvent.
• US5851421 discloses the use of polyacrylates to thicken hypochlorite formulations reducing irritancy during spraying.
• the compositions have a viscosity ranging of from 20 cps (20 mPa.s) up to a maximum thickness less than a gel condition, preferably with a maximum thickness of up to about 5,000 cps, measured on a Brookfield viscometer, but good surface cling, as is required for spot cleaning, remains to be desired.
• Another object is to provide the cleaning and hygiene benefits of thick bleach in a convenient format.
• Another object is to deliver the composition from a trigger spray dispenser, without clogging the dispenser.
• Another object is to provide a composition that does not drip/drain, but stays on the spot, resulting in more economical, targeted use of the composition.
• the present invention provides a sprayable thickened bleaching composition, comprising: 0.01-10% of an alkali metal hypochlorite; 0.02-10% bleach stable thickening surfactant; 0.01-10% of a polymeric thickener; and 0.01-10% of a colloidal inorganic thickener; wherein the rheology of the composition is defined by:
• the present invention provides sprayable thickened bleaching compositions, with good clinging to vertical and inclined surfaces. Accordingly, the invention provides compositions comprising a hypochlorite salt, and a thickening system comprised of bleach stable thickening surfactant and a combination of thickening polymer and inorganic colloidal thickener.
• the hypochlorite salt is generally an alkali metal or alkaline earth metal salt although other salts may be used.
• the Na and Ca salts are most widely used.
• the compositions used for the purposes of the invention generally comprise 0.01-10% NaOCl or an equivalent amount of other hypochlorite salt, which is equivalent to about 0.0095-9.5% available chlorine. More preferably the composition comprises 0.1-5% hypochlorite.
• the thickening surfactant may be any bleach stable surfactant, aiding to the gel stability and providing detergency. Most preferred are amine oxide surfactants.
• Suitable amine oxide surfactants for use in the thickening system are tertiary amine oxides of structure R 1 R 2 R 3 NO, where R 1 is an alkyl group of 8 to 20 carbon atoms and R 2 and R 3 are independently selected from alkyl or hydroxyalkyl groups of 1 to 3 carbon atoms, preferably methyl groups.
• the large alkyl group preferably has at least 12, more preferably at least 14 carbon atoms.
• bleach stable surfactants suitable for use in the compositions of the invention include alkycarboxybetaines, alkylbenzene sulphonates, alkylsulphates and sulphonates.
• the bleach stable surfactant is preferably used in an amount of at least 0.02%, more preferably at least 0.05%, most preferably at least 0.1 %, but preferably not above 10%, more preferably not above 5%.
• Thickening polymers for use in the present invention are preferably those showing good resistance to oxidative degradation by sodium hypochlorite, examples being cross linked polyacrylates such as Noveon's Carbopol 676 and 3V Sigma's Polygel GPN or styrene-methacrylate copolymers such as Alco's Narlex PPE 1196.
• the polymer is preferably used in an amount of at least 0.01 %, more preferably at least 0.1 %, most preferably at least 0.2%, but preferably not above 10%, more preferably not above 5%.
• the colloidal inorganic thickeners of the present invention preferably contain only low levels of transition metals that may catalyse hypochlorite bleach decomposition.
• Such commercially available high purity colloidal thickeners include fumed silica, such as Degussa's Aerosil 200 or hydrous sodium disilicate sold by PQ Europe under the trade name BRITESIL H20, and clays such as Rockwood's Laponite, synthetic hectorites and washed natural smectites such as R T Vandebilt's VANGEL O.
• the colloidal thickener is preferably used in an amount of at least 0.01%, more preferably at least 0.05%, most preferably at least 0.1%, but preferably not above 10%, more preferably not above 5%.
• compositions of the invention are preferably alkaline, i.e. have pH above 7.
• the pH is kept at or above 11, more preferably at least 12.
• Alkaline pH is preferred to stabilise the hypochlorite in the composition.
• the composition preferably comprises and alkalinity source, such as alkali metal hydroxide.
• alkalinity source such as alkali metal hydroxide.
• alkali metal hydroxide sodium hydroxide.
• compositions may also comprise a buffering agent to ensure long term pH stability.
• a buffering agent to ensure long term pH stability.
• Alkali metal carbonates and/or bicarbonates and silicates are particularly useful for that purpose.
• compositions may further comprise transition metal sequestering agents.
• transition metal sequestering agents are alkaline silicates and periodate and mixtures thereof.
• Other optional components include chlorine compatible perfumes, dyes builders, antioxidants and radical scavengers.
• composition of the invention preferably does not comprise abrasives due to the risk of blocking of the trigger head.
• the formulations are suitable for delivery from a range of trigger heads commonly available for household the delivery of household cleaning compositions.
• trigger heads commonly available for household the delivery of household cleaning compositions.
• One example is the "Dido" trigger-head ex Sprayplast.
• Another common example is the “Mixor” trigger head ex Calmar.
• the invention provides a method for spot cleaning a surface comprising the steps of spraying the composition according to the invention onto a soiled or stained hard the surface, waiting at least 30 seconds and wiping the composition and stain or soil from the surface. It is preferred that the compositions according to the invention do not drain in less than 30 seconds, more preferably they drain in more than 1 minute, more preferably in more than 2.5 minutes.
• the formulations of the present invention have specific rheological properties that allow them to be dispensed from a trigger spray head and to give good cling to vertical and inclined surfaces.
• the shear thinning behaviour is defined by comparing the low shear (3 s -1 ) and high shear (21 s -1 ) viscosity values.
• the compositions preferably have viscosities which fall into the following ranges: At low shear rate (3 s -1 ) the viscosity is 500-200,000 mPa.s, preferably 1,000-100,000 mPa.s, most preferably 2,000-60,000 mPa.s and at high shear rate (21 s -1 ) the viscosity is 500-20,000 mPa.s, preferably 1,000-10,000 mPa.s, most preferably 2,000-10,000 mPa.s.
• the formulations of the invention are further defined by having a yield stress of a magnitude that is exceeded during delivery of the formulation through the trigger spray mechanism.
• a complex fluid is said to show yield stress if below a critical stress (namely the yield stress) it does not flow (e.g. it behaves as a solid) and above it flows as a fluid.
• This definition corresponds to a flow bifurcation.
• a system with a yield stress exhibits a sudden decrease in effective viscosity as the shear forces exceed the critical, yield stress, value for example during dispensing.
• the yield stress may for instance be measured using an oscillatory shear method, as described in the examples below. Yield stress values may also be estimated from flow curves as the value of the shear stress at which shear thinning becomes apparent but these values are far less accurate than those obtained using oscillatory shear measurements.
• the compositions preferably have yield stresses in the range 1-100 Pa, preferably 2-50 Pa.
• the composition may be applied to the surface by a squeeze bottle, squeeze tube or any other targeted application device.
• Aqueous liquid bleaching compositions were prepared according to the formulations given in the tables below (amounts in % w/w).
• Table 1 show compositions comprising hypochlorite, thickening surfactant, organic thickening polymer and colloidal inorganic thickener in four concentration variations.
• Table 2 shows comparative example compositions In the compositions, Empigen OD is C 10 -C 18 alkyl-dimethylamine oxide marketed by Huntsman. Narlex PPE 1196 is a thickening polymer ex Alco and Laponite is a colloidal inorganic thickener ex Rockwood.
• the trigger heads used in the examples are the "Dido" trigger head, ex Sprayplast and the "Mixor” trigger head ex Calmar. Both are commonly available trigger heads.
• Table 1 Examples 1 2 3 4 Na hypochlorite 1.0 1.0 0.5 0.5 Empigen OD 1.0 1.0 1.0 1.0 Narlex PPE 1196 2.25 2.5 2.0 2.25 Laponite XLG 0.5 0.5 0.75 0.5 Alkaline Na silicate 0.05 0.05 0.05 0.05 0.05 Sodium hydroxide 0.9 0.9 0.9 0.9 High purity water To 100% To 100% To 100% To 100% To 100% To 100% Physical appearance Viscous gel Viscous gel Viscous gel Viscous gel Viscosity, mPas (at 1-3 s -1 ) 14,400 51,900 37,000 54,600 Viscosity, mPas (at 21 s -1 ) 3,300 8,100 4,930 9,350 Ratio of low shear to 21 s -1 viscosity 4.4 6.4 7.5 5.8 Yield stress (Pa
• Examples 1 to 4 show four compositions according to the invention, with a range of viscosities and yield stress set by the variation of the amount of thickening polymer and inorganic colloidal thickener. It can be seen in Table 1 that the compositions are all sprayable and have a long drainage time on the surface. The longer the drainage time, the better the composition stays on the spot and the better it cleans.
• Comparative examples A and B do not contain the thickening system of the invention.
• Comparative example C comprises only the thickening polymer and no inorganic colloidal thickener, while comparative example D contains only the inorganic colloidal thickener and no thickening polymer.
• the compositions of comparative examples A and B are sprayable, but drain immediately, within seconds.
• the composition of comparative example C blocks the trigger head, whereas composition D is unstable and therefore not suitable for spraying at all.
• the viscosity profiles were measured using a Haake RT20 Rotovisco rheometer fitted with a coaxial cylinder sensor DIN 53018 (Z41 rotor and Z43 measuring cylinder), using a 3 mm gap. Flow curves were obtained at 21° C over the shear rate range 0.1 to 1000 s -1 .
• Yield stress measurements were made on a TA ARES shear controlled rheometer, in parallel plate geometry using serrated plates of diameter 25 or 50 mm, and a gap between 0.7 and 2 mm (typically 1.5). Oscillatory measurements were made with the following protocol: The majority of measurements were made at an oscillation frequency of 1 s -1 and some checked further at frequencies of 0.01 and 5 s -1 . The measurement involves measuring the viscoelastic response of the sample at fixed frequency (G' and G”) vs strain (amplitude of oscillation) by increasing the relative strain from 1% to 600%. The outcome of the measurement is a shear stress vs strain curve.
• this curve shows a maximum, with a well defined decrease of stress at higher strains, the sample shows yield stress, with a value of the yield stress given by the amplitude of the maximum.
• the sample was loaded in the rheometer and the measurements started after 10 min. Measurements were repeated at least 3 times for reproducibility.
• Differences between the cling properties of compositions are appraised by measuring the time taken for the material dispensed from two repeat spray applications (approx. 2 g material) to the same point onto an inclined surface (a smooth piece of plate glass inclined at an angle of 60°) to drain a distance of 10 cm.
• the orifice of the trigger head is held at a constant 10 cm distance from the surface.
• Formulations that are defined as sprayable can be delivered through the spray head without blocking the trigger head (i.e. making the mechanism too stiff to pull) or dripping from the end of the trigger head.
• Compositions that block the trigger head, compositions that block the trigger mechanism and compositions that cause dripping of the trigger after or during use, are not suitable.
• all triggers are suitably primed before use, i.e. multiple pulls of the trigger are required in order to draw any liquid up into the dispensing head, before the product can be dispensed.

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Citations (6)

• 2006
  • 2006-10-13 EP EP06122235A patent/EP1911832A1/fr not_active Withdrawn

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