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
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/22—Carbohydrates or derivatives thereof
  • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
• • 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
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
  • C11D1/143—Sulfonic acid esters
• • 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
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
  • C11D1/146—Sulfuric acid esters
• • 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
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/22—Carbohydrates or derivatives thereof
  • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
  • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
• • 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
  • C11D3/43—Solvents

Definitions

• the present invention relates to liquid hard surface cleaning compositions and methods for cleaning hard surfaces.
• the invention relates to fizzing compositions.
• a fizzing composition can be obtained by a detergent mixture with such properties that the foam formation and collapse results in a fizzing sound.
• Foam is defined as a dispersion of gas in a liquid and cannot be formed from pure liquids but require a liquid plus a surface-active agent such as a surfactant.
• the appearance of the foam is related to the amount of air dispersed into the surfactant containing liquor.
• the amount and appearance of the foam the household cleaning product generates is desirably related to the expectation the consumer has from said product. It is desirable that the foam is easily formed.
• composition can be applied by a trigger spray dispenser.
• compositions comprising short chain surfactant, solvent and polymer, may have the fizzing properties as described above when mixed in the right concentration.
• compositions comprising similar components are disclosed in the art, but not in such concentration that the fizzing properties are obtained.
• acidic cleaning composition comprising decyl sulphate, solvent and polymer.
• WO99/18182 hard surface cleaning compositions comprising lower alkyl sulphonate, polymer and solvent are disclosed, but outside the boundaries for a fizzing composition.
• WO 96/34933 discloses glass cleaning compositions comprising linear alkyl sulphate surfactants, in particular long chain alkyl sulphate surfactants for contributing to the detergency and providing reduced filming and streaking.
• an aqueous liquid hard surface cleaning composition comprising:
• the invention further provides a method for treating hard surfaces with the composition of the invention and a spray dispenser comprising the composition.
• the fizzing properties of the invention are achieved by the following foam characteristics.
• the composition is able to form air bubbles (foam).
• the air bubbles in the foam have to be able to quickly coalesce and then also quickly collapse.
• the coalescing and collapsing gives a fizzing sound.
• the foam properties of the composition have to meet specific characteristics disclosed herein below.
• Foam is defined as a dispersion of gas in a liquid.
• Stable foams can not be formed from pure liquids but require a liquid plus a surface-active agent such as a surfactant.
• the appearance of the foam is related to the amount of air dispersed into the surfactant containing liquor. At low amounts of gas the foam is thick and creamy while at high gas / liquor ratios the foam bubbles are separated by thin lamellae.
• the critical micelle concentration is dependent on amongst others the molecule itself (alkyl chain length, level of branching, EO chain length, headgroup type, counter ion etc.), the ionic strength, temperature and the pH.
• Anionic surfactants generally have a much higher critical micelle concentration than nonionics with the same alkyl chain length.
• the foam is not only easily formed but also coalesces and collapses reasonable fast, thereby giving a fizzing found.
• compositions of the invention comprise a short chain anionic surfactant. This type of surfactants comprises a short alkyl chain and a charged head.
• short chain any alkyl chain from 6 to 9 carbon atoms.
• the charged head of the anionic surfactant is sulphonate.
• anionic surfactant of the invention is of the general formula 1: R--SO 3 - M + (1)
• C 7 - and C 8 -alkyl surfactants according to general formula 1 above More preferred are C 7 - and C 8 -alkyl surfactants according to general formula 1 above. Even more preferred are C 7 - and C 8 -alkyl surfactants according to general formula 1 above,
• the anionic surfactant is present in the composition in a concentration at or above 1 %w/w and at or below 10%w/w. More preferably, the concentration is at or below 8%w/w, more preferable at or below 6%w/w, most preferably at or below 5%w/w. The concentration is preferably at or above 2%w/w, most preferably at or above 2.5%w/w.
• the polymer of the invention is a thickening polymer, being natural gums and their derivatives as well as polysaccharide thickeners and their derivatives.
• Xanthan gums such as Xanthan gum, Guar gum, Locust been gum, Carrageenan Gum, etc.
• Xanthan gums are widely available.
• suitable gums are Rhodopol T (Rhodia), Kelzan ST and Rheozan (Rhodia), Keltrol (CP Kelco).
• cellulose based polysaccharide thickeners in particular hydroxy alkyl cellulose, preferably hydroxyethyl cellulose or hydroxy propyl methyl cellulose (e,g. Natrosol HR 250 ex ISP or Mecellose ex Sunsung).
• the Polymer is present in the composition in a concentration at or above 0.01%w/w and at or below 0.3%w/w. More preferably, the concentration is at or below 0.2%w/w, more preferable at or below 0.1%w/w, most preferably at or below 0.06%w/w. The concentration is preferably at or above 0.02%w/w.
• the polymers of the invention are preferably stable in an acidic environment. Polymers that are instable in acidic environment are not preferred. One of the polymers that are not preferred is polyethylene glycol (PEG).
• PEG polyethylene glycol
• a third component with an effect on the foam is the solvent used in the composition.
• the solvent is a water soluble solvent, wherein soluble means that the solvent is soluble in or miscible with water over the concentration range of the invention.
• the solvents in the composition of the invention are preferably linear or branched lower alcohols or glycol ethers.
• Preferred alcohols are methanol, ethanol and/or linear or branched propyl or butyl alcohol.
• the most preferred alcohol is 2-propanol.
• Preferred.glycol ethers are propylene glycol ethers, more preferably dipropylene glycol ethers, still more preferred are dipropylene glycol mono- and di-alkyl ethers. Most prefered is dipropylene glycol n-butyl ether (DPnB).
• DPnB dipropylene glycol n-butyl ether
• the solvent is present in the composition in a concentration at or above 0.1%w/w and at or below 10%w/w. More preferably, the concentration is at or below 8%w/w, more preferable at or below 6%w/w, most preferably at or below 5%w/w. The concentration is preferably at or above 0.5%w/w, more preferably at or above 1%, still more preferably at or above 2%, most preferably at or above 3%.
• compositions of the invention are aqueous and in all of the composition the mass of the composition is balanced to 100% with water. Water is not part of the solvent according to the invention.
• composition of the invention is preferably acidic to neutral, pH 1 to 7, preferably pH 3 to 7.
• Preferred pH adjustment compounds are organic and inorganic acids.
• Preferred acids are phosphoric acid, citric acid, formic acid, lactic acid, or a mix of bicarboxilic acids and sulphammic acid and mixtures thereof.
• composition may further comprise common additives such as preservative, hydrotrope, buffer, salt, perfume and/or dye.
• additives such as preservative, hydrotrope, buffer, salt, perfume and/or dye.
• Antifoams in particular silicon and its emulsions have a negative effect on the fizzing effect of the formulations.
• the composition may also comprise a further surfactant referred to as co-surfactant.
• co-surfactant if present, is balanced in such a way that it does not affect the fizzing properties of the composition.
• Suitable co-surfactants are nonionics and anionics.
• Suitable nonionic co-surfactants are C 9 -C 11 alcohols with 5-10 ethylene oxide groups (e.g. Neodol 91.5, ex Shell chemicals) and C 12 -C 15 alkyl polyglucosides (e.g. Glucopon 215 CS UP, ex Cognis).
• Suitable anionic co-surfactants are secondary sodium C 14 -C 17 alkyl sulphonates (e.g. Hostapur SAS 30, ex Clariant). These co-surfactants are present in a concentration of less than 1.5%.
• compositions may also comprise a low amount of C 12 -C 18 alkyl amine oxide or C 12 -C 18 alkyl betaine. These co-surfactants are present in the composition in a concentration of less than 1.0%.
• CMC critical micelle concentration
• the CMC can be calculated, for instance according to the methods as described in Hiemenz, P. C., and Rajogopalan, R., Principles of Colloid and Surface Chemistry, p370-375, Marcel Dekker, Inc., 1997, New York .
• the CMC can also be measured by adding surfactant to an aqueous solution and measuring the conductivity against the concentration.
• the addition of surfactant to an aqueous solution causes an increase in the number of charge carriers and consequently, an increase in the conductivity.
• further addition of surfactant increases the micelle concentration while the monomer concentration remains approximately constant (at the CMC level). Since a micelle is much larger than a monomer it diffuses more slowly through solution and so is a less efficient charge carrier. A plot of conductivity against surfactant concentration is, thus expected to show a break at the CMC.
• the CMC is preferably above 0.05 mol/1.
• the ratio between the molar concentration of surfactant in the mix and the CMC is below 5.0, more preferably below 2.0, most preferably below 1.5.
• the fizzing of the composition of the invention is determined by the formation of foam (bubbles), the coalescence of the foam bubbles and the collapse of the bubbles. It is particularly preferred that the foam collapses in less than 300 seconds, more preferably within 60 seconds, still more preferably within 30 seconds, or even in less than 20 seconds.
• the composition is preferably applied using a trigger spray applicator.
• a trigger spray application enables fast and easy use for the consumer and additionally it brings a suitable amount of air into the composition, which aides in the foam formation.
• compositions of the invention may be stored in and dispensed by any suitable means, but spray applicators are particularly preferred. Pump dispensers (whether spray or non-spray pumps) are also possible.
• the present invention provides a container for a liquid hard surface cleaner, the container comprising a reservoir containing the hard surface cleaning composition of the invention, and spray dispenser for dispensing the composition in the form of a spray.
• the spray dispenser is preferably a trigger spray but may be any mechanical means for ejecting the liquid in spray or aerosol form.
• the invention further provides a method for providing a fizzing sound by applying the composition of the invention to a hard surface, by means of a spray dispenser.
• the cleaning properties are measured as follows: White enamel tiles (10 by 10 cm) are cleaned and dried. The tiles are covered with typical greasy soap sebum soil mainly based on ca-stearate (Nova Chimica code 26411) and artificial sebum (WFK, code 9D) using a spray applicator. The soil is prepared mixing 86g calcium stearate, 14g sebum and 666,7g propan-2-ol. The amount of soil applied amounts to 0.04g after drying. The tiles are dried in an oven at 180°C for 35 minutes and left to cool down to room temperature for 2 hours.
• the cleaning is carried out using a WIRA (wool industries research abrasion tester) applicator device.
• the tile to be cleaned is placed in the "holder" of the applicator device.
• a Ballerina cloth impregnated with 20g of the composition of table 1 is fastened to the cleaning head of the applicator device, and this is rubbed across the surface of the tile using a pre-set pattern covering the whole tile for 16 full cycles for each of the compositions below.
• Table 1 Compositions Ingredient ⁇ (%w) 1 2 3 *) 4 *) 5 *) C7 alkyl sulphonate 5 C8 alkyl sulphonate 5 C8 alkyl sulphate 5 C10 alkyl sulphate 5 5 Citric acid 4 4 4 4 4 Hydroxy ethyl cellulose 0.05 0.05 0.05 0.05 0.05 DPnB 4 4 4 IPA 4 4 Water To 100% To 100% To 100% to 100% *) comparative examples.
• Table 2 The results for the soil removal are given in Table 2 below. Table 2 also shows the CMC and the calculated Molar Concentration/CMC ratio of the compositions.
• Table 2 further shows the corresponding foam volume and the speed of coalescence and disappearance of the foam.
• the foam volume and coalescence are marked by a panel of 5 members, wherein no foam volume or coalescence is marked 0 and a high volume and coalescence is marked 10.
• the foam disappearance is measured in seconds needed for the foam to disappear.
• compositions 1, 2 and 3 have a better foam coalescence and disappearance speed than compositions 4 and 5, with a lower CMC.
• compositions 1, 2 and 3 give a good fizzing sound, whilst compositions 4 and 5 do not.
• the CMC is the calculated critical micelle concentration of the surfactant.
• compositions of Table 3 are used.
• compositions from table 3 contain the short chain surfactant of the invention.
• Compositions 7 and 8 contain both polymer and solvent according to the invention, whereas composition 6 does not contain polymer and composition 9 does not contain solvent.
• Table 4 Results Composition 6 7 8 9 *) Soil removal (%) 70 81 70 74 Foam Volume (1-10) 1 10 9 6 Foam Coalescence (1-10) 0 9 7 3 Foam speed (s to disappear) 0 20 15 45
• compositions 7 and 8 show that the foam volume, coalescence and disappearance speed of the compositions according to the invention (compositions 7 and 8) is excellent and therefore result in good fizzing.
• the composition without solvent does not collapse adequately, whereas hardly any foam is formed in the composition without polymer, giving inadequate fizzing. All of the compositions 6-9 give adequate soil removal.

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• 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)
• Health & Medical Sciences (AREA)
• Molecular Biology (AREA)
• Emergency Medicine (AREA)
• Detergent Compositions (AREA)

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• 2007
  • 2007-05-21 ES ES07729309T patent/ES2349265T3/es active Active
  • 2007-05-21 AT AT07729309T patent/ATE474033T1/de not_active IP Right Cessation
  • 2007-05-21 AU AU2007256249A patent/AU2007256249B2/en not_active Ceased
  • 2007-05-21 EP EP07729309A patent/EP2029710B1/en not_active Not-in-force
  • 2007-05-21 RU RU2008152067/04A patent/RU2427617C2/ru not_active IP Right Cessation
  • 2007-05-21 DE DE602007007766T patent/DE602007007766D1/de active Active
  • 2007-05-21 MX MX2008015478A patent/MX2008015478A/es active IP Right Grant
  • 2007-05-21 BR BRPI0712452A patent/BRPI0712452B8/pt not_active IP Right Cessation
  • 2007-05-21 UA UAA200815115A patent/UA94949C2/ru unknown
  • 2007-05-21 WO PCT/EP2007/054865 patent/WO2007141128A2/en active Application Filing
  • 2007-06-08 AR ARP070102486A patent/AR061274A1/es not_active Application Discontinuation
• 2008
  • 2008-11-11 ZA ZA2008/09614A patent/ZA200809614B/en unknown
  • 2008-11-18 EG EG2008111852A patent/EG25120A/xx active

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