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
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/042—Acids
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3947—Liquid compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/40—Dyes ; Pigments

Definitions

• the present invention relates to colored acidic thickened aqueous liquid compositions, more particularly to acidic thickened aqueous compositions comprising a source of active oxygen and a given dye at a given level.
• Said compositions find particular application in the cleaning of hard-surfaces, especially inclined hard-surfaces, such as toilet bowls and the like.
• Bleaching/cleaning compositions comprising a source of active oxygen and formulated at low pH are particularly interesting for the cleaning of hard-surfaces, especially for the hygienic cleaning of sanitary fittings such as toilet bowls and the like.
• European co-pending application 94870184.2 discloses acidic thickened aqueous compositions comprising persulfate salts and as the thickening system a quaternary ammonium compound together with a short chain amine oxide (C6 to C10).
• compositions comprising a source of active oxygen such as persulfate salts with an adequate viscosity, so that said compositions have a consumer acceptable residence time on the surface to be cleaned.
• a source of active oxygen such as persulfate salts
• compositions be easily rinsed away from said surfaces, especially because viscous products have a good cling onto said surfaces.
• the consumer perception of the rinsing of a given thickened composition applied onto a non-horizontal surface like toilet bowls is driven not only by the real amount of said composition that remains onto said surface after having being rinsed away for example by flushing, but also by the level of dye present in said composition. It has been observed that the higher the dye level, the more product is perceived by the consumer to remain on said surface after flushing, which is detrimental from a consumer point of view.
• compositions comprising a source of active oxygen and a dye, said compositions being perceived concomitantly as being more viscous and easy to rinse away from a consumer standpoint.
• colorantic aqueous compositions which comprise a source of active oxygen such as monopersulfate salts
• stability problems appear, i.e., in general peroxy-bleaches raise compatibility issues in relation with the kind of dyes used and the levels of dyes because dyes themselves and/or the metals present in the dyes may catalyse the peroxide decomposition.
• It is thus also an object of the present invention to provide a colored acidic thickened aqueous composition comprising a source of active oxygen, in particularly a persulfate salt, which is chemically stable.
• compositions comprising a source of active oxygen with a dye which is chemically and physically stable in said medium, i.e., an ⁇ or ⁇ metal phthalocyanine dye, or mixtures thereof at optimised levels.
• a dye which is chemically and physically stable in said medium i.e., an ⁇ or ⁇ metal phthalocyanine dye, or mixtures thereof at optimised levels.
• the present invention allows to provide colored acidic thickened aqueous compositions which are perceived by the consumer as being more viscous, without increasing the total level of thickening ingredients present in said compositions such as surfactants. Also the present invention allows to optimise the rinsing perception by the consumer of colored acidic thickened aqueous compositions without decreasing the real viscosity of said compositions and/or modifying the hydrophilicity/lipophilicity balance (HLB) of said compositions.
• HLB hydrophilicity/lipophilicity balance
• compositions of the present invention are chemically stable for long storage periods. Indeed, by carefully defining the level of ⁇ or ⁇ metal phthalocyanine dyes, or mixtures thereof, chemically stable colored acidic aqueous compositions are provided.
• a further advantage of the present invention is that said colored acidic thickened aqueous compositions are efficient on various surfaces to clean various soils and stains. Additionally, said compositions when used to treat hard surfaces, especially toilet bowls, exhibit outstanding soil discoloration, soil solubilization, removal and emulsification properties together with a germicidal action, this when used both neat or diluted.
• compositions of the present invention which comprise a thickening surfactant system comprising quaternary ammonium compound and short chain amine oxide (C6-C10), exhibit improved thickening properties at low total thickening surfactant level.
• EP-A-265 979 discloses acidic thickened aqueous cleaning compositions comprising a disinfecting and/or oxidising agent, an organic anionic sulphonate and a surfactant selected from the group of (1) quaternary ammonium compounds wherein at least one of the hydrocarbon groups linked to the nitrogen is a linear or branched alkyl group containing at least 12 carbon atoms and of (2) tertiary amine oxides wherein at least one of the hydrocarbon groups linked to the nitrogen is a linear or branched alkyl group containing at least 16 carbon atoms.
• a source of active oxygen is disclosed.
• the composition in example 1 comprises a dye at a level of 0.001 % by weight.
• EP-A-188 025 discloses aqueous stable thickened low-pH bleaching compositions comprising an inorganic peroxy compound, a strong acid and a thickening surfactant. Dyes are mentioned in general. The examples comprise Latex red 41R, or Latex blue 842103 which are not ⁇ or ⁇ metal phthalocyanine dyes.
• EP-A-601 792 discloses thickened aqueous toilet cleaning compositions comprising an acidic limescale removing agent, hydrogen peroxide, one or more thickeners and up to 1.5% by weight of a colorant.
• the composition exemplified comprises Unisperse green® which is a chlorinated copper phthalocyanine dye at a level of 0.0045% by weight. No reference is made to the finding of the present invention, the existence of optimised levels of ⁇ or ⁇ metal phthalocyanine dyes which enable to have excellent perceived viscosity and excellent perceived ease of rinsing without compromising peroxy-bleach stability.
• the present invention encompasses a colored acidic thickened aqueous composition having a viscosity of from 150 cps and up at 20°C and comprising a source of active oxygen, or mixtures thereof and from 0.005% to 0.02% by weight of the total composition of an ⁇ or ⁇ metal phthalocyanine dye, or mixtures thereof.
• the present invention also encompasses a process of treating a hard-surface, especially toilet bowls, wherein a colored acidic thickened aqueous composition as mentioned herein before, is used.
• compositions of the present invention are colored acidic thickened aqueous liquid compositions comprising, as an essential ingredient, a source of active oxygen, or mixtures thereof, which is an acid-stable bleach.
• acid-stable it is meant herein a compound which is stable in the acidic environment of the compositions herein.
• stable it is meant herein that a composition of the present invention comprising a source of active oxygen, or mixtures thereof, such as persulfate salt, preferably does not undergo more than 50% persulfate loss, in six months at room temperature (20°C-25°C).
• Persulfate concentration can be measured by titration with potassium permanganate after reduction with a solution containing ammonium ferrous sulphate.
• the source of active oxygen acts as an oxidising agent, it increases the ability of the compositions to remove colored stains and organic stains in general, to destroy malodorous molecules and to kill germs.
• Suitable sources of active oxygen are hydrogen peroxide or sources thereof.
• a hydrogen peroxide source refers to any compound which produces hydrogen peroxide when said compound is in contact with water.
• Suitable water-soluble inorganic sources of hydrogen peroxide for use herein include persulfate salts (i.e., dipersulfate and monopersulfate salts), persulfuric acid, percarbonates, metal peroxides, perborates and persilicate salts.
• peroxides can be used as an alternative to hydrogen peroxide and sources thereof or in combination with hydrogen peroxide and sources thereof.
• Suitable classes include dialkylperoxides, diacylperoxide, performed percarboxylic acids, organic and inorganic peroxides and/or hydroperoxides.
• Suitable organic peroxides/hydroperoxides include diacyl and dialkyl peroxides/hydroperoxides such as dibenzoyl peroxide, t-butyl hydroperoxide, dilauroyl peroxide, dicumyl peroxide, and mixtures thereof.
• Suitable preformed peroxyacids for use in the compositions according to the present invention include diperoxydodecandioic acid DPDA, magnesium perphthalic acid, perlauric acid, perbenzoic acid, diperoxyazelaic acid and mixtures thereof.
• Persulfate salts are the preferred sources of active oxygen to be used in the compositions according to the present invention.
• Preferred persulfate salt to be used herein is the monopersulfate triple salt.
• monopersulfate salt commercially available is potassium monopersulfate commercialised by Peroxide Chemie GMBH under the trade name Curox®, by Degussa under the trade name Caroat and from Du Pont under the trade name Oxone.
• Other persulfate salts such as dipersulfate salts commercially available from Peroxide Chemie GMBH can be used in the compositions according to the present invention.
• compositions according to the present invention may comprise up to 30% by weight of the total composition of said source of active oxygen, or mixtures thereof, preferably from 0.1 % to 30%, more preferably from 0.1 % to 20%, and most preferably from 0.1 % to 15%.
• compositions of the present invention are thickened compositions. Accordingly the compositions of the present invention have a viscosity of from 150 cps and up at 20°C, preferably of from 250 cps to 1500 cps and more preferably of from 250 cps to 900 cps, when measured with a Brookfield viscometer at 60 rpm with a spindle n° 2 or with the Carri-med rheometer at 50 dyne/cm2.
• compositions herein are likely to be used on inclined surfaces such as bath tubs, sinks or toilet bowls. Thickened compositions have a better cling onto inclined surfaces, thus a longer residence time for the composition to remove mineral encrustations.
• surfactants suitable to be used in the compositions of the present invention may be thickening surfactants such as anionic, nonionic, zwitterionic and cationic surfactants in amount up to 50% by weight of the total composition.
• Suitable anionic surfactants include alkyl or alkylene sulfate or sulfonates, alkyl or alkylene ether sulfates or sulfonates, linear alkyl benzene sulfonate and the like.
• Suitable cationic surfactants include quaternary ammonium salts.
• Suitable nonionic surfactants for use herein include ethoxylated carboxylic acids, amine oxides and alcohol ethoxylates. Emulsions of nonionic surfactants, such as in co-pending European patent application EP 598 692, are also suitable to provide pseudoplastic and thixotropic compositions, which allow excellent spreading and clinging characteristics on dry surfaces.
• a suitable thickening surfactant system highly preferred herein that leads to excellent spreading and clinging on wet surface is constituted by mixtures of a quaternary ammonium compound, or mixtures thereof, together with a short chain amine oxide, or mixtures thereof. Said compositions are Newtonian. By “Newtonian” it is meant herein a composition which has the same viscosity within a very wide range of applied shear stresses.
• Said thickening surfactant system comprising a quaternary ammonium compound, or mixtures thereof, together with a short chain amine oxide, or mixtures thereof, allows to use low levels of total thickening surfactant to achieve a given viscosity for a colored acidic aqueous composition comprising a source of active oxygen.
• a lower level of total thickening surfactants quaternary ammonium compounds and short chain amine oxides
• Suitable quaternary ammonium compounds to be used herein are quaternary ammonium compounds wherein one or two of the hydrocarbon groups linked to nitrogen are a linear or branched alkyl group of 6 to 30 carbon atoms, preferably of 10 to 25 carbon atoms and more preferably 12 to 20 carbon atoms, saturated or unsaturated, and wherein the other hydrocarbon groups (i.e.
• the quaternary ammonium compound is preferably a non-chloride quaternary ammonium compound.
• the counterion used in said quaternary ammonium compounds are compatible with any source of active oxygen and are selected from the group of fluoride or methyl sulfate, or methylsulfonate, or hydroxide and the like. Particularly preferred to be used herein are trimethyl quaternary ammonium compounds like myristyl trimethyl ammonium methylsulfate, cetyl trimethyl ammonium methylsulfate and/or tallow trimethyl ammonium methylsulfate. Such trimethyl quaternary ammonium compounds are commercially available from Hoechst or from Albright & Wilson under the trade name EMPIGEN CM®.
• compositions according to the present invention comprise up to 20% by weight of a quaternary ammonium compound, or mixtures thereof, preferably of from 0.1 % to 15%, more preferably of from 0.1 % to 10% and most preferably of from 1% to 5%.
• Suitable short chain amine oxides to be used herein are amine oxides having the following formula R 1 R 2 R 3 NO wherein R1 is a C6 to C10 alkyl group, preferably a C8 to C10 alkyl group and wherein R2 and R3 are independently substituted or unsubstituted, linear or branched alkyl groups of from 1 to 4 carbon atoms, preferably of from 1 to 3 carbon atoms and more preferably are methyl groups.
• R1 may be a linear or branched alkyl group, being saturated or unsaturated.
• Suitable short chain amine oxides for use herein are preferably compatible with any source of active oxygen.
• Preferred short chain amine oxides for use herein are for instance natural blend C8/C10 amine oxide available from Hoechst.
• compositions according to the present invention comprise up to 15% by weight of a short chain amine oxide, or mixtures thereof, preferably of from 0.1% to 10% more preferably of from 0.1% to 5% and most preferably of from 0.1% to 3%.
• the total level of thickening surfactant system i.e. of quaternary ammonium compound and of short chain amine oxide, to be used in a given aqueous acidic composition of the present invention depends on the thickening desired for said composition, said level being up to 20%, preferably between 1% and 15%, more preferably between 1% and 10% and most preferably between 1% and 6%.
• Suitable weight ratios of said short chain amine oxide to said quaternary ammonium compound range from 1:2 to 1:100, preferably from 1:4 to 1:30 and more preferably from 1:10 to 1:20.
• compositions of the present invention are colored acidic thickened aqueous compositions comprising as an essential ingredient an ⁇ or ⁇ metal phthalocyanine dye, or mixtures thereof.
• Suitable ⁇ or ⁇ metal phthalocyanine dyes to be used herein are acid-stable and bleach-stable dyes.
• acid-stable it is meant herein a compound which is chemically and physically stable in the acidic environment of the compositions herein.
• bleach-stable it is meant herein a compound which is chemically and physically stable in presence of bleaches.
• the ⁇ or ⁇ metal phthalocyanine dyes suitable to be used in the compositions of the present invention are light-fast organic pigments with four isoindole groups, (C 6 H 4 )C 2 N, linked by four nitrogen atoms to form a conjugated chain.
• substituent X may be one of the following groups :H, Cl, HSO 3 , COO-M+, Br, NO 2 , OCH 3 or a C 1 to C 10 alkyl group and where Me is copper, chromium, vanadium, magnesium, nickel, platinum, aluminium, cobalt, lead, barium or zinc.
• Preferred ⁇ or ⁇ metal phthalocyanine dyes to be used herein are ⁇ or ⁇ copper phthalocyanine dyes.
• compositions of the present invention comprise from 0.005% to 0.02% by weight of the total composition of ⁇ or ⁇ metal phthalocyanine dye, or mixtures thereof, preferably from 0.006% to 0.015% and more preferably from 0.006% to 0.012%.
• the present invention is based on the finding that by carefully defining the level of said ⁇ or ⁇ metal phthalocyanine dye, or mixtures thereof, colored acidic thickened aqueous compositions are provided which (1) are perceived as being more viscous by the consumer, without increasing the total level of thickening ingredients present in said compositions and (2) are perceived by the consumer as being easily rinsed away from a non-horizontal surface after having been applied thereto without decreasing the real viscosity of said compositions and/or modifying the hydrophilicity/lipophylicity balance (HLB) of said compositions, this without compromising peroxy-bleach stability.
• HLB hydrophilicity/lipophylicity balance
• compositions of the present invention are acidic. Accordingly, the compositions herein are formulated at a pH between 0 to 6, preferably at a pH between 0 and 4 and more preferably at a pH between 0 and 2. Acidity further contributes to formulate compositions according to the present invention which exhibit good mineral encrustations removal performance while having also good disinfecting properties.
• the compositions of the present invention comprise organic and/or inorganic acids. Particularly suitable organic acids to be used herein are aryl and/or alkyl sulfonate, such as methane sulfonic acids, succinic acid, sulphamic acid and the like. Particularly suitable inorganic acids to be used herein are sulphuric acid, phosphoric acid, nitric acid and the like and preferably sulphuric acid.
• compositions according to the present invention are aqueous.
• the compositions according to the present invention comprise from 40% to 99% by weight of the total composition of water, preferably from 60% to 95%, most preferably from 70% to 90%.
• Deionized water is preferably used.
• compositions according to the present invention may further comprise a variety of other ingredients including organic or inorganic alkalis, optical brighteners, builders, chelants, pigments, colorants, enzymes, dye transfer inhibitors, solvents, buffering agents, stabilisers, perfumes and the like.
• Preferred chelating agents to be used herein are the ones having a pKa being not higher than 4, such as phosphonate-based chelants having a number of phosphonate groups ranging from 1 to 6 and being preferably selected from the following group, or mixtures thereof : amino poly alkyl phosphonic acids, metaphosphoric acid (HPO 3 ) n, pyrophosphoric acid (H 4 P 2 O 7 ), methylidene di phosphonic acid CH 2 (H 2 PO 3 ) 2.
• phosphonate-based chelants having a number of phosphonate groups ranging from 1 to 6 and being preferably selected from the following group, or mixtures thereof : amino poly alkyl phosphonic acids, metaphosphoric acid (HPO 3 ) n, pyrophosphoric acid (H 4 P 2 O 7 ), methylidene di phosphonic acid CH 2 (H 2 PO 3 ) 2.
• Suitable amino poly alkyl phosphonic acids are diethylenetriamine penta methylene phosphonic acid, commercially available from Monsanto under the trade name Dequest ® 2066A; amino trimethylene phosphonic acid commercially available from Albright&Wilson under the trade name Briquest ®301 -50A; tetraethylene pentaamine hepta methylene phosphonic acid commercially available from Albright&Wilson under the trade name Briquest ® 785; pentaethylene hexaamine octa methylene phosphonic acid commercially available from Albright&Wilson under the trade name Briquest ® 8106.
• Preferred amino poly alkyl phosphonic acid to be used herein is diethylenetriamine penta methylene phosphonic acid.
• Metaphosphoric acid and pyrophosphoric acid suitable to be used herein may be the ones commercially available from Carlo Erba.
• the addition of such chelating agents in the colored acidic thickened aqueous compositions of the present invention, where the acid is sulfuric acid, allows to inhibit the formation and subsequent precipitation of calcium sulfate, when the compositions are applied on inorganic soils like calcium carbonate or calcium phosphonate encrustations commonly found in hard-surfaces, like toilets bowls, resulting thereby in improved surface appearance (i.e., better shine and/or cleaning performance).
• the present invention further encompasses a process of treating a hard-surface wherein a colored acidic thickened aqueous composition as described herein before, is used.
• compositions may be used neat or in its diluted form.
• in its diluted form it is meant herein that said compositions may be diluted with water up to 99% of water. Said dilution may occur either before, after or while said composition is applied to a hard-surface.
• compositions herein find a preferred application in the cleaning of toilet bowls and bath tubs. While cleaning toilet bowls compositions according to the present invention may be diluted while or after they are applied to the surface to be cleaned. For example, said compositions may be dispensed from a container onto said hard-surface, then diluted in water and left to act onto said surfaces, then removed by rinsing or flushing.
• the expression "treating" includes bleaching as the compositions of the present invention comprise a source of active oxygen, preferably persulfate salts, removal of mineral encrustations as the compositions used in the process according to the present invention comprise acids, and/or washing as the compositions used in the process according to the present invention may further comprise surfactants.
• compositions are made which comprise the listed ingredients in the listed proportions (weight %).
• Curox® is one of the commercial names of monopersulfate salts.
• **Unisperse blue B-E® is an ⁇ copper phthalocyanine dye of the formula as described herein before where X is H and is commercially available from Ciba-Geigy.
• each of the ⁇ or ⁇ metal phthalocyanine dye or mixtures thereof to be used in a colored acidic thickened aqueous liquid composition there is an optimum level which enables to have excellent perceived viscosity and excellent perceived ease of rinsing by the consumer without compromising peroxy-bleach stability.
• Composition #1 is taken as the reference.
• Composition #2 is representative of the present invention, it comprises ⁇ copper phthalocyanine dye of the formula as described herein before where X is H at its optimum level, i.e., 0.009% by weight of the total composition.
• Composition #3 comprises ⁇ copper phthalocyanine dye of the formula as described herein before where X is H at a level of 0.015% by weight of the total composition.
• the above compositions were evaluated for their perceived viscosity and perceived ease of rinsing by 30 panelists, i.e., the panelists were asked to compare compositions #2 and #3 to the reference composition, i.e.
• composition #1 and to judge which composition was thicker (higher perceived viscosity) and which composition was more easily rinsed away from the surface to which it has been previously applied. This test was performed on inclined surfaces (toilet bowl). The compositions were applied neat, left to act for 5 minutes and then rinsed away by flushing. The results were as following: Compositions #1 #2 #3 Perceived viscosity reference higher much higher Perceived ease of rinsing reference equal much worse Overall preference reference better worse B) Above compositions #1, #2 and #3 were further evaluated to asses the stability of the persulfate salts in said compositions over long periods of time. The stability test used was an accelerated storage test where the above compositions were left for 3 days at 50° C.
• compositions (% by weight) #1 Sulphuric acid 6 *Curox® 6 C16 trimethyl ammonium methylsulfate 3.5 C8/C10 amine oxides 0.3 Diethylene triamine penta (methylene phosphonic acid) 0.1 **Pigmosol Green 8730 ® 0.01 Water and minors up to 100 pH 0.5 viscosity (m Pa s) 350 * Curox® is one of the commercial names of monopersulfate salts. **Pigmosol Green 8730 is an ⁇ copper phthalocyanine dye of the formula as described herein before where X is Cl and is commercially available from BASF.
• the above mentioned colored acidic thickened aqueous composition provides excellent perceived viscosity, excellent perceived ease of rinsing without compromising peroxy-bleach stability.

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• 1995
  • 1995-05-31 EP EP95870064A patent/EP0745663A1/fr not_active Withdrawn
• 1996
  • 1996-04-19 MX MX9709359A patent/MX9709359A/es unknown
  • 1996-04-19 JP JP08536456A patent/JP2001503072A/ja active Pending
  • 1996-04-19 WO PCT/US1996/005335 patent/WO1996038377A1/fr active Application Filing
  • 1996-04-19 CA CA 2222631 patent/CA2222631A1/fr not_active Abandoned

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