EP0919610B1 - Compositions liquides acides pour enlever le tartre emballées dans un atomiseur - Google Patents

Compositions liquides acides pour enlever le tartre emballées dans un atomiseur Download PDF

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Publication number
EP0919610B1
EP0919610B1 EP97870174A EP97870174A EP0919610B1 EP 0919610 B1 EP0919610 B1 EP 0919610B1 EP 97870174 A EP97870174 A EP 97870174A EP 97870174 A EP97870174 A EP 97870174A EP 0919610 B1 EP0919610 B1 EP 0919610B1
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EP
European Patent Office
Prior art keywords
acid
composition
group
alkyl
composition according
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 - Lifetime
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EP97870174A
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German (de)
English (en)
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EP0919610A1 (fr
Inventor
Luigi Pace, (Nmn)
Barbara Delucca, (Nmn)
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Procter and Gamble Co
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Procter and Gamble Co
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Publication date
Priority to EP97870174A priority Critical patent/EP0919610B1/fr
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to ES97870174T priority patent/ES2241029T3/es
Priority to DE69732777T priority patent/DE69732777T2/de
Priority to AT97870174T priority patent/ATE291073T1/de
Priority to CA002308295A priority patent/CA2308295C/fr
Priority to US09/530,496 priority patent/US6333299B1/en
Priority to EP98956506A priority patent/EP1027417A1/fr
Priority to PCT/US1998/023377 priority patent/WO1999023194A1/fr
Publication of EP0919610A1 publication Critical patent/EP0919610A1/fr
Application granted granted Critical
Publication of EP0919610B1 publication Critical patent/EP0919610B1/fr
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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
    • 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
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic acids-salts thereof
    • 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
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3409—Alkyl -, alkenyl -, cycloalkyl - or terpene sulfates or sulfonates
    • 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
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3418—Toluene -, xylene -, cumene -, benzene - or naphthalene sulfonates or sulfates
    • 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
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776—Heterocyclic compounds, e.g. lactam
    • 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 liquid acidic limescale removal compositions packaged in a spray-type dispenser.
  • Tap water contains a certain amount of solubilized ions which upon water evaporation eventually deposit as salts such as calcium carbonate on hard-surfaces which are often in contact with water, resulting in an anaesthetic aspect of the surfaces. This limescale formation and deposition phenomenon is even more acute in places where water is particularly hard.
  • limescale deposits can be chemically removed with acidic solutions, and a great variety of acidic limescale removal compositions have been described for this purpose.
  • liquid acidic compositions should have, in addition to the ability to effectively remove limescale deposits present on a surface, the ability to provide good shine to the surfaces treated.
  • surface shine is often compromised because, when water comes in contact with hard-surfaces it has the tendency to form droplets on the surface rather than forming a thin film uniformly spread over the surface or to run off the surface. This results, as water evaporates, in precipitation of poorly water soluble inorganic salts such as calcium/magnesium carbonate and/or phosphate salts with consequent formation of watermarks on the surface and, eventually limescale deposits, resulting in an anaesthetic aspect of the surface.
  • poorly water soluble inorganic salts such as calcium/magnesium carbonate and/or phosphate salts
  • the European patent application EP 0 013 585 discloses a light duty, hand dishwashing, liquid composition
  • a light duty, hand dishwashing, liquid composition comprising (a) an anionic and/or nonionic surfactant, (b) a copolymer of N-vinylpyrrolidone and dimethylamino-ethylmethacrylate and (c) an alkali metal salt of casein.
  • the composition possess drainage modification characteristics that produce rapid and uniform drainage of rinse water from washed utensils and apparatus without the disadvantage of spotting and filming.
  • the European patent document EP 0 091 194 discloses a thioxotropic coating composition in the form of a paste or gel for removing rust from metal surfaces comprising (a) 2-15% of an acid, (b) 3-15% of xanthan gum and (c) 10-40% of polyvinylpyrrolidone.
  • the present invention overcomes these problems by formulating liquid acidic compositions comprising an acid, a polysaccharide polymer (0.001%-20%) and a vinylpyrrolidone homopolymer or copolymer (0.001%-20%), said compositions being packaged in a spray type-dispenser.
  • a polysaccharide polymer preferably xanthan gum
  • vinylpyrrolidone homopolymer or copolymer in a liquid acidic composition, reduces or even prevents the formation of limescale deposits on a surface having first been treated with such a composition.
  • less formation of watermarks are observed on a surface having been first treated with the compositions as described herein and then contacted with water, for example, during a rinse operation, thereby providing improved shine to said surface.
  • the shine benefit delivered to a hard-surface treated with the compositions of the present invention persists even after several cycles of rinsing, thus providing long lasting protection against formation of watermarks and/or even limescale deposits on the surface, and hence long lasting shiny surfaces.
  • the house wife will have the advantage to delay the next descaling operation.
  • the shine benefits herein are obtained at very low total levels of both a polysaccharide polymer and a vinylpyrrolidone homopolymer or copolymer, in the acidic compositions of the present invention.
  • liquid acidic compositions of the present invention Another advantage of the liquid acidic compositions of the present invention is that the surfaces treated become smoother (this can be perceived by touching said surfaces). This may also contribute to convey to consumer perception of surface perfectly descaled.
  • compositions according to the present invention deliver the benefits mentioned herein (e.g., reduction or prevention of the formation of watermarks and/or even limescale deposits, resulting in good shine benefit and even long lasting shine benefit), when used to treat a variety of surfaces including metal surfaces such as aluminium, chromed steel, stainless steel, synthetic materials like vinyl, linoleum, glazed or non-glazed ceramic tiles, and/or enamel surfaces.
  • benefits mentioned herein e.g., reduction or prevention of the formation of watermarks and/or even limescale deposits, resulting in good shine benefit and even long lasting shine benefit
  • surfaces including metal surfaces such as aluminium, chromed steel, stainless steel, synthetic materials like vinyl, linoleum, glazed or non-glazed ceramic tiles, and/or enamel surfaces.
  • compositions herein comprise maleic acid together with a second acid typically sulfamic acid. These compositions have been found to be particularly safe to various types of hard-surfaces treated therewith as well as milder to the skin.
  • compositions herein are easily applied to the surface to treat while using a minimum amount of said composition, as compared to applying a liquid composition by directly pouring it onto the surface to treat, instead of spraying it according to the present invention. Also spraying the composition on the surface to treat allows to treat a larger area with a give amount of product versus pouring the liquid composition on the surface to treat. Furthermore, the risk of spillage as well as the tendency of the liquid compositions to be messy when applied onto the surface is reduced when said application is made by using a spray-type dispenser.
  • the liquid acidic compositions of the present invention are applied to the surfaces to treat by the means of a spray-type dispenser while being safe both to the user and to the surfaces treated therewith.
  • the acidic compositions herein may be sprayed onto the surfaces to treat with minimal inhalation by the user of said acidic compositions and thus by avoiding any potential health issue due to the presence of an acid in said compositions.
  • Limescale compositions comprising acids are known in the art.
  • EP-A- 666 305 discloses acidic limescale removing compositions comprising maleic acid and a second acid like sulphamic acid.
  • no liquid acidic compositions as described in the present invention comprising a polysaccharide polymer together with a vinylpyrrolidone homopolymer or copolymer are disclosed therein.
  • EP-A-467 472 discloses a hard-surface liquid composition with anti-static/anti-soiling cationic quaternized polymers.
  • Cationic quaternized polymethacrylate include beta(trialkyl ammonium) ethylmethacrylatesl acrylates.
  • no liquid acidic compositions as described in the present invention comprising a polysaccharide polymer together with a vinylpyrrolidone homopolymer or copolymer are disclosed therein.
  • WO 94/26858 discloses acidic compositions (pH 2-8) comprising a nonionic surfactant and an anionic polymer having an average molecular weight less than 1 000 000 said polymer being free of quaternary nitrogen groups.
  • acidic compositions pH 2-8 comprising a nonionic surfactant and an anionic polymer having an average molecular weight less than 1 000 000 said polymer being free of quaternary nitrogen groups.
  • no liquid acidic compositions as described in the present invention comprising a polysaccharide polymer together with a vinylpyrrolidone homopolymer or copolymer are disclosed therein
  • the present invention relates to a liquid acidic composition suitable for removing limescale-containing stains from a hard-surface, comprising an acid, from 0.001% to 20% by weight of the total composition of a polysaccharide polymer and from 0.001% to 20% by weight of the total composition of a vinylpyrrolidone homopolymer or copolymer, said composition being packaged in a spray type-dispenser.
  • the present invention also encompasses a process of treating hard-surfaces wherein an acidic liquid composition according to the present invention is applied onto said surfaces from a spray-type dispenser, then left to act onto said surfaces and then removed by rinsing.
  • liquid acidic compositions are liquid acidic compositions:
  • compositions of the present invention are acidic compositions. Accordingly, the compositions of the present invention are typically formulated at a pH below 7, preferably below 5, more preferably below 4, more preferably at a pH between 0 and 3, even more preferably at a pH between 0.1 and 2.5, even more preferably between 0.1 and 2, and most preferably at a pH between 0.3 and 1.5.
  • the liquid compositions according to the present invention are preferably aqueous compositions. Therefore, they typically comprise from 50% to 98% by weight of the total composition of water, preferably from 60% to 95% and more preferably from 70% to 90%.
  • compositions according to the present invention are designed for removing limescale deposits.
  • they comprise as a first essential ingredient an acid or a mixture thereof.
  • the acids to be used herein may be any inorganic or organic acid well-known to those skilled in the art, or a mixture thereof.
  • Suitable acids for use herein include maleic acid, citric acid, adipic acid, sulfamic acid, phosphoric acid, nitric acid, malic acid, sulfonic acid, sulphuric acid or their salts or mixtures thereof.
  • such acids can be used in their acidic form or in the form of their salts (mono-, di-, tri- salts) and in all their anhydrous and hydrated forms, or mixtures thereof.
  • Such acids may typically be used in the form of their alkali metal salts (e.g. sodium salt, potassium salt, and then like) or their alkali hydrogen acid salts.
  • Said compositions comprise from 0.1% to 70% by weight of the total composition of an acid or a mixture thereof.
  • compositions of the present invention comprise at least maleic acid.
  • the compositions according to the present invention comprise from 0.1% to 45% by weight of the total composition of maleic acid, preferably from 1% to 25% and more preferably from 3% to 20%. This percentage is calculated on the basis of the molecular weight of the acid form, but maleic anhydride is equally convenient for use in the compositions according to the present invention. Indeed, maleic anhydride is generally cheaper and it is transformed into the acid form when incorporated in an aqueous medium.
  • maleic acid is used alone as the acid of the acidic compositions of the present invention.
  • a second acid is added on top of said maleic acid.
  • Said second acid is desired to strengthen the limescale removal performance.
  • the second acids to be used herein which are particularly efficient to remove limescale on many surfaces, have their first pKa not exceeding 5, more preferably not exceeding 3, and most preferably not exceeding 2.
  • said acids can be organic or inorganic acids.
  • sulphamic acid particularly suitable for use herein is sulphamic acid.
  • Sulphamic acid may be added in the compositions according to the present invention in its acid form or as an alkali metal salts thereof.
  • sulphamic acid may be added for example as sulphamate.
  • Sulphamic acid is for example commercially available under its chemical name from Albright & Wilson or Nissan chemicals. Indeed, it has been found that the addition of sulphamic acid on top of maleic acid in the compositions of the present invention improves the skin mildness of said compositions. Indeed, less skin irritation is perceived by the user when its skin comes into contact with these compositions as compared to the same compositions but without sulphamic acid.
  • Suitable second acids are sulphonic acid derivatives including alkyl sulphonic acids and aryl sulphonic acids.
  • Suitable aryl sulphonic acids for use herein are according to the formula : wherein R 1 , R 2 , R 3 , R 4 and R 5 are each H or SO 3 H, or linear or branched C 1 -C 4 alkyl chain; or mixtures thereof.
  • Preferred acids having a first pKa not exceeding 5 for use herein are sulphamic acid, sulphuric acid, aryl sulphonic acids, alkyl sulphonic acids, citric acid, nitric acid, phosphoric acid, hydrochloric acid or mixtures thereof, more preferred are sulphamic acid, citric acid or mixtures thereof and highly preferred is sulphamic acid.
  • compositions of the present invention comprise from 0.1% to 25% by weight of the total composition of a second acid which has a first pKa not exceeding 5, or mixtures thereof, preferably from 0.1% to 20%, more preferably from 0.1% to 10% and most preferably from 0.1% to 7%.
  • the liquid acidic compositions of the present invention comprise as a second essential ingredient a vinylpyrrolidone homopolymer or copolymer, or a mixture thereof at a level of from 0.001% to 20% by weight of the total composition.
  • the compositions of the present invention comprise from 0.01% to 5% by weight of the total composition of a vinylpyrrolidone homopolymer or copolymer, or a mixture thereof, more preferably from 0.01% to 3% and most preferably from 0.01% to 1%.
  • Suitable vinylpyrrolidone homopolymers for use herein are homopolymers of N-vinylpyrrolidone having the following repeating monomer: wherein n (degree of polymerisation) is an integer of from 10 to 1,000,000, preferably from 20 to 100,000, and more preferably from 20 to 10,000.
  • suitable vinylpyrrolidone homopolymers for use herein have an average molecular weight of from 1,000 to 100,000,000, preferably from 2,000 to 10,000,000, more preferably from 5,000 to 1,000,000, and most preferably from 50,000 to 500,000.
  • Suitable vinylpyrrolidone homopolymers are commercially available from ISP Corporation, New York, NY and Montreal, Canada under the product names PVP K-15® (viscosity molecular weight of 10,000), PVP K-30® (average molecular weight of 40,000), PVP K-60® (average molecular weight of 160,000), and PVP K-90® (average molecular weight of 360,000).
  • vinylpyrrolidone homopolymers which are commercially available from BASF Cooperation include Sokalan HP 165®, Sokalan HP 12®, Luviskol K30®, Luviskol K60®, Luviskol K80®, Luviskol K90®; vinylpyrrolidone homopolymers known to persons skilled in the detergent field (see for example EP-A-262,897 and EP-A-256,696).
  • Suitable copolymers of vinylpyrrolidone for use herein include copolymers of N-vinylpyrrolidone and alkylenically unsaturated monomers or mixtures thereof.
  • the alkylenically unsaturated monomers of the copolymers herein include unsaturated dicarboxylic acids such as maleic acid, chloromaleic acid, fumaric acid, itaconic acid, citraconic acid, phenylmaleic acid, aconitic acid, acrylic acid, N-vinylimidazole and vinyl acetate. Any of the anhydrides of the unsaturated acids may be employed, for example acrylate, methacrylate. Aromatic monomers like styrene, sulphonated styrene, alpha-methyl styrene, vinyl toluene, t-butyl styrene and similar well known monomers may be used.
  • the molecular weight of the copolymer of vinylpyrrolidone is not especially critical so long as the copolymer is water-soluble, has some surface activity and is adsorbed to the hard-surface from the liquid composition comprising it in such a manner as to increase the hydrophilicity of the surface.
  • the preferred copolymers of N-vinylpyrrolidone and alkylenically unsaturated monomers or mixtures thereof have a molecular weight of between 1,000 and 1,000,000, preferably between 10,000 and 500,000 and more preferably between 10,000 and 200,000.
  • N-vinylimidazole N-vinylpyrrolidone polymers for use herein have an average molecular weight range from 5,000 to 1,000,000, preferably from 5,000 to 500,000, and more preferably from 10,000 to 200,000.
  • the average molecular weight range was determined by light scattering as described in Barth H.G. and Mays J.W. Chemical Analysis Vol 113,"Modem Methods of Polymer Characterization".
  • Such copolymers of N-vinylpyrrolidone and alkylenically unsaturated monomers like PVP/vinyl acetate copolymers are commercially available under the trade name Luviskol® series from BASF.
  • copolymers of vinylpyrrolidone for use in the compositions of the present invention also include quaternized or unquaternized vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymers.
  • the polymers can be prepared
  • the preferred quaternized or unquaternized vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymers for use herein have a molecular weight of between 1,000 and 1,000,000, preferably between 10,000 and 500,000 and more preferably between 10,000 and 100,000.
  • Such vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymers are commercially available under the name copolymer 845®, Gafquat 734®, or Gafquat 755® from ISP Corporation, New York, NY and Montreal, Canada or from BASF under the tradename Luviquat®.
  • Preferred second essential ingredient for use herein are the vinylpyrrolidone homopolymers.
  • the liquid acidic compositions of the present invention comprise as a third essential ingredient a polysaccharide polymer or a mixture thereof at a level of from 0.001% to 20% by weight of the total composition.
  • the compositions of the present invention comprise from 0.01% to 10% by weight of the total composition of a polysaccharide polymer or a mixture thereof, more preferably from 0.01% to 5% and most preferably from 0.01% to 2%.
  • Suitable polysaccharide polymers for use herein include substituted cellulose materials like carboxymethylcellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxymethyl cellulose, succinoglycan and naturally occurring polysaccharide polymers like xanthan gum, guar gum, locust bean gum, tragacanth gum or derivatives thereof, or mixtures thereof.
  • xanthan gum and derivatives thereof are xanthan gum and derivatives thereof.
  • Xanthan gum and derivatives thereof may be commercially available for instance from Kelco under the trade name Keltrol RD®, Kelzan S® or Kelzan T®.
  • Other suitable Xanthan gum are commercially available by Rhone Poulenc under the trade name Rhodopol T® and Rhodigel X747®.
  • Succinoglycan gum for use herein is commercially available by Rhone Poulenc under the trade name Rheozan ®.
  • the polysaccharide polymers herein may act as a thickening agent, accordingly the liquid acidic compositions herein have a viscosity of from 1 cps to 1500 cps, preferably from 20 cps to 800 cps and more preferably from 50 cps to 600 cps, when measured with a Carri-med rheometer CLS 100® at 5 N/m 2 at 20°C.
  • polysaccharide polymers preferably xanthan gum or derivatives thereof, and vinylpyrrolidone homopolymer or copolymers, are advantageously physically and chemically stable in the acidic conditions of the compositions herein, this even at very low pH typically below 1.5.
  • the acidic liquid compositions herein are chemically stable, i.e., there is virtually no chemical changes of the different ingredients due to reaction between different ingredients, and physically stable, i.e., that no phase separation occurs when stored in rapid aging test (RAT) at 50 °C for 10 days.
  • RAT rapid aging test
  • polysaccharide polymers preferably xanthan gum or derivatives thereof, and vinylpyrrolidone homopolymers or copolymers described herein, when added into a liquid acidic composition packaged in spray-type dispenser deliver improved shine while not compromising the limescale removal performance of said composition.
  • the present invention is based on the finding that the polysaccharide polymers and vinylpyrrolidone homopolymers or copolymers present in the compositions of the present invention are able to modify the surface by depositing on the surface itself treated therewith.
  • hard surfaces typically found in a household are neither highly hydrophobic nor highly hydrophilic. This means that, when water gets in contact with hard-surfaces, its spreading, which is controlled by the interfacial energy (i.e., solid/liquid surface tension), is very limited. Indeed, it has been observed that the most stable configuration for the water is grouping in spherical droplets rather than forming a thin film uniformly spread over the surface or than running off the surface. Then, as water droplets evaporate, their content of salt progressively becomes higher and higher so that carbonate salts eventually precipitate resulting in watermarks or even limescale deposits. The end result is a reduction of surface shine.
  • the polysaccharide polymers and vinylpyrrolidone homopolymers or copolymers have not only the ability to adhere on a surface treated with the liquid acidic compositions of the present invention comprising the same and being packaged in a spray-type dispenser, but to still remain adhered on the surface even after several cycles of rinsing (e.g., when water comes onto this surface later on for example in a sink during daily household operation), thus providing long lasting protection against formation of watermarks and/or deposition of limescale deposits, hence, long lasting shiny surfaces.
  • polysaccharide polymers, and vinylpyrrolidone homopolymers or copolymers also have the ability to form a film on the surface of the user skin thereby further contributing to the skin mildness characteristics delivered due to the presence of sulphamic acid on top of maleic acid otherwise perceived to be more irritant to skin, this in the preferred embodiment of the present invention where indeed sulphamic acid is used on top of maleic acid.
  • An additional advantage related to the use of the polysaccharide polymers, and vinylpyrrolidone homopolymers or copolymers in the acidic compositions herein, is that as they adhere on hard surface making them more hydrophilic, the surfaces themselves become smoother (this can be perceived by touching said surfaces) and this contribute to convey perception of surface perfectly descaled.
  • the liquid acidic compositions according to the present invention comprise from 0.002% to 5% by weight of the total composition of a polysaccharide polymer or mixture thereof together with a vinylpyrrolidone homopolymer and/or copolymer, preferably from 0.005 % to 2%, more preferably from 0.01% to 2% and most preferably from 0.01% to 1%.
  • liquid acidic compositions according to the present invention are packaged in a spray-type dispenser.
  • spray dispenser any spray dispenser known to those skilled in the art including trigger spray dispensers or pump spray dispensers.
  • Suitable spray-type dispensers to be used according to the present invention include manually operated foam trigger-type dispensers sold for example by Specialty Packaging Products, Inc. or Continental Sprayers, Inc. These types of dispensers are disclosed, for instance, in US-4,701,311 to Dunnining et al. and US-4,646,973 and US-4,538,745 both to Focarracci. Particularly preferred to be used herein are spray-type dispensers such as T 8500® or T 8900® commercially available from Continental Spray International or T 8100® commercially available from Canyon, Northen Ireland. In such a dispenser the liquid composition is divided in fine liquid droplets resulting in a spray that is directed onto the surface to be treated.
  • the composition contained in the body of said dispenser is directed through the spray-type dispenser head via energy communicated to a pumping mechanism by the user as said user activates said pumping mechanism. More particularly, in said spray-type dispenser head the composition is forced against an obstacle, e.g. a grid or a cone or the like, thereby providing shocks to help atomise the liquid composition, i.e. to help the formation of liquid droplets.
  • an obstacle e.g. a grid or a cone or the like
  • Preferred foam trigger-type dispensers for use herein have a cone as impingement zone.
  • the two most important dimensions determining the foam character, size and distribution of pattern are orifice diameter and spinner channel width. The interaction of these two factors also determine amount of flow and velocity of that flow trough the nozzle.
  • Preferred foam trigger spray type dispenser for use herein is the model known as T8900® commercially available by CSI.
  • This foam spray-type dispenser has a piston pump with an impingement tube that contacts the spray cone causing turbulence and creating foam.
  • this foam spray dispenser has a orifice diameter of 0.028" (0.028 inches) and a two spinner channels 0.0425" (0.0425 inches) width.
  • Such a commercially available spray may also undergone modifications to improve the spray pattern and reduced the misting effect.
  • preferred configurations are those with smaller spinner channels and larger orifices that will result in a foam spray with less misting.
  • More preferred configuration has a diameter orifice of 0.030" or 0.032" width and spinner channels of 0.0425" or 0.030" width.
  • Most preferred foam spray-type dispenser has 0.030" orifice and 0.0425" spinner channels.
  • the foam trigger spray dispensers mentioned in the present invention have preferably a bayonet closure instead of a threaded closure, thereby providing a child resistant device.
  • the bayonet package (having two or four lugs) allows the spray-type dispenser to be fastened to the bottle in a safer way avoiding ease of opening by children and messiness in use.
  • An advantage of the present invention is that the acidic liquid compositions of the present invention may be applied uniformly to a relatively large area of a surface to be treated via a spray-type dispenser, thereby ensuring excellent limescale removal performance while being particularly safe to the surface treated and the user.
  • liquid acidic compositions of the present invention may be easily dispensed onto the surfaces to treat.
  • a further advantage according to the present invention is that the surface treatment is carried out in an economical way, i.e. no more product that what is really necessary is used.
  • compositions according to the present invention may further comprise a variety of other ingredients including surfactants, colorants, bactericides, thickeners, dyes, chelants, pigments, solvents, stabilizers, perfumes, corrosion inhibitors and the like.
  • a highly preferred optional ingredient suitable for use in the compositions of the present invention is a surfactant or a mixture thereof.
  • Surfactants are desired herein as they contribute to the cleaning benefits of the limescale removal compositions of the present invention. Indeed, the presence of a surfactant contributes to the greasy soap scum cleaning of the compositions herein. More generally, the presence of a surfactant in the liquid acidic compositions according to the present invention allows to lower the surface tension and to improve the wettability of the surfaces being treated with the liquid acidic compositions of the present invention. The presence of a surfactant or a mixture thereof in the liquid acidic compositions of the present invention helps to solubilize the soils.
  • compositions according to the present invention may comprise a surfactant or a mixture thereof.
  • the compositions according to the present invention may comprise up to 40% by weight of the total composition of a surfactant or a mixture thereof, more preferably from 0.05% to 15%, even more preferably from 0.1% to 10%, and most preferably from 0.1% to 5%.
  • All types of surfactants may be used in the present invention including nonionic, anionic, cationic, zwitterionic or amphoteric surfactants. It is also possible to use mixtures of such surfactants without departing from the spirit of the present invention.
  • Highly preferred surfactants for use herein are zwitterionic surfactants. Indeed, they have the ability when added in the acidic compositions of the present invention to maintain the limescale removal performance of the acidic system (i.e. similar limescale removing performance as compared to the same acidic compositions but without any surfactant), while providing excellent grease soap scum cleaning ability to the compositions of the present invention.
  • Suitable zwitterionic surfactants for use herein contain both basic and acidic groups which form an inner salt giving both cationic and anionic hydrophilic groups on the same molecule at a relatively wide range of pH's.
  • the typical cationic group is a quaternary ammonium group, although other positively charged groups like phosphonium, imidazolium and sulfonium groups can be used.
  • the typical anionic hydrophilic groups are carboxylates and sulfonates, although other groups like sulfates, phosphonates, and the like can be used.
  • a generic formula for preferred zwitterionic surfactants for use herein is: R 1 -N + (R 2 )(R 3 )R 4 X - wherein R 1 is a hydrophobic group; R 2 is hydrogen, C 1 -C 6 alkyl, hydroxy alkyl or other substituted C 1 -C 6 alkyl group; R 3 is C 1 -C 6 alkyl, hydroxy alkyl or other substituted C 1 -C 6 alkyl group which can also be joined to R 2 to form ring structures with the N, or a C 1 -C 6 carboxylic acid group or a C 1 -C 6 sulfonate group; R 4 is a moiety joining the cationic nitrogen atom to the hydrophilic group and is typically an alkylene, hydroxy alkylene, or polyalkoxy group containing from 1 to 10 carbon atoms; and X is the hydrophilic group which is a carboxylate
  • Preferred hydrophobic groups R are aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted hydrocarbon chains that can contain linking groups such as amido groups, ester groups. More preferred R 1 is an alkyl group containing from 1 to 24 carbon atoms, preferably from 8 to 18, and more preferably from 10 to 16. These simple alkyl groups are preferred for cost and stability reasons. However, the hydrophobic group R 1 can also be an amido radical of the formula R a -C(O)-NR b -(C(R c ) 2 ) m .
  • R a is an aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted hydrocarbon chain containing from 8 up to 20 carbon atoms, preferably an alkyl group containing from 8 up to 20 carbon atoms, preferably up to 18, more preferably up to 16,
  • R b is either a hydrogen a short chain alkyl or substituted alkyl containing from 1 to 4 carbon atoms, preferably a group selected from the group consisting of methyl, ethyl, propyl, hydroxy substituted ethyl or propyl and mixtures thereof, more preferably methyl or hydrogen
  • R c is selected from the group consisting of hydrogen and hydroxy groups
  • m is from 1 to 4, preferably from 2 to 3, more preferably 3, with no more than one hydroxy group in any (C(R c ) 2 ) moiety.
  • Preferred R 2 is hydrogen, or an alkyl or substituted alkyl containing from 1 to 4 carbon atoms, preferably a group selected from the group consisting of methyl, ethyl, propyl, hydroxy substituted ethyl or propyl and mixtures thereof, more preferably methyl.
  • Preferred R 3 is a C 1 -C 4 carboxylic acid group, a C1-C4 sulfonate group, or an alkyl or substituted alkyl containing from 1 to 4 carbon atoms, preferably a group selected from the group consisting of methyl, ethyl, propyl, hydroxy substituted ethyl or propyl and mixtures thereof, more preferably methyl.
  • Preferred R 4 is (CH2) n wherein n is an integer from 1 to 10, preferably from 1 to 6, more preferably is from 1 to 3.
  • betaine/sulphobetaine Some common examples of betaine/sulphobetaine are described in U.S. Pat. Nos. 2,082,275, 2,702,279 and 2,255,082.
  • alkyldimethyl betaines examples include coconut-dimethyl betaine, lauryl dimethyl betaine, decyl dimethyl betaine, 2-(N-decyl-N, N-dimethyl-ammonia)acetate, 2-(N-coco N, N-dimethylammonio) acetate, myristyl dimethyl betaine, palmityl dimethyl betaine, cetyl dimethyl betaine, stearyl dimethyl betaine.
  • coconut dimethyl betaine is commercially available from Seppic under the trade name of Amonyl 265®.
  • Lauryl betaine is commercially available from Albright & Wilson under the trade name Empigen BB/L®.
  • betaine is Lauryl-immino-dipropionate commercially available from Rhone-Poulenc under the trade name Mirataine H2C-HA ®.
  • Particularly preferred zwitterionic surfactants for use in the acidic compositions of the present invention are the sulfobetaine surfactants as they deliver optimum limescale removal benefits and soap scum cleaning benefits.
  • sulfobetaine surfactants include tallow bis(hydroxyethyl) sulphobetaine, cocoamido propyl hydroxy sulfobetaines which are commercially available from Rhone Poulenc and Witco, under the trade name of Mirataine CBS® and Rewoteric AM CAS 15® respectively.
  • amidobetaines/amidosulfobetaine include cocoamidoethylbetaine, cocoamidopropyl betaine or C10-C14 fatty acylamidopropylene(hydropropylene)sulfobetaine.
  • C10-C14 fatty acylamidopropylene(hydroprcpylene)sulfobetaine is commerdatly available from Sherex Company under the trade name "Varion CAS® sulfobetaine".
  • Suitable amine oxides for use herein are according to the following formula R 1 R 2 R 3 NO wherein each of R1, R2 and R3 is independently a saturated or unsaturated, substituted or unsubstituted, linear or branched alkyl group containing from 1 to 30 carbon atoms, and preferably from 1 to 20 carbon atoms.
  • Particutarly preferred amine oxides to be used according to the present invention are amine oxides having the following formula R 1 R 2 R 3 NO wherein R1 is a saturated or unsaturated, substituted or unsubstituted, linear or branched alkyl group containing from 1 to 30 carbon atoms, preferably from 8 to 20 carbon atoms, more preferably from 6 to 16, most preferably from 8 to 14, and wherein R2 and R3 are independentty substituted or unsubstituted, linear or branched alkyl groups containing from 1 to 4 carbon atoms, preferably from 1 to 3 carbon atoms, and more preferably are methyl groups, or mixtures thereof.
  • Suitable amine oxides for use herein are for instance coconut dimethyl amine oxides, C12-C16 dimethyl amine oxides. Said amine oxides may be commercially available from Hoechst, Stephan, AKZO (under the trade name Aromox®) or FINA (under the trade name Radiamox®).
  • Suitable amines for use herein are according to the following formula RR'R"N wherein R is a saturated or unsaturated, substituted or unsubstituted, linear or branched alkyl groups containing from 1 to 30 carbon atoms, and preferably from 1 to 20 carbon atoms and wherein R' and R" are independently saturated or unsaturated, substituted or unsubstituted, linear or branched alkyl groups containing from 1 to 30 carbon atoms or hydrogen.
  • Particularly preferred amines to be used according to the present invention are amines having the following formula RR'R"N wherein R is a saturated or unsaturated, linear or branched alkyl group containing from 1 to 30 carbon atoms, preferably from 8 to 20 carbon atoms, more preferably from 6 to 16, most preferably from 8 to 14, and wherein R' and R" are independently substituted or unsubstituted, linear or branched alkyl groups containing from 1 to 4 carbon atoms, preferably from 1 to 3 carbon atoms, and more preferably are methyl groups, or mixtures thereof.
  • Suitable amines for use herein are for instance C12 dimethyl amine, coconut dimethyl amine, C12-C16 dimethyl amine. Said amines may be commercially available from Hoechst under the trade name Genamin®, AKZO under the trade name Aromox® or Fina under the trade name Radiamine®.
  • Suitable quaternary ammonium surfactants for use herein are according to the formula R 1 R 2 R 3 R 4 N + X - .
  • X is a counteranion such as halogen, methyl sulphate, methyl sulphonate, or hydroxide
  • R 1 is a saturated or unsaturated, substituted or unsubstituted, linear or branched alkyl group containing from 1 to 30 carbon atoms, preferably from 12 to 20, more preferably from 8 to 20
  • R 2 , R 3 and R 4 are independently hydrogen, or saturated or unsaturated, substituted or unsubstituted, linear or branched alkyl groups containing from 1 to 4 carbon atoms, preferably from 1 to 3 and more preferably methyl.
  • R 1 is a C 10 -C 18 hydrocarbon chain, most preferably C 12 , C 14 , or C 16 , and R 2 , R 3 and R 4 are all three methyl, and X is halogen, preferably bromide or chloride, most preferably bromide.
  • quaternary ammonium surfactants are myristyl trimethylammonium methyl sulphate, cetyl trimethylammonium methyl sulphate, lauryl trimethyl ammonium bromide, stearyl trimethyl ammonium bromide (STAB), cetyl trimethyl ammonium bromide (CTAB) and myristyl trimethyl ammonium bromide (MTAB). Highly preferred herein are lauryl trimethyl ammonium salts.
  • Such trimethyl quaternary ammonium surfactants may be commercially available from Hoechst, or from Albright & Wilson under the trade name Empigen CM®.
  • the surfactant used in the acidic compositions of the present invention is a surfactant system comprising a zwitterionic surfactant with a second surfactant, e.g. an amine oxide and/or amine and/or a quaternary ammonium surfactant as described herein at a weight ratio of the zwitterionic surfactant to the second surfactant of at least 1:1, preferably at least 2:1.
  • a surfactant system provides to the acidic compositions according to the present invention both optimum limescale removing performance (i.e, comparable to the limescale removing performance of the same compositions without any surfactant) as well as optimum greasy soap scum cleaning performance.
  • Suitable nonionic surfactants for use herein are alkoxylated alcohol nonionic surfactants which can be readily made by condensation processes which are well-known in the art. However, a great variety of such alkoxylated alcohols, especially ethoxylated and/or propoxylated alcohols is also conveniently commercially available. Surfactants catalogs are available which list a number of surfactants, including nonionics.
  • preferred alkoxylated alcohols for use herein are nonionic surfactants according to the formula RO(E)e(P)pH where R is a hydrocarbon chain of from 2 to 24 carbon atoms, E is ethylene oxide and P is propylene oxide, and e and p which represent the average degree of, respectively ethoxylation and propoxylation, are of from 0 to 24.
  • the hydrophobic moiety of the nonionic compound can be a primary or secondary, straight or branched alcohol having from 8 to 24 carbon atoms.
  • Preferred nonionic surfactants for use in the compositions according to the invention are the condensation products of ethylene oxide with alcohols having a straight alkyl chain, having from 6 to 22 carbon atoms, wherein the degree of ethoxylation is from 1 to 15, preferably from 5 to 12.
  • Such suitable nonionic surfactants are commercially available from Shell, for instance, under the trade name Dobanol® or from BASF under the trade name Lutensol®. These nonionics are preferred because they have been found to allow the formulation of a stable product without requiring the addition of stabilisers or hydrotopes.
  • Suitable alkyl sulphonates for use herein include water-soluble salts or acids of the formula RSO 3 M wherein R is a C 6 -C 20 linear or branched, saturated or unsaturated alkyl group, preferably a C 12 -C 18 alkyl group and more preferably a C 14 -C 16 alkyl group, and M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium), or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof).
  • R is a C 6 -C 20 linear or branched
  • secondary C6-C20 alkyl or C6-C20 alkyl aryl sulphonates it is meant herein that in the formula as defined above, the SO3M or aryl-SO3M group is linked to a carbon atom of the alkyl chain being placed between two other carbons of the said alkyl chain (secondary carbon atom).
  • C14-C16 alkyl sulphonate is Hostapur® SAS available from Hoechst.
  • An example of commercially available alkyl aryl sulphonate is Lauryl aryl sulphonate from Su.Ma.
  • Particularly preferred alkyl aryl sulphonates are alkyl benzene sulphonates commercially available under trade name Nansa® available from Albright&Wilson.
  • Suitable alkyl sulphate surfactants for use herein are according to the formula R 1 SO 4 M wherein R 1 represents a hydrocarbon group selected from the group consisting of straight or branched alkyl radicals containing from 6 to 20 carbon atoms and alkyl phenyl radicals containing from 6 to 15 carbon atoms in the alkyl group.
  • M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium, calcium, magnesium and the like) or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
  • alkali metal cation e.g., sodium, potassium, lithium, calcium, magnesium and the like
  • ammonium or substituted ammonium e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and
  • Suitable alkyl alkoxylated sulphate surfactants for use herein are according to the formula RO(A) m SO 3 M wherein R is an unsubstituted C 6 -C 20 alkyl or hydroxyalkyl group having a C 6 -C 20 alkyl component, preferably a C 12 -C 20 alkyl or hydroxyalkyl, more preferably C 12 -C 18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation.
  • R is an unsubstituted C 6 -C 20 alkyl or hydroxyalkyl group having a C 6 -C 20 alkyl component, preferably a C
  • Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
  • Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium and quaternary ammonium cations, such as tetramethyl-ammonium, dimethyl piperdinium and cations derived from alkanolamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like.
  • Exemplary surfactants are C 12 -C 18 alkyl polyethoxylate (1.0) sulfate, C 12 -C 18 E(1.0)M), C 12 -C 18 alkyl polyethoxylate (2.25) sulfate, C 12 -C 18 E(2.25)M), C 12 -C 18 alkyl polyethoxylate (3.0) sulfate C 12 -C 18 E(3.0), and C 12 -C 18 alkyl polyethoxylate (4.0) sulfate C 12 -C 18 E(4.0)M). wherein M is conveniently selected from sodium and potassium.
  • Suitable C 6 -C 20 alkyl alkoxylated linear or branched diphenyl oxide disulphonate surfactants for use herein are according to the following formula: wherein R is a C 6 -C 20 linear or branched, saturated or unsaturated alkyl group, preferably a C 12 -C 18 alkyl group and more preferably a C 14 -C 16 alkyl group, and X+ is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium, calcium, magnesium and the like).
  • R is a C 6 -C 20 linear or branched, saturated or unsaturated alkyl group, preferably a C 12 -C 18 alkyl group and more preferably a C 14 -C 16 alkyl group
  • X+ is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium, calcium, magnesium and the like).
  • Particularly suitable C 6 -C 20 alkyl alkoxylated linear or branched diphenyl oxide disulphonate surfactants to be used herein are the C12 branched di phenyl oxide disulphonic acid and C16 linear di phenyl oxide disulphonate sodium salt respectively commercially available by DOW under the trade name Dowfax 2A1® and Dowfax 8390®.
  • anionic surfactants useful herein include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C 8 -C 24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No.
  • alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl ester sulfonates such as C 14-16 methyl ester sulfonates; acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C 12 -C 18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C 6 -C 14 diesters), acyl sarcosinates, sulfates of alkylpolysaccharides such as the sulfates
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23.
  • Preferred anionic surfactants herein include the primary and secondary C 6 -C 20 alkyl suplonates and the primary and secondary C 6 -C 20 alkyl aryl sulphonates or a mixture thereof.
  • the liquid compositions according to the present invention may be coloured. Accordingly, they may comprise a dye or a mixture thereof.
  • Suitable dyes for use herein are acid-stable dyes. By “acid-stable”, it is meant herein a compound which is chemically and physically stable in the acidic environment of the compositions herein.
  • Suitable dyes for use herein include ⁇ or ⁇ metal phthalocyanines and/or trimethyl methane dyes.
  • the ⁇ or ⁇ metal phthalocyanine dyes suitable to be used in the compositions of the present invention are lightfast organic pigments with four isoindole groups, (C 6 H 4 )C 2 N, linked by four nitrogen atoms to form a conjugated chain.
  • Their general structure is the following: where the 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.
  • trimethyl methane dyes are commercially available from Hoescht under the name Vitasyn® or from BASF under the name Acid Blue® .
  • Suitable dyes for use herein are polymeric liquid colours such as the liquid polymer-blue supplied by Milliken Company under the name Liquitint® Blue 65, Liquitint® Patent Blue and Liquitint® Bright Blue.
  • compositions of the present invention may comprise up to 0.2% by weight of the total composition of a dye or a mixture thereof, preferably from 0.0001% to 0.015% and more preferably from 0.001% to 0.010%.
  • compositions of the present invention may comprise a radical scavenger or a mixture thereof.
  • Suitable radical scavengers for use herein include the well-known substituted mono and dihydroxy benzenes and their analogs, alkyl and aryl carboxylates and mixtures thereof.
  • Preferred such radical scavengers for use herein include di-tert-butyl hydroxy toluene (BHT), hydroquinone, di-tert-butyl hydroquinone, mono-tert-butyl hydroquinone, tert-butyl-hydroxy anysole, benzoic acid, toluic acid, catechol, t-butyl catechol, benzylamine, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl) butane, n-propyl-gallate or mixtures thereof and highly preferred is di-tert-butyl hydroxy toluene.
  • Such radical scavengers like N-propyl-gallate may be commercially available from Nipa Laboratories under the trade name Nip
  • Radical scavengers when used are typically present herein in amounts up to 10% by weight of the total composition and preferably from 0.001% to 0.5% by weight.
  • radical scavengers may contribute to the chemical stability of the acidic compositions of the present invention.
  • compositions according to the present invention are particularly suitable for treating hard-surfaces soiled by limescale-containing stains.
  • limescale-containing stains it is meant herein any pure limescale stains, i.e., any stains composed essentially of mineral deposits as well as limescale-containing stains typically found, for example, in a kitchen or in a bathroom, i.e., stains which contain not only mineral deposits like calcium and/or magnesium carbonate but also soap scum (e.g., calcium stearate) and other grease (e.g. body grease).
  • compositions of the present invention exhibit excellent limescale removing performance when used to treat any types of surfaces soiled by limescale-containing stains comprising not only pure limescale deposits but also at least 10% by weight of the total stain of organic deposits like soap scum and grease, preferably more than 30%.
  • surfaces can be found in bathrooms, kitchens, but also in appliances including large appliances such as automatic dish washers and/or washing machines.
  • the present invention encompasses a process of treating hard-surfaces soiled by limescale-containing stains wherein an aqueous acidic liquid composition according to the present invention is applied onto said surfaces from a spray-type dispenser, then left to act onto said surfaces and then removed by rinsing.
  • treating indudes removing limescale deposits while being safe to the surfaces treated and optionally cleaning greasy soap scum stains especially when surfactants are present.
  • the limescale removal capacity of a composition according to the present invention may be evaluated spraying the composition on encrusted ceramic tiles prepared using the auto dish washing machine.
  • Black glazed ceramic tiles typically 20 cm x 20 cm
  • Each cycle is performed using 15 g of Sodium Carbonate (instead of the detergent) at temperature of 80 °C and rinsing water at 70 °C.
  • the resulting tiles will have an homogeneous thin layer of limescale (calcium carbonate precipitated during the washing cycle).
  • two vertical encrusted tiles are sprayed three times (equivalent at about 5 g of product) with a composition according to the present invention and a reference composition, e.g.
  • compositions are sprayed using the T8900® foamer spray dispenser (having orifice diameter modified at 0.030" width and spinner channels 0.0425" width). Surfaces are rinsed after 30 seconds with water (until all residues of product are removed) and then left to dry. After the surfaces treated with the compositions according to the present invention and those treated with the reference composition get dried, they are compared side by side and evaluated by visual grading to evaluate limescale removal difference.
  • Performance evaluation may be generally done by applying the Panel Score Unit (PSU).
  • PSU Panel Score Unit
  • enamel white tiles typically 24 cm 4 cm
  • typical greasy soap scum soils mainly based on calcium stearate and artificial body soils commercially available (e.g. 0.3 grams with a sprayer).
  • the soiled tiles are then dried in an oven at a temperature of 140 °C for 30 minutes and then aged overnight at room temperature (around 15°C-20°C).
  • the soiled tiles are cleaned using 3 ml of the liquid acidic composition of the present invention poured directly on a Spontex® sponge.
  • the ability of the composition to remove greasy soap scum is measured through the number of strokes needed to perfectly clean the surface. The lower the number of strokes, the higher the greasy soap scum cleaning ability of the composition.
  • Obtaining a good shine end result results from a good spreading of a liquid composition over the surface when the surface is treated therewith and from the reduced formation of watermarks and reduced precipitation of poorly water soluble salts when water evaporates.
  • the ability of a composition to provide "shine" to the surface refers to the composition's ability to leave no watermarks after evaporation of water. This can be evaluated by human visual grading.
  • the test method as mentioned above may be carried out, but the rinsing and drying cycle are repeated several times. Each time, after both the surfaces get dried they are compared side by side and evaluated by visual grading to see shine difference. Evaluation is generally done by applying the Panel Score Unit (PSU).
  • PSU Panel Score Unit
  • compositions were made comprising the listed ingredients in the listed proportions (weight %).
  • Ingredients (% by weight) I II III IV V VI Maleic acid 10 10 10 10 6 10 Sulphamic acid 2 2 - - 2 2 Citric acid - - 2 - - 2 Dobanol ® 91-8 2.2 - - 2.0 2.2 Mirataine CBS® - 2 2 - - 2.0 Aromox ® C12-C14 - - - - - 0.5 Kelzan T ® 0.35 0.35 0.30 0.40 0.35 0.30 PVP ® K60 0.05 0.05 0.05 0.03 0.05 0.04 Waters & Minors up to 100 Ingredients : (% by weight) VII VIII IX X XI XII Maleic acid 8 10 12 10 12 12 Sulphamic acid 2 2 2 - - - Citric acid - 1 - 2 2 - Dobanol 91-10® - 3 - 1 4 - Rewoteric AM CAS 15® 2
  • compositions were packaged in a spray-type dispenser, for example the model T8900® (Continental Spray International) modified with orifice diameter 0.030" (0.030 inches) width and spinner channels 0.0425" (0.0425 inches) width. They all exhibit excellent immediate and long lasting shine benefits on the surface treated while providing excellent limescale removal performance. Also the redeposition of limescale deposits on a hard-surface that has been first treated with one of the compositions exemplified above, is reduced or even prevented, when said surface comes again in contact with water, upon prolonged period of time, this both when used neat or in diluted form.

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Claims (15)

  1. Composition liquide de caractère acide appropriée à l'élimination des taches contenant du tartre sur une surface dure, comprenant un acide, de 0,001 % à 20 %, en poids de la composition totale, d'un polymère polysaccharidique et de 0,001 % à 20 %, en poids de la composition totale, d'un homopolymère ou d'un copolymère de vinylpyrrolidone, ladite composition étant conditionnée dans un distributeur de type pulvérisateur.
  2. Composition selon la revendication 1, dans laquelle ledit acide est un acide organique ou inorganique ou un mélange de tels acides, typiquement à une concentration de 0,1 % à 70 % en poids de la composition totale.
  3. Composition selon l'une quelconque des revendications précédentes, dans laquelle ledit acide est l'acide maléique seul ou en combinaison avec un second acide dont le premier pKa ne dépasse pas 5, ou des mélanges de tels acides.
  4. Composition selon la revendication 3, dans laquelle ledit second acide est l'acide sulfamique, un acide alkylsulfonique, un acide arylsulfonique, l'acide citrique, l'acide nitrique, l'acide sulfurique, l'acide phosphorique, l'acide chlorhydrique ou un mélange de ceux-ci, et de préférence l'acide sulfamique.
  5. Composition selon la revendication, 3 ou 4, ladite composition comprenant de 0,1 % à 45 %, en poids de la composition totale, d'acide maléique, de préférence de 1 % à 25 %, et plus préférablement de 6 % à 20 %, et facultativement de 0,1 % à 25 %, en poids de la composition totale, dudit second acide, ou de mélanges de tels acides, de préférence de 0,1 % à 20 %, et plus préférablement de 0,1 % à 10%.
  6. Composition selon l'une quelconque des revendications précédentes dans laquelle ledit homopolymère de vinylpyrrolidone est un homopolymère de N-vinylpyrrolidone comprenant le monomère répété suivant:
    Figure 00300001
    dans lequel n est un entier de 10 à 1.000.000, de préférence de 20 à 100.000 et plus préférablement de 20 à 10.000.
  7. Composition selon l'une quelconque des revendications précédentes, dans laquelle ledit copolymère de vinylpyrrolidone est un copolymère de N-vinylpyrrolidone et d'un monomère à insaturation alkylénique de préférence choisi dans le groupe consistant en acide maléique, acide chloromaléique, acide fumarique, acide itaconique, acide citraconique, acide phénylmaléique, acide aconitique, acide acrylique, N-vinylimidazole, acétate de vinyle, et leurs anhydrides, styrène, styrène sulfoné, alpha-méthylstyrène, vinyltoluène, t-butylstyrène, et leurs mélanges.
  8. Composition selon l'une quelconque des revendications précédentes, dans laquelle ledit copolymère de vinylpyrrolidone est un copolymère de vinylpyrrolidone et d'acrylate ou de méthacrylate de dialkylaminoalkyle, quartemaire ou non, répondant à la formule suivante:
    Figure 00300002
    dans laquelle n est compris entre 20 et 99 et de préférence entre 40 et 90 % en mole et m est compris entre 1 et 80 et de préférence entre 5 et 40 % en mole; R1 représente H ou CH3; y est égal à 0 ou 1; R2 est -CH2-CHOH-CH2- ou CxH2x, où x=2 à 18; R3 représente un groupe alkyle inférieur ayant de 1 à 4 atomes de carbone, de préférence méthyle ou éthyle, ou
    Figure 00310001
    R4 représente un groupe alkyle inférieur ayant de 1 à 4 atomes de carbone, de préférence méthyle ou éthyle; X est choisi dans le groupe consistant en Cl, Br, I, 1/2SO4, HSO4 et CH3SO3, et de préférence un copolymère de vinylpyrrolidone et de méthacrylate de diméthylaminoéthyle quartemaire.
  9. Composition selon l'une quelconque des revendications précédentes comprenant de 0,01 % à 5 % en poids de la composition totale d'un homopolymère ou d'un copolymère de vinylpyrrolidone ou d'un mélange de tels polymères, de préférence de 0,01% à 3 %, plus préférablement de 0,01 % à 1 %.
  10. Composition selon l'une quelconque des revendications précédentes dans laquelle ledit polymère polysaccharidique est une matière cellulosique substituée ou un polymère polysaccharidique naturel ou un mélange de ceux-ci, de préférence la carboxyméthylcellulose, l'éthylcellulose, l'hydroxyéthylcellulose, l'hydroxypropylcellulose, l'hydroxyméthylcellulose, le succinoglycane, la gomme de xanthane, la gomme de guar, la gomme de caroube, la gomme adragante ou leurs dérivés, ou leurs mélanges, et plus préférablement la gomme de xanthane ou ses dérivés ou un de leurs mélanges.
  11. Composition selon l'une quelconque des revendications précédentes, comprenant de 0,01 % à 10 %, en poids de la composition totale, d'un polymère polysaccharidique ou d'un mélange de tels polymères, de préférence de 0,01 % à 5 %, plus préférablement de 0,01 % à 2 %.
  12. Composition selon l'une quelconque des revendications précédentes comprenant en outre un agent tensioactif ou un mélange d'agents tensioactifs en concentration allant jusqu'à 40 % en poids de la composition totale, typiquement choisi dans le groupe consistant en agents tensioactifs anioniques, non ioniques, cationiques, amphotères, zwittérioniques et leurs mélanges, plus préférablement au moins un agent tensioactif zwittérionique de formule: R1-N+(R2)(R3)R4X- dans laquelle R1 est une chaíne hydrocarbonée aliphatique ou aromatique, saturée ou insaturée, substituée ou non substituée qui peut contenir des groupes de liaison tels que des groupes amido, des groupes esters, de préférence un groupe alkyle contenant de 1 à 24 atomes de carbone, plus préférablement de 8 à 18, ou un radical amido de formule Ra-C(O)-NRb-(C(Rc)2)m, dans laquelle Ra est une chaíne hydrocarbonée aliphatique ou aromatique, saturée ou insaturée, substituée ou non substituée contenant de 8 jusqu'à 20 atomes de carbone, Rb est soit un hydrogène, soit un groupe alkyle à chaíne courte ou alkyle substitué contenant de 1 à 4 atomes de carbone, de préférence un groupe choisi dans le groupe consistant en méthyle, éthyle, propyle, éthyle ou propyle à substitution hydroxy, et leurs mélanges, plus préférablement le groupe méthyle ou l'hydrogène, Rc est choisi dans le groupe consistant en l'hydrogène et le groupe hydroxy, et m varie de 1 à 4, de préférence de 2 à 3, plus préférablement vaut 3, chaque fragment (C(Rc)2) ne comportant pas plus d'un groupe hydroxy;
    R2 est un hydrogène, un groupe alkyle ou hydroxyalkyle en C1-C6, ou un autre groupe alkyle en C1-C6 substitué;
    R3 est un groupe alkyle ou hydroxyalkyle en C1-C6, ou un autre groupe alkyle en C1-C6 substitué pouvant aussi être lié à R2 pour former des structures cycliques avec le N, ou un groupe acide carboxylique en C1-C6 ou un groupe sulfonate en C1-C6;
    R4 est un fragment liant l'atome d'azote cationique au groupe hydrophile et est typiquement un groupe alkylène, hydroxyalkylène, ou polyalkoxy contenant de 1 à 10 atomes de carbone;
    et X est le groupe hydrophile qui est un groupe carboxylate ou sulfonate, ou un de leurs mélanges.
  13. Composition selon l'une quelconque des revendications précédentes, dans laquelle ladite composition a un pH inférieur à 7, de préférence inférieur à 4, de préférence un pH allant de 0,1 à 2,5 et plus préférablement de 0,1 à 2.
  14. Composition selon l'une quelconque des revendications précédentes, dans laquelle ledit distributeur de type pulvérisateur est un distributeur de mousse de type pulvérisateur à gâchette.
  15. Procédé d'élimination de dépôts de tartre d'une surface dure souillée par des taches contenant du tartre, dans lequel une composition liquide de caractère acide selon l'une quelconque des revendications précédentes est appliquée sur ladite surface au moyen d'un distributeur de type pulvérisateur, puis laissée agir sur ladite surface, et enfin éliminée par rinçage.
EP97870174A 1997-10-31 1997-10-31 Compositions liquides acides pour enlever le tartre emballées dans un atomiseur Expired - Lifetime EP0919610B1 (fr)

Priority Applications (8)

Application Number Priority Date Filing Date Title
ES97870174T ES2241029T3 (es) 1997-10-31 1997-10-31 Composiciones liquidas acidas para eliminar la cal envasadas en un dispensador de tipo pulverizador.
DE69732777T DE69732777T2 (de) 1997-10-31 1997-10-31 Saure flüssige Zusammensetzungen zum Entfernen von Kesselstein verpackt in einem Sprühspender
AT97870174T ATE291073T1 (de) 1997-10-31 1997-10-31 Saure flüssige zusammensetzungen zum entfernen von kesselstein verpackt in einem sprühspender
EP97870174A EP0919610B1 (fr) 1997-10-31 1997-10-31 Compositions liquides acides pour enlever le tartre emballées dans un atomiseur
CA002308295A CA2308295C (fr) 1997-10-31 1998-11-02 Compositions acides liquides servant a eliminer des depots de calcaire, conditionnees dans un distributeur de type pulverisateur
US09/530,496 US6333299B1 (en) 1997-10-31 1998-11-02 Liquid acidic limescale removal composition packaged in a spray-type dispenser
EP98956506A EP1027417A1 (fr) 1997-10-31 1998-11-02 Compositions acides liquides servant a eliminer des depots de calcaire, conditionnees dans un distributeur de type pulverisateur
PCT/US1998/023377 WO1999023194A1 (fr) 1997-10-31 1998-11-02 Compositions acides liquides servant a eliminer des depots de calcaire, conditionnees dans un distributeur de type pulverisateur

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP97870174A EP0919610B1 (fr) 1997-10-31 1997-10-31 Compositions liquides acides pour enlever le tartre emballées dans un atomiseur

Publications (2)

Publication Number Publication Date
EP0919610A1 EP0919610A1 (fr) 1999-06-02
EP0919610B1 true EP0919610B1 (fr) 2005-03-16

Family

ID=8231059

Family Applications (2)

Application Number Title Priority Date Filing Date
EP97870174A Expired - Lifetime EP0919610B1 (fr) 1997-10-31 1997-10-31 Compositions liquides acides pour enlever le tartre emballées dans un atomiseur
EP98956506A Withdrawn EP1027417A1 (fr) 1997-10-31 1998-11-02 Compositions acides liquides servant a eliminer des depots de calcaire, conditionnees dans un distributeur de type pulverisateur

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP98956506A Withdrawn EP1027417A1 (fr) 1997-10-31 1998-11-02 Compositions acides liquides servant a eliminer des depots de calcaire, conditionnees dans un distributeur de type pulverisateur

Country Status (6)

Country Link
EP (2) EP0919610B1 (fr)
AT (1) ATE291073T1 (fr)
CA (1) CA2308295C (fr)
DE (1) DE69732777T2 (fr)
ES (1) ES2241029T3 (fr)
WO (1) WO1999023194A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0957156B1 (fr) * 1998-05-15 2005-04-20 The Procter & Gamble Company Composition de nettoyage liquide acide pour surfaces dures
JP4509384B2 (ja) * 1998-11-02 2010-07-21 ザ プロクター アンド ギャンブル カンパニー 低減された布帛磨耗性を有する布帛ケア組成物
WO2000077143A1 (fr) * 1999-06-15 2000-12-21 The Procter & Gamble Company Produit de nettoyage
US20030017960A1 (en) 1999-06-15 2003-01-23 The Procter & Gamble Company Cleaning compositions
US6562142B2 (en) 2001-01-30 2003-05-13 The Procter & Gamble Company System and method for cleaning and/or treating vehicles and the surfaces of other objects
US7264678B2 (en) 2000-06-14 2007-09-04 The Procter & Gamble Company Process for cleaning a surface
US7381279B2 (en) 2000-06-14 2008-06-03 The Procter & Gamble Company Article for deionization of water
US6869028B2 (en) 2000-06-14 2005-03-22 The Procter & Gamble Company Spraying device
EP1341882A4 (fr) * 2000-11-24 2004-09-01 Henkel Kgaa Compositions de lavage a tensioactifs melanges a effets de trainees reduits
US7256167B2 (en) 2001-08-31 2007-08-14 Reckitt Benckiser Inc. Hard surface cleaner comprising suspended particles and oxidizing agent
GB2379223A (en) 2001-08-31 2003-03-05 Reckitt Benckiser Inc Cleaning composition comprising citric acid
US7119055B2 (en) 2001-08-31 2006-10-10 Reckitt Benckiser Inc. Hard surface cleaners comprising a thickening gum mixture
GB2398792A (en) 2003-02-22 2004-09-01 Reckitt Benckiser Inc Acidic hard surface cleaning and/or disinfecting composition
AR043906A1 (es) 2003-02-22 2005-08-17 Reckitt Benckiser Inc Composiciones limpiadoras para superficies duras
US20070086971A1 (en) 2005-10-19 2007-04-19 Patrick Diet Acidic Cleaning Compositions
EP1994129B1 (fr) * 2006-03-10 2010-06-02 Reckitt Benckiser Inc. Compositions aqueuses hautement acides de nettoyage de surfaces dures
EP1997874A1 (fr) 2007-05-25 2008-12-03 JohnsonDiversey, Inc. Système de nettoyage d'articles contenant du polysaccharide
EP3184620A1 (fr) * 2007-12-28 2017-06-28 Colgate-Palmolive Company Compositions de nettoyage acides comprenant un polymère
EP3263681B1 (fr) * 2016-06-27 2020-09-16 The Procter and Gamble Company Nettoyage par acide liquide de surfaces dures permettant d'améliorer des compositions de traitement de surfaces métalliques
WO2021022045A1 (fr) 2019-07-31 2021-02-04 Ecolab Usa Inc. Compositions de détartrage sans équipement de protection individuelle

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NZ192549A (en) * 1979-01-12 1981-11-19 Unilever Ltd Liquid detergent comprising a copolymer of n-vinylpyrrolidone
US4578407A (en) * 1982-03-31 1986-03-25 Gaf Corporation Thixotropic rust removal coating and process
DE4343728C2 (de) * 1993-12-21 1997-04-24 Gernot Dr Loehnert Verfahren zur Herstellung von verdicktem Wasser und seine Verwendung
DE69426260T2 (de) * 1994-02-03 2001-06-07 Procter & Gamble Saure Reinigungszusammensetzungen
GB9600030D0 (en) * 1996-01-03 1996-03-06 Johnson & Son Inc S C Cleaning compositions

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Publication number Publication date
CA2308295C (fr) 2005-07-26
CA2308295A1 (fr) 1999-05-14
ES2241029T3 (es) 2005-10-16
WO1999023194A1 (fr) 1999-05-14
DE69732777T2 (de) 2006-04-06
EP1027417A1 (fr) 2000-08-16
EP0919610A1 (fr) 1999-06-02
DE69732777D1 (de) 2005-04-21
ATE291073T1 (de) 2005-04-15

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