EP0875555B1 - Utilisation d'un polymère de polysaccharide dans des compositions liquides acides - Google Patents

Utilisation d'un polymère de polysaccharide dans des compositions liquides acides Download PDF

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Publication number
EP0875555B1
EP0875555B1 EP97870055A EP97870055A EP0875555B1 EP 0875555 B1 EP0875555 B1 EP 0875555B1 EP 97870055 A EP97870055 A EP 97870055A EP 97870055 A EP97870055 A EP 97870055A EP 0875555 B1 EP0875555 B1 EP 0875555B1
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EP
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Prior art keywords
acid
composition
mixture
hard
polysaccharide polymer
Prior art date
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Revoked
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EP97870055A
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German (de)
English (en)
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EP0875555A1 (fr
Inventor
Luigi Pace, (Nmn)
Elisabetta L. Russo
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Procter and Gamble Co
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Procter and Gamble Co
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Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to AT97870055T priority Critical patent/ATE245690T1/de
Priority to ES97870055T priority patent/ES2201263T3/es
Priority to EP97870055A priority patent/EP0875555B1/fr
Priority to DE69723672T priority patent/DE69723672T2/de
Priority to PCT/IB1998/000639 priority patent/WO1998049260A1/fr
Priority to CA002287969A priority patent/CA2287969C/fr
Priority to JP54677298A priority patent/JP2001522304A/ja
Publication of EP0875555A1 publication Critical patent/EP0875555A1/fr
Publication of EP0875555B1 publication Critical patent/EP0875555B1/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
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • 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
    • 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
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin

Definitions

  • the present invention is related to acidic hard-surfaces compositions, especially limescale removal compositions.
  • Tap water contains a certain amount of solubilized ions which upon water evaporation eventually deposit as salts such as calcium carbonate on 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.
  • liquid acidic compositions should have, in addition to the ability to effectively remove limescale deposits present on a surface, the ability to provide improved shine to the surface treated. It has now been observed that surface shine is often compromised by the low affinity the hard surface has with water when it comes in contact with it. Indeed, water has the tendency to form droplets on the surface rather than forming a thin film uniformly spread over the surface. This results as water evaporates in precipitation of poorly water soluble inorganic salts such as 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 carbonate and/or phosphate salts
  • the present invention overcomes these problems by the use of a polysaccharide polymer, in a liquid acidic composition suitable for descaling hard-surfaces. Indeed, it has been found that the addition of a polysaccharide polymer, preferably xanthan gum, 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. Also 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.
  • a polysaccharide polymer preferably xanthan gum
  • the shine benefit delivered to a hard surface treated with the compositions according to the present invention persists even after several cycles of rinsing thus providing long lasting protection against limescale redeposition/formation and/or watermarks formation on said surface, and hence long lasting shiny surfaces.
  • the house wife will have the advantage to delay the next descaling operation.
  • Another advantage of the use of the polysaccharide polymer according to the present invention in a liquid acidic composition is that the surfaces treated become smoother (this can be perceived by touching said surfaces). This may also contribute to convey to consumers the perception of surface perfectly descaled.
  • compositions described herein may be used on 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.
  • Limescale compositions comprising polysaccharide polymers like xanthan gum are known in the art.
  • EP-A-758 017 discloses acidic compositions with an acidic system and an acid-stable thickener, e.g. xanthan gum.
  • EP-A-758 017 fails to disclose that polysaccharide polymers when added in a liquid acidic composition reduce the formation of watermarks and/or limescale deposits on a surface having been first treated with said composition, and thus provide improved shine to the surface.
  • the present invention encompasses the use of a polysaccharide polymer or a mixture thereof, in a liquid acidic composition, to treat a hard-surface, whereby after said hard-surface has first been treated with said composition, the formation of limescale deposits on said hard-surface when it comes in contact with water is reduced.
  • the present invention further encompasses the use of a polysaccharide polymer or a mixture thereof, in a liquid acidic composition, to treat a hard-surface whereby improved shine is delivered to the surface treated with said composition.
  • the present invention also encompasses the use of a polysaccharide polymer or a mixture thereof, in a liquid acidic composition, to treat a hard-surface whereby long lasting shine is delivered to the surface treated with said composition.
  • An essential feature of the present invention is a polysaccharide polymer or a mixture thereof.
  • Suitable polysaccharide polymers to be used 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 particularly polysaccharide polymers to be used herein.
  • Xanthan gum and derivatives thereof may be commercially available for instance from Kelco under the trade name Keltrol RD®, Kelzan S® or Kelzan T®.
  • Xanthan gum or derivatives thereof 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
  • compositions comprise from 0.001% to 10% by weight of the total composition of a polysaccharide polymer, or a mixture thereof, preferably from 0.01% to 3% by weight, more preferably from 0.01% to 1%, even more preferably from 0.05% to 0.8% and most preferably from 0.05% to 0.6%.
  • 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 at 20°C, 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 .
  • compositions according to the present invention are acidic compositions. Accordingly, the compositions of the present invention are formulated at a pH below 5, 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.
  • compositions according to the present invention are designed for removing limescale deposits.
  • they typically comprise 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.
  • compositions according to the present invention comprise from 0.1% to 70% by weight of the total composition of an acid or a mixture thereof.
  • compositions according to the present invention comprise at least maleic acid. Accordingly, 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 8% 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. In one embodiment herein maleic acid is used alone as the acid of the acidic compositions according to 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 to be used herein is sulphamic acid.
  • the addition of sulphamic acid to maleic acid-containing compositions improves the skin safety profile of said compositions.
  • the skin will be less subject to become inflamed, red, sore and/or itchy when in contact with those acidic compositions according to the present invention comprising sulphamic acid on top of maleic acid, as compared to the same compositions without said 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, or mixtures thereof, more preferred are sulphamic acid, sulphuric acid, benzene sulphonic acid or mixtures thereof and highly preferred is sulphamic acid.
  • compositions according to 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 polysaccharide polymers described herein when added into a liquid acidic composition typically comprising an acid or a mixture thereof, preferably maleic acid and sulphamic acid reduce the formation of limescale deposits and/or watermarks on a surface that has been first treated with said composition, when said surface comes into contact with water. This results in improved shine to the surface so treated when it comes into contact with both hard and/or soft water.
  • the polysaccharide polymers of the present invention have not only the ability to adhere on a surface treated with the acidic compositions herein comprising the same but to still remain adhered on the surface even after several cycles of rinsing (e.g., when water comes into contact with this surface later on, for example, during current household operation in a sink), thus providing long lasting protection against formation of limescale deposits/watermarks and, hence, long lasting shiny surfaces.
  • An additional advantage related to the use of the polysaccharide polymers of the present invention 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 compositions according to the present invention are preferably aqueous compositions. Therefore, they 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 may further comprise a variety of other ingredients including surfactants, colorants, bactericides, thickeners, other polymers, dyes, chelants, pigments, solvents, stabilizers, perfumes and, corrosion inhibitors.
  • a highly preferred optional ingredient suitable to be used in the compositions according to 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 allows to boost 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 according to the present invention helps to solubilize the soils.
  • compositions herein 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 said 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.
  • 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 and, phosphonates, 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 carboxy
  • R 1 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.
  • 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 , wherein R a is an aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted hydrocarbon chain, 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, and 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 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 ®.
  • 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 include cocoamidoethylbetaine, cocoamidopropyl betaine or C10-C14 fatty acylamidopropylene(hydropropylene)sulfobetaine.
  • C10-C14 fatty acylamidopropylene(hydropropylene)sulfobetaine is commercially 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 groups containing from 1 to 30 carbon atoms, and preferably from 1 to 20 carbon atoms.
  • Particularly 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 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 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 Radiamox®.
  • Suitable quaternary ammonium surfactants for use herein are according to the formula R 1 R 2 R 3 R 4 N + X - , wherein 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 and 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®.
  • Suitable nonionic surfactants for use in the compositions according to the present invention 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 Shell 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 tetramethylammonium 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,
  • Suitable alkyl aryl sulphonates for use herein include water- soluble salts or acids of the formula RSO 3 M wherein R is an aryl, preferably a benzyl, substituted by 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, calcium, magnesium ) or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethylammonium and dimethyl piperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethyl
  • secondary C6-C20 alkyl or C6-C20 alkyl aryl sulphonates it is meant herein that in the formula as defined above, the S03M 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 the 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) or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethylammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof).
  • an alkali metal cation e.g., sodium, potassium, lithium, calcium, magnesium
  • ammonium or substituted ammonium e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethylammonium and dimethyl piperdinium cations and quaternary ammonium cations
  • 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 0.5 and 6, more preferably between 0.5 and 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium), 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 12 -C 20 alky
  • Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
  • Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethylammonium and quaternary ammonium cations, such as tetramethylammonium, dimethyl piperidinium and cations derived from alkanolamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof .
  • 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)M), 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).
  • 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).
  • Particularly suitable C 6 -C 20 alkyl alkoxylated linear or branched diphenyl oxide disulphonate surfactants to be used herein are the C12 branched diphenyl oxide disulphonic acid and C16 linear diphenyl 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 for use 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 colored. Accordingly, they may comprise a dye or a mixture thereof.
  • Suitable dyes to be used 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 to be used 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 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.
  • 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® .
  • compositions according to 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%.
  • liquid acidic compositions according to the present invention may be packaged in a variety of suitable detergent packaging known to those skilled in the art. Indeed they may be easily dispensed onto the surface to be treated via a spray-type dispenser such as for instance a trigger-sprayer.
  • 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.
  • 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.
  • 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.
  • the composition is forced against an obstacle, e.g. a grid or a cone , thereby providing shocks to help atomise the liquid composition, i.e. to help the formation of liquid droplets.
  • the limescale removal capacity of an acidic composition may be evaluated by soaking a marble block (marble blocks are chemically speaking very similar to limescale, i.e. they are essentially made of calcium carbonate) into 20 g of this composition. The marble is weighed before and after the experiment, and the performance is expressed in grams of marble block dissolved over time. Alternatively, limescale removal performance can also be evaluated by detecting the release of CO2.
  • Obtaining a good shine end result results from a good spreading of the liquid acidic composition over the surface when the surface is treated therewith and from the reduced formation of watermarks and even reduced precipitation of poorly water soluble salts that otherwise typically occurs in presence of hard water, 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.
  • a composition according to the present invention in a suitable test method two rectangular areas (10cmx4cm) of a sink (made of either stainless steel or ceramic) are treated with a composition according to the present invention and a reference composition, e.g. the same composition but without said polysaccharide polymer. 3 grams of composition is first poured onto each surfaces to be treated and, then wiped (10 strokes) by using a Spontex® sponge. Then each treated surface is rinsed with 200 grams of tap water and 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 shine difference. Evaluation may be generally done by applying the Panel Score Unit (PSU).
  • PSU Panel Score Unit
  • 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 14 - 10 12 Sulphamic acid 2 2 - 2 - 2 Citric acid - - - 2 2 2 Mirataine CBS® 2.0 2.0 - 2.0 - 2.0 HLAS - - - - 0.50 - Xanthan Gum 0.2 0.1 0.1 0.3 0.4 0.5 Waters & Minors ------------------------- up to 100 ----------------------- Ingredients : (% by weight) VII VIII IX X XI XII Maleic acid 10 10 10 8 6 - Sulphamic acid 2 2 2 - - 2 Citric acid - 1 - 2 4 8 Dobanol® 91.8 2 2 - 1 - - Mirataine CBS® - - 2 - - 2.2 Xanthan Gum - - 0.05 - 0.50 0.1 Succinoglycan
  • compositions of the above examples exhibit excellent immediate and long lasting shine benefits on the surface treated while providing excellent limescale removal performance. Also good greasy soap scum cleaning performance have been obtained when these compositions are used to treat limescale-containing stains found in a kitchen and in a bathroom, this both when used neat or in diluted form.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Inorganic Chemistry (AREA)
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Claims (11)

  1. Utilisation d'un polymère de polysaccharide ou d'un mélange de celui-ci, dans une composition acide liquide, pour traiter une surface dure, moyennant quoi après que ladite surface dure a été traitée une première fois avec ladite composition, la formation de dépôts de tartre sur ladite surface dure, quand elle vient en contact avec de l'eau, est réduite.
  2. Utilisation d'un polymère de polysaccharide ou d'un mélange de celui-ci, dans une composition acide liquide, pour traiter une surface dure, moyennant quoi un brillant amélioré est conféré à la surface traitée avec ladite composition.
  3. Utilisation d'un polymère de polysaccharide ou d'un mélange de celui-ci, dans une composition acide liquide, pour traiter une surface dure, moyennant quoi un brillant de longue durée est conféré à la surface traitée avec ladite composition.
  4. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle ladite composition comprend 0,001 % à 10 % en poids de la composition totale d'un polymère de polysaccharide, ou d'un mélange de celui-ci, de préférence 0,01 % à 3 % en poids, plus préférablement 0,05 % à 0,8 % et le plus préférablement 0,05 % à 0,6 %.
  5. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle ledit polymère de polysaccharide est une matière cellulosique substituée ou un polymère de polysaccharide présent dans la nature ou un mélange 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 des dérivés de ceux-ci, ou des mélanges de ceux-ci et plus préférablement la gomme de xanthane ou des dérivés de celle-ci ou un mélange de ceux-ci.
  6. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle ladite composition comprend un acide organique ou inorganique ou un mélange de ceux-ci, typiquement à un niveau de 0,1 % à 70 % en poids de la composition totale.
  7. Utilisation selon la revendication 6, dans laquelle ledit acide est l'acide maléique seul ou avec un second acide dont le premier pKa ne dépasse pas 5, ou un mélange de ceux-ci.
  8. Utilisation selon la revendication 7, dans laquelle ledit second acide est l'acide sulfamique, l'acide alkylsulfonique, l'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.
  9. Utilisation selon les revendications 7 ou 8, dans laquelle ladite composition comprend 0,1 % à 45 % en poids de la composition totale d'acide maléique, de préférence 1 % à 25 %, et plus préférablement 8 % à 20 %, et éventuellement 0,1 % à 25 % en poids de la composition totale dudit second acide, ou des mélanges de ceux-ci, de préférence 0,1 % à 20 %, et plus préférablement 0,1 % à 10 %.
  10. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle ladite composition comprend en outre un tensioactif ou un mélange de celui-ci jusqu'à un niveau de 40 % en poids de la composition totale, choisis typiquement dans le groupe constitué de tensioactifs anioniques, non-ioniques, cationiques, amphotériques, zwitterioniques et des mélanges de ceux-ci, plus préférablement au moins un tensioactif zwitterionique ou un mélange de celui-ci.
  11. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle ladite composition a un pH inférieur à 4, de préférence un pH de 0,1 à 2,5, et plus préférablement de 0,1 à 2.
EP97870055A 1997-04-30 1997-04-30 Utilisation d'un polymère de polysaccharide dans des compositions liquides acides Revoked EP0875555B1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
AT97870055T ATE245690T1 (de) 1997-04-30 1997-04-30 Verwendung von polysacchariden in flüssigen sauren zusammensetzungen
ES97870055T ES2201263T3 (es) 1997-04-30 1997-04-30 Uso de un polimero de polisacarido en composiciones acidas liquidas.
EP97870055A EP0875555B1 (fr) 1997-04-30 1997-04-30 Utilisation d'un polymère de polysaccharide dans des compositions liquides acides
DE69723672T DE69723672T2 (de) 1997-04-30 1997-04-30 Verwendung von Polysacchariden in flüssigen sauren Zusammensetzungen
PCT/IB1998/000639 WO1998049260A1 (fr) 1997-04-30 1998-04-24 Utilisation d'un polymere de polysaccharide dans une composition acide liquide
CA002287969A CA2287969C (fr) 1997-04-30 1998-04-24 Utilisation d'un polymere de polysaccharide dans une composition acide liquide
JP54677298A JP2001522304A (ja) 1997-04-30 1998-04-24 液状酸性組成物中へのポリサッカライドポリマーの使用

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP97870055A EP0875555B1 (fr) 1997-04-30 1997-04-30 Utilisation d'un polymère de polysaccharide dans des compositions liquides acides

Publications (2)

Publication Number Publication Date
EP0875555A1 EP0875555A1 (fr) 1998-11-04
EP0875555B1 true EP0875555B1 (fr) 2003-07-23

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EP97870055A Revoked EP0875555B1 (fr) 1997-04-30 1997-04-30 Utilisation d'un polymère de polysaccharide dans des compositions liquides acides

Country Status (7)

Country Link
EP (1) EP0875555B1 (fr)
JP (1) JP2001522304A (fr)
AT (1) ATE245690T1 (fr)
CA (1) CA2287969C (fr)
DE (1) DE69723672T2 (fr)
ES (1) ES2201263T3 (fr)
WO (1) WO1998049260A1 (fr)

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DE60038458T2 (de) * 1999-12-08 2009-04-02 Unilever N.V. Verwendung von polymerem material zur behandlung harter oberflächen
GB2379214A (en) 2001-09-04 2003-03-05 Reckitt Benckiser Nv Thickened aqueous compositions
US6362148B1 (en) * 2001-09-06 2002-03-26 Colgate-Palmolive Co. Anti-lime scale cleaning composition comprising polyoxyethylene oxide polycarboxylic acid copolymer
US20070086971A1 (en) 2005-10-19 2007-04-19 Patrick Diet Acidic Cleaning Compositions
FR2897611B1 (fr) * 2006-02-20 2008-05-30 Gilles Allard Produit de traitement d'un reservoir et d'une cuvette de chasse d'eau
US8674021B2 (en) 2006-07-21 2014-03-18 Akzo Nobel N.V. Sulfonated graft copolymers
US8815791B2 (en) 2008-12-02 2014-08-26 Diversey, Inc. Cleaning of a cooking device or appliance with a composition comprising a built-in rinse aid
AU2009322574B2 (en) 2008-12-02 2014-05-15 Diversey, Inc. Ware washing system containing cationic starch
EP2459607B1 (fr) 2009-07-31 2021-04-14 Nouryon Chemicals International B.V. Compositions de copolymère hybride et leurs utilisations pour des applications de soins personnels
US8853144B2 (en) 2011-08-05 2014-10-07 Ecolab Usa Inc. Cleaning composition containing a polysaccharide graft polymer composition and methods of improving drainage
US8636918B2 (en) 2011-08-05 2014-01-28 Ecolab Usa Inc. Cleaning composition containing a polysaccharide hybrid polymer composition and methods of controlling hard water scale
US8679366B2 (en) 2011-08-05 2014-03-25 Ecolab Usa Inc. Cleaning composition containing a polysaccharide graft polymer composition and methods of controlling hard water scale
US8841246B2 (en) 2011-08-05 2014-09-23 Ecolab Usa Inc. Cleaning composition containing a polysaccharide hybrid polymer composition and methods of improving drainage
BR112014008874A2 (pt) 2011-11-04 2017-04-25 Akzo Nobel Chemicals Int Bv composição de copolímero híbrido de dendrito
EP2773321B1 (fr) 2011-11-04 2015-09-09 Akzo Nobel Chemicals International B.V. Copolymères dendritiques greffés, et procédés de production associés
US8945314B2 (en) 2012-07-30 2015-02-03 Ecolab Usa Inc. Biodegradable stability binding agent for a solid detergent
CN103346903B (zh) * 2013-06-20 2017-02-15 北京捷成世纪科技股份有限公司 一种双机备份的方法和装置
US9365805B2 (en) 2014-05-15 2016-06-14 Ecolab Usa Inc. Bio-based pot and pan pre-soak
US10988712B1 (en) 2017-06-05 2021-04-27 Miguel Angel Regalado, Sr. Water mineral cleaning solutions and related methods
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Also Published As

Publication number Publication date
JP2001522304A (ja) 2001-11-13
EP0875555A1 (fr) 1998-11-04
DE69723672T2 (de) 2004-04-15
ATE245690T1 (de) 2003-08-15
CA2287969C (fr) 2007-02-06
ES2201263T3 (es) 2004-03-16
WO1998049260A1 (fr) 1998-11-05
DE69723672D1 (de) 2003-08-28
CA2287969A1 (fr) 1998-11-05

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