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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/29—Sulfates of polyoxyalkylene ethers
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/395—Bleaching agents
  • C11D3/3956—Liquid compositions

Definitions

• the present invention relates to liquid bleaching compositions, in particular to liquid hypochlorite bleaching compositions, which can be used to bleach various surfaces including but not limited to, hard-surfaces likes walls, tiles, floors, glass, bathrooms surfaces, kitchen surfaces, toilet bowls, dishes as well as fabrics, clothes, and carpets.
• Bleaching compositions are well-known in the art. Amongst the different bleaching compositions available, those relying on bleaching by hypohalite bleaches such as hypochlorite are often preferred, mainly for bleaching performance reasons.
• liquid bleaching compositions When formulating such liquid bleaching compositions it is desirable to add thereto surfactants to deliver good cleaning performance, i.e. good stain removal performance on a variety of stains including greasy stains and/or enzymatic stains.
• a problem associated with such hypohalite bleach-based compositions containing surfactants, especially those containing high levels of surfactants, i.e. more than 3% by weight of the total composition is their tendency to be unstable upon prolonged periods of storage. More particularly, there is a need for liquid bleaching compositions based on hypohalite bleach and a surfactant, especially high level of surfactants, that are chemically stable upon ageing of the compositions, i.e. for prolonged periods of storage after their manufacturing.
• a liquid bleaching composition comprising a hypohalite bleach, and an alkyl (alkoxy) sulphate, said alkyl (alkoxy) sulphate containing less than 10% by weight of unsulfated material on alkyl (alkoxy) sulphate active basis and/or less than 0.0015% by weight of metal impurities on alkyl (alkoxy) sulphate active basis.
• a particular surfactant in a hypohalite bleach-containing composition allows excellent stain removal performance while delivering improved chemical stability to the composition upon ageing as compared to a similar composition but with an alkyl (alkoxy) sulphate having more undesirable by products, i.e. more unsulfated material and/or more metal impurities as the ones used herein.
• compositions of the present invention are that the desired viscosity is delivered by the presence of said alkyl (alkoxy) sulphate without the need of any particular thickening aids.
• the level of the alkyl (alkoxy) sulphate and/or its alkoxylation degree will be adjusted.
• compositions of the present invention further comprise a stabilising agent preferably a radical scavenger, a chelating agent or a mixture thereof.
• a stabilising agent preferably a radical scavenger, a chelating agent or a mixture thereof.
• compositions of the present invention deliver effective bleaching performance, more particularly effective whiteness performance when used in any laundry application, as well as effective stain removal performance on various stains including greasy stains like lipstick, make up, sebum, oil (mineral and vegetable), mayonnaise, eggs and/or enzymatic stains like grass, cocoa, blood, even upon ageing of the composition.
• the liquid compositions of the present invention further comprise a stabilising agent, the presence of such a stabilizing agent further contributes to deliver effective bleaching performance and/or effective stain removal performance on various stains upon ageing of the compositions.
• compositions of the invention are suitable for the bleaching of different types of surfaces including hard-surfaces like floors, walls, tills, glass, kitchen surfaces, bathrooms surfaces, toilet bowls and/or dishes as well as fabrics.
• liquid bleaching compositions of the present invention are particularly suitable for various laundry bleaching applications both when used in diluted conditions, e.g. as a detergent additive or a fully formulated laundry detergent composition, and when used in neat condition, e.g. as a liquid pretreater (spotter).
• diluted conditions e.g. as a detergent additive or a fully formulated laundry detergent composition
• neat condition e.g. as a liquid pretreater (spotter).
• the present invention is a liquid bleaching composition
• a hypohalite bleach and an alkyl (alkoxy) n sulphate wherein n is from 0.5 to 20, said alkyl (alkoxy) n sulphate containing less than 10% by weight of unsulfated material on alkyl (alkoxy) n sulphate active basis and/or less than 0.0015% by weight of metal impurities on alkyl (alkoxy) n sulphate active basis.
• compositions used in the present invention further comprise a stabilizing agent and/or a pH buffering component.
• a stabilizing agent in the compositions herein contributes to the rheological stability of the compositions upon ageing.
• the presence of such a stabilizing agent further contributes to deliver effective bleaching performance and/or effective stain removal performance on various stains upon ageing of the compositions.
• the presence of a pH buffering component in the compositions herein further contributes to the effective whiteness performance of these compositions as well as to their fabric safety, when used to bleach fabrics. Indeed, the pH buffering component allows to control the alcalinity in the bleaching solution, i.e.
• the present invention further encompasses the use, in a liquid bleaching composition comprising a hypohalite bleach, of an alkyl (alkoxy) n sulphate, wherein n is from 0.5 to 20, said alkyl (alkoxy) n sulphate containing less than 10% by weight of unsulfated material on alkyl (alkoxy) n sulphate active basis and/or less than 0.0015% by weight of metal impurities on alkyl (alkoxy) n sulphate active basis, for improving chemical stability of the composition upon ageing.
• a liquid bleaching composition comprising a hypohalite bleach, of an alkyl (alkoxy) n sulphate, wherein n is from 0.5 to 20, said alkyl (alkoxy) n sulphate containing less than 10% by weight of unsulfated material on alkyl (alkoxy) n sulphate active basis and/or less than 0.0015% by weight of metal impurities on alkyl (al
• the present invention also encompasses a process of bleaching a surface (including fabrics, hard-surfaces and/or dishes) where said surface is contacted with a bleaching composition according to the present invention, in its neat or diluted form.
• Liquid bleaching compositions are:
• compositions according to the present invention are in liquid form.
• the compositions of the invention are in liquid aqueous form. More preferably, they comprise water in an amount of from 60% to 98% by weight, more preferably of from 80% to 97% and most preferably of from 85% to 97% by weight of the total aqueous liquid bleaching composition.
• Hypohalite bleaches may be provided by a variety of sources, including bleaches that are oxidative bleaches and subsequently lead to the formation of positive halide ions as well as bleaches that are organic based sources of halides such as chloroisocyanurates.
• Suitable hypohalite bleaches for use herein include the alkali metal and alkaline earth metal hypochlorites, hypobromites, hypoiodites, chlorinated trisodium phosphate dodecahydrates, potassium and sodium dichloroisocyanurates, potassium and sodium trichlorocyanurates, N-chloroimides, N-chloroamides, N-chloroamines and chlorohydantoins.
• the preferred hypohalite bleaches among the above described are the alkali metal and/or alkaline earth metal hypochlorites selected from the group consisting of sodium, potassium, magnesium, lithium and calcium hypochlorites, and mixtures thereof, more preferably the alkali metal sodium hypochlorite.
• the liquid compositions according to the present invention comprise said hypohalite bleach or mixture thereof such that the content of active halide in the composition is of from 0.1% to 20% by weight, more preferably from 0.25% to 8% by weight, most preferably from 0.5% to 6% by weight of the composition.
• alkyl (alkoxy) sulphates The alkyl (alkoxy) sulphates
• An essential component of the invention is an alkyl (alkoxy) n sulphate, wherein n is from 0.5 to 20, or a mixture thereof, said alkyl (alkoxy) n sulphate containing less than 10% by weight of unsulfated material on alkyl (alkoxy) n sulphate active basis and/or less than 0.0015% by weight of metal impurities on alkyl (alkoxy) n sulphate active basis.
• Suitable alkyl (alkoxy) n sulphate surfactants for use herein are water-soluble salts or acids of the formula : RO(A) n SO 3 M, wherein
• the alkyl (alkoxy) n sulphate suitable for use herein contains less than 10% by weight of unsulfated material on alkyl (alkoxy) n sulphate active basis, preferably less than 5%, more preferably less than 3% and most preferably less than 2.5% and/or less than 0.0015% by weight of metal impurities on alkyl (alkoxy) n sulphate active basis, preferably less than 0.001%, more preferably less than 0.0003%, most preferably less than 0.00015%.
• the alkyl (alkoxy) n sulphates contain less than 10% by weight of unsulfated material on alkyl (alkoxy) n sulphate active basis and less than 0.0015% by weight of metal impurities on alkyl (alkoxy) n sulphate active basis.
• unsulfated material it is meant herein unsulfated by product resulting from the sulfonation of alcohol alkoxylates to alkyl alkoxy sulphates.
• unsulfated material it is meant herein the alcohol alkoxylates that has not been sulfonated when submitted to a sulfonation process to obtain alkyl alkoxy sulphates.
• on alkyl (alkoxy) n sulphate active basis it is meant the total amount of alkyl (alkoxy) n sulphate per se resulting from sulfonation of alcohol alkoxylates, i.e., alkyl (alkoxy) n sulphate without any by product/impurity.
• alkyl alkoxy sulphates may be obtainable by the following manufacturing process which includes :
• metal impurities any metal salt, metal ion or metal oxide present as metal by product in the alkyl (alkoxy) n sulphate.
• Unsulfated material level can be for example determined by gas chromatography and metal impurities level by induced coupled plasma or atomic absorption spectrometry.
• Alkyl (ethoxy) 2 sulphates and alkyl (ethoxy) 3 sulphates are preferred 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.
• Sodium C12/C14 E3 sulphate may be for example commercially available from Albright & Wilson under the name EMPICOL ESC3®.
• the liquid compositions according to the present invention comprise said alkyl (alkoxy) n sulphate or a mixture thereof in amount of from 1% to 20% by weight, more preferably from more than 3% to 20%, even more preferably from 4% to 15%, even more preferably from 4.5% to 10% by weight, most preferably from 5% to 8% by weight of the composition.
• alkyl (alkoxy) n sulphate as defined herein, preferably an alkyl (ethoxy) n sulphate, provides excellent stain removal performance on various types of stains including greasy stains while delivering excellent chemical stability. More advantageously the present invention allows to formulate hypohalite bleach containing compositions with high level of surfactants while delivering excellent chemical stability.
• hypohalite bleaching compositions of the present invention do not undergo more than 50% loss of available chlorine after 5 days of storage at 50°C ⁇ 0.5°C, preferably not more than 40%.
• the % loss of available chlorine may be measured using the method described, for instance, in “Analyses des Eaux et Extraits de Javel” by "Lachner syndicalerance de L'eau de Javel et des building connexes", pages 9-10 (1984). Said method consists in measuring the available chlorine in the fresh compositions, i.e. just after they are made, and in the same compositions after 5 days at 50° C.
• the alkyl alkoxy sulphates used herein provide the desired viscosity to the compositions herein.
• the compositions may be thin or thick.
• the compositions herein have a viscosity when measured with a Carri-med CSL2-100® rheometer at the following viscosity parameters : angle : 1°58', gap : 60 ⁇ m, diameter : 4.0 cm, inner : 63.60 dyne*cm*s 2 , temperature of 25°C and a shear rate of 30 sec -1 of from 1 cps to 2000 cps, preferably from 10 cps to 1000 cps, more preferably from 50 cps to 800 cps.
• the whitening effect, i.e. the yellowing-prevention effect, of the present invention can be evaluated by both visual and instrumental grading.
• Visually the difference in yellowing between items treated with different compositions can be determined by a team of expert panellists. Instrumentally, the assessment can be determined with the help of Colorimeters such as Ganz Griesser® instruments (e.g., Datacolor® Spectraflash® SF 500, Machbet White-eye® 500) or a ZEISS ELREPHO® or others which are available for instance from Hunterlab® or Gardner®.
• the stain removal performance of the compositions of the present invention can be evaluated by instrumental or visual grading on different type of stains like greasy stains.
• the pH of the liquid compositions according to the present invention is typically from 12 to 14 measured at 25°C.
• the liquid compositions of the invention have a pH of from 7.5 to 13, preferably from 8 to 12, more preferably from 8.5 to 11.5, when diluted into 1 to 500 times its weight of water. It is in this alkaline range that the optimum stability and performance of the hypohalite as well as fabric whiteness and/or safety are obtained.
• the pH range is suitably provided by the pH buffering component if present and the hypohalite bleach mentioned hereinbefore, which are alkalis. However, in addition to these components, a strong source of alkalinity may also optionally be used.
• Suitable sources of alkalinity are the caustic alkalis such as sodium hydroxide, potassium hydroxide and/or lithium hydroxide, and/or the alkali metal oxides such as sodium and/or potassium oxide.
• a preferred strong source of alkalinity is a caustic alkali, more preferably sodium hydroxide and/or potassium hydroxide. Typical levels of such caustic alkalis, when present, are of from 0.1% to 1.5% by weight, preferably from 0.5% to 1.5% by weight of the composition.
• composition according to the invention may comprise other optional components such as pH buffering components, stabilizing agents, co-surfactants, other bleach-stable surfactants, organic or inorganic alkalis, builders, polymers, pigments, dyes, solvents, perfumes, brighteners, and mixtures thereof.
• pH buffering components stabilizing agents, co-surfactants, other bleach-stable surfactants, organic or inorganic alkalis, builders, polymers, pigments, dyes, solvents, perfumes, brighteners, and mixtures thereof.
• a pH buffering component is a preferred optional component for the compositions of the invention.
• the pH buffering component ensures that the pH of the composition is buffered to a pH value ranging from 7.5 to 13, preferably from 8 to 12, more preferably from 8.5 to 11.5 after the composition has been diluted into 1 to 500 times its weight of water.
• Suitable pH buffering components for use herein are selected from the group consisting of alkali metal salts of carbonates, polycarbonates, sesquicarbonates, silicates, polysilicates, boron salts, phosphates, stannates, aluminates and mixtures thereof.
• the preferred alkali metal salts for use herein are sodium and potassium.
• Suitable boron salts or mixtures thereof for use herein include alkali metal salts of borates and alkyl borates and mixtures thereof.
• Examples of boron salts include boric acid, alkali metal salts of metaborate, tetraborate, octoborate, pentaborate, dodecaboron, borontrifluoride and alkyl borate containing from 1 to 12 carbon atoms, preferably from 1 to 4.
• Suitable alkyl borate includes methyl borate, ethyl borate and propyl borate.
• Particularly preferred boron salts herein are the alkali metal salts of metaborate, such as sodium metaborate, potassium metaborate, and the alkali metal salts of borate, such as sodium borate, or mixtures thereof.
• Boron salts like sodium metaborate and sodium tetraborate are commercially available from Borax and Societa Chimica Larderello under the name sodium metaborate and Borax®.
• pH buffering components are selected from the group consisting of sodium carbonate, sodium silicate, sodium borate, sodium metaborate and mixtures thereof.
• the raw materials involved in the preparation of hypohalite bleaches usually contain by-products, e.g calcium carbonate resulting in an amount of up to 0.4% by weight of by-product within the hypohalite composition. However, at such amount, the by-product will not have the buffering action defined above.
• Liquid bleaching compositions herein may contain an amount of pH buffering component of from 0.5% to 9% by weight, preferably from 0.5% to 5% by weight, and more preferably in an amount of from 0.6% to 3% by weight of the composition.
• Another highly preferred optional component of the invention is a stabilising agent or mixture thereof, preferably a radical scavenger, a chelating agent or a mixture thereof.
• the stabilizing agents have to be stable to the hypohalite bleach.
• the stabilising agent is a radical scavenger or a mixture thereof alone, or together with a chelating agent or a mixture thereof.
• Suitable radical scavengers for use herein include aromatic radical scavengers comprising an unsaturated ring system of from 3 to 20 carbon atoms, preferably of from 3 to 18 and more preferably of from 5 to 14 and having a double bond set comprising a total of 4n+2 electrons, wherein n is an integer of from 0 to 4, preferably of from 1 to 3.
• aromatic radical scavengers include benzene derivatives, naphthalene derivatives, annulene derivatives, cyclopentadiene derivatives, cyclopropene derivatives, especially aryl carboxylates and/or aryl sulfonates.
• radical scavengers for use in the present invention have one of the following formulas: wherein each X, Y, and Z are -H, -COO-M + , -Cl, -Br, -SO 3 -M + , -NO 2 , -OCH 3 , or a C 1 to C 10 primary and secondary alkyl groups and M is H or an alkali metal, or mixtures thereof.
• these components include pyromellitic acid, i.e. where X, Y and Z are -COO-H + ; hemimellitic acid, trimellitic acid, i.e.
• radical scavengers are phthalic acid; sulfophthalic acid; other mono-substituted phthalic acids; di-substituted benzoic acids; alkyl-, chloro-, bromo-, sulfo-, nitro- and alkoxy- benzoic acids, i.e. where Y and Z are -H and X is a C 1 to C 10 primary and secondary alkyl groups, -Cl, -Br, -SO 3 -H + , -NO 2 or -OCH 3 (anisic acid) respectively and substituted sulfonic acids.
• radical scavengers useful in the present invention are benzoic acid, toluic acid, 4-toluene sulfonic acid, 3-nitro benzoic acid, 2 n-octyl benzoic acid, 2 n-octyl sulfonic acid, anisic acid or mixtures thereof. Most preferred herein are n-anisic acid, benzoic acid, methoxy benzoic acid and/or 3-nitrobenzoic acid.
• radical scavengers described above are the acidic form of the species, i.e. M is H. It is intended that the present invention also covers the salt derivatives of these species, i.e. M is an alkali metal, preferably sodium or potassium. In fact, since the pH of the compositions of the present invention is in the alkaline range, the radical scavengers of the present invention exist primarily as the ionized salt in the aqueous composition herein.
• the anhydrous derivatives of certain species described herein above can also be used in the present invention, e.g. pyromellitic dianhydride, phthalic anhydride, and sulphthalic anhydride.
• Suitable chelating agents for use herein may be any of those known to those skilled in the art such as the ones selected from the group comprising phosphonate chelating agents, phosphate chelating agents, polyfunctionally-substituted aromatic chelating agents, ethylenediamine N,N'- disuccinic acids, or mixtures thereof.
• Suitable phosphonate chelating agents to be used herein may include alkali metal ethane 1-hydroxy diphosphonates (HEDP), alkylene poly (alkylene phosphonate), as well as amino phosphonate compounds, including amino aminotri(methylene phosphonic acid) (ATMP), nitrilo trimethylene phosphonates (NTP), ethylene diamine tetra methylene phosphonates, and diethylene triamine penta methylene phosphonates (DTPMP).
• the phosphonate compounds may be present either in their acid form or as salts of different cations on some or all of their acid functionalities.
• Preferred phosphonate chelating agents to be used herein are diethylene triamine penta methylene phosphonate (DTPMP) and ethane 1-hydroxy diphosphonate (HEDP). Such phosphonate chelating agents are commercially available from Monsanto under the trade name DEQUEST®.
• Suitable phosphate chelating agents are as following: Phosphonic acid can be condensed in the reaction
• reaction can be repeated with any of the reactive OH groups, and phosphate ingredients are obtained which can be
• phosphate ingredients are suitable for use herein, and preferred are linear phosphate ingredients (i.e. R is M) where n is 1 (pyrophosphate) and n is 2 (tripolyphosphate (STPP)), most preferably where n is 2.
• R linear phosphate ingredients
• n is 1 (pyrophosphate) and n is 2 (tripolyphosphate (STPP)
• STPP tripolyphosphate
• M is Sodium
• Phytic acid which is a chelating agent particularly suitable for use herein, is a hexa-phosphoric acid that occurs naturally in the seeds of many cereal grains, generally in the form of the insoluble calcium-magnesium salt. It may also be derived from corn steep liquor. Commercial grade phytic acid is commercially available from J.T.Baker Co., e.g. as a 40% aqueous solution. It is intended that the present invention covers the acidic form of phytic acid as well as alkali metal salt derivatives thereof, particularly sodium or potassium salts thereof. Sodium phytate is available from Jonas Chemical Co (Brooklyn, N.Y.).
• the phytic acid component exists primarily as the ionized salt in the liquid compositions herein even if it is added in its acidic form. Mixtures of such salts of phytic acid are also covered.
• Polyfunctionally-substituted aromatic chelating agents may also be useful in the compositions herein. See U.S. patent 3,812,044, issued May 21, 1974, to Connor et al.
• Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy -3,5-disulfobenzene.
• a preferred biodegradable chelating agent for use herein is ethylene diamine N,N'- disuccinic acid, or alkali metal, or alkaline earth, ammonium or substitutes ammonium salts thereof or mixtures thereof.
• Ethylenediamine N,N'- disuccinic acids, especially the (S,S) isomer have been extensively described in US patent 4,704,233, November 3, 1987, to Hartman and Perkins.
• Ethylenediamine N,N'- disuccinic acids is, for instance, commercially available under the tradename ssEDDS® from Palmer Research Laboratories.
• Particularly preferred chelating agents for use herein are phosphate chelating agents like sodium tripolyphosphate, sodium pyrophosphate, phytic acid, and mixtures thereof.
• compositions according to the present invention may comprise from 0.01% to 10% by weight of the total composition of a stabilising agent, or mixtures thereof, preferably from 0.01% to 8% by weight, more preferably from 0.1% to 5%, and most preferably from 0.2% to 3%.
• a stabilising agent especially a radical scavenger alone or together with a chelating agent, increases the rheological stability of the compositions of the present invention.
• compositions of the present invention do not loose more than 30% initial viscosity after 10 days at 50°C, preferably not more than 20%.
• radical scavenger react with the free radicals present and prevent them from reacting/oxidising the alkyl (alkoxy) n sulphates.
• the chelating agents present bind metal ion impurities (e.g., copper, iron, and manganese) present in the compositions (e.g. as by product of the raw material) and thus prevent them from attacking the hypochlorite bleach thereby limiting the generation of free radicals, that would otherwise be generated in presence of such metal impurities.
• metal ion impurities e.g., copper, iron, and manganese
• adding the chelating agents on top of the radical scavengers further contribute to deliver excellent rheological stability upon ageing of the compositions.
• the presence of the stabilising agents may also contribute to reduce tensile strength loss of fabrics and/or colour damage, especially in a laundry pretreatment application.
• Fabric safety may be evaluated by different test methods including the degree of polymerisation test method according to UNI (Ente Nazionale Italiano di Unificazione) official method UNI 8282-Determinazione della viscosità intrinseca in soluée di cuprietilendiammina (CED).
• the liquid compositions of the present invention may further comprise a co-surfactant or a mixture thereof as a desirable optional ingredient to regulate the viscosity of the compositions herein.
• the co-surfactants for use herein have the properties to modify the initial viscosity provided by the presence of the alkyl (alkoxy) n sulphate in the compositions of the present invention, i.e. to lower or higher the viscosity provided by the sole presence of such alkyl (alkoxy) n sulphate, in the compositions herein.
• such a co-surfactant will be chosen depending on the initial viscosity desired for the compositions of the present invention.
• the presence of the co-surfactants in the bleaching compositions according to the present invention further contributes to deliver effective stain removal performance and/or whiteness performance to fabrics treated therewith.
• compositions according to the present invention may comprise said co-surfactant in amounts of from 0.01% to 10% by weight of the total composition, preferably of from 0.1% to 5% and more preferably of from 1% to 2.5%.
• Suitable co-surfactants for use herein are typically selected from the group consisting of alkyl sulphates, alkyl aryl sulphonates, zwitterionic surfactants like betaine surfactants, cationic surfactants like alkyl trimethylammonium halogenides and mixture thereof.
• Suitable alkyl sulphates for use in the compositions herein include water-soluble salts or acids of the formula ROSO 3 M wherein R preferably is a C 4 -C 24 hydrocarbyl, preferably linear or branched alkyl having a C 6 -C 20 alkyl component, more preferably a C 6 - C 18 linear or branched alkyl, most preferably a C 6 - C 16 linear or branched alkyl 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 trimethylammonium cations and quaternary ammonium cations, such as tetramethylammonium and dimethyl piperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethy
• 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 4 -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 trimethylammonium cations and quaternary ammonium cations, such as tetramethylammonium and dimethyl piperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine
• Suitable zwitterionic betaine surfactants for use herein contain both a cationic hydrophilic group, i.e., a quaternary ammonium group, and anionic hydrophilic group on the same molecule at a relatively wide range of pH's.
• the typical anionic hydrophilic groups are carboxylates and sulfonates, although other groups like sulfates, phosphonates can be used.
• 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 or sulfonate group.
• 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)-NH-(C(R b ) 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 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 b ) 2 ) moiety.
• Preferred R 2 is hydrogen, or a C 1 -C 3 alkyl and more preferably methyl.
• Preferred R 3 is a C 1 -C 4 carboxylic acid group or C1-C4 sulfonate group, or a C 1 -C 3 alkyl and 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®.
• 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".
• betaine is Lauryl-immino-dipropionate commercially available from Rhone-Poulenc under the trade name Mirataine H2C-HA ®.
• Suitable cationic surfactants are alkyl trimethylammonium halogenides and those surfactants having the formula: [R 2 (OR 3 ) y ][R 4 (OR 3 ) y ] 2 R 5 N + X - wherein R 2 is an alkyl or alkyl benzyl group having from 8 to 18 carbon atoms in the alkyl chain, each R 3 is selected from the group consisting of -CH 2 CH 2 -, -CH 2 CH(CH 3 )-, -CH 2 CH 2 CH 2 -, and mixtures thereof; each R 4 is selected from the group consisting of C 1 -C 4 alkyl, benzyl ring structures formed by joining the two R 4 groups, and hydrogen when y is not 0; R 5 is the same as R 4 or is an alkyl chain wherein the total number of carbon atoms of R 2 plus R 5 is not more than 18; each y is from 0 to 10 and the sum of the y values is from 0 to 15; and
• the liquid compositions of the present invention may further comprise another surfactant or a mixture thereof on top of the alkyl (alkoxy) n sulphate and optional co-surfactant mentioned herein before.
• Said other surfactants may be present in the compositions according to the present invention in amounts up to 30% by weight of the total composition, preferably of from 0.1% to 20% and more preferably of from 1% to 10%.
• Surfactants for use herein include other anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, and mixtures thereof as long as they do not affect the viscosity and rheological properties of the compositions according to the present invention.
• the additional surfactants have to be stable to the hypohalite bleach.
• compositions herein is a polymer. That polymer, has surprisingly been found to also reduce the yellowing of the fabrics treated therewith, i.e. improve whiteness, as well as improve fabric safety. Naturally, for the purpose of the invention, the polymer has to be stable to the hypohalite bleach.
• Suitable polymers for use are polymers comprising monomeric units selected from the group consisting of unsaturated carboxylic acids, polycarboxylic acids, sulphonic acids, phosphonic acids and mixtures thereof. Co-polymerisation of the above monomeric units among them or with other co-monomers such -as styrenesulfonic acid is also suitable.
• Preferred examples of such polymers are the polymers and co-polymers of monomeric units selected from the group consisting of acrylic acid, maleic acid, vinylsulphonic acid and mixtures thereof. Also suitable for use herein are the above mentioned polymers and co-polymers which are modified in order to contain other functional groups such as aminophosphonic and/or phosphonic units. More preferred polymers are selected from the group consisting of polyacrylate polymers, co-polymers of acrylic and maleic acid, co-polymers of styrene sulphonic acid and maleic acid, and mixtures thereof, preferably modified with aminophosphonic and/or phosphonic groups.
• the molecular weight for these polymers and co-polymers is preferably below 100,000, most preferably between 500 and 50,000. Most suitable polymers and co-polymers for use herein will be soluble in an amount up to 0.1% by weight, in an aqueous composition comprising 5% by weight of sodium hypochlorite with its pH adjusted to 13 with sodium hydroxide.
• polymers suitable for use herein, are the polyacrylate polymers sold under the tradename Good-Rite® from BF Goodrich, Acrysol® from Rohm & Haas, Sokalan® from BASF, Norasol® from Norso Haas. Also suitable for use herein are the co-polymers of styrene sulphonic acid and maleic acid, commercially available under the tradename Versaflex® from National Starch such as Versaflex 157, as well as Acumer® terpolymers from Rohm and Haas, in particular Acumer® 3100.
• Preferred commercially available polymers are the polyacrylate polymers, especially the Norasol® polyacrylate polymers and more preferred are the polyacrylate polymer Norasol® 410N (MW 10,000) and the polyacrylate polymer modified with phosphonic groups Norasol® 440N (MW 4000) and its corresponding acid form Norasol® QR 784 (MW 4000).
• a preferred polymer for use herein is a polyacrylate polymer modified with phosphonic groups commercially available under the tradename Norasol® 440N (MW 4000) and its corresponding acid form Norasol® QR 784 (MW 4000) from Norso-Haas.
• Polymers herein are preferably present in low amounts, i.e. in amounts of up to 10% by weight, preferably up to 1%, more preferably from 0.001% to 0.5% by weight, most preferably from 0.005% to 0.2% by weight of the liquid composition.
• compositions according to the present invention may also comprise a brightener or a mixture thereof as an optional ingredient.
• the brightener has to be stable to the hypohalite bleach.
• the brighteners may be desired herein to further enhance the whiteness performance of the compositions herein.
• Brighteners are compounds which have the ability to fluorescent by absorbing ultraviolet wave-lengths of light and re-emitting visible light. Brighteners, also referred to as fluorescent whitening agent (FWA), have been extensively described in the art, see for instance EP-A-0 265 041, EP-A-0 322 564, EP-A-0 317 979 or "Fluorescent whitening agents" by A.K. Sarkar, published by MERROW, especially page 71-72.
• FWA fluorescent whitening agent
• optical brighteners which may be useful in the present invention can be classified into subgroups, which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiophene-5,5-dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982). Further optical brighteners which may also be used in the present invention include naphthlimide, benzoxazole, benzofuran, benzimidazole and any mixtures thereof.
• optical brighteners which are useful in the present compositions are those identified in U.S. Patent 4,790,856. These brighteners include the PHORWHITE® series of brighteners from Verona. Other brighteners disclosed in this reference include: Tinopal-UNPA®, Tinopal CBS® and Tinopal 5BM® available from Ciba-Geigy; Artic White CC® and Artic White CWD®; the 2-(4-styryl-phenyl)-2H-naptho[1,2-d]triazoles; 4,4'-bis(1,2,3-triazol-2-yl)-stilbenes; 4,4'-bis(styryl)bisphenyls; and the aminocoumarins.
• brighteners useful herein include 4-methyl-7-diethyl-amino coumarin; 1,2-bis(-benzimidazol-2-yl)ethylene; 1,3-diphenyl-pyrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2-styryl-naptho-[1,2-d]oxazole; 2-(stilbene-4-yl)-2H-naphtho[1,2-d]triazole, 3-phenyl-7-(isoindolinyl) coumarin; 3-methyl-7-(isoindolinyl) coumarin; 3-chloro-7-(isoindolinyl) coumarin; 4-(isoindolinyl)-4'-methylstilbene; 4-(isoindolinyl)-4'-methoxystilbene; sodium 4-(isoindolinyl)-4'-stilbenesulfonate; 4-(isoindolinyl)-4'-phenylstilbene;
• optical brighteners useful in the present invention are those having the structural formula: wherein R 1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R 2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.
• R 1 is anilino
• R 2 is N-2-bis-hydroxyethyl and M is a cation such as sodium
• the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt.
• This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
• R 1 is anilino
• R 2 is N-2-hydroxyethyl-N-2-methylamino
• M is a cation such as sodium
• the brightener is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt.
• This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.
• R 1 is anilino
• R 2 is morphilino
• M is a cation such as sodium
• the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid, sodium salt.
• This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.
• substituted stilbene 2,2'-disulfonic acid derivatives also include 4,4'-bis (2,2' styryl sulfonate) biphenyl, commercially available from Ciba-Geigy under the trade name Brightener 49® or other hydrophilic brighteners like for example Brightener 3® or Brightener 47®, also commercially available from Ciba-Geigy.
• brighteners useful in the present invention include the polycyclic oxazole derivatives such as benzo-oxazole derivatives, or mixtures thereof and particularly preferred herein the benzo-oxazole derivatives.
• An example of such a brightener is benzoxazole; 2,2'-(thiophenaldyl)bis having the following formula C18H10N2O2S, commercially available from Ciba-Geigy under the trade name Tinopal SOP®.
• This brightener is almost insoluble in water, i.e. it has a solubility being lower than 1 gram per liter.
• Another example of such a brightener is bis(sulfobenzofuranyl)biphenyl, commercially available from Ciba-Geigy under the trade name Tinopal PLC®.
• compositions according to the present invention comprise up to 1.0% by weight of the total composition of a brightener or a mixture thereof, preferably from 0.005% to 0.5%, more preferably from 0.005% to 0.3% and most preferably from 0.008% to 0.1%.
• the liquid bleaching composition of the present invention needs to be contacted with the surface to treat.
• surfaces any inanimate surface.
• inanimate surfaces include, but are not limited to, hard-surfaces typically found in houses like kitchens, bathrooms, or in car interiors, e.g., tiles, walls, floors, chrome, glass, smooth vinyl, any plastic, plastified wood, table top, sinks, cooker tops, dishes, sanitary fittings such as sinks, showers, shower curtains, wash basins, and WCs, as well as fabrics including clothes, curtains, drapes, bed linens, bath linens, table cloths, sleeping bags, tents, and upholstered furniture, and carpets.
• Inanimate surfaces also include household appliances including, but not limited to, refrigerators, freezers, washing machines, automatic dryers, ovens, microwave ovens, and dishwashers.
• treating a surface it is meant herein bleaching and/or disinfecting said surfaces as the compositions of the present invention comprise a hypohalite bleach and cleaning, i.e. removing various types of stains from the surfaces, as said compositions comprise an alkyl (alkoxy) n sulphate.
• the present invention also encompasses a process of treating (e.g. bleaching) a fabric, as the inanimate surface.
• a composition according to the present invention is contacted with the fabrics to be treated.
• pretreatment mode where a liquid bleaching composition, as defined herein, is applied neat onto said fabrics before the fabrics are rinsed, or washed then rinsed, or in a "soaking mode” where a liquid bleaching composition, as defined herein, is first diluted in an aqueous bath and the fabrics are immersed and soaked in the bath, before they are rinsed, or in a "through the wash mode", where a liquid bleaching composition, as defined herein, is added on top of a wash liquor formed by dissolution or dispersion of a typical laundry detergent. It is also essential in both cases, that the fabrics be rinsed after they have been contacted with said composition, before said composition has completely dried off.
• the processes of treating surfaces fabrics according to the present invention delivers effective whiteness performance and/or effective stain removal performance upon ageing of the compositions.
• compositions according to the present invention are preferably contacted to fabrics in a liquid form. Indeed, by "in a liquid form”, it is meant herein the liquid compositions according to the present invention per se in neat or diluted form.
• compositions according to the present invention are typically used in diluted form in a laundry operation.
• in diluted form it is meant herein that the compositions for the bleaching of fabrics according to the present invention may be diluted by the user, preferably with water. Such dilution may occur for instance in hand laundry applications as well as by other means such as in a washing machine.
• Said compositions can be diluted up to 500 times, preferably from 5 to 200 times and more preferably from 10 to 80 times.
• the process of bleaching fabrics according to the present invention comprises the steps of first contacting said fabrics with a bleaching composition according to the present invention, in its diluted form, then allowing said fabrics to remain in contact with said composition, for a period of time sufficient to bleach said fabrics, typically 1 to 60 minutes, preferably 5 to 30 minutes, then rinsing said fabrics with water. If said fabrics are to be washed, i.e., with a conventional composition comprising at least one surface active agent, said washing may be conducted together with the bleaching of said fabrics by contacting said fabrics at the same time with a bleaching composition according to the present invention and said detergent composition, or said washing may be conducted before or after that said fabrics have been bleached.
• said process according to the present invention allows to bleach fabrics and optionally to wash fabrics with a detergent composition comprising at least one surface active agent before the step of contacting said fabrics with said bleaching composition and/or in the step where said fabrics are contacted with said bleaching composition and/or after the step where said fabrics are contacted with the bleaching composition and before the rinsing step and/or after the rinsing step.
• the process of bleaching fabrics comprises the step of contacting fabrics with a liquid bleaching composition according to the present invention, in its neat form, of allowing said fabrics to remain in contact with said bleaching composition for a period of time sufficient to bleach said fabrics, typically 5 seconds to 30 minutes, preferably 1 minute to 10 minutes and then rinsing said fabrics with water. If said fabrics are to be washed, i.e., with a conventional composition comprising at least one surface active agent, said washing may be conducted before or after that said fabrics have been bleached.
• the level of hypohalite bleach is from 0.01% to 5%, preferably from 0.1% to 3.5%, more preferably from 0.2% to 2% and most preferably from 0.2% to 1%.
• the present invention provides liquid hypohalite bleach-containing compositions that may be applied neat onto a fabric to bleach, despite a standing prejudice against using hypochlorite-containing compositions neat on fabrics.
• the bleaching pre-treatment operation may also be followed by the diluted bleaching process as described herein before either in bucket (hand operation) or in a washing machine.
• the present invention also encompasses a process of treating a hard-surface, as the inanimate surface.
• a composition as defined herein, is contacted with the hard-surfaces to be treated.
• the present invention also encompasses a process of treating a hard-surface with a composition, as defined herein, wherein said process comprises the step of applying said composition to said hard-surface, preferably only soiled portions thereof, and optionally rinsing said hard-surface.
• composition as defined herein, may be applied to the surface to be treated in its neat form or in its diluted form typically up to 200 times their weight of water, preferably into 80 to 2 times their weight of water, and more preferably 60 to 2 times.
• compositions of the present invention are easy to rinse and provide good shine characteristics on the treated surfaces.
• hard-surfaces any hard-surfaces as mentioned herein before as well as dishes.
• Na C 12 -C 14 E3S is an alkyl C 12/14 (ethoxy)3 sulphate commercially available from Rhone Poulenc and Albright & Wilson.
• the unsulfated material in the alkyl alkoxy sulphate used in the compositions above is below 3% by weight of the sulfated active basis and metal impurities level is below 0.00015% of the sulfated active basis.
• NaC 8 S is sodium C 8 alkyl sulphate.
• Betaine is lauryl dimethyl amine betaine from Albright & Wilson.
• LAS sodium paraffin benzene sulphonate from Albright & Wilson.
• compositions above are chemically stable, i.e., they do not undergo more than 35% loss of available chlorine after 5 days of storage at 50°C.
• compositions above comprising stabilizing agent deliver improved rheological stability upon prolonged periods of storage, e.g. they do not undergo more than 30% loss of initial viscosity after 10 days of storage at 50°C.
• compositions deliver effective stain removal performance as well as effective whiteness performance when used in a laundry application in their neat or diluted form, e.g. 200 times their weight of water, after prolonged periods of storage, e.g., after 3 months of storage at room temperature (25°C) after their manufacturing.
• compositions also deliver effective cleaning performance when used in any household cleaning application.

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• 1998
  • 1998-02-23 EP EP19980870035 patent/EP0903403B1/en not_active Revoked
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