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
  • C11D3/395—Bleaching agents
  • C11D3/3956—Liquid compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/83—Mixtures of non-ionic with anionic compounds
• • 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
  • C11D1/86—Mixtures of anionic, cationic, and non-ionic compounds
• • 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
  • C11D1/88—Ampholytes; Electroneutral compounds
• • 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
  • C11D1/88—Ampholytes; Electroneutral compounds
  • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
• • 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
• • 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
  • C11D3/2003—Alcohols; Phenols
  • C11D3/2006—Monohydric alcohols
  • C11D3/2034—Monohydric alcohols aromatic
• • 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
  • C11D3/2068—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
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/40—Dyes ; Pigments
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/40—Dyes ; Pigments
  • C11D3/42—Brightening agents ; Blueing agents

Definitions

• the present invention relates to bleaching compositions, in particular to hypohalite bleaching compositions which can be used to treat various surfaces.
• Bleach-containing compositions for bleaching various surfaces are well known in the art.
• those relying on bleaching by hypohalite bleach, such as hypochlorite are often preferred, mainly for bleaching performance reasons.
• hypohalite bleach composition often faced stability problems.
• an objective of bleach manufacturers has always been to obtain a bleach product that is chemically and physically stable over time, for example, over periods of storage.
• hypohalite bleach-containing compositions it is often desirable to add further ingredients, such as dyes or pigments, to hypohalite bleach-containing compositions in order to improve the aesthetics of such compositions.
• further ingredients such as dyes or pigments
• coloured bleaching compositions are particularly preferred compositions.
• the distinct appearance of the composition facilitates it's recognition by consumers, thereby reducing potential misuse or consumption of a potentially irritant composition .
• hypohalite bleach- containing compositions A drawback associated with coloured hypohalite bleach- containing compositions is that pigments and/or dyes, present herein, are decomposed by the bleach. Indeed, hypohalite bleaches are oxidising agents and pigments and dyes are very prone to attacks. In some cases such compounds can even be completely decomposed by such oxidising agents.
• oxidizing agents of the bleaching composition may also cause degradation of optical brighteners present in the composition to increase whitening performances of the same.
• hypohalite-containing composition comprising a pigment and/or a brightener, in which this compound is chemically stable and wherein the cleaning performances of the composition are maintained.
• hypohalite bleach-containing compositions it is known in the art to add a stabilising agent to hypohalite bleach-containing compositions in order to prevent, or at least reduce, the decomposition of further ingredients, in particular pigments and/or dye, present in such compositions.
• EP-A-0668345 and EP-A-1001010 relates to bleaching compositions comprising a hypohalite bleach and a radical scavenger.
• stabilization systems and especially radical scavengers, are capable of stabilising further ingredients, it has been found that pigments and/or dyes are still particularly prone to attacks by hypohalite bleaches and hence are extremely difficult to be stably incorporated into bleaching compositions comprising the known stabilization systems.
• EP 2112218 discloses the use of trimethoxy benzoic acid (TMBA) or a salt thereof as stabilizer of pigments and/or dyes in hypohalite bleach-containing composition.
• TMBA trimethoxy benzoic acid
• TMBA is able to stabilize also the Brightener 49, which is rapidly oxidised by the hypochlorite.
• Brightener 49 which is rapidly oxidised by the hypochlorite.
• TMBA is an expensive chemical, then a cheaper and more efficient substitute of TMBA would be really attractive.
• JP2006077199 teaching the use of a compound of formula ]3 ⁇ 4- 0- (R3CHCH2O) S -H, such as phenoxyethanol , to stabilize a synthetic dyes in a bleaching composition containing a hypohalite, an alkali agent, an alkali metal salt of sulfonic acid.
• a compound of formula ]3 ⁇ 4- 0- (R3CHCH2O) S -H such as phenoxyethanol
• the composition containing phenoxyethanol although stable, causes staining of the hard surfaces to which it is applied when the dye is a copper phtalocyanine pigment.
• compositions according to claim 1 uses of compound of formula (I) according to claim 10 or 11 and a process of treating a surface according to claim 12 are provided.
• the bleaching compositions herein described are formulated as liquid compositions, including gel and paste form.
• the bleaching compositions are, preferably, but not necessarily, formulated as aqueous compositions.
• Preferred liquid bleaching compositions of the present invention are aqueous and therefore, preferably, may comprise water, more preferably may comprise water in an amount of from 60% to 98%, even more preferably of from 80% to 96% and most preferably 85% to 97% by weight of the total composition.
• compositions of the present invention typically do not undergo more than 36% loss of available oxidising agent after 10 days of storage at 50°C ⁇ 0.5°C and more preferably not more than 32%.
• the percentage of loss of available chlorine (%AvCl) 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 oxidising agent in the fresh compositions, i.e. just after they are made, and in the same compositions after 5 days at 50°C.
• compositions according to the present invention are preferably alkaline compositions.
• the pH of the liquid compositions herein is from 9.0 to 14, preferably from 10.5 to 14 when measured at 25°C. It is in this alkaline range that the optimum stability and performance of the composition as well as fabric whiteness and/or safety are obtained .
• compositions herein may comprise an acid or a source of alkalinity to adjust the pH as appropriate.
• 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 source of alkalinity is a caustic alkali, more preferably sodium hydroxide and/or potassium hydroxide.
• Typical levels of such sources of alkalinity, when present, are of from 0.1% to 2% by weight, preferably from 0.5% to 1.5% by weight of the composition.
• the bleaching compositions of the present invention comprise a hypohalite bleach .
• Suitable hypohalite bleaches may be provided by a variety of sources, including bleaches that lead to the formation of positive halide ions and/or hypohalite ions, as well as bleaches that are organic based sources of halides, such as chloroisocyanurates .
• 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 .
• said hypohalite bleach is an alkali metal and/or alkaline earth metal hypochlorite.
• said hypohalite bleach is an alkali metal and/or alkaline earth metal hypochlorite selected from the group consisting of sodium hypochlorite, potassium hypochlorite, magnesium hypochlorite, lithium hypochlorite and calcium hypochlorite, and mixtures thereof. Even more preferably, said hypohalite bleach is sodium hypochlorite.
• the liquid bleaching compositions herein comprise hypohalite bleach such that the content of active halide (for hypochlorite : AvC12) in the composition is of from 0.01% to 15% by weight, more preferably from 0.1% to 10% by weight, even more preferably from 0.5% to 7% by weight and most preferably from 1% to 6% by weight of the composition .
• active halide for hypochlorite : AvC12
• the bleaching compositions of the present invention comprises a surfactant system.
• Said surfactant system may be present in the compositions herein in amounts of at least 0.01% by wight, preferably from 0.5% to 50% by weight, more preferably from 0.5% to 30% by weight and even more preferably from 0.5% to 10% by weight of the composition.
• the amount of surfactant must be superior to 0.5% in order to avoid staining of surfaces.
• the surfactant system suitable for use herein is selected from the group consisting of:
• Suitable anionic surfactants for use in the compositions herein include water-soluble salts or acids of the formula ROSO 3 M wherein R preferably is a C10-C2 hydrocarbyl, preferably linear or branched alkyl having a C10- C20 alkyl component, more preferably a C12-C18 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 trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethyl
• R preferably is a C10-C2 hydrocarbyl, preferably linear or branched alkyl having
• anionic surfactants for use herein are water-soluble salts or acids of the formula (II)
• R 3 is an unsubstituted C6-C2 linear or branched alkyl group having a C6-C2 alkyl component, preferably a C10- C20 linear or branched alkyl, more preferably C12-C18 linear or branched alkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 30, more preferably between about 0.5 and about 5, and Mi is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation.
• a metal cation e.g., sodium, potassium, lithium, calcium, magnesium, etc.
• Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
• Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium and quaternary ammonium cations, such as tetramethyl-ammonium, dimethyl piperdinium and cations derived from alkanolamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like.
• Exemplary surfactants are C12-C18 alkyl polyethoxylate ( 1.0 ) sulfate, Ci2 - Ci 8 E ( 1.0 ) sulfate, C12-C18 alkyl polyethoxylate (2.25) sulfate, Ci2 - Ci 8 E (2.25) sulfate, C12-C18 alkyl polyethoxylate (3.0) sulfate, C12 -
• the surfactant system used is an anionic surfactant system, namely alkyl alkoxy (preferably ethoxy) sulphate alone for example alkyl (ethoxy) 3 sulphate (AE3S) or in combination with a co-surfactant, preferably a C2 - C10 alkyl sulphate and/or a C 8 - C22 alkyl or aryl sulphonate like C 8 - C22 benzene sulphonate and/or another alkyl alkoxy sulphate apart the 3 ethoxylated one.
• AE3S alkyl alkoxy
• co-surfactant preferably a C2 - C10 alkyl sulphate and/or a C 8 - C22 alkyl or aryl sulphonate like C 8 - C22 benzene sulphonate and/or another alkyl alkoxy sulphate apart the 3 ethoxylated one.
• compositions according to the present invention have a viscosity between 25 cps and 1500 cps, preferably between 50 cps and 200 cps, depending of the ratio between AE3S and the co-surfactant, when measured with a Rheometer like Carri-med CSL2-100® at the following viscosity parameters: angle: 1°58, gap: 60, diameter: 4.0 cm, iner.: 63.60 at a temperature of 25°C and a shear rate of 30 1/sec.
• anionic surfactants for use herein are water-soluble salts or acids of the formula (III)
• R is an unsubstituted C6-C2 linear or branched alkyl group having a C6-C2 alkyl component, preferably a C10- C20 linear or branched alkyl, more preferably C12-C18 linear or branched alkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 30, more preferably between about 0.5 and about 5, and Mi is as defined above.
• Alkyl ethoxylated carboxylates as well as alkyl propoxylated carboxylates are contemplated herein.
• Exemplary surfactants are C12-C18 alkyl ethoxylated (2.0) carboxylate, C12-C18 alkyl ethoxylated ( 5.0 ) carboxylate, C12-C18 alkyl ethoxylated ( 7.0 ) carboxylate, wherein the counterion is conveniently selected from sodium and potassium.
• anionic surfactants useful for detersive purposes can also be used herein.
• the anionic surfactant may be selected in the group consisting of alkyl sulphates, alkyl ether sulphates, sarcosinates, taurates, ether carboxylate, alkyl ethoxylated sulphates, alkyl propoxylated sulfates or their mixtures.
• Suitable nonionic surfactants for use herein are capped nonionic ethoxylated surfactants according to the formula ( IV) :
• R5 is a Cs -Cis linear or branched alkyl or alkenyl group, aryl group, alkaryl group, preferably, R5 is a C10-C15 alkyl or alkenyl group, more preferably a C10-C15 alkyl group;
• R6 is a C2 - C10 linear or branched alkyl group, preferably a C group;
• R 7 is a C1- C10 alkyl or alkenyl group, preferably a C1-C5 alkyl group, and n is an integer ranging in the range of from 1 to 20, preferably from 1 to 10, more preferably from 1 to 5; or mixtures thereof.
• surfactants are commercially available from BASF under the trade name Plurafac ® , from HOECHST under the trade name Genapol ® or from ICI under the trade name Symperonic ® .
• Preferred capped nonionic ethoxylated surfactant of the above formula are those commercially available under the tradename Genapol ® L 2 . 5 NR from Hoechst, and Symperonic ® LF/CS 1 1 00 from ICI.
• nonionic surfactants for use herein include a class of compounds which may be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be branched or linear aliphatic (e.g. Guerbet or secondary alcohol) or alkyl aromatic in nature.
• the length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
• Suitable zwitterionic surfactants for use herein are that include the amine oxides corresponding to the formula (V) :
• R 8 is a primary alkyl group containing 6- 24 carbons, preferably 1 0 - 18 carbons, and wherein Rg and Rio are, each, independently, an alkyl group containing 1 to 6 carbon atoms.
• the arrow in the formula is a conventional representation of a semi-polar bond.
• the preferred amine oxides are those in which the primary alkyl group has a straight chain in at least most of the molecules, generally at least 7 0 % , preferably at least 90 % of the molecules, and the amine oxides which are especially preferred are those in which R contains 1 0 - 18 carbons and Rs and R9 are both methyl.
• Exemplary of the preferred amine oxides are the N- decyldimethylamine oxide, N-dodecyl dimethylamine oxide, the corresponding amine oxides in which one or both of the methyl groups are replaced with ethyl or 2-hydroxyethyl groups and mixtures thereof.
• a most preferred amine oxide for use herein is N-decyldimethylamine oxide.
• Suitable zwitterionic surfactants for the purpose of the invention are the phosphine or sulfoxide surfactants of formula (VI) :
• A is phosphorus or sulfur atom
• Rn is a primary alkyl group containing 6-24 carbons, preferably 10- 18 carbons
• R 1 2 and R13 are, each, independently selected from methyl, ethyl and 2-hydroxyethyl.
• the arrow in the formula is a conventional representation of a semi- polar bond.
• Suitable surfactants with multiple charges for use herein are zwitterionic detergents that comprise the betaine and betaine-like detergents wherein the molecule contains both basic and acidic groups which form an inner salt giving the molecule both cationic and anionic hydrophilic groups over a broad range of pH values.
• Some common examples of these detergents are described in U.S. Pat. Nos. 2082275, 2702279 and 2255082.
• Amphoteric and ampholytic detergents which can be either cationic or anionic depending upon the pH of the system are represented by detergents such as dodecylbeta- alanine, N-alkyltaurines such as the one prepared by reacting dodecylamine with sodium isethionate according to the teaching of U.S. Pat. No. 2658072, N-higher alkylaspartic acids such as those produced according to the teaching of U.S. Pat. No. 2438091 , and the products sold under the trade name "Miranol", and described in U.S. Pat. No. 2,528,378.
• detergents such as dodecylbeta- alanine, N-alkyltaurines such as the one prepared by reacting dodecylamine with sodium isethionate according to the teaching of U.S. Pat. No. 2658072, N-higher alkylaspartic acids such as those produced according to the teaching of U.S. Pat. No
• R14 is an unsubstituted C2-C2 linear or branched alkyl group having a C4-C24 alkyl component, preferably a C4- C2 0 linear or branched alkyl, more preferably C4-C18 linear or branched alkyl, and A, m and Ml are as defined above, in particular, m is typically between about 0 . 5 and about 50 , more preferably between about 5 and about 30 .
• Quaternary diamine alkyl ether sulfates as well as quaternary amine alkyl ether sulfates are contemplated herein.
• Exemplary surfactants are Lutensit z96 form BASF®.
• Cationic surfactants suitable for use in compositions of the present invention are those having a long-chain hydrocarbyl group.
• cationic surfactants include the ammonium surfactants such as alkyltrimethylammonium halogenides, and those surfactants having the formula (VIII) :
• R15 is an alkyl or alkyl benzyl group having from 8 to 1 8 carbon atoms in the alkyl chain
• each Ri 6 is selected from the group consisting of - CH2CH2 - , - CH2CH(CH 3 ), - CH2CH2CH2 - , and mixtures thereof
• each R i7 is selected from the group consisting of C 1 -C4 alkyl, benzyl ring structures formed by joining the two Ri 7 groups, and hydrogen when y is not 0
• R 18 is the same as Ri 7 or is an alkyl chain wherein the total number of carbon atoms of R15 plus Ris is not more than about 1 8
• each y is from 0 to about 1 0 and the sum of the y values is from 0 to about 15
• X is any compatible anion.
• R19 is a short chain length alkyl (C6-C10), whereby R20 is H or a C1-C3 alkyl,
• x is 0-4, preferably 0-2, most preferably 0, whereby R21 , R22 and R23 are either the same or different and can be either a short chain alkyl (C1-C3) or alkoxylated alkyl of the formula X,
• X ⁇ is a counterion, preferably a halide, e.g. chloride or methylsulfate .
• R24 is C1-C4 and z is 1 or 2.
• Highly preferred cationic surfactants are the water- soluble quaternary ammonium compounds useful in the present composition having the formula :
• R25 is C8-C16 alkyl
• each of R26, R27 and R28 is independently C1-C4 alkyl, benzyl, and -(C 2 H ) X H where x has a value from 2 to 5, and X is an anion.
• R26, R27 and R28 should be benzyl.
• preferred alkyl chain length for Rl is C12-C15 particularly where the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fat or is derived synthetically by olefin build up or OXO alcohols synthesis.
• Preferred groups for R2R3 and R4 are methyl and the anion X may be selected from halide, methosulphate, acetate and phosphate ions.
• coconut trimethyl ammonium chloride or bromide coconut trimethyl ammonium chloride or bromide
• lauryl dimethyl benzyl ammonium chloride or bromide lauryl dimethyl (ethenoxy)4 ammonium chloride or bromide ;
• alkyl and R26R27R28 are methyl.
• compositions of the present invention comprise a stabilizer of formula (I) :
• Ri represents an optionally substituted phenyl group or benzyl group
• R2 represents a hydrogen atom or a methyl group
• s represents an integer from 0 to 4.
• Ri is a phenyl group
• R2 represents a hydrogen atom and s represents an integer from 1 to 2.
• the stabilizer of formula (I) is phenoxyethanol .
• the bleaching composition herein may comprise from 0.001% to 5%, preferably from 0.005% to 3.0% and more preferably from 0.03% to 2.0% by weight of the total composition of said stabilizer of formula (I) . It is has been found that the use of a stabilizer of formula (I), such as phenoxyethanol , in combination with the specific surfactant system described above has a synergetic effect on the stability of the pigment and/or of the brightener and on the bleaching composition itself.
• a stabilizer of formula (I) such as phenoxyethanol
• compositions of the present invention may comprise at least one metal-phthalocyanine pigment.
• the presence of a pigment in the composition of the present invention is essential to provide a colored bleaching composition.
• the metal, in the metal-phthalocyanine pigment can be any metal with which phthalocyanine forms a metal chelate complex, such as Cu, Ni, Mg, Pt, Al, Co, Pb, Ba .
• the metal-phthalocyanine pigments contained in the bleaching composition of the present invention is a copper-phthalocyanine pigment.
• the pigment used in the present invention herein is a blue or green copper phthalocyanine pigment.
• Blue copper phtalocyanine is commercially available under the tradename Dye Pigmosol Blue 15 ® , from BASF; Direct Blue 86 (commercially available under the tradename Iragon Blue DBL86 ® from Clariant) ; Pigment Blue 15:1 (commercially available under the tradename Disperse Blue 69-007 ® from BASF) ; and Pigment Blue 15:3 ( commercially available under the tradename Hostafine Blue B2G ® from Clariant) .
• the pigment, or mixture thereof is present in the compositions of the present invention at levels of from 0.0001% to 0.5% by weight, preferably from 0.0002% to 0.05%, more preferably from 0.0005% to 0.005% and most preferably from 0.0005% to 0.003% by weight.
• compositions according to the present invention may also comprise a brightener or mixture thereof.
• 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- 0265041 , EP-A-0322564 , EP-A-0317979 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; Artie White CC ® and Artie White CWD ® ; the 2- (4- styryl-phenyl ) -2H-naptho [l,2-d]triazoles; 4, 4' -bis (1,2,3- triazol-2-yl ) -stilbenes ; 4 , 4 ' -bis ( styryl ) bisphenyls ; and the aminocoumarins .
• 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 C 18 H 10 N2O2 S , 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 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% by weight.
• compositions of the present invention may comprise an alkali metal salt of silicate. Indeed, when this ingredient is present in the composition according to the present invention a synergetic effect on stability of the pigment and of the oxidising agent is obtained.
• alkali metal salt of silicate it is meant herein an alkali metal salt of silicate or polysilicates , or mixtures thereof.
• the preferred alkali metal salt of silicate to be used herein is sodium silicate.
• Preferred compositions of the present invention comprise from 0.005% to 5% by weight of the total composition of an alkali metal salt of silicate, preferably from 0.01 % to 2% and more preferably from 0.05% to 1%.
• alkali metal salt of silicate such as sodium silicate
• alkali metal salt of silicate such as sodium silicate
• alkali metal salts of silicate such as sodium silicate
• pigments such as copper-phthalocyanine when decomposed by oxidizing agent, release free metal ion, such as copper, which results in the acceleration of hypohalite decomposition.
• a further advantage of the bleaching compositions according to the present invention is that they show excellent bleaching performances upon storage. The cleaning performances of the bleaching composition are therefore maintained.
• compositions of the present invention the presence of a pH buffering component is not compulsory, but is preferred.
• the presence of a pH buffering component in the compositions of the present invention further contributes to the stability of these compositions, effective whiteness performance as well as to the fabric safety.
• the pH buffering component allows to control the alkalinity in the bleaching solution, i.e. maintain the pH of the bleaching solution at a pH of at least 7.5, preferably at least 8, and more preferably at least 8.5 for a longer period of time starting from the moment at which the dilution is completed (e.g. when the bleaching composition of the present invention is diluted in the bleaching solution at a dilution level of 500:1 (water: composition)) .
• the pH buffering component may also contribute to stability of the bleach- unstable ingredients herein.
• 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, alluminates and mixtures thereof. More preferably alkali metal salts of carbonate, silicate and borate.
• the preferred alkali metal salts for use herein are sodium and potassium.
• 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.
• by-products e.g. calcium carbonate resulting in an amount of up to 0.4% by weight of by-product within the hypohalite composition.
• the by-product will not have the buffering action defined above.
• Liquid bleaching compositions of the invention may contain a mixture of inorganic alkaline compounds, preferably a mixture of at least an hydroxide and at least a carbonate.
• 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 .
• compositions according to the present invention may optionally also comprise a chelating agent as an optional ingredient.
• Suitable chelating agents 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 ⁇ , ⁇ '- disuccinic acids, or mixtures thereof.
• Chelating agents may be desired in the compositions of the present invention, preferably phosphate chelating agents like phytic acid, as they further contribute to the benefit delivered by the stabilizer herein by further improving the stability of the brighteners, thus delivering effective whiteness performance in any laundry application upon ageing of the compositions, i.e. after prolonged periods of storage.
• Suitable phosphonate chelating agents for use 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) .
• DTPMP diethylene triamine penta methylene phosphonate
• HEDP ethane 1-hydroxy diphosphonate
• Such phosphonate chelating agents are commercially available from Monsanto under the trade name REQUEST ® .
• Suitable phosphate chelating agents for use in the compositions of the present invention are described in EP- A-0 867 502 in the section titled "The Phosphate ingredient", such ingredients are specifically incorporated herein by reference, especially for their fabric whitening benefit (i.e., yellowing prevention effect) and/or fabric safety benefit. All phosphate ingredients described in EP- A-0 867 502 in the section titled "The Phosphate ingredient” are suitable for use herein.
• Preferred phosphate chelating agents for use herein are linear phosphate ingredients, wherein R in the formula in the section titled "The Phosphate ingredient" of EP-A-0867502 is M and wherein n is 1 (pyrophosphate) or n is 2 (tripolyphosphate (STPP) ) , most preferably wherein n is 2.
• R in the formula in the section titled "The Phosphate ingredient" of EP-A-0867502 is M and wherein n is 1 (pyrophosphate) or n is 2 (tripolyphosphate (STPP) ) , most preferably wherein n is 2.
• M is Sodium.
• preferred phosphate chelating agents for use in the compositions of the present invention are pyrophosphate and/or tripolyphosphate (STPP) , more preferably Na phosphate and/or Na tripolyphosphate (STPP) .
• Phytic acid which is 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 3812044, 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 ⁇ , ⁇ '- disuccinic acids, especially the (S,S) isomer have been extensively described in US patent 4704233, November 3, 1987, to Hartman and Perkins.
• Ethylenediamine ⁇ , ⁇ '- 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 pyrophosphate, sodium tripolyphosphate, phytic acid, and mixtures thereof.
• compositions herein comprise up to 10%, preferably from 0.01% to 5% by weight, more preferably from 0.03% to 2% by weight of the composition of a chelating agent or mixture thereof.
• a further optional ingredient of the present composition is a builder.
• Highly preferred builder compounds for use in the present invention are water- soluble phosphate builders.
• Specific examples of water- soluble phosphate builders are the alkali metal tripolyphosphates , sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerisation ranges from 6 to 21, and salts of phytic acid.
• water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from 6 to 21, and salts of phytic acid.
• the bleaching compositions herein may further comprise a variety of optional ingredients such as bleach activators, soil suspenders, soil suspending polyamine polymers, polymeric soil release agents, foam reducing systems/agents, catalysts, dye transfer agents, perfumes, hydrotropes and solvents.
• optional ingredients such as bleach activators, soil suspenders, soil suspending polyamine polymers, polymeric soil release agents, foam reducing systems/agents, catalysts, dye transfer agents, perfumes, hydrotropes and solvents.
• the bleaching composition can be used to treat surfaces.
• 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, WCs and the like, as well as fabrics including clothes, curtains, drapes, bed linens, bath linens, table cloths, sleeping bags, tents, upholstered furniture and the like, and carpets.
• Inanimate surfaces also include household appliances including, but not limited to, refrigerators, freezers, washing machines, automatic dryers, ovens, microwave ovens, dishwashers and so on.
• 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 .
• the present invention also encompasses a process of treating (e.g. bleaching) a fabric, as the inanimate surface.
• a fabric is contacted with a composition according to the present invention.
• pretreatment mode where a liquid bleaching composition, as defined herein, is applied neat onto said fabrics before the fabrics are rinsed, or washed and 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 avoiding staining of the treated surface 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 a 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, or said washing may be conducted before or after that said fabrics have been bleached.
• said process 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 said fabrics have been bleached.
• the level of hypohalite bleach is from 0.01% to 6%, preferably from 0.1% to 5%, more preferably from 0.3% to 4.5% and most preferably from 1.0% to 4.0%.
• 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 it is understood any hard-surfaces as mentioned herein before as well as dishes.
• compositions are made by mixing the listed ingredients in the listed proportions (weight percent unless otherwise specified) .
• the pH of these samples is between 13.0 and 14.0.
• compositions of Table I were tested in a Rapid Aging Test (RAT) for 10 days at 50°C.
• RAT Rapid Aging Test
• Rapid Aging Test has been performed storing 100 mL of sample at 50°C ( ⁇ 0.5°C) into a ventilated oven.
• the bottles used for the test were 100 mL square bottle with plug cap in HDPE.
• Hypochlorite stability was evaluated as % of AvCl loss after 10 days. The following criteria was used: AvCl loss under 30%: Good stability;
• Brightner 49 stability was evaluated as % of Br49 loss after 10 days (for compositions VII-XXI) .
• the stabilization of the pigment (Blue copper phtalocyanine ) by 2-PE is better with respect to TMBA at the same concentration of 0.10% (composition I vs composition II in table 2) .
• concentration II vs composition IV in table 2 increases, but also the loss of AvCl increases, probably due to the oxidation of the same 2-PE.
• concentration II vs composition V in table 2 slightly reduces the stabilization of the pigment (composition II vs composition V in table 2), but also decrease the loss of AvCl .
• compositions XXII, XXIII and XIV of table I are suitable surfactants for these systems (compositions XXII, XXIII and XIV of table I), but it is worth to note that a level of surfactant lower than 0.5 % w/w causes the pigment to stain the surfaces where the product is used (see composition XXIII) .
• compositions VII-XII Analogue trends about pigment and AvCl were observed when the samples were prepared with the Br49 (compositions VII-XII) . Moreover, the stabilization of the brightener by 2-PE is better in comparison with TMBA at the same concentration of 0.10% (composition VIII vs composition VII in table 2) . Increasing the level of 2-PE, the stabilization of Br49 increases (composition VIII vs compositions IX-XII in table 2) . The stabilization of the brightener provided by 0.10% of TMBA is comparable with the one obtained with 0.066% of 2-PE (composition VII vs composition XI in Table 2) .
• hypochlorite-containing formulations develops molecular oxygen as main degradation product of the oxidant.
• This reaction is catalytically enhanced by metal impurities which are usually present in water, such as copper and iron.
• metal impurities which are usually present in water, such as copper and iron.
• This phenomenon is very relevant for bleach products, because large values of gas evolution rate may cause bulging of bottles, which would cause drawbacks in terms of aesthetics and safety of the packaging. For this reason, GER is a key parameter for the assessment of the robustness of new formulations.
• the Gas Evolution Rate test has been performed measuring the pressure increase in a close bottle containing a known volume of product at 50°C ( ⁇ 0.5°C) .
• the pressure increase and the gas evolution rate were related on the basis of the following equation:
• V s volume of the solution (L) ;
• V hs volume of the headspace (cc) ;
• T temperature (K) ;
• composition I and II were tested also with a contamination of Iron (500 ppb) and copper (250 ppb) , which was added on top of the product.
• the product already contains about 200 ppb of iron and 200 ppb of copper coming from raw materials .
• composition II (Table 3) .
• compositions XIII to XXI The performances of the stabilizer have been evaluated on compositions XIII to XXI. Hypo stability (%AvCl loss) e brightener stability (% Br49 loss) have been measured according to the methods indicated in example 2.

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