EP0753565A2 - Detergent compositions - Google Patents

Abstract

There is provided a detergent composition comprising a cationic ester surfactant and an organo diphosphonic acid crystal growth inhibitor component or its salts or complexes, which provide effective soil removal and fabric care.

Description

Field of the invention
• The present invention relates to detergent compositions and in particular to detergent compositions adapted for use in laundry washing processes. More specifically, the present invention relates to detergent compositions comprising a surfactant in combination with a crystal growth inhibitor and which provide unexpectedly good detergency performance on greasy and oily soils as well as improved fabric care.
Background of the invention
• Cationic surfactants have generally been used in laundry detergent compositions for providing fabric care benefit.
• Detergent compositions designed for use in laundry washing machines comprising a cationic surfactant and a nonionic surfactant for providing effective soil removal and fabric care are known in the art.
• US 4,228,042 discloses a detergent composition comprising mixtures of nonionic and cationic surfactant such as choline ester surfactant types in specific ratios to provide effective removal of particulate soils and fabric care.
• US 4,239,660 discloses a laundry detergent composition comprising mixtures of nonionic and cationic surfactants such as choline ester surfactants together with defined alkalinity sources. The described detergent composition is asserted to provide effective removal of particulate and greasy/oily soils, as well as fabric care benefit.
• Detergent compositions comprising a cationic surfactant, a nonionic surfactant and a builder for providing effective soil removal and fabric care are also known in the art. An exemplary disclosure is given in EP 0,021,491 which describes detergent compositions comprising mixtures of nonionic and cationic surfactant together with a combination of aluminosilicate and polycarboxylate builder materials. The described composition is asserted to provide effective soil removal performance and fabric care benefits.
• The Applicant has found a problem encountered with the use of such detergent compositions upon multiwash cycles, namely the formation of insoluble carbonate, especially calcium carbonate deposits, which result in a general loss in the desired fabric appearance and feel. This problem is more noticeable when non-phosphate containing detergent formulations are employed. In general this can be explained by the slightly inferior builder capacity of the typically employed non-phosphate builder systems in comparison to phosphate builder formulations. A consequence of this insoluble carbonate deposition is that access by the cationic ester to the soiled substrate is hindered which thus leads to a loss in the soil removal performance, especially on fatty oily soils.
• The formulator of a detergent composition is thus faced with the challenge of formulating a detergent composition which provide effective soil removal and effective fabric care benefits.
• The Applicant has now surprisingly found that the provision of a crystal growth inhibitor to the detergent composition containing a cationic ester surfactant ameliorates these problems. In addition, the provision of said crystal growth inhibitor in the detergent composition has been found to provide an effective softness benefit on the laundered fabrics as well as an enhanced soil removal performance, especially on highly adsorbed soils.
• The Applicant has also found that the addition of a water-soluble organic polymeric polycarboxylic compound to the detergent composition of the invention ameliorates a tendency towards insoluble carbonate deposition which thus results in an enhanced soil removal performance.
• It is therefore an object of the present invention to provide compositions suitable for use in laundry washing machine methods producing enhanced stain removal together with an effective softness ability on laundered fabrics as well as fabric care.
Summary of the invention
• According to the present invention there is provided a detergent composition comprising a cationic ester surfactant and an organo diphosphonic acid crystal growth inhibitor component or its salts or complexes.
• In a preferred embodiment, the cationic ester surfactant is a water-dispersible surfactant selected from those having the formula:

  

  wherein R₁ is a C₅-C₃₁ linear or branched alkyl, alkenyl or alkaryl chain or M^-. N⁺(R₆R₇R₈)(CH₂)_s; X and Y, independently, are selected from COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO wherein at least one of X or Y is a COO, OCO, OCOO, OCONH or NHCOO group; R₂, R₃, R₄, R₆, R₇, and R₈ are independently selected from alkyl, alkenyl, hydroxyalkyl, hydroxy-alkenyl and alkaryl groups having from 1 to 4 carbon atoms; and R₅ is independently H or a C₁-C₃ alkyl group; wherein the values of m, n, s and t independently lie in the range of from 0 to 8, the value of b lies in the range from 0 to 20, and the values of a, u and v independently, are either 0 or 1 with the proviso that at least one of u or v must be 1; and wherein M is a counter anion.
• Preferred water-dispersible cationic ester surfactants are the choline ester surfactants.
• In a further embodiment of the invention, the detergent composition of the invention additionally comprises a water-soluble organic polymeric polycarboxylic compounds which enhances the fabric care of said detergent composition by further reducing the encrustation and thus resulting in an enhanced overall soil removal performance.
Detailed description of the invention Cationic ester surfactant
• An essential component of the surfactant system is a water dispersible cationic ester surfactant. That is, a water dispersible compound having surfactant properties comprising at least one ester (ie -COO-) linkage and at least one cationically charged group.
• Preferably, the cationic ester surfactant is present in amount from 0.01 % to 30%, preferably 0.05% to 15% and more preferably 0.1% to 10% by weight of the detergent composition.
• Suitable cationic ester surfactants, including choline ester surfactants, have for example been disclosed in US Patents No.s 4228042, 4239660 and 4260529.
• Preferred water dispersible cationic ester surfactants are those having the formula:

  

  wherein R₁ is a C₅-C₃₁ linear or branched alkyl, alkenyl or alkaryl chain or M^-. N⁺(R₆R₇R₈)(CH₂)_s; X and Y, independently, are selected from COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO wherein at least one of X or Y is a COO, OCO, OCOO, OCONH or NHCOO group; R₂, R₃, R₄, R₆, R₇, and R₈ are independently selected from alkyl, alkenyl, hydroxyalkyl, hydroxy-alkenyl and alkaryl groups having from 1 to 4 carbon atoms; and R₅ is independently H or a C₁-C₃ alkyl group; wherein the values of m, n, s and t independently lie in the range of from 0 to 8, the value of b lies in the range from 0 to 20, and the values of a, u and v independently, are either 0 or 1 with the proviso that at least one of u or v must be 1; and wherein M is a counter anion.
• Preferably R₂, R₃ and R₄ are independently selected from CH₃ and -CH₂CH₂OH.
• Preferably M is selected from halide, methyl sulfate, sulfate, and nitrate, more preferably methyl sulfate, chloride, bromide or iodide.
• Preferred water dispersible cationic ester surfactants are the choline esters having the formula:

  

  wherein R₁ is a C₁₁-C₁₉ linear or branched alkyl chain.
• Particularly preferred choline esters of this type include the stearoyl choline ester quaternary methylammonium halides (R¹=C₁₇ alkyl), palmitoyl choline ester quaternary methylammonium halides (R¹=C₁₅ alkyl), myristoyl choline ester quaternary methylammonium halides (R¹=C₁₃ alkyl), lauroyl choline ester methylammonium halides (R¹=C₁₁ alkyl), cocoyl choline ester quaternary methylammonium halides (R¹=C_11-C₁₃ alkyl), tallowyl choline ester quaternary methylammonium halides (R¹=C_15-C₁₇ alkyl), and any mixtures thereof.
• Most preferred choline ester compounds among the above disclosed are cocoyl choline ester quaternary methylammonium halides.
• The particularly preferred choline esters, given above, may be prepared by the direct esterification of a fatty acid of the desired chain length with dimethylaminoethanol, in the presence of an acid catalyst. The reaction product is then quaternized with a methyl halide, forming the desired cationic material. They may also be prepared by the direct esterification of a long chain fatty acid of the desired chain length together with 2-haloethanol, in the presence of an acid catalyst material. The reaction product is then quaternized with trimethylamine, forming the desired cationic material.
• Other suitable cationic ester surfactants have the structural formulas below, wherein d may be from 0 to 20.

  
Crystal growth inhibitor
• The other essential component of the compositions in accord with the invention is an organo diphosphonic acid or one of its salts or complexes. The organo diphosphonic acid component is preferably present at a level of from 0.005% to 20%, more preferably from 0.05% to 15%, most preferably from 0.1% to 2% by weight of the compositions.
• By organo diphosphonic acid it is meant herein an organo diphosphonic acid which does not contain nitrogen as part of its chemical structure. This definition therefore excludes the organo aminophosphonates, which however may be included in compositions of the invention as heavy metal ion sequestrants.
• The organo diphosphonic acid component may be present in its acid form or in the form of one of its salts or complexes with a suitable counter cation. Preferably any salts/complexes are water soluble, with the alkali metal and alkaline earth metal salts/complexes being especially preferred.
• The organo diphosphonic acid is preferably a C₁-C₄ diphosphonic acid and more preferably a C₂ diphosphonic acid selected from ethylene diphosphonic acid, α-hydroxy-2 phenyl ethyl diphosphonic acid , methylene diphosphonic acid , vinylidene 1,1 diphosphonic acid , 1,2 dihydroxyethane 1,1 diphosphonic acid and hydroxy-ethane 1,1 diphosphonic acid and any salts thereof and mixtures thereof.
• A most preferred organo diphosphonic acid is hydroxy-ethane 1,1 diphosphonic acid (HEDP).
• The detergent composition of the invention has further been found to produce an enhanced fabric care benefit in presence of one or more water-soluble organic polymeric polycarboxylic compounds which thus results in an enhanced soil removal performance. Salts of these polycarboxylic compounds are also considered herein.
Water-soluble organic polymeric polycarboxylic compounds
• Polymeric polycarboxylic compounds are utilised at levels from 0.005% to 20%, preferably from 0.01% to 10%, more preferably from 0.1% to 5% by weight of the composition.
  Additionally, the Applicants have surprisingly found that the presence of said polymeric polycarboxylic compounds at low levels (e.g less than 3% by weight of the composition) still provide enhanced soil removal performance and fabric care.
• Preferably these compounds are a homo- or co-polymeric polycarboxylic compounds and most preferably a co-polymeric polycarboxylic compounds in which the acid monomer of said polycarboxylic compound comprises at least two carboxyl groups separated by not more than two carbon atoms.
• Polymeric polycarboxylate materials can be prepared by polymerising or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids that can be polymerised to form suitable polymeric polycarboxylates are selected from acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence in the polymeric polycarboxylates herein of monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than 40% by weight.
  Polymeric polycarboxylate materials can also optionally include further monomeric units such as nonionic spacing units. For example, suitable nonionic spacing units may include vinyl alcohol or vinyl acetate.
• Particularly preferred polymeric polycarboxylates are co-polymers derived from monomers of acrylic acid and maleic acid. The average molecular weight of such polymers in the acid form preferably ranges from 2,000 to 10,000, more preferably from 4,000 to 7,000 and most preferably from 4,000 to 5,000. Water-soluble salts of such acrylic/maleic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Patent 3,308,067, issued march 7, 1967. The ratio of acrylate to maleate segments in such copolymers will generally range from 30:1 to 1:1, more preferably from 10:1 to 2:1. Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published December 15, 1982, as well as in EP 193,360, published September 3, 1986, which also describes such polymers comprising hydroxypropylacrylate. Of these acrylic/maleic-based copolymers, the water-soluble salts of copolymers of acrylic acid and maleic acid are preferred.
• Another class of polymeric polycarboxylic acid compounds suitable for the purpose of the invention are the homo-polymeric polycarboxylic acid compounds derived from acrylic acid. The average molecular weight of such homo-polymers in the acid form preferably ranges from 2,000 to 100,000, more preferably from 3,000 to 75,000, most preferably from 4,000 to 65,000.
• A further example of polymeric polycarboxylic compounds suitable for the purpose of the invention include the maleic/acrylic/vinyl alcohol terpolymers. Such materials are also disclosed in EP 193,360, including, for example, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.
• Another example of polymeric polycarboxylic compounds suitable for the purpose of the invention include the polyamino acid compounds. Preferred among these polyamino acid species are the biodegradable polyaspartic acid and polyglutamic acid compounds.
• Optionally, the detergent composition of the invention may further comprise additional components which are not detrimental to the composition. Such components include additional surfactants, builders, alkaline hydrogen peroxide sources, peroxyacid bleach precursors, heavy metal ion sequestrants, enzymes and conventional detersive adjuncts.
Additional surfactants
• The total amount of additional surfactants will be generally up to 70%, typically 1 to 55%, preferably 1 to 30%, more preferably 5 to 25% and especially 10 to 20% by weight of the total composition.
• Non limiting examples of surfactants useful herein include the conventional C₁₁-C₁₈ alkyl benzene sulfonates ("LAS") and primary, branched-chain and random C₁₀-C₂₀ alkyl sulfates ("AS"), the C₁₀-C₁₈ secondary (2,3) alkyl sulfates of the formula CH₃(CH₂)_x(CHOSO₃ ^-M⁺) CH₃ and CH₃ (CH₂)_y(CHOSO₃ ^-M⁺) CH₂CH₃ where x and (y + 1) are integers of at least 7, preferably at least 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the C₁₀-C₁₈ alkyl alkoxy sulfates ("AE_xS"; especially EO 1-7 ethoxy sulfates), C₁₀-C₁₈ alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the C_10-18 glycerol ethers, the C₁₀-C₁₈ alkyl polyglycosides and their corresponding sulfated polyglycosides, and C₁₂-C₁₈ alpha-sulfonated fatty acid esters. If desired, the conventional nonionic and amphoteric surfactants such as the C₁₂-C₁₈ alkyl ethoxylates ("AE"), including the so-called narrow peaked alkyl ethoxylates and C₆-C₁₂ alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C₁₂-C₁₈ betaines and sulfobetaines ("sultaines"), C₁₀-C₁₈ amine oxides, and the like, can also be included in the overall compositions. The C₁₀-C₁₈ N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C₁₂-C₁₈ N-methylglucamides. See WO 9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C₁₀-C₁₈ N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C₁₂-C₁₈ glucamides can be used for low sudsing. C₁₀-C₂₀ conventional soaps may also be used. If high sudsing is desired, the branched-chain C₁₀-C₁₆ soaps may be used.
• Other suitable surfactants suitable for the purpose of the invention are the anionic alkali metal sarcosinates of formula:
  
          R-CON(R¹)CH₂COOM
  
  wherein R is a C₉-C₁₇ linear or branched alkyl or alkenyl group, R¹ is a C₁-C₄ alkyl group and M is an alkali metal ion. Preferred examples are the lauroyl, cocoyl (C₁₂-C₁₄), myristyl and oleyl methyl sarcosinates in the form of their sodium salts.
• Additional cationic surfactants can also be used in the detergent compositions herein. Suitable cationic surfactants include the quaternary ammonium surfactants selected from mono C₆-C₁₆, preferably C₆-C₁₀ N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
• Other conventional useful surfactants are listed in standard texts.
Builders
• Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils.
• The level of builder can vary widely depending upon the end use of the composition and its desired physical form. When present, the compositions will typically comprise at least 1% builder. Granular formulations typically comprise from 10% to 80%, more typically from 15% to 50% by weight, of the detergent builder. Lower or higher levels of builder, however, are not meant to be excluded.
  Inorganic or phosphate-containing detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates).
  Non-phosphate builders may also be used. These can include, but are not restricted to phytic acid, silicates, alkali metal carbonates (including bicarbonates and sesquicarbonates), sulphates, aluminosilicates, monomeric polycarboxylates. Examples of silicate builders are the crystalline layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839. NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate builder does not contain aluminium. NaSKS-6 has the delta-Na₂Si₂O₅ morphology form of layered silicate. It can be prepared by methods such as those described in German DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSi_xO_2x+1.yH₂O wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein. Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms. As noted above, the delta-Na₂Si₂O₅ (NaSKS-6 form) is most preferred for use herein. Other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilising agent for oxygen bleaches, and as a component of suds control systems.
• Aluminosilicate builders are especially useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula:
  
          Na_z[(AlO₂)_z(SiO₂)_y].xH₂O
  
  wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to 0.5, and x is an integer from 15 to 264.
• Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:
  
          Na₁₂[(AlO₂)₁₂(SiO₂)₁₂].xH₂O
  
  wherein x is from 20 to 30, especially 27. This material is known as Zeolite A. Dehydrated zeolites (x = 0 - 10) may also be used herein. Preferably, the aluminosilicate has a particle size of 0.1-10 microns in diameter.
• Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates. Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralised salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
• Included among the polycarboxylate builders are a variety of categories of useful materials. One important category of polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in U.S. Patent 3,128,287 and U.S. Patent 3,635,830. See also "TMS/TDS" builders of U.S. Patent 4,663,071. Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
• Other useful detergency builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, or acrylic acid, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
• Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations.
• Also suitable in the compositions containing the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in U.S. Patent 4,566,984. Useful succinic acid builders include the C₅-C₂₀ alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in EP 0,200,263.
• Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226 and in U.S. Patent 3,308,067. See also U.S. Pat. 3,723,322.
• Fatty acids, e.g., C₁₂-C₁₈ monocarboxylic acids, can also be incorporated into the compositions alone, or in combination with the aforesaid builders, especially citrate and/or the succinate builders, to provide additional builder activity. Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.
Alkaline hydrogen peroxide sources
• Detergent compositions of the present invention may include an inorganic perhydrate bleach, normally in the form of the sodium salt, as the source of alkaline hydrogen peroxide in the wash liquor. This perhydrate is normally incorporated at a level of from 1% to 40% by weight, more preferably from 5% to 35% by weight and most preferably from 8% to 30% by weight of the composition.
• The perhydrate may be any of the alkali metal inorganic salts such as perborate monohydrate or tetrahydrate, percarbonate, perphosphate and persilicate salts, but is conventionally an alkali metal perborate or percarbonate.
• Sodium percarbonate, which is the preferred perhydrate, is an addition compound having a formula corresponding to 2Na₂CO₃.3H₂O₂, and is available commercially as a crystalline solid. Most commercially available material includes a low level of a heavy metal sequestrant such as EDTA, 1-hydroxyethylidene 1, 1-diphosphonic acid (HEDP) or an aminophosphonate, that is incorporated during the manufacturing process. For the purposes of the detergent composition aspect of the present invention, the percarbonate can be incorporated into detergent compositions without additional protection, but preferred executions of such compositions utilise a coated form of the material. A variety of coatings can be used including borosilicate borate, boric acid and citrate or sodium silicate of SiO₂:Na₂O ratio from 1.6:1 to 3.4:1, preferably 2.8:1, applied as an aqueous solution to give a level of from 2% to 10%, (normally from 3% to 5%) of silicate solids by weight of the percarbonate. However the most preferred coating is a mixture of sodium carbonate and sulphate or sodium chloride.
Peroxyacid bleach precursor
• Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach precursors may be represented as

  

  where L is a leaving group and X is essentially any functionality, such that on perhydrolysis the structure of the peroxyacid produced is

  

  Peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.1% to 60% by weight, more preferably from 0.5% to 40% by weight of the detergent composition.
Leaving groups
• The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilise for use in a bleaching composition.
• Preferred L groups are selected from the group consisting of:

  

  and mixtures thereof, wherein R¹ is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms, R³ is an alkyl chain containing from 1 to 8 carbon atoms, R⁴ is H or R³, and Y is H or a solubilizing group. Any of R¹, R³ and R⁴ may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammonium groups
• The preferred solubilizing groups are -SO₃ ^-M⁺, -CO₂ ^-M⁺, -SO₄ ^-M⁺, -N⁺(R³)₄X^- and O<--N(R³)₃ and most preferably -SO₃ ^-M⁺ and -CO₂ ^-M⁺ wherein R³ is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.
• Suitable peroxyacid bleach precursor materials are compounds containing one or more N- or O-acyl groups. These can be selected from a wide range of classes that include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A-1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.
• Detergent compositions containing mixtures of any of the precursors hereinafter disclosed are also contemplated by the present invention.
Perbenzoic acid precursor
• Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.
• Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulfonates, including for example benzoyl oxybenzene sulfonate:

  
• Also suitable are the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, including for example:

  
• Ac = COCH3; Bz = Benzoyl
• Perbenzoic acid precursor compounds of the imide type include N-benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substituted ureas. Suitable imidazole type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole and other useful N-acyl group-containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.
• Other perbenzoic acid precursors include the benzoyl diacyl peroxides, the benzoyl tetraacyl peroxides, and the compound having the formula:

  
• Phthalic anhydride is another suitable perbenzoic acid precursor compound herein:

  
• Suitable N-acylated precursor compounds of the lactam class are disclosed generally in GB-A-855735.
• Suitable caprolactam bleach precursors which may be used herein are of the formula:

  

  wherein R⁶ is H or an alkyl, aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbon atoms, preferably from 6 to 12 carbon atoms.
• Suitable valero lactams have the formula:

  

  wherein R⁶ is H or an alkyl, aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbon atoms, preferably from 6 to 12 carbon atoms. In highly preferred embodiments, R⁶ is selected from phenyl, heptyl, octyl, nonyl, 2,4,4-trimethylpentyl, decenyl and mixtures thereof.
• The most preferred materials are those which are normally solid at <30°C, particularly the phenyl derivatives, ie. benzoyl valerolactam, benzoyl caprolactam and their substituted benzoyl analogues such as chloro, amino alkyl, alkyl, aryl and alkyloxy derivatives.
• Caprolactam and valerolactam precursor materials wherein the R⁶ moiety contains at least 6, preferably from 6 to about 12, carbon atoms provide peroxyacids on perhydrolysis of a hydrophobic character which afford nucleophilic and body soil clean-up. Precursor compounds wherein R⁶ comprises from 1 to 6 carbon atoms provide hydrophilic bleaching species which are particularly efficient for bleaching beverage stains. Mixtures of 'hydrophobic' and 'hydrophilic' caprolactams and valero lactams, typically at weight ratios of 1:5 to 5:1, preferably 1:1, can be used herein for mixed stain removal benefits.
Perbenzoic acid derivative precursors
• Perbenzoic acid derivative precursors provide substituted perbenzoic acids on perhydrolysis.
• Suitable substituted perbenzoic acid derivative precursors include any of the herein disclosed perbenzoic precursors in which the benzoyl group is substituted by essentially any non-positively charged (ie; non-cationic) functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl and amide groups.
• A preferred class of substituted perbenzoic acid precursor compounds are the amide substituted compounds of the following general formulae:

  

  wherein R¹ is an aryl or alkaryl group with from 1 to 14 carbon atoms, R² is an arylene, or alkarylene group containing from 1 to 14 carbon atoms, and R⁵ is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any leaving group. R¹ preferably contains from 6 to 12 carbon atoms. R² preferably contains from 4 to 8 carbon atoms. R¹ may be aryl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R². The substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds. R⁵ is preferably H or methyl. R¹ and R⁵ should not contain more than 18 carbon atoms in total. Amide substituted bleach activator compounds of this type are described in EP-A-0170386.
Cationic peroxyacid precursors
• Cationic peroxyacid precursor compounds produce cationic peroxyacids on perhydrolysis.
• Typically, cationic peroxyacid precursors are formed by substituting the peroxyacid part of a suitable peroxyacid precursor compound with a positively charged functional group, such as an ammonium or alkyl ammonium group, preferably an ethyl or methyl ammonium group. Cationic peroxyacid precursors are typically present in the solid detergent compositions as a salt with a suitable anion, such as a halide ion.
• The peroxyacid precursor compound to be so cationically substituted may be a perbenzoic acid, or substituted derivative thereof, precursor compound as described hereinbefore. Alternatively, the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid precursor as described hereinafter
• Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; GB 1,382,594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332.
• Examples of preferred cationic peroxyacid precursors are described in GB Patent Application No. 9407944.9 and US Patent Application Nos. 08/298903, 08/298650, 08/298904 and 08/298906.
• Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides.
• A preferred cationically substituted benzoyl oxybenzene sulfonate is the 4-(trimethyl ammonium) methyl derivative of benzoyl oxybenzene sulfonate:

  
• A preferred cationically substituted alkyl oxybenzene sulfonate has the formula:

  
• Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams, particularly trimethyl ammonium methylene benzoyl caprolactam:

  
• Other preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene alkyl caprolactams:

  

  where n is from 0 to 12.
• Another preferred cationic peroxyacid precursor is 2-(N,N,N-trimethyl ammonium) ethyl sodium 4-sulphophenyl carbonate chloride.
Alkyl percarboxylic acid bleach precursors
• Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis. Preferred precursors of this type provide peracetic acid on perhydrolysis.
• Preferred alkyl percarboxylic precursor compounds of the imide type include the N-,N,N¹N¹ tetra acetylated alkylene diamines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly preferred.
• Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-trimethyl hexanoyloxybenzene sulfonate (ISONOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.
Amide substituted alkyl peroxyacid precursors
• Amide substituted alkyl peroxyacid precursor compounds are also suitable, including those of the following general formulae:

  

  wherein R¹ is an alkyl group with from 1 to 14 carbon atoms, R² is an alkylene group containing from 1 to 14 carbon atoms, and R⁵ is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group. R¹ preferably contains from 6 to 12 carbon atoms. R² preferably contains from 4 to 8 carbon atoms. R¹ may be straight chain or branched alkyl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R². The substitution can include alkyl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds. R⁵ is preferably H or methyl. R¹ and R⁵ should not contain more than 18 carbon atoms in total.
• Amide substituted bleach activator compounds of this type are described in EP-A-0170386.
Benzoxazin organic peroxyacid precursors
• Also suitable are precursor compounds of the benzoxazin-type, as disclosed for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula:

  

  including the substituted benzoxazins of the type

  

  wherein R₁ is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R₂, R₃, R₄, and R₅ may be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkyl amino, COOR₆ (wherein R₆ is H or an alkyl group) and carbonyl functions.
• An especially preferred precursor of the benzoxazin-type is:

  
• Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein. One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminium phthalocyanines. See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If used, detergent compositions will typically contain from 0.025% to 1.25%, by weight, of such bleaches, especially sulfonate zinc phthalocyanine.
• If desired, the bleaching compounds can be catalysed by means of a manganese compound. Such compounds are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Pat. 5,246,621, U.S. Pat. 5,244,594; U.S. Pat. 5,194,416; U.S. Pat. 5,114,606; and European Pat. 549,271A1, 549,272A1, 544,440A2, and 544,490A1; Preferred examples of these catalysts include Mn^IV ₂(u-O)₃(1,4,7-trimethyl-1,4,7-triazacyclononane)₂(PF₆)₂, Mn^III ₂(u-O)₁(u-OAc)₂(1,4,7-trimethyl-1,4,7-triazacyclononane)_2-(ClO₄)₂, Mn^IV ₄(u-O)₆(1,4,7-triazacyclononane)₄(ClO₄)₄, Mn^IIIMn^IV ₄(u-O)₁(u-OAc)_2-(1,4,7-trimethyl-1,4,7-triazacyclononane)₂(ClO₄)₃, Mn^IV(1,4,7-trimethyl-1,4,7-triazacyclononane)- (OCH₃)₃(PF₆), and mixtures thereof. Other metal-based bleach catalysts include those disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611. The use of manganese with various complex ligands to enhance bleaching is also reported in the following United States Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; 5,227,084;
• As a practical matter, and not by way of limitation, the compositions and processes herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in the aqueous washing liquor, and will preferably provide from 0.1 ppm to 700 ppm, more preferably from 1 ppm to 500 ppm, of the catalyst species in the laundry liquor.
Heavy metal ion sequestrants
• Heavy metal ion sequestrants may be used herein. By heavy metal ion sequestrants it is meant components which act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelation capacity, but preferentially they bind heavy metal ions such as iron, manganese and copper.
• Heavy metal ion sequestrants are preferably present at a level of from 0.005% to 20%, more preferably from 0.1% to 10%, most preferably from 0.2% to 5% by weight of the compositions.
• Heavy metal ion sequestrants, which are acidic in nature, having for example phosphonic acid or carboxylic acid functionalities, may be present either in their acid form or as a complex/salt with a suitable counter cation such as an alkali or alkaline metal ion, ammonium, or substituted ammonium ion, or any mixtures thereof. Preferably any salts/complexes are water soluble. The molar ratio of said counter cation to the heavy metal ion sequestrant is preferably at least 1:1.
• Suitable heavy metal ion sequestrants for use herein include the organo aminophosphonates, such as the amino alkylene poly (alkylene phosphonates) and nitrilo trimethylene phosphonates. Preferred organo aminophosphonates are diethylene triamine penta (methylene phosphonate) and hexamethylene diamine tetra (methylene phosphonate).
• Other suitable heavy metal ion sequestrants for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenetriamine pentacetic acid, or ethylenediamine disuccinic acid. Especially preferred is ethylenediamine-N,N'-disuccinic acid (EDDS), most preferably present in the form of its S,S isomer, which is preferred for its biodegradability profile.
• Still other suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-0,317,542 and EP-A-0,399,133.
Enzyme
• Still another ingredient useful in the detergent compositions is one or more additional enzymes.
• Preferred additional enzymatic materials include the commercially available lipases, amylases, neutral and alkaline proteases, esterases, cellulases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
• Preferred commercially available protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001% to 4% active enzyme by weight of the composition.
  A most preferred protease is Savinase.
• Preferred amylases include, for example, α-amylases obtained from a special strain of B licheniformis, described in more detail in GB-1,269,839 (Novo). Preferred commercially available amylases include for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tradename Termamyl and BAN by Novo Industries A/S. Amylase enzyme may be incorporated into the composition in accordance with the invention at a level of from 0.0001% to 2% active enzyme by weight of the composition.
• Lipolytic enzyme (lipase) may be present at levels of active lipolytic enzyme of from 0.0001% to 2% by weight, preferably 0.001% to 1% by weight, most preferably from 0.001% to 0.5% by weight of the compositions.
• The lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp., Thermomyces sp. or Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomonas fluorescens. Lipase from chemically or genetically modified mutants of these strains are also useful herein.
• A preferred lipase is derived from Pseudomonas pseudoalcaligenes, which is described in Granted European Patent, EP-B-0218272.
• Another preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza, as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Patent 4,810,414, Huge-Jensen et al, issued March 7, 1989.
• Also suitable are cutinases [EC 3.1.1.50] which can be considered as a special kind of lipase, namely lipases which do not require interfacial activation. Addition of cutinases to detergent compositions have been described in e.g. EP-B-0,322,429 (Genencor) and EP-A-0,652,939 (Unilever).
Conventional detersive adjuncts
• The compositions herein can optionally include one or more other detergent adjunct materials or other materials for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition (e.g., perfumes, colorants, dyes, etc.). The following are illustrative examples of such adjunct materials.
• Clay Soil Removal/Anti-redeposition Agents - The compositions according to the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and antiredeposition properties. Granular detergent compositions which contain these compounds typically contain from 0.01% to 10.0% by weight of the water-soluble ethoxylates amines; liquid detergent compositions typically contain 0.01% to 5%.
• The most preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1, 1986. Another group of preferred clay soil removal-antiredeposition agents are the cationic compounds disclosed in EP 111,965. Other clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in EP 111,984; the zwitterionic polymers disclosed in EP 112,592; and the amine oxides disclosed in U.S. Patent 4,548,744. Other clay soil removal and/or anti redeposition agents known in the art can also be utilized in the compositions herein. Another type of preferred antiredeposition agent includes the carboxy methyl cellulose (CMC) materials. These materials are well known in the art.
• Polymeric Soil Release Agent - Any polymeric soil release agent known to those skilled in the art can optionally be employed in the compositions and processes of this invention. Polymeric soil release agents are characterised by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.
  The polymeric soil release agents useful herein especially include those soil release agents having: (a) one or more nonionic hydrophile components consisting essentially of (i) polyoxyethylene segments with a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene segments with a degree of polymerization of from 2 to 10, wherein said hydrophile segment does not encompass any oxypropylene unit unless it is bonded to adjacent moieties at each end by ether linkages, or (iii) a mixture of oxyalkylene units comprising oxyethylene and from 1 to 30 oxypropylene units wherein said mixture contains a sufficient amount of oxyethylene units such that the hydrophile component has hydrophilicity great enough to increase the hydrophilicity of conventional polyester synthetic fiber surfaces upon deposit of the soil release agent on such surface, said hydrophile segments preferably comprising at least 25% oxyethylene units and more preferably, especially for such components having 20 to 30 oxypropylene units, at least 50% oxyethylene units; or (b) one or more hydrophobe components comprising (i) C₃ oxyalkylene terephthalate segments, wherein, if said hydrophobe components also comprise oxyethylene terephthalate, the ratio of oxyethylene terephthalate:C₃ oxyalkylene terephthalate units is 2:1 or lower, (ii)C₄-C₆ alkylene or oxy C₄-C₆ alkylene segments, or mixtures therein, (iii) poly (vinyl ester) segments, preferably polyvinyl acetate), having a degree of polymerization of at least 2, or (iv) C₁-C₄ alkyl ether or C₄ hydroxyalkyl ether substituents, or mixtures therein, wherein said substituents are present in the form of C₁-C₄ alkyl ether or C₄ hydroxyalkyl ether cellulose derivatives, or mixtures therein, and such cellulose derivatives are amphiphilic, whereby they have a sufficient level of C₁-C₄ alkyl ether and/or C₄ hydroxyalkyl ether units to deposit upon conventional polyester synthetic fiber surfaces and retain a sufficient level of hydroxyls, once adhered to such conventional synthetic fiber surface, to increase fiber surface hydrophilicity, or a combination of (a) and (b).
• Typically, the polyoxyethylene segments of (a)(i) will have a degree of polymerization of from 200, although higher levels can be used, preferably from 3 to 150, more preferably from 6 to 100. Suitable oxy C₄-C₆ alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric soil release agents such as MO₃S(CH₂)_nOCH₂CH₂O-, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink.
• Polymeric soil release agents useful in the present invention also include cellulosic derivatives such as hydroxyether cellulosic polymers, copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like. Such agents are commercially available and include hydroxyethers of cellulose such as METHOCEL (Dow) and carboxy alkyl of cellulose such as Metolose (Shin Etsu). Cellulosic soil release agents for use herein also include those selected from the group consisting of C₁-C₄ alkyl and C₄ hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et al.
• Soil release agents characterised by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., C₁-C₆ vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones (see EP 0 219 048). Commercially available soil release agents of this kind include the SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (West Germany).
• One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. The molecular weight of this polymeric soil release agent is in the range of from 25,000 to 55,000. See U.S.3,959,230 to Hays and U.S. 3,893,929.
• Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units which contains 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000. Examples of this polymer include the commercially available material ZELCON 5126 (from Dupont) and MILEASE T (from ICI). See also U.S. Patent 4,702,857.
• Another preferred polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone. These soil release agents are described fully in U.S. Patent 4,968,451. Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. Patent 4,711,730, the anionic end-capped oligomeric esters of U.S. Patent 4,721,580 and the block polyester oligomeric compounds of U.S. Patent 4,702,857.
• Preferred polymeric soil release agents also include the soil release agents of U.S. Patent 4,877,896, which discloses anionic, especially sulfoarolyl, end-capped terephthalate esters.
• If utilized, soil release agents will generally comprise from 0.01% to 10.0%, by weight, of the compositions herein, typically from 0.1% to 5%, preferably from 0.2% to 3.0%.
• Still another preferred soil release agent is an oligomer with repeat units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-1,2-propylene units. The repeat units form the backbone of the oligomer and are preferably terminated with modified isethionate end-caps. A particularly preferred soil release agent of this type comprises one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a ratio of from 1.7 to 1.8, and two end-cap units of sodium 2-(2-hydroxyethoxy)-ethanesulfonate. Said soil release agent also comprises from 0.5% to 20%, by weight of the oligomer, of a crystalline-reducing stabilizer, preferably selected from xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
Dye Transfer Inhibiting Agents
• The compositions according to the present invention may also include one or more materials effective for inhibiting the transfer of dyes from one fabric to another during the cleaning process. Generally, such dye transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof. If used, these agents typically comprise from 0.01% to 10% by weight of the composition, preferably from 0.01% to 5%, and more preferably from 0.05% to 2%.
• More specifically, the polyamine N-oxide polymers preferred for use herein contain units having the following structural formula: R-A_x-P; wherein P is a polymerizable unit to which an N-O group can be attached or the N-O group can form part of the polymerizable unit or the N-O group can be attached to both units; A is one of the following structures: -NC(O)-, - C(O)O-, -S-, -O-, -N=; x is 0 or 1; and R is aliphatic, ethoxylated aliphatics, aromatics, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the N-O group can be attached or the N-O group is part of these groups. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
• The N-O group can be represented by the following general structures:

  

  wherein R₁, R₂, R₃ are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof, x, y and z are 0 or 1; and the nitrogen of the N-O group can be attached or form part of any of the aforementioned groups. The amine oxide unit of the polyamine N-oxides has a pKa <10, preferably pKa <7, more preferred pKa <6.
• Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties. Examples of suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide. The amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation. The polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1,000,000; more preferred 1,000 to 500,000; most preferred 5,000 to 100,000. This preferred class of materials can be referred to as "PVNO".
• The most preferred polyamine N-oxide useful in the compositions herein is poly(4-vinylpyridine-N-oxide) which as an average molecular weight of 50,000 and an amine to amine N-oxide ratio of 1:4.
• Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as a class as "PVPVI") are also preferred for use herein. Preferably the PVPVI has an average molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average molecular weight range is determined by light scattering as described in Barth, et al., Chemical Analysis, Vol 113. "Modem Methods of Polymer Characterization".) The PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1. These copolymers can be either linear or branched.
• The present invention compositions also may employ a polyvinylpyrrolidone ("PVP") having an average molecular weight of from 5,000 to 400,000, preferably from 5,000 to 200,000, and more preferably from 5,000 to 50,000. PVP's are known to persons skilled in the detergent field; see, for example, EP-A-262,897 and EP-A-256,696. Compositions containing PVP can also contain polyethylene glycol ("PEG") having an average molecular weight from 500 to 100,000, preferably from 1,000 to 10,000. Preferably, the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from 2:1 to 50:1, and more preferably from 3:1 to 10:1.
• The detergent compositions herein may also optionally contain from 0.005% to 5% by weight of certain types of hydrophilic optical brighteners which also provide a dye transfer inhibition action. If used, the compositions herein will preferably comprise from 0.01% to 1.2% by weight of such optical brighteners.
• The hydrophilic optical brighteners useful in the present invention are those having the structural formula:

  

  wherein R₁ is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R₂ 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.
• When in the above formula, R₁ is anilino, R₂ 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 compositions herein.
• When in the above formula, R₁ is anilino, R₂ is N-2-hydroxyethyl-N-2-methylamino and 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.
• When in the above formula, R₁ is anilino, R₂ is morphilino and 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.
• Other specific optical brightener species which may be used in the present invention provide especially effective dye transfer inhibition performance benefits when used in combination with the selected polymeric dye transfer inhibiting agents hereinbefore described. The combination of such selected polymeric materials (e.g., PVNO and/or PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX) provides significantly better dye transfer inhibition in aqueous wash solutions than does either of these two detergent composition components when used alone. Without being bound by theory, it is believed that such brighteners work this way because they have high affinity for fabrics in the wash solution and therefore deposit relatively quick on these fabrics. The extent to which brighteners deposit on fabrics in the wash solution can be defined by a parameter called the "exhaustion coefficient". The exhaustion coefficient is in general as the ratio of a) the brightener material deposited on fabric to b) the initial brightener concentration in the wash liquor. Brighteners with relatively high exhaustion coefficients are the most suitable for inhibiting dye transfer in the context of the present invention.
• Of course, it will be appreciated that other conventional optical brightener types of compounds can optionally be used in the present compositions to provide conventional fabric "brightness" benefits, rather than a true dye transfer inhibiting effect. Such usage is conventional and well-known to detergent formulations.
• Conventional optical brighteners or other brightening or whitening agents known in the art can be incorporated at levels typically from 0.005% to 5%, preferably from 0.01% to 1.2% and most preferably from 0.05% to 1.2%, by weight, into the detergent compositions herein. Commercial 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 brightener which may also be used in the present invention include naphthalimide, benzoxazole, benzofuran, benzimidazole and any mixtures thereof.
• Specific examples of 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. Specific examples of these brighteners 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; and 2-(stilbene-4-yl)-2H-naphtho[1,2-d]triazole. See also U.S. Patent 3,646,015.
• Suds Suppressors - Compounds for reducing or suppressing the formation of suds can be incorporated into the compositions of the present invention. Suds suppression can be of particular importance in the so-called "high concentration cleaning process" and in front-loading European-style washing machines.
• A wide variety of materials may be used as suds suppressors, and suds suppressors are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). One category of suds suppressor of particular interest encompasses monocarboxylic fatty acid and soluble salts therein. See U.S. Patent 2,954,347. The monocarboxylic fatty acids and salts thereof used as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.
• The detergent compositions herein may also contain non-surfactant suds suppressors. These include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C₁₈-C₄₀ ketones (e.g., stearone), etc. Other suds inhibitors include N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g., K, Na, and Li) phosphates and phosphate esters. The hydrocarbons such as paraffin and haloparaffin can be utilized in liquid form. The liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range of -40°C and 50°C, and a minimum boiling point not less than 110°C (atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferably having a melting point below 100°C. The hydrocarbons constitute a preferred category of suds suppressor for detergent compositions. Hydrocarbon suds suppressors are described, for example, in U.S. Patent 4,265,779. The hydrocarbons, thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from 12 to 70 carbon atoms. The term "paraffin," as used in this suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.
• Another preferred category of non-surfactant suds suppressors comprises silicone suds suppressors. This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto the silica. Silicone suds suppressors are well known in the art and are, for example, disclosed in U.S. Patent 4,265,779 and EP 354016.
• Other silicone suds suppressors are disclosed in U.S. Patent 3,455,839 which relates to compositions and processes for defoaming aqueous solutions by incorporating therein small amounts of polydimethylsiloxane fluids.
• Mixtures of silicone and silanated silica are described, for instance, in German Patent Application DOS 2,124,526. Silicone defoamers and suds controlling agents in granular detergent compositions are disclosed in U.S. Patent 3,933,672 and in U.S. Patent 4,652,392.
• An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of:
• (i) polydimethylsiloxane fluid having a viscosity of from 20 cs. to 1,500 cs. at 25°C;
• (ii) from 5 to 50 parts per 100 parts by weight of (i) of siloxane resin composed of (CH₃)₃SiO_1/2 units of SiO₂ units in a ratio of from (CH₃)₃ SiO_1/2 units and to SiO₂ units of from 0.6:1 to 1.2:1; and
• (iii) from 1 to 20 parts per 100 parts by weight of (i) of a solid silica gel.
• In the preferred silicone suds suppressor used herein, the solvent for a continuous phase is made up of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol. The primary silicone suds suppressor is branched/crosslinked and preferably not linear.
• To illustrate this point further, typical liquid laundry detergent compositions with controlled suds will optionally comprise from 0.001 to 1, preferably from 0.01 to 0.7, most preferably from 0.05 to 0.5, weight % of said silicone suds suppressor, which comprises (1) a nonaqueous emulsion of a primary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone resin-producing silicone compound, (c) a finely divided filler material, and (d) a catalyst to promote the reaction of mixture components (a), (b) and (c), to form silanolates; (2) at least one nonionic silicone surfactant; and (3) polyethylene glycol or a copolymer of polyethylene-polypropylene glycol having a solubility in water at room temperature of more than 2 weight %; and without polypropylene glycol. Similar amounts can be used in granular compositions, gels, etc. See also U.S. Patents 4,978,471 and 4,983,316; 5,288,431 and U.S. Patents 4,639,489 and 4,749,740, Aizawa et al at column 1, line 46 through column 4, line 35.
• The silicone suds suppressor herein preferably comprises polyethylene glycol and a copolymer of polyethylene glycol/polypropylene glycol, all having an average molecular weight of less than 1,000, preferably between 100 and 800. The polyethylene glycol and polyethylene/polypropylene copolymers herein have a solubility in water at room temperature of more than 2 weight %, preferably more than 5 weight %.
• The preferred solvent herein is polyethylene glycol having an average molecular weight of less than 1,000, more preferably between 100 and 800, most preferably between 200 and 400, and a copolymer of polyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300. Preferred is a weight ratio of between 1:1 and 1:10, most preferably between 1:3 and 1:6, of polyethylene glycol:copolymer of polyethylene-polypropylene glycol.
• The preferred silicone suds suppressors used herein do not contain polypropylene glycol, particularly of 4,000 molecular weight. They also preferably do not contain block copolymers of ethylene oxide and propylene oxide, like PLURONIC L101.
• Other suds suppressors useful herein comprise the secondary alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones disclosed in U.S. 4,798,679, 4,075,118 and EP 150,872. The secondary alcohols include the C₆-C₁₆ alkyl alcohols having a C₁-C₁₆ chain. A preferred alcohol is 2-butyl octanol, which is available from Condea under the trademark ISOFOL 12. Mixtures of secondary alcohols are available under the trademark ISALCHEM 123 from Enichem. Mixed suds suppressors typically comprise mixtures of alcohol + silicone at a weight ratio of 1:5 to 5:1.
• For any detergent compositions to be used in automatic laundry washing machines, suds should not form to the extent that they overflow the washing machine. Suds suppressors, when utilized, are preferably present in a "suds suppressing amount. By "suds suppressing amount" is meant that the formulator of the composition can select an amount of this suds controlling agent that will sufficiently control the suds to result in a low-sudsing laundry detergent for use in automatic laundry washing machines.
• The compositions herein will generally comprise from 0% to 5% of suds suppressor. When utilized as suds suppressors, monocarboxylic fatty acids, and salts therein, will be present typically in amounts up to 5%, by weight, of the detergent composition. Preferably, from 0.5% to 3% of fatty monocarboxylate suds suppressor is utilized. Silicone suds suppressors are typically utilized in amounts up to 2.0%, by weight, of the detergent composition, although higher amounts may be used. This upper limit is practical in nature, due primarily to concern with keeping costs minimised and effectiveness of lower amounts for effectively controlling sudsing. Preferably from 0.01% to 1% of silicone suds suppressor is used, more preferably from 0.25% to 0.5%. As used herein, these weight percentage values include any silica that may be utilized in combination with polyorganosiloxane, as well as any adjunct materials that may be utilized. Monostearyl phosphate suds suppressors are generally utilized in amounts ranging from 0.1% to 2%, by weight, of the composition. Hydrocarbon suds suppressors are typically utilized in amounts ranging from 0.01% to 5.0%, although higher levels can be used. The alcohol suds suppressors are typically used at 0.2%-3% by weight of the finished compositions.
• Fabric Softeners - Various through-the-wash fabric softeners, especially the impalpable smectite clays of U.S. Patent 4,062,647, as well as other softener clays known in the art, can optionally be used typically at levels of from 0.5% to 10%, preferably from 0.5% to 2% by weight in the present compositions to provide fabric softener benefits concurrently with fabric cleaning. Clay softeners can be used in combination with amine and cationic softeners as disclosed, for example, in U.S. Patent 4,375,416 and U.S. Patent 4,291,071.
• Other Ingredients - A wide variety of other functional ingredients useful in detergent compositions can be included in the compositions herein, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for bar compositions.
• The detergent compositions herein will preferably be formulated such that, during use in aqueous cleaning operations, the wash water will have a pH of between 6.5 and 11, preferably between 7.5 and 10.5. Laundry products are typically at pH 9-11. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.
Other optional ingredients
• Other optional ingredients suitable for inclusion in the compositions of the invention include perfumes, colours and filler salts, with sodium sulfate being a preferred filler salt.
Form of the compositions
• The detergent compositions of the invention can be formulated in any desirable form such as powders, granulates, pastes, liquids, and gels.
Liquid compositions
• The detergent compositions of the present invention may be formulated as liquid detergent compositions. Such liquid detergent compositions typically comprise from 94% to 35% by weight, preferably from 90% to 40% by weight, most preferably from 80% to 50% by weight of a liquid carrier, e.g., water, preferably a mixture of water and organic solvent.
Gel compositions
• The detergent compositions of the present invention may also be in the form of gels. Such compositions are typically formulated with polyakenyl polyether having a molecular weight of from about 750,000 to about 4,000,000.
Solid compositions
• The detergent compositions of the invention may also be in the form of solids, such as powders and granules.
• Preferably, the mean particle size of the components of granular compositions in accordance with the invention should be such that no more that 5% of particles are greater than 1.4mm in diameter and not more than 5% of particles are less than 0.15 mm in diameter.
• The term mean particle size as defined herein is determined by sieving a sample of the composition into a number of fractions (typically 5 fractions) on a series of Tyler sieves. The weight fractions thereby obtained are plotted against the aperture size of the sieves. The mean particle size is taken to be the aperture size through which 50% by weight of the sample would pass.
• The bulk density of granular detergent compositions in accordance with the present invention are particularly useful in concentrated granular detergent compositions that are characterised by a relatively high density in comparison with conventional laundry detergent compositions. Such high density compositions typically have a bulk density of at least 400 g/litre, more preferably from 650 g/litre to 1200 g/litre, most preferably from 800g/litre to 1000g/litre.
• Bulk density is measured by means of a simple tunnel and cup device consisting of a conical funnel moulded rigidly on a base and provided with a flap valve at its lower extremity to allow the contents of the funnel to be emptied into an axially aligned cylindrical cup disposed below the funnel. The funnel is 130 mm high and has internal diameters of 130 mm and 40 mm at its respective upper and lower extremities. It is mounted so that the lower extremity is 140 mm above the upper surface of the base. The cup has an overall height of 90 mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal volume is 500 ml.
• To carry out a measurement, the funnel is filled with powder by hand pouring, the flap valve is opened and powder allowed to overfill the cup. The filled cup is removed from the frame and excess powder removed from the cup by passing a straight edged implement eg; a knife, across its upper edge. The filled cup is then weighed and the value obtained for the weight of powder doubled to provide a bulk density in g/litre. Replicate measurements are made as required.
Making processes - granular compositions
• In general, granular detergent compositions in accordance with the present invention can be made via a variety of methods including dry mixing, spray drying, agglomeration and granulation.
• The invention is illustrated in the following non limiting examples, in which all percentages are on a weight basis unless otherwise stated.
• In the detergent compositions of the invention, the abbreviated component identifications have the following meanings:

LAS

: Sodium linear C₁₂ alkyl benzene sulphonate

TAS

: Sodium tallow alcohol sulphate

C45AS

: Sodium C₁₄-C₁₅ linear alkyl sulphate

CxyEzS

: Sodium C_1x-C_1y branched alkyl sulphate condensed with z moles of ethylene oxide

C45E7

: A C_14-15 predominantly linear primary alcohol condensed with an average of 7 moles of ethylene oxide

C25 E3

: A C_12-15 branched primary alcohol condensed with an average of 3 moles of ethylene oxide

C25E5

: A C_12-15 branched primary alcohol condensed with an average of 5 moles of ethylene oxide

QAS

: R₂.N⁺(CH₃)₂(C₂H₄OH) with R₂ = C₁₂ - C₁₄

CEQ

: R₁COOCH₂CH₂.N⁺(CH₃)₃ with R₁ = C₁₁-C₁₃

Soap

: Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow and a coconut oils.

TFAA

: C₁₆-C₁₈ alkyl N-methyl glucamide

TPKFA

: C12-C14 topped whole cut fatty acids

STPP

: Anhydrous sodium tripolyphosphate

Zeolite A

: Hydrated Sodium Aluminosilicate of formula
Na₁₂(A10₂SiO₂)₁₂. 27H₂O
having a primary particle size in the range from 0.1 to 10 micrometers

NaSKS-6

: Crystalline layered silicate of formula
δ -Na₂Si₂O₅

Citric acid

: Anhydrous citric acid

Carbonate

: Anhydrous sodium carbonate with a particle size between 200µm and 900µm

Bicarbonate

: Anhydrous sodium bicarbonate with a particle size distribution between 400µm and 1200µm

Silicate

: Amorphous Sodium Silicate (SiO₂:Na₂O; 2.0 ratio)

Sulphate

: Anhydrous sodium sulphate

Citrate

: Tri-sodium citrate dihydrate of activity 86.4% with a particle size distribution between 425µm and 850µm

MA/AA

: Copolymer of 1:4 maleic/acrylic acid, average molecular weight about 70,000.

CMC

: Sodium carboxymethyl cellulose

Savinase

: Proteolytic enzyme of activity 4KNPU/g

Alcalase

: Proteolytic enzyme of activity 3AU/g

Carezyme

: Cellulytic enzyme of activity 1000 CEVU/g

Termamyl

: Amylolytic enzyme of activity 60KNU/g

Lipolase

: Lipolytic enzyme of activity 100kLU/g

Endolase

: Endoglunase enzyme of activity 3000 CEVU/g

   all sold by NOVO Industries A/S and of activity mentioned above unless otherwise specified

PB4

: Sodium perborate tetrahydrate of nominal formula NaBO₂.3H₂O.H₂O₂

PB1

: Anhydrous sodium perborate bleach of nominal formula NaBO₂.H₂O₂

Percarbonate

: Sodium Percarbonate of nominal formula
2Na₂CO₃.3H₂O₂

NOBS

: Nonanoyloxybenzene sulfonate in the form of the sodium salt.

TAED

: Tetraacetyl ethylene diamine

DTPMP

: Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the Trade name Dequest 2060

Photoactivated bleach

: Sulphonated Zinc Phthalocyanin encapsulated in dextrin soluble polymer

Brightener 1

: Disodium 4,4'-bis(2-sulphostyryl)biphenyl

Brightener 2

: Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-triazin-2-yl)amino) stilbene-2:2'-disulphonate.

HEDP

: 1,1-hydroxyethane diphosphonic acid

PVNO

: Polyvinylpyridine N-oxide

PVPVI

: Copolymer of polyvinylpyrolidone and vinylimidazole

Metolose

: Carboxy methoxy ether

SRP 1

: Sulfobenzoyl end capped esters with oxyethylene oxy and terephtaloyl backbone

SRP 2

: Diethoxylated poly (1, 2 propylene terephtalate) short block polymer

Silicone antifoam

: Polydimethyldiloxane foam controller with Siloxane-oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10:1 to 100:1.

Example 1
• The following laundry detergent compositions A, B and C according to the present invention were prepared.

  Components (% by weight)	A	B	C
  LAS	8.0	5.61	4.76
  TAS	-	1.86	1.57
  C45AS	-	2.24	3.89
  AE3S	-	0.76	1.18
  C25E3	3.4	-	-
  C25E5	-	5.47	-
  C45E7	-	-	5.0
  CEQ	0.7	2.0	2.0
  Zeolite	18.10	19.52	19.52
  SKS-6	-	8.21	8.21
  Citric acid	-	2.24	2.24
  Carbonate	22.50	21.44	21.44
  Bicarbonate	-	2.0	2.0
  Silicate	2.50	-	-
  Na Sulphate	26.11	-	14.3
  MA/AA	0.30	1.65	1.65
  CMC	0.22	0.36	0.36
  Savinase	0.85	2.75	2.75
  Termamyl	0.10	0.13	0.13
  PB4	9.0	12.67	-
  TAED	1.50	3.13	-
  DTPMP	0.25	0.20	0.20
  MgSO4	0.30	0.20	0.20
  Photoactivated bleach	15ppm	27ppm	27ppm
  Suds suppressor	0.55	2.4	2.4
  Brightener 1	0.09	0.23	0.23
  Perfume	0.26	0.47	0.47
  HEDP	0.22	0.27	0.27
  Miscellaneous to balance

Example 2
• The following detergent formulations, according to the present invention were prepared, where formulation D is a phosphorus-containing detergent composition, formulation E is a zeolite-containing detergent composition and formulation F is a compact detergent composition:

  	D	E	F
  Blown Powder
  STPP	24.0	-	24.0
  Zeolite A	-	24.0	-
  Sulphate	9.0	6.0	13.0
  MA/AA	2.0	4.0	2.0
  LAS	6.0	8.0	11.0
  TAS	2.0	-	-
  CEQ	0.7	0.7	2.0
  Silicate	7.0	3.0	3.0
  CMC	1.0	1.0	0.5
  Brightener 2	0.2	0.2	0.2
  Soap	1.0	1.0	1.0
  DTPMP	0.4	0.4	0.2
  Metolose	0.2	0.5	-

  Spray On
  C45E7	2.5	2.5	2.0
  C25E3	2.5	2.5	2.0
  Silicone antifoam	0.3	0.3	0.3
  Perfume	0.3	0.3	0.3

  Dry additives
  Carbonate	6.0	13.0	15.0
  PB4	18.0	18.0	10
  PB1	4.0	4.0	-
  TAED	3.0	3.0	1.0
  Photoactivated bleach	0.02%	0.02%	0.02%
  Savinase	1.0	1.0	1.0
  Lipolase	0.4	0.4	0.4
  Termamyl	0.25	0.30	0.15
  Sulphate	3.0	3.0	5.0
  HEDP	0.25	0.4	0.30
  Balance (Moisture & Miscellaneous)	100.0	100.0	100.0
  Density (g/litre)	630	670	670

Example 3
• The following nil bleach-containing detergent formulations G to I of particular use in the washing of colored clothing, according to the present invention were prepared:

  	G	H	I
  Blown Powder
  Zeolite A	15.0	15.0	-
  Sulphate	-	5.0	-
  LAS	3.0	3.0	-
  CEQ	2.0	1.5	1.3
  DTPMP	0.4	0.5	-
  CMC	0.4	0.4	-
  MA/AA	4.0	4.0	-

  Agglomerates
  C45AS	-	-	11.0
  LAS	6.0	5.0	-
  TAS	3.0	2.0	-
  Silicate	4.0	4.0	-
  Zeolite A	10.0	15.0	13.0
  CMC	-	-	0.5
  MA/AA	-	-	2.0
  Carbonate	9.0	7.0	7.0

  Spray On
  Perfume	0.3	0.3	0.5
  C45E7	4.0	4.0	4.0
  C25E3	2.0	2.0	2.0

  Dry additives
  MA/AA	-	-	3.0
  NaSKS-6	-	-	12.0
  Citrate	10.0	-	8.0
  Bicarbonate	7.0	3.0	5
  Carbonate	8.0	5	7
  PVPVI/PVNO	0.5	0.5	0.5
  Alcalase	0.5	0.3	0.9
  Lipolase	0.4	0.4	0.4
  Termamyl	0.6	0.6	0.6
  Carezyme	0.6	0.6	0.6
  Silicone antifoam	5.0	5.0	5.0
  Sulphate	-	9.0	-
  HEDP	0.3	0.5	0.2
  Balance (Moisture and Miscellaneous)	100.0	100.0	100.0
  Density (g/litre)	700	700	700

Example 4
• The following detergent formulations J to M, according to the present invention were prepared:

  	J	K	L	M
  LAS	20.0	14.0	24.0	22.0
  QAS	0.7	1.0	-	0.7
  TFAA	-	1.0	-	-
  C25E5/C45E7	-	2.0	-	0.5
  C45E3S	-	2.5	-	-
  CEQ	2.0	1.5	1.0	0.5
  STPP	30.0	18.0	30.0	-
  Silicate	9.0	5.0	10.0	-
  Carbonate	13.0	7.5	-	5.0
  Bicarbonate	-	7.5	-	-
  DTPMP	0.7	1.0	-	-
  SRP 1	0.3	0.2	-	0.1
  MA/AA	2.0	1.5	2.0	1.0
  CMC	0.8	0.4	0.4	0.2
  Savinase	0.8	1.0	0.5	0.5
  Termamyl	0.8	0.4	-	0.25
  Lipolase	0.2	0.1	0.2	0.1
  Carezyme (5T)	0.15	0.05	-	-
  Photoactivated bleach (ppm)	70ppm	45ppm	-	10ppm
  Brightener 1	0.2	0.2	0.08	0.2
  PB1	6.0	2.0	-	-
  NOBS	2.0	1.0	-	-
  HEDP	0.2	0.6	0.15	0.2
  Balance (Moisture and Miscellaneous)	100.0	100.0	100.0	100.0

Example 5
• The following detergent formulations N to P, according to the present invention were prepared:

  	N	O	P
  Blown Powder
  Zeolite A	30.0	22.0	6.0
  Sulphate	19.0	10.0	7.0
  MA/AA	3.0	3.0	6.0
  LAS	14.0	12.0	22.0
  C45AS	8.0	7.0	7.0
  CEQ	2.0	2.0	2.0
  Silicate	-	1.0	5.0
  Soap	-	-	2.0
  Brightener 1	0.2	0.2	0.2
  Carbonate	8.0	16.0	20.0
  DTPMP	-	0.4	0.4

  Spray On
  C45E7	1.0	1.0	1.0

  Dry additives
  PVPVI/PVNO	0.5	0.5	0.5
  Savinase	1.0	1.0	1.0
  Lipolase	0.4	0.4	0.4
  Termamyl	0.1	0.1	0.1
  Carezyme	0.1	0.1	0.1
  NOBS	-	6.1	4.5
  PB1	1.0	5.0	6.0
  Sulphate	-	6.0	-
  HEDP	0.15	0.3	0.5
  Balance (Moisture and Miscellaneous)	100	100	100

Example 6
• The following high density and bleach-containing detergent formulations Q to S, according to the present invention were prepared:

  	Q	R	S
  Blown Powder
  Zeolite A	15.0	15.0	15.0
  Sulphate	-	5.0	-
  LAS	3.0	3.0	3.0
  QAS	-	1.5	1.5
  CEQ	2.0	1.5	2.0
  DTPMP	0.4	0.4	0.4
  CMC	0.4	0.4	0.4
  MA/AA	4.0	2.0	2.0

  Agglomerates
  LAS	5.0	5.0	5.0
  TAS	2.0	2.0	2.0
  Silicate	3.0	3.0	4.0
  Zeolite A	8.0	8.0	8.0
  Carbonate	8.0	8.0	4.0

  Spray On
  Perfume	0.3	0.3	0.3
  C45E7	2.0	2.0	2.0
  C25E3	2.0	-	-

  Dry additives
  Citrate	5.0	-	2.0
  Bicarbonate	-	3.0	-
  Carbonate	8.0	15.0	10.0
  TAED	6.0	2.0	5.0
  PB1	14.0	7.0	10.0
  Polyethylene oxide of MW 5,000,000	-	-	0.2
  Bentonite	-	-	10.0
  Savinase	1.0	1.0	1.0
  Lipolase	0.4	0.4	0.4
  Termamyl	0.6	0.6	0.6
  Carezyme	0.6	0.6	0.6
  Silicone antifoam granule	5.0	5.0	5.0
  Sulphate	-	3.0	-
  HEDP	0.15	0.40	0.30
  Balance (Moisture and Miscellaneous)	100.0	100.0	100.0
  Density (g/litre)	850	850	850

Example 7
• The following high density detergent formulations T and U, according to the present invention were prepared:

  	T	U
  Agglomerate
  C45AS	11.0	14.0
  CEQ	3.0	3.5
  Zeolite A	15.0	6.0
  Carbonate	4.0	8.0
  MA/AA	4.0	2.0
  CMC	0.5	0.5
  DTPMP	0.4	0.4
  Metolose	0.6	0.2

  Spray On
  C25E5	5.0	5.0
  Perfume	0.5	0.5

  Dry Additives
  HEDP	0.5	0.3
  SKS 6	13.0	10.0
  Citrate	3.0	1.0
  TAED	5.0	7.0
  PC	20.0	20.0
  SRP 1	0.3	0.3
  Savinase	1.4	1.4
  Lipolase	0.4	0.4
  Carezyme	0.6	0.6
  Termamyl	0.6	0.6
  Silicone antifoam particle	5.0	5.0
  Brightener 1	0.2	0.2
  Brightener 2	0.2	-
  Balance (Moisture and Miscellaneous)	100	100
  Density (g/litre)	850	850

Example 8
• The following liquid detergent formulations V to AC, according to the present invention were prepared:

  	V	W	X	Y	Z	AA	AB	AC
  LAS	10.0	13.0	9.0	-	25.0	-	-	-
  C25AS	4.0	1.0	2.0	10.0	-	13.0	18.0	15.0
  C25E3S	1.0	-	-	3.0	-	2.0	2.0	4.0
  C25E7	6.0	8.0	13.0	2.5	-	-	4.0	4.0
  TFAA	-	-	-	4.5	-	6.0	8.0	8.0
  QAS	-	-	-	-	3.0	1.0	-	-
  CEQ	0.5	1.5	1.0	0.75	2.0	1.5	1.8	2.0
  TPKFA	2.0	-	13.0	2.0	-	15.0	7.0	7.0
  Rapeseed fatty acids	-	-	-	5.0	-	-	4.0	4.0
  Citric acid	2.0	3.0	1.0	1.5	1.0	1.0	1.0	1.0
  Dodecenyl /tetradecenyl succinic acid	12.0	10.0	-	-	15.0	-	-	-
  Oleic acid	4.0	2.0	1.0	-	1.0	-	-	-
  Ethanol	4.0	4.0	7.0	2.0	7.0	2.0	3.0	2.0
  1,2 Propanediol	4.0	4.0	2.0	7.0	6.0	8.0	10.0	13.0
  Mono Ethanol Amine	-	-	-	5.0	-	-	9.0	9.0
  Tri Ethanol Amine	-	-	8.0	-	-	-	-	-
  NaOH up to pH	8.0	8.0	7.6	7.7	8.0	7.5	8.0	8.2
  Ethoxy-lated tetraethylene pentamine	0.5	-	0.5	0.2	-	-	0.4	0.3
  DTPMP	1.0	1.0	0.5	1.0	2.0	1.2	1.0	-
  SRP 2	0.3	-	0.3	0.1	-	-	0.2	0.1
  PVNO	-	-	-	-	-	-	-	0.10
  Protease	0.5	0.5	0.4	0.25	-	0.5	0.3	0.6
  Alcalase	-	-	-	-	1.5	-	-	-
  Lipolase (109 KLU/g)	-	0.10	-	0.01	-	-	0.15	0.15
  Termamyl (300 KNU/g)	0.05	0.05	0.12	0.10	0.05	0.15	0.10	0.10
  Carezyme (5000 CEVU/g)	-	-	-	0.01	-	-	0.03	0.03
  Endoglucanase	-	-	-	0.10	-	-	0.07	-
  Boric acid	0.1	0.2	-	2.0	1.0	1.5	2.5	2.5
  Sodium formate	-	-	1.0	-	-	-	-	-
  Calcium chloride	-	0.015	-	0.01	-	-	-	-
  Bentonite clay	-	-	-	-	4.0	4.0	-	-
  HEDP	0.15	0.15	0.5	0.22	0.4	0.35	0.3	0.2
  Metolose	0.3	-	-	-	-	-	-	-
  Balance (Moisture and Miscellaneous)	100.0	100.0	100.0	100.0	100.0	100.0	100.0	100.0

Claims (17)

1. A detergent composition comprising a cationic ester surfactant and an organo diphosphonic acid crystal growth inhibitor component or its salts or complexes.
2. A detergent composition according to Claim 1, wherein said crystal growth inhibitor is a C₁ to C₄ organo diphosphonic acid component and salt thereof.
3. A detergent composition according to either one of Claim 1 or 2, wherein said crystal growth inhibitor is selected from ethylene diphosphonic acid, α-hydroxy-2 phenyl ethyl diphosphonic acid, methylene diphosphonic acid, vinylidene 1,1 diphosphonic acid, 1,2 dihydroxyethane 1,1 diphosphonic acid and hydroxy-ethane 1,1 diphosphonic acid and any salts thereof and mixture thereof.
4. A detergent composition according to any one of Claim 1-3, wherein said crystal growth inhibitor is hydroxy-ethane 1,1 diphosphonic acid.
5. A detergent composition according to any one of Claims 1-4, wherein said crystal growth inhibitor is present in amount from 0.005% to 20%, preferably from 0.05% to 15% by weight of the composition.
6. A detergent composition according to any one of Claims 1-5, wherein the cationic ester surfactant is selected from cationic ester surfactants having the formula:

   

   wherein R₁ is a C₅-C₃₁ linear or branched alkyl, alkenyl or alkaryl chain or M^-. N⁺(R₆R₇R₈)(CH₂)_s; X and Y, independently, are selected from COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO wherein at least one of X or Y is a COO, OCO, OCOO, OCONH or NHCOO group; R₂, R₃, R₄, R₆, R₇, and R₈ are independently selected from alkyl, alkenyl, hydroxyalkyl, hydroxy-alkenyl and alkaryl groups having from 1 to 4 carbon atoms; and R₅ is independently H or a C₁-C₃ alkyl group; wherein the values of m, n, s and t independently lie in the range of from 0 to 8, the value of b lies in the range from 0 to 20, and the values of a, u and v independently, are either 0 or 1 with the proviso that at least one of u or v must be 1; and wherein M is a counter anion.
7. A detergent composition according to any one of Claims 1-6, wherein the cationic ester surfactant is selected from cationic ester surfactants having the formula:

   

   wherein R₁ is a C₁₁-C₁₉ linear or branched alkyl chain, and wherein M is a counter anion.
8. A detergent composition according to any one of Claims 1-7, wherein said cationic ester surfactant is selected from stearoyl choline ester quaternary methylammonium halides, palmitoyl choline ester quaternary methylammonium halides, myristoyl choline ester quaternary methylammonium halides, lauroyl choline ester methylammonium halides, cocoyl choline ester quaternary methylammonium halides, tallowyl choline ester quaternary methylammonium halides, and any mixtures thereof.
9. A detergent composition according to any one of Claims 1-8, wherein said cationic ester surfactant is cocoyl choline ester quaternary methylammonium halides.
10. A detergent composition according to any one of Claims 1-9, wherein said cationic ester surfactant is present in amount from 0.01% to 30%, preferably from 0.05% to 15% by weight of the composition.
11. A detergent composition according to any one of Claims 1-10, wherein said detergent composition ether comprises one or more water-soluble organic polymeric polycarboxylic compounds and salts thereof.
12. A detergent composition according to Claim 11, wherein said polycarboxylic compound is a co-polymeric polycarboxylic acid having monomeric unit selected from acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid and mixtures thereof.
13. A detergent composition according to either one of Claim 11 or 12, wherein said polymeric polycarboxylic compound is a co-polymer derived from monomers of acrylic acid and maleic acid.
14. A detergent composition according to Claim 11, wherein said polymeric polycarboxylic compound is a polyamino acid compound selected from polyaspartic acid and polyglutamic acid.
15. A detergent composition according to any one of Claims 11-14, wherein said polymeric polycarboxylic compound is present in amount from 0.005% to 20%, preferably from 0.01% to 10% by weight of the composition.
16. A detergent composition according to any one of Claims 1-15, wherein said detergent composition further comprises additional surfactants, builders, alkaline hydrogen peroxide sources, peroxyacid bleach precursors, enzymes and conventional detersive adjuncts.
17. A detergent composition according to any one of Claims 1-16, wherein said detergent is formulated in a form selected from powder, granulate, paste, liquid and gel.