Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/10—Carbonates ; Bicarbonates
• • 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
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
  • C11D1/146—Sulfuric acid esters
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
  • C11D17/065—High-density particulate detergent 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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/12—Water-insoluble compounds
  • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
  • C11D3/1246—Silicates, e.g. diatomaceous earth
  • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
  • C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/12—Water-insoluble compounds
  • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
  • C11D3/1246—Silicates, e.g. diatomaceous earth
  • C11D3/128—Aluminium silicates, e.g. zeolites

Definitions

• the present invention relates to detergent compositions comprising mid-branched surfactant, low levels of a builder system and an alkalinity system comprising carbonate salts.
• the compositions are solid laundry detergent compositions.
• JP-A-57-133200 discloses dishwashing compositions comprising ⁇ -mono (methyl branched alkyl) glycerol ethers.
• WO97/38956 and WO97/39088 disclose solid laundry detergent compositions comprising mid-branched alkyl sulphate surfactant, zeolite A and carbonate.
• Hard water conditions due to the presence of Ca and Mg ions in the washing water and on the fabrics, can cause a reduction of the performance of the various components in detergents, especially charged surfactants, such as anionic surfactants.
• builders are traditionally employed in detergent compositions, to build the Ca and Mg ions, thereby softening the water.
• a disadvantage of high levels of builders is that many of these builders are not water-soluble, or only partially water soluble. This can result in a poor solubility of the detegrent in the washing water and it can lead to deposition of builder material on the washed fabrics and/ or on the (dish) washing machine, resulting in for example greying of the fabrics.
• the use of high levels of builder materials can be very expensive.
• an alkalinity source preferably carbonate salts
• the inventors have found that the introduction in detergent compositions of small amount of an alkalinity source, preferably carbonate salts, can deliver the required alkalinity for an optimum performance of the mid-chain branched surfactants, whilst allowing the reduction of the levels of builder materials
• the invention relates to solid detergent compositions having a density of from 330 grams /litre to 1400 grams/litre, comprising a total amount of surfactant from 1 to 25% by weight of the detergent composition,
• the surfactant system a) comprises mid-chain branched primary alkyl sulfate or sulfonate surfactants.
• the detergent compositions of the invention comprise at least 0.5%, preferably at least 5%, more preferably at least 10% by weight of the composition of a surfactant system, comprising longer alkyl chain, mid-chain branched surfactant compounds, selected from the group consisting of surfactant compounds having the formula as defined above.
• Preferred surfactant systems herein comprise longer alkyl chain, mid-chain branched surfactant compounds of the above formula wherein the A b moiety is a branched primary alkyl moiety having the formula: wherein the total number of carbon atoms in the branched primary alkyl moiety of this formula (including the R, R 1 , and R 2 branching) is from 13 to 19; R, R 1 , and R 2 are each independently selected from hydrogen and C 1 -C 3 alkyl (preferably methyl), provided R, R 1 , and R 2 are not all hydrogen and, when z is 0, at least R or R 1 is not hydrogen; w is an integer from 0 to 13; x is an integer from 0 to 13; y is an integer from 0 to 13; z is an integer from 0 to 13; and w + x + y + z is from 7 to 13.
• mid-chain branched surfactant compounds of the surfactant system certain points of branching (e.g., the location along the chain of the R, R 1 , and/or R 2 moieties in the above formula) are preferred over other points of branching along the backbone of the surfactant.
• the formula below illustrates the mid-chain branching range (i.e., where points of branching occur), preferred mid-chain branching range, and more preferred mid-chain branching range for mono-methyl branched alkyl A b moieties useful according to the present invention. It should be noted that for the mono-methyl substituted surfactants these ranges exclude the two terminal carbon atoms of the chain and the carbon atom immediately adjacent to the -X - B group.
• the formula below illustrates the mid-chain branching range, preferred mid-chain - branching range, and more preferred mid-chain branching range for di-methyl substituted alkyl A b moieties useful according to the present invention.
• Preferred are surfactant compounds wherein in the above formula the A b moiety does not have any quaternary substituted carbon atoms (i.e., 4 carbon atoms directly attached to one carbon atom).
• mid-chain branched surfactants compounds for use in the detergent compositions herein are mid-chain branched primary alkyl sulfonate and, even more preferably, sulfate surfactants.
• Preferred mid-chain branched primary alkyl sulfate surfactants are of the formula These surfactants have a linear primary alkyl sulfate chain backbone (i.e., the longest linear carbon chain which includes the sulfated carbon atom) which preferably comprises from 12 to 19 carbon atoms and their branched primary alkyl moieties comprise preferably a total of at least 14 and preferably no more than 20, carbon atoms.
• the average total number of carbon atoms for the branched primary alkyl moieties is preferably within the range of from greater than 14.5 to about 17.5.
• the surfactant system preferably comprises at least one branched primary alkyl sulfate surfactant compound having a longest linear carbon chain of not less than 12 carbon atoms or not more than 19 carbon atoms, and the total number of carbon atoms including branching must be at least 14, and further the average total number of carbon atoms for the branched primary alkyl moiety is within the range of greater than 14.5 to about 17.5.
• R, R 1 , and R 2 are each independently selected from hydrogen and C 1 -C 3 alkyl - group (preferably hydrogen or C 1 -C 2 alkyl, more preferably hydrogen or methyl, and most preferably methyl), provided R, R 1 , and R 2 are not all hydrogen. Further, when z is 1, at least R or R 1 is not hydrogen.
• M is hydrogen or a salt forming cation depending upon the method of synthesis.
• salt forming cations are lithium, sodium, potassium, calcium, magnesium, quaternary alkyl amines having the formula wherein R 3 , R 4 , R 5 and R 6 are independently hydrogen, C 1 -C 22 alkylene, C 4 -C 22 branched alkylene, C 1 -C 6 alkanol, C 1 -C 22 alkenylene, C 4 -C 22 branched alkenylene, and mixtures thereof.
• Preferred cations are ammonium (R 3 , R 4 , R 5 and R 6 equal hydrogen), sodium, potassium, mono-, di-, and trialkanol ammonium, and mixtures thereof.
• the monoalkanol ammonium compounds of the present invention have R 3 equal to C 1 -C 6 alkanol, R 4 , R 5 and R 6 equal to hydrogen; dialkanol ammonium compounds of the present invention have R 3 and R 4 equal to C 1 -C 6 alkanol, R 5 and R 6 equal to hydrogen; trialkanol ammonium compounds of the present invention have R 3 , R 4 and R 5 equal to C 1 -C 6 alkanol, R 6 equal to hydrogen.
• Preferred alkanol ammonium salts of the present invention are the mono-, di- and tri- quaternary ammonium compounds having the formulas: H 3 N + CH 2 CH 2 OH, H 2 N + (CH 2 CH 2 OH) 2 , HN + (CH 2 CH 2 OH) 3 .
• Preferred M is sodium, potassium and the C 2 alkanol ammonium salts listed above; most preferred is sodium.
• Another preferred surfactant system of the present invention have one or more branched primary alkyl sulfates having the formula wherein the total number of carbon atoms, including branching, is from 15 to 18, and when more than one of these sulfates is present, the average total number of carbon atoms in the branched primary alkyl moieties having the above formula is within the range of greater than 14.5 to about 17.5;
• R 1 and R 2 are each independently hydrogen or C 1 -C 3 alkyl;
• M is a water soluble cation;
• x is from 0 to 11;
• y is from 0 to 11;
• z is at least 2; and
• x + y + z is from 9 to 13; provided R 1 and R 2 are not both hydrogen.
• the surfactant system comprises at least 20% by weight of the system, more preferably at least 60% by weight, even more preferably at least 90% by weight of the system, of mid-chain branched primary alkyl sulfates, preferably having R 1 and R 2 independently hydrogen or methyl, provided R 1 and R 2 are not both hydrogen; x + y is equal to 8, 9, or 10 and z is at least 2, whereby the average total number of carbon atoms in these sulfate surfactants is preferably from 14 to 18, more preferably from 15 to 17, even more preferably from 16 to 17.
• Preferred mono-methyl branched primary alkyl sulfates are selected from the group consisting of: 3-methyl pentadecanol sulfate, 4-methyl pentadecanol sulfate, 5-methyl pentadecanol sulfate, 6-methyl pentadecanol sulfate, 7-methyl pentadecanol sulfate, 8-methyl pentadecanol sulfate, 9-methyl pentadecanol sulfate, 10-methyl pentadecanol sulfate, 11-methyl pentadecanol sulfate, 12-methyl pentadecanol sulfate, 13-methyl pentadecanol sulfate, 3-methyl hexadecanol sulfate, 4-methyl hexadecanol sulfate, 5-methyl hexadecanol sulfate, 6-methyl hexadecanol
• Preferred di-methyl branched primary alkyl sulfates are selected from the group consisting of: 2,3-methyl tetradecanol sulfate, 2,4-methyl tetradecanol sulfate, 2,5-methyl tetradecanol sulfate, 2,6-methyl tetradecanol sulfate, 2,7-methyl tetradecanol sulfate, 2,8-methyl tetradecanol sulfate, 2,9-methyl tetradecanol sulfate, 2,10-methyl tetradecanol sulfate, 2,11-methyl tetradecanol sulfate, 2,12-methyl tetradecanol sulfate, 2,3-methyl pentadecanol sulfate, 2,4-methyl pentadecanol sulfate, 2,5-methyl pentadecanol sulfate, 2,6-methyl penta
• branched primary alkyl sulfates comprising 16 carbon atoms and having one branching unit are examples of preferred branched surfactants useful in the present invention compositions:
• branched primary alkyl sulfates comprising 17 carbon atoms and having two branching units are examples of preferred branched surfactants according to the present invention:
• Both water-soluble and partially water-soluble or water-insoluble builder compounds can be comprised in the builder system of the present invention
• Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts.
• the polycarboxylic acids or their salts comprise at least two carboxylic radicals separated from each other by not more that two carbon atoms, borates, and mixtures of any of the foregoing.
• the carboxylate or polycarboxylate builder or its salt can be momomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.
• Suitable carboxylates or their acids containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof.
• Polycarboxylates or their acids containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates.
• Polycarboxylates or their acids containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No.
• the most preferred polycarboxylic acid containing three carboxy groups is citric acid, mono-hydrate anhydrous or optionally in a liquid form, preferably present a t a level of from 0.1% to 15%, more preferably from 0.5% to 8% by weight of the composition.
• Polycarboxylates or their acids containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates.
• Polycarboxylates or their acids containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000.
• Preferred polycarboxylates or their acids are hydroxycarboxylates or acids containing up to three carboxy groups per molecule, more particularly citrates or citric acid, as descibed above.
• parent acids of the monomeric or oligomeric polycarboxylate or mixtures thereof with their salts e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder compounds for the builder system of the invention.
• Organic polymeric compounds are preferred builder compounds of the builder system of the detergent composition in accord with the invention, and are preferably present as components of any particulate components where they may act such as to bind the particulate component together.
• organic polymeric builder compound it is meant herein essentially any polymeric organic compound commonly used as builder, dispersant, and anti-redeposition and soil suspension agent in detergent, not being a polymeric or oligomeric (poly)carboxylate compound described above.
• Organic polymeric compound is typically incorporated in the builder system of the invention at a level of from 0.1 % to 50%, preferably from 0.5% to 35%, most preferably from 1% to 20% by weight of the builder system.
• Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid/ maleic anhydride.
• the average molecular weight of such copolymers in the acid form preferably can range from 1,000 to 100,000, more preferably from 2,000 to 75,000 or even more preferred to 70,000, but most preferred are the co-polymers with a average molecular weight of from 2,500 to 20,000 or in another preferred embodiment from 60,000 to 75,000 or even 70,000.
• the ratio of acrylate to maleate segments in such copolymers will generally range from 30:1 to 1:30, more preferably from 10:1 to 1:1, most preferably from 4:1 to 7:3.
• Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts.
• 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.
• acrylic acid-based polymers which are useful herein are for example the water-soluble salts of polymerized acrylic acid.
• the average molecular weight of such homo-polymers in the acid form preferably ranges from 1,800 to 100,000, more preferably from 2,000 to 10,000, most preferably from 3,000 to 5,000.
• polyamino-based compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
• polymeric carboxylate-containing builder 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.
• Terpolymers containing monomer units selected from maleic acid, acrylic acid and polyaspartic acid, particularly those having an average molecular weight of from 5,000 to 20,000, are also suitable herein.
• polymeric carboxylate-containing builder compounds are the polyelectrolyte-containing glycols, particularly those of molecular weight 1,000-10,000, more particularly 2,000 to 8,000 and most preferably about 4,000.
• polymeric carboxylate-containing builder compounds are those which typically have a hydrophilic backbone and at least one hydrophobic side chain.
• this type of polymeric carboxylate-containing builder compounds have a molecular weight of between 500 and 100,000, more preferred from 1,000 to 70,000, especially preferred from 1,500 to 10,000, or in another preferred embodiment from 2,800 to 6,000.
• Polymeric carboxylate-containing builder compounds for use herein may for example be prepared by using conventional aqueous polymerisation procedures, suitable methods are for example described in GB 89 24477, GB 89 24478 and GB 89 24479.
• the hydrophilic backbone of the polymer is predominantly linear (the main chain of the backbone constitutes at least 50%, preferably more than 75%, most preferred more than 90% by weight of the backbone), suitable monomer constituents of the hydrophilic backbone are for example unsaturated C 1 -C 6 acids, ethers, alcohols, aldehydes, ketones or esters, sugar units, alkoxy units, maleic anhydride and saturated polyalcohols such as glycerol.
• the hydrophobic side groups are composed of alkoxy groups for example butylene oxide and/or propylene oxide and/or alkyl or alkenyl chains having from 5 to 24 carbon atoms.
• the hydrophobic groups may be connected to the hydrophilic backbone via relatively hydrophilic bonds for example a poly ethoxy linkage.
• Preferred polymeric carboxylate-containing builder compounds of this type are the polymers described in WO 91/ 08281.
• Preferred counterions for the polymeric organic (carboxylate-containing) builder compounds are for example sodium, magnesium or calcium ions.
• the builder system of the invention can comprise phosphate-containing builder material. It can however be preferred that the builder system is substantially free of phosphate-containing builders. Suitable 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 polymerization ranges from about 6 to 21, and salts of phytic acid.
• the builder system can also comprise silicate-containing builder compounds.
• Preferred can be, amorphous sodium silicate.
• silicate containing builder compounds are crystalline layered silicates, preferably sodium silicates.
• Preferred can be the crystalline layered silicate of formula ⁇ -Na 2 Si 2 O 5 , known as NaSKS-6 (Hoechst).
• aluminosilicate zeolites which preferably have the unit cell formula Na z[ (AlO 2 ) z (SiO 2 )y]- xH 2 O, wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264.
• the aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22%by wieght of the material of water in bound form.
• the aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula: Na 12 [AlO 2 ) 12 (SiO 2 ) 12 ]. xH 2 O wherein x is from 20 to 30, especially 27. Zeolite X has the formula Na 86 [(AlO 2 ) 86 (SiO 2 ) 106 ]. 276 H 2 O.
• zeolite MAP builder Another preferred aluminosilicate zeolite is zeolite MAP builder.
• Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkali metal alumino-silicate of the zeolite P type having a silicon to aluminium ratio not greater than 1.33, preferably within the range from 0.9 to 1.33 and more preferably within the range of from 0.9 to 1.2.
• zeolite MAP having a silicon to aluminium ratio not greater than 1.15 and, more particularly, not greater than 1.07.
• the zeolite MAP detergent builder has a particle size, expressed as a d 50 value of from 1.0 to 10.0 micrometres, more preferably from 2.0 to 7.0 micrometres, most preferably from 2.5 to 5.0 micrometres.
• the d 50 value indicates that 50% by weight of the particles have a diameter smaller than that figure.
• the particle size may, in particular be determined by conventional analytical techniques such as microscopic determination using a scanning electron microscope or by means of a laser granulometer. Other methods of establishing d 50 values are disclosed in EP 384070A.
• the detergent compositions of the present invention comprise from 5% to 30%, more preferably from 8% to 20%, even more preferably from 10% to 15% by weight of the composition of an alkalinity system, comprising carbonate salts.
• Examples of preferred carbonates are the alkaline earth and alkali metal carbonates, including sodium carbonate, bicarbonate and sesqui-carbonate and any mixtures thereof with ultra-fine calcium carbonate such as are disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.
• Alkali metal percarbonate salts may also be included in the alkalinity system of the detergent compositions and are also suitable carbonate and are described below in more detail.
• Highly suitable carbonates can be anhydrous sodium carbonate. It can be preferred that the carbonate salts are comprised in particles of a particle size between 200 ⁇ m and 900 ⁇ m and anhydrous sodium bicarbonate with a particle size distribution between 400 ⁇ m and 1200 ⁇ m.
• the detergent compositions in accord with the invention may also contain additional detergent components.
• additional detergent components and levels of incorporation thereof will depend on the physical form of the composition or component, and the precise nature of the washing operation for which it is to be used.
• compositions or components thereof, of the invention preferably contain one or more additional detergent components selected from other surfactants, bleaches, bleach catalysts, additional organic polymeric compounds, enzymes, suds suppressors, lime soap, dispersants, soil suspension and anti-redeposition agents soil releasing agents, perfumes, brightners, photobleaching agents and additional corrosion inhibitors.
• additional detergent components selected from other surfactants, bleaches, bleach catalysts, additional organic polymeric compounds, enzymes, suds suppressors, lime soap, dispersants, soil suspension and anti-redeposition agents soil releasing agents, perfumes, brightners, photobleaching agents and additional corrosion inhibitors.
• additional surfactants selected from the group consisting of anionic zwitterionic, ampholytic and amphoteric surfactants can be present.
• the total amount of surfactants is from 1% to 25% by weight of the detergent composition.
• a preferred aspect of the present invention is a granular detergent composition.
• One or more of the surfactants can be comprised in a base composition, containing optionally hydrophobic peroxyacid bleaching component and/or hydrophilic nonionic surface-active component.
• the base composition may be prepared by spray-drying and or dry-mixing/agglomeration, as described herein.
• the detergent composition of the present invention can comprise one or more additional anionic surfactants.
• Any anionic surfactant useful for detersive purposes is suitable. Examples include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate surfactants are preferred.
• anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C 12 -C 18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C 6 -C 14 diesters), N-acyl sarcosinates.
• Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.
• the anionic surfactant is preferably present at a level of 0.5% to 60%, preferably at a level of from 3% to 50%, more preferably of from 5% to 35%, most preferably from 6% to 20% by weight of the composition.
• Additional anionic sulfate surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C 5 -C 17 acyl-N-(C 1- C 4 alkyl) and -N-(C 1 -C 2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).
• Alkyl sulfate surfactants are preferably selected from the linear and branched primary C 9 -C 22 alkyl sulfates, more preferably the C 11 -C 15 branched chain alkyl sulfates and the C 12 -C 14 linear chain alkyl sulfates.
• Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C 10 -C 18 alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C 11 -C 18 , most preferably C 11 -C 15 alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.
• a particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124.
• Anionic sulfonate surfactant Anionic sulfonate surfactant
• Additional anionic sulfonate surfactants suitable for use herein include the salts of C 5 -C 20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C 6 -C 22 primary or secondary alkane sulfonates, C 6 -C 24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.
• Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein.
• Suitable alkyl ethoxy carboxylates include those with the formula RO(CH 2 CH 2 O) x CH 2 COO - M + wherein R is a C 6 to C 18 alkyl group, x ranges from O to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than 20 % and M is a cation.
• Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHR 1 -CHR 2 -O) X -R 3 wherein R is a C 6 to C 18 alkyl group, x is from 1 to 25, R 1 and R 2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R 3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.
• Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon.
• Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps may also be included as suds suppressors.
• alkali metal sarcosinates of formula R-CON (R 1 ) CH 2 COOM, wherein R is a C 5 -C 17 linear or branched alkyl or alkenyl group, R 1 is a C 1 -C 4 alkyl group and M is an alkali metal ion.
• R is a C 5 -C 17 linear or branched alkyl or alkenyl group
• R 1 is a C 1 -C 4 alkyl group
• M is an alkali metal ion.
• the nonionic surfactants are preferably present in low levels, preferably from 0.5% to 20%, more preferably from 1% to 15%, even more preferably from 1.5% to 8% by weight.
• the ratio of the nonionic surfactants, when present, to the surfactant system is preferably from 5:1 to 1:20, more preferably from 5:1 to 1:10, even more preferably from 1:1 to 1:10.
• any alkoxylated nonionic surfactants are suitable herein.
• the ethoxylated and propoxylated nonionic surfactants are preferred.
• Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene diamine adducts.
• the condensation products of aliphatic alcohols with from 1 to 25 moles of alkylene oxide, particularly ethylene oxide and/or propylene oxide, are suitable for use herein.
• the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms.
• Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms or more preferably 9 to 15 with from 3 to 12 moles of ethylene oxide per mole of alcohol.
• Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R 2 CONR 1 Z wherein : R1 is H, C 1 -C 4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl, more preferably C 1 or C 2 alkyl, most preferably C 1 alkyl (i.e., methyl); and R 2 is a C 5- C 31 hydrocarbyl, preferably straight-chain C 5 -C 19 alkyl or alkenyl, more preferably straight-chain C 9 -C 17 alkyl or alkenyl, most preferably straight-chain C 11 -C 17 - alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof
• Suitable fatty acid amide surfactants include those having the formula: R 6 CON(R 7 ) 2 wherein R 6 is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and each R 7 is selected from the group consisting of hydrogen, C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, and -(C 2 H 4 O) x H, where x is in the range of from 1 to 3.
• Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent 4,565,647, LIenado, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from 1.3 to 10 saccharide units.
• Preferred alkylpolyglycosides have the formula: R 2 O(C n H 2n O)t(glycosyl) x wherein R 2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8.
• the glycosyl is preferably derived from glucose.
• Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids.
• Suitable amine oxides include those compounds having the formula - R 3 (OR 4 ) x N 0 (R 5 ) 2 wherein R 3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R 4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R 5 is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups.
• Preferred are C 10 -C 18 alkyl dimethylamine oxide, and C 10-18 acylamido alkyl dimethylamine oxide.
• a suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Conc. manufactured by Miranol, Inc., Dayton, NJ.
• Zwitterionic surfactants can also be incorporated into the detergent in accord with the invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.
• Suitable betaines are those compounds having the formula R(R') 2 N + R 2 COO - wherein R is a C 6 -C 18 hydrocarbyl group, each R 1 is typically C 1 -C 3 alkyl, and R 2 is a C 1 -C 5 hydrocarbyl group.
• Preferred betaines are C 12-18 dimethyl-ammonio hexanoate and the C 10-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines.
• Complex betaine surfactants are also suitable for use herein.
• Suitable cationic surfactants to be used in the detergent herein include the quaternary ammonium surfactants.
• the quaternary ammonium surfactant is a mono C 6 -C 16 , preferably C 6 -C 10 N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
• Preferred are also the mono-alkoxylated and bis-alkoxylated amine surfactants.
• cationic ester surfactants Another suitable group of cationic surfactants which can be used in the detergent compositions or components thereof herein are cationic ester surfactants.
• the cationic ester surfactant is a, preferably water dispersible, compound having surfactant properties comprising at least one ester (i.e. -COO-) linkage and at least one cationically charged group.
• Suitable cationic ester surfactants including choline ester surfactants, have for example been disclosed in US Patents No.s 4228042, 4239660 and 4260529.
• ester linkage and cationically charged group are separated from each other in the surfactant molecule by a spacer group consisting of a chain comprising at least three atoms (i.e. of three atoms chain length), preferably from three to eight atoms, more preferably from three to five atoms, most preferably three atoms.
• the atoms forming the spacer group chain are selected from the group consisting of carbon, nitrogen and oxygen atoms and any mixtures thereof, with the proviso that any nitrogen or oxygen atom in said chain connects only with carbon atoms in the chain.
• spacer groups having, for example, -O-O- (i.e.
• spacer groups having, for example - CH 2 -O- CH 2 - and -CH 2 -NH-CH 2 - linkages are included.
• the spacer group chain comprises only carbon atoms, most preferably the chain is a hydrocarbyl chain.
• the cationic mono-alkoxylated amine surfactant are preferably of the general formula I: wherein R 1 is an alkyl or alkenyl moiety containing from about 6 to about 18 carbon atoms, preferably 6 to about 16 carbon atoms, most preferably from about 6 to about 14 carbon atoms; R 2 and R 3 are each independently alkyl groups containing from one to about three carbon atoms, preferably methyl, most preferably both R 2 and R 3 are methyl groups; R 4 is selected from hydrogen (preferred), methyl and ethyl; X- is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, to provide electrical neutrality; A is a alkoxy group, especially a ethoxy, propoxy or butoxy group; and p is from 0 to about 30, preferably 2 to about 15, most preferably 2 to about 8, with the proviso that if A is ethoxy and R 4 is hydrogen and p is 1, R 1 is
• Particularly preferred ApR 4 groups are ⁇ CH 2 CH 2 OH, ⁇ CH 2 CH 2 CH 2 OH, ⁇ CH 2 CH(CH 3 )OH and ⁇ CH(CH 3 )CH 2 OH, with ⁇ CH 2 CH 2 OH being particularly preferred.
• Preferred R 1 groups have have no greater than 10 carbon atoms, or even no greater than 8 or 9 carbon atoms.
• Preferred R 1 groups are linear alkyl groups.
• R 1 groups having from 8 to 11 carbon atoms, or from 8 to 10 carbon atoms are preferred.
• Such a cationic surfactant which is highly preferred has a formula wherein R 1 is a C 8 -C 10 alkyl group, p is 1, A is ethoxy and R 2 and R 3 are methyl groups.
• R 1 is C 10 -C 18 hydrocarbyl and mixtures thereof, especially C 10 -C 14 alkyl, preferably C 10 and C 12 alkyl, and X is any convenient anion to provide charge balance, preferably chloride or bromide.
• compounds of the foregoing type include those wherein the ethoxy (CH 2 CH 2 O) units (EO) are replaced by butoxy, isopropoxy [CH(CH 3 )CH 2 O] and [CH 2 CH(CH 3 O] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and/or i-Pr units.
• EO ethoxy
• i-Pr isopropoxy units
• Pr n-propoxy units
• the levels of the cationic mono-alkoxylated amine surfactants used in detergent compositions of the invention is preferably from 0.1% to 20%, more preferably from 0.4% to 7%, most preferably from 0.5% to 3.0% by weight of the composition.
• the cationic bis-alkoxylated amine surfactant preferably has the general formula II: wherein R 1 is an alkyl or alkenyl moiety containing from about 8 to about 18 carbon atoms, preferably 10 to about 16 carbon atoms, most preferably from about 10 to about 14 carbon atoms; R 2 is an alkyl group containing from one to three carbon atoms, preferably methyl; R 3 and R 4 can vary independently and are selected from hydrogen (preferred), methyl and ethyl, X - is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, sufficient to provide electrical neutrality.
• a and A' can vary independently and are each selected from C 1 -C 4 alkoxy, especially ethoxy, (i.e., -CH 2 CH 2 O-), propoxy, butoxy and mixtures thereof; p is from 1 to about 30, preferably 1 to about 4 and q is from I to about 30, preferably 1 to about 4, and most preferably both p and q are 1.
• Highly preferred cationic bis-alkoxylated amine surfactants for use herein are of the formula wherein R 1 is C 10 -C 18 hydrocarbyl and mixtures thereof, preferably C 10 , C 12 , C 14 alkyl and mixtures thereof.
• X is any convenient anion to provide charge balance, preferably chloride.
• cationic bis-alkoxylated amine surfactants useful herein include compounds of the formula: wherein R 1 is C 10 -C 18 hydrocarbyl, preferably C 10 -C 14 alkyl, independently p is 1 to about 3 and q is 1 to about 3, R 2 is C 1 -C 3 alkyl, preferably methyl, and X is an anion, especially chloride or bromide.
• the levels of the cationic bis-alkoxylated amine surfactants used in detergent compositions of the invention is preferably from 0.1% to 20%, more preferably from 0.4% to 7%, most preferably from 0.5% to 3.0% by weight of the composition.
• Suitable optional soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon.
• Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps may also be included as suds suppressors.
• anionic surfactants are the carboxylate-based anionic surfactants known in the art and alkali metal sarcosinates of formula R-CON (R 1 ) CH 2 COOM, wherein R is a C 5 -C 17 linear or branched alkyl or alkenyl group, R 1 is a C 1 -C 4 alkyl group and M is an alkali metal ion.
• R is a C 5 -C 17 linear or branched alkyl or alkenyl group
• R 1 is a C 1 -C 4 alkyl group
• M is an alkali metal ion.
• Preferred examples are the - myristyl and oleoyl methyl sarcosinates in the form of their sodium salts
• An preferred additional components of the detergent is a perhydrate bleach, such as metal perborates, metal percarbonates, particularly the sodium salts.
• Perborate can be mono or tetra hydrated.
• Sodium percarbonate has the formula corresponding to 2Na 2 CO 3 .3H 2 O 2 , and is available commercially as a crystalline solid.
• Potassium peroxymonopersulfate, sodium per is another optional inorganic perhydrate salt of use in the detergent compositions herein.
• a preferred feature of detergent composition is an organic peroxyacid bleaching system.
• the bleaching system contains a hydrogen peroxide source and an organic peroxyacid bleach precursor compound.
• the production of the organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide.
• Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches, such as the perborate bleach of the claimed invention.
• a preformed organic peroxyacid is incorporated directly into the composition.
• Compositions containing mixtures of a hydrogen peroxide source and organic peroxyacid precursor in combination with a preformed organic peroxyacid are also envisaged.
• Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid.
• peroxyacid bleach precursors may be represented as where L is a leaving group and X is essentially any functionality, such that on perhydroloysis the structure of the peroxyacid produced is
• Peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.5% to 20% by weight, more preferably from 1% to 15% by weight, most preferably from 1.5% to 10% by weight of the detergent compositions.
• Suitable peroxyacid bleach precursor compounds typically contain one or more Nor O-acyl groups, which precursors can be selected from a wide range of classes.
• Suitable classes 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.
• L group 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 stabilize for use in a bleaching composition.
• Preferred L groups are selected from the group consisting of: and mixtures thereof, wherein R 1 is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms, R 3 is an alkyl chain containing from 1 to 8 carbon atoms, R 4 is H or R 3 , and Y is H or a solubilizing group. Any of R 1 , R 3 and R 4 may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium groups.
• the preferred solubilizing groups are -SO 3 - M + , -CO 2 - M + , -SO 4 - M + , -N + (R 3 ) 4 X - and O ⁇ --N(R 3 ) 3 and most preferably -SO 3 - M + and -CO 2 - M + wherein R 3 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.
• 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.
• 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,N 1 N 1 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.
• the TAED is preferably not present in the agglomerated particle of the present invention, but preferably present in the detergent composition, comprising the particle.
• alkyl percarboxylic acid precursors include sodium 3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.
• Amide substituted alkyl peroxyacid precursor compounds are suitable herein, including those of the following general formulae: wherein R 1 is an alkyl group with from 1 to 14 carbon atoms, R 2 is an alkylene group containing from 1 to 14 carbon atoms, and R 5 is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group.
• Amide substituted bleach activator compounds of this type are described in EP-A-0170386.
• Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.
• Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulfonates, and the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, and those of the imide type including 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.
• Other useful N-acyl group-containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.
• Cationic peroxyacid precursor compounds produce cationic peroxyacids on perhydrolysis.
• 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 ammmonium 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.
• 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; U.K. 1,382,594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332.
• 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.
• Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams and the trialkyl ammonium methylene alkyl caprolactams.
• 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: wherein R 1 is H, alkyl, alkaryl, aryl, or arylalkyl.
• the detergent composition may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid , typically at a level of from 1% to 15% by weight, more preferably from 1% to 10% by weight of the composition.
• a preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae: wherein R 1 is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, R 2 is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms, and R 5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms.
• Amide substituted organic peroxyacid compounds of this type are described in EP-A-0170386.
• organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid.
• diacyl and tetraacylperoxides especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid.
• Mono- and diperazelaic acid, mono- and diperbrassylic acid and N-phthaloylaminoperoxicaproic acid are also suitable herein.
• the detergent composition can contain a transition metal containing bleach catalyst.
• One suitable type of bleach catalyst is a catalyst system comprising a transition metal cation of defined bleach catalytic activity, such as copper, iron or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof.
• a transition metal cation of defined bleach catalytic activity such as copper, iron or manganese cations
• an auxiliary metal cation having little or no bleach catalytic activity such as zinc or aluminum cations
• a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof.
• bleach catalysts include the manganese-based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of these catalysts include Mn IV 2 (u-O) 3 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 -(PF 6 ) 2 , Mn III 2 (u-O) 1 (u-OAc) 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 -(ClO 4 ) 2 , Mn IV 4 (u-O) 6 (1,4,7-triazacyclononane) 4 -(ClO 4 ) 2 , Mn III Mn IV 4 (u-O) 1 (u-OAc) 2 -(1,4,7-trimethyl-1,4,7-triazacyclononane) 2 -(ClO 4 ) 3 , and mixtures thereof.
• ligands suitable for use herein include 1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane, and mixtures thereof.
• the bleach catalysts useful herein may also be selected as appropriate for the present invention.
• suitable bleach catalysts see U.S. Pat. 4,246,612 and U.S. Pat. 5,227,084. See also U.S. Pat. 5,194,416 which teaches mononuclear manganese (IV) complexes such as Mn(1,4,7-trimethyl-1,4,7-triazacyclononane)(OCH 3 ) 3 -(PF 6 ).
• Still another type of bleach catalyst is a water-soluble complex of manganese (III), and/or (IV) with a ligand which is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups.
• Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylithol, arabitol, adonitol, meso-erythritol, meso-inositol, lactose, and mixtures thereof.
• U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe, or Cu, with an non-(macro)-cyclic ligand.
• B is a bridging group selected from O, S.
• R 5 , R 6 , and R 7 can each be H, alkyl, or aryl groups, including substituted or unsubstituted groups.
• Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings.
• said rings may be substituted with substituents such as alkyl, aryl, alkoxy, halide, and nitro.
• substituents such as alkyl, aryl, alkoxy, halide, and nitro.
• Particularly preferred is the ligand 2,2'-bispyridylamine.
• Preferred bleach catalysts include Co, Cu, Mn, Fe,-bispyridylmethane and - bispyridylamine complexes.
• Highly preferred catalysts include Co(2,2'-bispyridylamine)Cl 2 , Di(isothiocyanato)bispyridylamine-cobalt (II), trisdipyridylamine-cobalt(II) perchlorate, Co(2,2-bispyridylamine) 2 O 2 ClO 4 , Bis-(2,2'-bispyridylamine) copper(II) perchlorate, tris(di-2-pyridylamine) iron(II) perchlorate, and mixtures thereof.
• binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands including N 4 Mn III (u-O) 2 Mn IV N 4 ) + and [Bipy 2 Mn III (u-O) 2 Mn IV bipy 2 ]-(ClO 4 ) 3 .
• bleach catalysts are described, for example, in European patent application, - publication no. 408,131 (cobalt complex catalysts), European patent applications, publication nos. 384,503, and 306,089 (metallo-porphyrin catalysts), U.S. 4,728,455 (manganese/multidentate ligand catalyst), U.S. 4,711,748 and European patent application, publication no. 224,952, (absorbed manganese on aluminosilicate catalyst), U.S. 4,601,845 (aluminosilicate support with manganese and zinc or magnesium salt), U.S. 4,626,373 (manganese/ligand catalyst), U.S. 4,119,557 (ferric complex catalyst), German Pat.
• the bleach catalyst is typically used in a catalytically effective amount in the compositions and processes herein.
• catalytically effective amount is meant an amount which is sufficient, under whatever comparative test conditions are employed, to enhance bleaching and removal of the stain or stains of interest from the target substrate.
• the test conditions will vary, depending on the type of washing appliance used and the habits of the user. Some users elect to use very hot water; others use warm or even cold water in laundering operations. Of course, the catalytic performance of the bleach catalyst will be affected by such considerations, and the levels of bleach catalyst used in fully-formulated detergent and bleach compositions can be appropriately adjusted.
• 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 about 1 ppm to about 200 ppm of the catalyst species in the wash liquor.
• 3 micromolar manganese catalyst is effective at 40°C, pH 10 under European conditions using perborate and a bleach precursor. An increase in concentration of 3-5 fold may be required under U.S. conditions to achieve the same results.
• Another preferred ingredient useful in the detergent is one or more additional enzymes.
• Preferred additional enzymatic materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
• 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.
• Preferred amylases include, for example, ⁇ -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 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 Pseudomas 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.
• the detergent compositions of the invention when formulated for use in machine washing compositions, preferably comprise a suds suppressing system present at a level of from 0.01% to 15%, preferably from 0.05% to 10%, most preferably from 0.1% to 5% by weight of the composition.
• Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds and 2-alkyl alcanol antifoam compounds.
• antifoam compound any compound or mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution.
• Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component. Such silicone antifoam compounds also typically contain a silica component.
• silicone antifoam compounds as used herein, and in general throughout the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types.
• Preferred silicone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units.
• Suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in US Patent 2,954,347, issued September 27, 1960 to Wayne St. John.
• the monocarboxylic fatty acids, and salts thereof, for use 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.
• Suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C 18 -C 40 ketones (e.g. stearone) 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, bis stearic acid amide and monostearyl di-alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters.
• high molecular weight fatty esters e.g. fatty acid triglycerides
• fatty acid esters of monovalent alcohols e.g. fatty acid esters of monovalent alcohols
• a preferred suds suppressing system comprises:
• the detergent compositions herein may also comprise from 0.01% to 10 %, preferably from 0.05% to 0.5% by weight of polymeric dye transfer inhibiting agents.
• the polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof, whereby these polymers can be cross-linked polymers.
• Polyamine N-oxide polymers suitable for use herein contain units having the following structure formula: wherein P is a polymerisable unit, and R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or-any combination thereof whereto the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group is part of these groups.
• the N-O group can be represented by the following general structures : wherein R1, R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group forms part of these groups.
• the N-O group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.
• Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
• R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
• One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the R-group.
• Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.
• polyamine N-oxides are the polyamine oxides whereto the N-O group is attached to the polymerisable unit.
• a preferred class of these polyamine N-oxides comprises the polyamine N-oxides having the general formula (I) wherein R is an aromatic,heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is part of said R group.
• R is an aromatic,heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is part of said R group.
• examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives thereof.
• the polyamine N-oxides can be obtained in almost any degree of polymerisation.
• the degree of polymerisation is not critical provided the material has the desired water-solubility and dye-suspending power.
• the average molecular weight is within the range of 500 to 1000,000.
• Suitable herein are coploymers of N-vinylimidazole and N-vinylpyrrolidone having an average molecular weight range of from 5,000 to 50,000.
• the preferred copolymers have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2.
• the detergent compositions herein may also utilize polyvinylpyrrolidone ("PVP") having an average molecular weight of from 2,500 to 400,000.
• PVP polyvinylpyrrolidone
• Suitable polyvinylpyrrolidones are commercially vailable from ISP Corporation, New York, NY and Montreal, Canada under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of 360,000).
• PVP K-15 is also available from ISP Corporation.
• Other suitable polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12.
• the detergent compositions herein may also utilize polyvinyloxazolidones as polymeric dye transfer inhibiting agents.
• Said polyvinyloxazolidones have an average molecular weight of from 2,500 to 400,000.
• the detergent compositions herein may also utilize polyvinylimidazole as polymeric dye transfer inhibiting agent.
• Said polyvinylimidazoles preferably have an average molecular weight of from 2,500 to 400,000.
• the detergent compositions herein also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners.
• Hydrophilic optical brighteners useful herein include those having the structural formula: wherein R 1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R 2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.
• R 1 is anilino
• R 2 is N-2-bis-hydroxyethyl and M is a cation such as sodium
• the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt.
• This particular brightener species is commercially marketed under the tradename Tinopal-LINPA-GX by Ciba-Geigy Corporation.
• Tinopal-LTNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
• R 1 is anilino
• R 2 is N-2-hydroxyethyl-N-2-methylamino
• M is a cation such as sodium
• the brightener is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt.
• This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.
• R 1 is anilino
• R 2 is morphilino
• M is a cation such as sodium
• the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid, sodium salt.
• This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.
• SRA polymeric soil release agents
• SRA's will generally comprise from 0.0 1 % to 10.0%, typically from 0.1 % to 5%, preferably from 0.2% to 3.0% by weight, of the compositions.
• Preferred SRA's typically have 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, thereby serving as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the SRA to be more easily cleaned in later washing procedures.
• Preferred SRA's include oligomeric terephthalate esters, typically prepared by processes involving at least one transesterification/oligomerization, often with a metal catalyst such as a titanium(IV) alkoxide.
• esters may be made using additional monomers capable of being incorporated into the ester structure through one, two, three, four or more positions, without, of course, forming a densely crosslinked overall structure.
• Suitable SRA's include a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and allyl-derived sulfonated terminal moieties covalently attached to the backbone, for example as described in U.S. 4,968,451, November 6, 1990 to J.J. Scheibel and E.P. Gosselink.
• ester oligomers can be prepared by: (a) ethoxylating allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate (“DMT”) and 1,2-propylene glycol (“PG”) in a two-stage transesterification/oligomerization procedure; and (c) reacting the product of (b) with sodium metabisulfite in water.
• DMT dimethyl terephthalate
• PG 1,2-propylene glycol
• SRA's include the nonionic end-capped 1,2-propylene/polyoxyethylene terephthalate polyesters of U.S.
• Gosselink et al. for example those produced by transesterification/oligomerization of poly(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol) ("PEG").
• SRA's include: the partly-and fully- anionic-end-capped oligomeric esters of U.S. 4,721,580, January 26, 1988 to Gosselink, such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8-hydroxyoctanesulfonate; the nonionic-capped block polyester oligomeric compounds of U.S.
• Gosselink for example produced from DMT, methyl (Me)-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate; and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U.S.
• SRA's also include: simple copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see U.S. 3,959,230 to Hays, May 25, 1976 and U.S. 3,893,929 to Basadur, July 8, 1975; cellulosic derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow; the C 1 -C 4 alkyl celluloses and C 4 hydroxyalkyl celluloses, see U.S.
• methyl cellulose ethers having an average degree of substitution (methyl) per anhydroglucose unit from about 1.6 to about 2.3 and a solution viscosity of from about 80 to about 120 centipoise measured at 20°C as a 2% aqueous solution.
• Such materials are available as METOLOSE SM100 and METOLOSE SM200, which are the trade names of methyl cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.
• SRA's include: (I) nonionic terephthalates using diisocyanate coupling agents to link polymeric ester structures, see U.S. 4,201,824, Violland et al. and U.S. 4,240,918 Lagasse et al.; and (II) SRA's with carboxylate terminal groups made by adding trimellitic anhydride to known SRA's to convert terminal hydroxyl groups to trimellitate esters. With the proper selection of catalyst, the trimellitic anhydride forms linkages to the terminals of the polymer through an ester of the isolated carboxylic acid of trimellitic anhydride rather than by opening of the anhydride linkage.
• Either nonionic or anionic SRA's may be used as starting materials as long as they have hydroxyl terminal groups which may be esterified. See U.S. 4,525,524 Tung et al..
• Other classes include: (III) anionic terephthalate-based SRA's of the urethane-linked variety, see U.S. 4,201,824, Violland et al.;
• compositions of the invention include colours and filler salts, with sodium sulfate being a preferred filler salt.
• compositions preferably contain from about 2% to about 10% by weight of an organic citric acid, preferably citric acid. Also preferably in combination with a carbonate salt, minor amounts (e.g., less than about 20% by weight) of neutralizing agents, buffering agents, phase regulants, hydrotropes, enzyme stabilizing agents, polyacids, suds regulants, opacifiers, anti-oxidants, bactericides, dyes, perfumes, such as those described in US Patent 4,285,841 to Barrat et al., issued August 25, 1981 (herein incorporated by reference), can be present in the compositions.
• neutralizing agents e.g., less than about 20% by weight
• buffering agents e.g., phase regulants, hydrotropes, enzyme stabilizing agents, polyacids, suds regulants, opacifiers, anti-oxidants, bactericides, dyes, perfumes, such as those described in US Patent 4,285,841 to Barrat et al., issued
• the detergent composition of the invention can be made via a variety of methods, including dry-mixing and agglomerating of the various compounds comprised in the detergent composition.
• compositions in accordance with the invention can take a variety of physical solid forms such as tablet, flake, pastille and bar, and preferably granular forms.
• the detergent compositions can be formulated such that they are chlorine-based bleach-compatible, thus ensuring that a chlorine based bleach can be added to the detergent composition by the user at the beginning or during the washing process.
• 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 mid-chain branched surfactant system herein preferably with additional surfactants, is preferably present in granular compositions in the form of surfactant agglomerate particles, preferably not comprising the bleach precursors, which may take the form of flakes, prills, marumes, noodles, ribbons, but preferably take the - form of granules.
• the most preferred way to process the particles is by agglomerating powders (e.g. aluminosilicate, carbonate) with high active surfactant pastes and to control the particle size of the resultant agglomerates within specified limits.
• Such a process involves mixing an effective amount of powder with a high active surfactant paste in one or more agglomerators such as a pan agglomerator, a Z-blade mixer or more preferably an in-line mixer such as those manufactured by Schugi (Holland) BV, 29 Chroomstraat 8211 AS, Lelystad, Netherlands, and Gebruder Lodige Maschinenbau GmbH, D-4790 Paderborn 1, Elsenerstrasse 7-9, Postfach 2050, Germany. Most preferably a high shear mixer is used, such as a Lodige CB (Trade Name).
• a high active surfactant paste in one or more agglomerators such as a pan agglomerator, a Z-blade mixer or more preferably an in-line mixer such as those manufactured by Schugi (Holland) BV, 29 Chroomstraat 8211 AS, Lelystad, Netherlands, and Gebruder Lodige Maschinenbau GmbH, D-4790 Paderborn 1, Elsenerstrasse
• a high active surfactant paste comprising from 50% by weight to 95% by weight, preferably 70% by weight to 85% by weight of the surfactants, including the mid-chain branched surfactants, is typically used.
• the paste may be pumped into the agglomerator at a temperature high enough to maintain a pumpable viscosity, but low enough to avoid degradation of the anionic surfactants used.
• An operating temperature of the paste of 50°C to 80°C is typical.
• the mean particle size of the components of granular compositions in accordance with the invention should preferably be such that no more that 25% of the particles are greater than 1.8mm in diameter and not more than 25% of the particles are less than 0.25mm in diameter.
• the mean particle size is such that from 10% to 50% of the particles has a particle size of from 0.2mm to 0.7mm in diameter.
• mean particle size as defined herein is calculated by sieving a sample of the composition into a number of fractions (typically 5 fractions) on a series of sieves, preferably 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 the solid detergent compositions in accordance with the present is from 330 g/litre to 1240 g/litre, more preferably from 380g/litre to 1200 g/litre, most preferably from 420 g/litre to 850 g/ litre.
• Bulk density is measured by means of a simple funnel 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.
• 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.
• Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry detergent composition in accord with the invention.
• an effective amount of the detergent composition it is meant from 10g to 300g of product dissolved or dispersed in a wash solution of volume from 5 to 65 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods.
• the detergent composition is formulated such that it is suitable for hand washing.
• the detergent composition is a pre-treatment or soaking composition, to be used to pre-treat or soak soiled and stained fabrics.
• the abbreviated component identifications have the following meanings: LAS : Sodium linear C 12 alkyl benzene sulfonate TAS : Sodium tallow alkyl sulfate C45AS : Sodium C 14 -C 15 linear alkyl sulfate MES : -sulpho methylester of C 18 fatty acid - CxyEzS : Sodium C 1x -C 1y branched alkyl sulfate condensed with z moles of ethylene oxide MBAS x,y : Sodium mid-chain branched alkyl sulfate having an average of x carbon atoms, whereof an average of y carbon atoms are comprised in (a) the branching unit(s).
• TPKFA C12-C14 topped whole cut fatty acids
• STPP Anhydrous sodium tripolyphosphate
• Zeolite A Hydrated Sodium Aluminosilicate of formula Na 12 (Al0 2 SiO 2 ) 12 .
• NOBS Nonanoyl oxybenzene sulfonate in the form of the sodium salt
• DPDA Diperoxydodecanedioic acid
• PAP N-phthaloylamidoperoxicaproic acid
• NAPAA Nonanoylamido peroxo-adipic acid
• NACA 6 nonylamino - 6 oxo - capronic acid.
• TAED Tetraacetylethylenediamine
• DTPMP Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the Trade name Dequest 2060
• Photoactivated Sulfonated Zinc or aluminium Phthlocyanine encapsulated
• 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'-disulfonate.
• HEDP 1,1-hydroxyethane diphosphonic acid
• PVNO Polyvinylpyridine N-oxide
• PVPVI Copolymer of polyvinylpyrolidone and vinylimidazole
• 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 Polydimethylsiloxane foam controller with siloxane-oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10:
• the following granular laundry detergent composition I of bulk density 750. g/litre is a composition according to the invention: I LAS 11.5 TAS 1.57 C45AS 2.0 C25AE3S 1.0 C45E7 - C25E3 3.5 QAS I - MBAS 17, 1.5 5.0 STPP Zeolite A 5.0 NaSKS-6/silicate 10.6 Citric acid/citrate 1.0 Carbonate 21.4 Bicarbonate 2.0 Silicate - Sodium sulfate 7.0 PB4 - TAED - NAC OBS - DTPMP 0.2 HEDP 0.3 Protease 0.85 Lipase 0.15 Cellulase 0.28 Amylase 0.1 MA/AA 1.6 CMC 0.4 PVP 0.8 Photoactivated bleach (ppm) 27 ppm Brightener 1 0.19 Brightener 2 0.04 Perfume 0.3 Silicone antifoam 2.4 Minors/misc to 100%
• J is a phosphorus-containing detergent composition
• K is a zeolite-containing detergent composition
• L is a compact detergent composition: J K L M Blown Powder STPP 8.0 - 12.0 - Zeolite A - 14.0 - 7.0 C45AS 4.0 - 4.0 5.0 QAS I - 1.0 - - MBAS 17. 1.5 4.0.
• detergent formulations according to the present invention: N P LAS - 8.0 TAS - 4.0 MBAS 16.5, 1.8 15.0 6.0 C45AS 4.0 6.0 MES 3.0 - QAS II 0.4 1.0 TFAA - - C25E5/C45E7/C 2 5 E 3 - - STPP 16.0 8.0 Silicate 2.0 5.0 Carbonate 13.0 4.0 Bicarbonate - - DTPMP 0.7 - SRP1 0.3 - MA/AA 2.0 - AA - 2.0 CMC 0.8 0.4 Protease 0.8 0.5 Amylase 0.8 - Lipase 0.2 0.2 Cellulase 0.15 - Photoactivated bleach (ppm) 70ppm - Brightener 1 0.2 0.08 PBt 1 6.0 - NACA - - NAC OBS 2.0 0.9 Balance (Moisture and Miscellaneous) 100 100 100
• the following laundry detergent composition AT is prepared in accord with the invention: AT MBAS 16.5, 1.7 5.5 C45 AS 4 C45E1S 1 LAS 4 C16 SAS - MES - C23E6.5 1.5 Zeolite A 14.0 AA 2.3 Carbonate 25.0 Silicate 0.6 Perborate 1.0 Protease 0.3 Cellulase 0.3 SRP1 0.4 Brightener 0.2 PEG 1.6 Sulfate 5.5 Silicone Antifoam 0.42 Moisture & Minors ---Balance--- Density (g/L) 660

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• 1997
  • 1997-10-10 EP EP97911755A patent/EP1021509B1/en not_active Expired - Lifetime
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