Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/38—Cationic compounds
  • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/83—Mixtures of non-ionic with anionic compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D10/00—Compositions of detergents, not provided for by one single preceding group
  • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/26—Organic compounds containing nitrogen
  • C11D3/32—Amides; Substituted amides
• • 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
  • 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
  • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/29—Sulfates of polyoxyalkylene ethers
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds

Definitions

• This invention relates to improved detergent compositions, more specifically to detergent compositions containing hydroxamic acids and their derivatives which assist in the removal of stains from fabrics during laundering.
• Detergency builders are usually included in detergent compositions to assist in controlling mineral hardness in water.
• Such builders are sequestrants of calcium and magnesium ions, and include such compounds as alkali metal phosphates, polyphosphates, polycarboxylates, for example the sodium salts of copolymers of maleic acid or of polyacetal carboxylates, and alkali metal aminopolycarboxylates, for example sodium nitrilotriacetates and ethylene tetraacetates.
• Sequestrants are also generally thought to have an effect in enhancing stain removal during the laundering of fabrics, especially in the absence of peroxides or other bleaches.
• the aforementioned sequestrants are alkali metal salts, and they are of general applicability in dry granular detergent formulations. However, although they are water-soluble solids, the small amount of water in a typical liquid detergent formulation limits the level of such sequestrants that can be incorporated. In consequence, a typical liquid detergent formulation has limited sequestering capacity for calcium and magnesium. Detergent compositions containing a limited amount of sequestering agents are referred to as "under-built" detergent compositions.
• Hydroxamic acids have been proposed as extractants for metals.
• neo-alkyl­hydroxamic acids can be employed as ion-exchange agents in processes for liquid-liquid extraction, with the aim of separating sor purifying dissolved metals and of converting a metal salt solution into a solution of a salt of the same metal but with a different anion.
• US-A-3 707 502 discloses detergent compositions containing sodium nitrilotriacetate, peroxy compounds and alkali metal salts of mono- and di-hydroxamic acids.
• the purpose of the hydroxamates is to reduce the corrosivity to copper shown by aqueous solutions of similar detergent compositions not containing the hydroxamates.
• a detergent composition of the invention is a bleach-free, under-built composition containing at least one surfactant and having a sequestration value such that an aqueous solution containing 7000 ppm of the detergent composition sequesters a maximum of 30 mg CaO per gram of detergent composition at 20°C, characterised in that the composition contains a hydroxamic acid or a salt thereof, the hydroxamic acid having the formula R- - R′ where R represents an optionally substituted straight- or branched- chain C5 ⁇ 21 alkyl or C5 ⁇ 21 alkenyl group, or an optionally-substituted phenyl group, and R′ represents hydrogen, an optionally substituted C1 ⁇ 6 alkyl group, or an optionally-substituted phenyl group, but with the limitation that the hydroxamic acid has a hydrophile-lipophile balance (HLB) within the same range as the range of HLB's of hydroxamic acids of the above formula wherein R is an unsubstituted
• hydroxamic acids and their salts useful in the present invention are known compounds. They can be made from esters or acid halides of the corresponding carboxylic acids RCOOH by reaction with hydroxylamine or an alkyl hydroxylamine RNR′OH.
• R represents an unsubstituted alkyl or alkenyl group
• the preferred compounds are those wherein R is a straight-chain alkyl or alkenyl group of from 9 to 15 carbon atoms.
• R′(when an unsubstituted alkyl group) preferably contains 1 to 3 carbon atoms.
• unsubstituted alkyl and alkenyl groups R are nonyl, undecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, 8-undecenyl, 4-tridecenyl, 8-pentadecenyl, and 8-­heptadecenyl.
• Preferred examples of unsubstituted alkyl groups R′ are methyl, ethyl and n-propyl, especially methyl.
• the hydroxyl hydrogen is replaced by a neutralising cation.
• a neutralising cation can be, for example, an alkali metal ion, for example sodium or potassium, or an ammonium, alkylammonium or alkanolammonium ion, for example a tri(ethanol) ammonium ion.
• hydroxamic acids and their salts useful in the present invention are nonanohydroxamic acid, H-methyl nonano-hydroxamic acid, dodecanohydroxamic acid, N-methyl dodecanohydroxamic acid, N-ethyl dodecanohydroxamic acid, tetra­decanohydroxamic acid, hexadecanohydroxamic acid, octadecano­hydroxamic acid, and the sodium, potassium, di(ethanol)ammonium and tri(ethanol)ammonium salts of these acids.
• Optional substituents in the groups R and R′ include halogen atoms, for instance chlorine or bromine, and substituent groups selected from hydroxy, alkoxy, phenyl, phenoxy, carboxy, and hydroxamido groups -CONR′OH.
• halogen atoms for instance chlorine or bromine
• substituent groups selected from hydroxy, alkoxy, phenyl, phenoxy, carboxy, and hydroxamido groups -CONR′OH an example of a hydroxy-substituted alkenyl group R occurs in the hydroxamic acid derived from ricinoleic (12-hydroxy-9-octadecenoic) acid, while R′ can be, for example, a hydroxymethyl or 2-hydroxyethyl group.
• substituents can, for example, be selected from the optional substituents mentioned above.
• a phenyl group also include alkyl groups, for example C1 ⁇ 3 alkyl groups, so that R or R′ can be, for instance, a tolyl, xylyl or isopropylphenyl group.
• alkyl groups can have longer chains, so that R or R′ can be, for instance a (C5 ⁇ 21 alkyl)phenyl group.
• Examples of hydroxamic acids where R represents a phenyl or alkyl phenyl group are N-methyl benzohydroxamic acid, N-methyl p-isopropylbenzohydroxamic acid and the various isomeric(C14 ⁇ 18 alkyl) benzohydroxamic acids.
• the occurrence of one carboxyl group as a substituent in the group R represents a mono-hydroxamic acid derivative of a di­carboxylic acid.
• compounds having a carboxyl group in the alpha- or beta- position of an alkyl group R in the above formula are derivatives respectively of alkyl or alkenyl malonic or succinic acids.
• Other examples are monohydroxamic derivatives of azeleic and of suberic acids.
• R′ can be a group containing one or more, normally one or two, carboxyl groups as substituents.
• it can be, for example, a 2-carboxyethyl or 1,2-dicarboxyethyl group.
• a compound having one hydroxamido group as a substituent in the group R is a dihydroxamic acid.
• Dihydroxamic acids which are derivatives of malonic and succinic acids are exemplified in US-A-3704 502 and include dodecane-1,1-dihydroxamic acid and hexadecane-1,1-dihydroxamic acid.
• Other examples of dihydroxamic acids are octane-1,8-dihydroxamic acid (from sebacic acid) and undecane-1,11-dihydroxamic acid (from brassylic acid).
• the hydroxamido group may also occur as a substituent in the group R′.
• R′ groups are 2-hydroxamidoethyl and 1,2-di(hydroxamido) ethyl.
• a characteristic of any hydroxamic acid suitable for use in a composition of the invention is that it should have an HLB within the same range as the range of HLB's of the hydroxamic acids wherein R is an unsubstituted C5 ⁇ 21 alkyl group and R′ is hydrogen or an unsubstituted C1 ⁇ 6 alkyl group.
• the most lipophilic will be hydroxamic acids wherein R contains 21 carbon atoms and R′ contains 6 carbon atoms.
• the most hydrophilic will be hydroxamic acids wherein R contains 5 carbon atoms and R′ is hydrogen.
• the optional substituents are groups, for example hydroxy or carboxy, which increase hydrophilicity.
• compounds within the required HLB range and containing such substituents will usually be those where the number of carbon atoms in R lies towards the upper end of the C5 ⁇ 21 range, for example, within the C12 ⁇ 21 range.
• the surfactant component in a detergent composition of the invention can be a surfactant or a mixture of surfactants selected from one or more classes of surfactants.
• Useful non-ionic surfactants include the condensation products of alkylphenols with ethylene oxide and containing from about 5 to about 25 ethylene oxide units per alkylphenol unit; condensation products of C8-C22 aliphatic alcohols with about 2 to about 25 moles of ethylene oxide; block copolymers of propylene oxide and ethylene oxide, the central block of the molecule being poly(propylene oxide) and the end groups being poly(ethylene oxide); block copolymers of a) ethylene oxide and b) propylene oxide/ethylene diamine condensates; water-soluble amine oxides containing one alkyl group of from about 10 to about 18 carbon atoms and two alkyl or hydroxyalkyl groups of from 1 to 3 carbon atoms; alkylpolysaccharides having a hydrophobic group containing from about 6 to about 30 carbon atoms and a hydrophilic poly­saccharide group containing up to 10 saccharide units; and fatty acid amides containing an alkyl group of from about
• compositions of the invention are anionic surfactants such as the higher fatty carboxylates, for example laurates, myristates, palmitates, stearates and oleates, C10-C20 alkyl sulphates, (C8 ⁇ 18 alkyl) benzene sulphonates, alkyl glyceryl ether sulphonates, e.g. those derived from tallow or coconut oil, or C10-C22 alkyl poly­ethoxylate sulphates wherein the polyethoxylate chain contains from 1 to about 6 ethylene oxide units.
• anionic surfactants such as the higher fatty carboxylates, for example laurates, myristates, palmitates, stearates and oleates, C10-C20 alkyl sulphates, (C8 ⁇ 18 alkyl) benzene sulphonates, alkyl glyceryl ether sulphonates, e.g. those derived from t
• Ampholytic, zwitterionic and/or cationic surfactants may also be used in the compositions of the invention, but they are not present in significant amounts in preferred compositions.
• compositions of the invention are liquid formulations. These formulations will normally contain water and water-miscible organic solvents. Such solvents may be low molecular weight alcohols such as ethanol or isopropanol, and/or polyols containing from 2 to about 6 hydroxyl groups, for example ethylene glycol, propylene glycol, diethylene glycol, and glycerine.
• solvents may be low molecular weight alcohols such as ethanol or isopropanol, and/or polyols containing from 2 to about 6 hydroxyl groups, for example ethylene glycol, propylene glycol, diethylene glycol, and glycerine.
• the surfactant component is typically a mixture of a non-ionic surfactant component and a sulphonate and/or sulphate, and a fatty carboxylate.
• the sulphonate, sulphate and carboxylate ions are at least partially balanced by cations derived from alkanolamines, for example triethanolamine.
• Typical formulations may contain an amount of (C8-C18 alkyl) benzenesulphonate equivalent to up to 35% by weight of (C8-C18 alkyl)benzenesulphonic acid, an amount of C10-C20 alkyl sulphate or alkyl ether sulphate equivalent to up to 15% by weight of the corresponding acids, up to 15% by weight (expressed as the equivalent of fatty acid) of fatty acid carboxylate, and up to 25% of non-ionic surfactant.
• the formulations will contain at least sufficient of an alkanolamine such as triethanolamine, or of a mixture of alkanolamine and sodium hydroxide, to neutralise the sulphonic, alkylsulphuric and fatty acids.
• a small excess of base is present so that the final composition has a pH in the range 7.0 to 9.5.
• the amount of the hydroxamic acid or derivative incorporated in the composition will depend on a number of factors, including the wash temperature, water quality etc. Usefully, the amount may be such as to provide from 20 to 500 ppm, preferably from 50 to 200 ppm of hydroxamic acid or hydroxamate in the wash solution. Relative to the total weight of the composition, this amount may represent from about 0.1 to 10% by weight, more usually from about 0.5 to 5 % by weight of the composition.
• compositions of the invention may contain small amounts of sequestrants, which may be carboxylates or polycarboxylates, for example citrates, alkylenesuccinates, tartrate monosuccinates, tartrate disuccinates (US-A-4 663 071) or polymeric acetal carboxylates (EP-A-0 001 004), or aminomethylenephosphonates such as diethylenetriaminepenta(methylenephosphonates), but they will normally be free from phosphate and polyphosphate builders.
• sequestrants may be carboxylates or polycarboxylates, for example citrates, alkylenesuccinates, tartrate monosuccinates, tartrate disuccinates (US-A-4 663 071) or polymeric acetal carboxylates (EP-A-0 001 004), or aminomethylenephosphonates such as diethylenetriaminepenta(methylenephosphonates), but they will normally be free from phosphate and polyphosphate builders.
• compositions of the invention may also contain various other additives, for example soil-suspending agents, perfumes, opotical brighteners, bactericides and enzymes.
• hydroxamic acids show an advantageous effect in compositions containing enzymes in that they retard the loss of enzymatic activity on storage.
• Enzymes used in detergent formulations are preferably proteolytic enzymes, for example subtilisin, bromelin, trypsin, and pepsin, but amylase-type or lipase-type enzymes may also be used.
• Enzyme stabilisers such as sodium formate may also be included.
• Conformity of the compositions of the invention with the requirement concerning the maximum sequestration value can be determined by known methods. For example, a solution containing 7000 ppm of the composition in demineralised water can be titrated at 20° with a 0.1 M solution of calcium chloride, using a calcium-­selective electrode to determine the end point of the titration.
• This Example shows the effect of a hydroxamate in improving the bleaching performance of a liquid detergent composition containing an enzyme.
• a liquid detergent having the following composition was added to water of 20° German hardness and an iron contamination of 2 ppm to give a solution having a detergent concentration of 0.6%.
• Linear alkylbenzenesulfonic acid 10.4 Triethanolamine 4.6 (C9-C11 linear alcohol)ethoxylate (6 ethylene oxide units) 20.0 Coconut soap 10.0 Polyethylene glycol 200 15.0 Enzyme (Maxatase P) 1.0 Water Balance
• the swatches were dried and lightly ironed. Washing efficiency was assessed by brightness measurements on the swatches defined as the reflectance of stimulus Z ("blue" light) relative to a standard white reference with an IEC three stimulus colorimeter. The reflectance of both sides of the swatches was measured and the reflectance values averaged. The average reflectance was 8.3 units higher for the swatches washed using the formulation containing sodium dodecano­hydroxamate than for the control swatches.
• This Example shows the effect of a hydroxamate in reducing loss of enzymatic activity on storage of a liquid detergent formulation.
• Example 1 The control formulation of Example 1 and a formulation containing the control ingredients and 2% by weight of the composition of sodium dodecanohydroxamate were stored in closed plastic containers at 40°C. The enzymatic activity was monitored by washing trials as described in Example 1 using standard blood-­stained cotton swatches. After 13 days, the control formulation had lost 33% of its original activity, while the formulation containing sodium dodecanohydroxamate has lost only 22% of its original activity.
• Example 3 This Example shows the compositions of various liquid detergent formulations of the invention.

Landscapes

• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Detergent Compositions (AREA)

Applications Claiming Priority (2)

Publications (2)

Family

ID=10653467

Family Applications (1)

Country Status (3)

Cited By (20)

Citations (3)

• 1989
  • 1989-03-16 GB GB898906089A patent/GB8906089D0/en active Pending
• 1990
  • 1990-03-15 EP EP19900870041 patent/EP0388389A3/fr not_active Withdrawn
  • 1990-03-15 ZA ZA902000A patent/ZA902000B/xx unknown

Patent Citations (3)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events