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
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2075—Carboxylic acids-salts thereof
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/395—Bleaching agents
  • C11D3/3956—Liquid compositions

Definitions

• the present invention relates to a bleaching composition, in particular to hypochlorite bleaching compositions, suitable for use in laundry applications such as hand washing as well as washing with automatic laundry washing machines.
• Bleaching compositions are well-known in the art. Amongst the different bleaching compositions available, those relying on bleaching by hypohalite bleaches such as hypochlorite are often preferred, mainly for performance reasons, especially at lower temperature.
• hypohalite bleach-containing compositions like hypochlorite-based compositions
• hypochlorite-based compositions a problem encountered with the use of hypohalite bleach-containing compositions like hypochlorite-based compositions is the resulting damage and/or yellowing of the fabrics being bleached.
• hypohalite bleach-containing composition suitable for use in laundry applications, which provides improved fabric whiteness to fabrics treated therewith.
• Fabrics made of cotton and/or synthetic materials have free hydroxyl groups. It is believed that the fabric damage and/or yellowing that may occur when bleaching a fabric may be due to the oxidation of the hydroxyl groups of the fabric by the bleach.
• the hypochlorite bleach is present in various forms, including hypochlorous acid, and in the form of various molecules fragments which result from its decomposition. Hypochlorous acid and these molecules fragments which result form the hypochlorite decomposition pathways are reactive with components having hydroxyl groups such as cotton fabrics or synthetic fabrics, oxidise them and thus contribute to damaging and/or yellowing these fabrics.
• hypohalite bleach-containing compositions especially a hypochlorite-containing bleaching compositions, delivering improved fabric safety and/or whiteness.
• compositions comprising a hypohalite bleach and a particular organic catalyst as defined herein after.
• the hypohalite-bleach containing compositions of the present invention comprising such an organic catalyst, preferably diphenyl acetic acid or a derivative thereof, provide improved fabric whiteness and/or improved fabric safety on fabrics bleached therewith, as compared to the same compositions without such an organic catalyst as described herein after.
• the compositions according to the present invention further comprise a ph buffering component, preferably an alkali metal salt of silicate and/or a boron salt to deliver further improved fabric whiteness and/or
• compositions of the present invention are suitable for the bleaching of different types of fabrics including natural fabrics, (e.g., fabrics made of cotton, and linen), synthetic fabrics such as those made of polymeric fibres of synthetic origin (e.g., polyamide-elasthane), as well as those made of both natural and synthetic fibres.
• the bleaching compositions of the present invention based on hypohalite bleaches such as hypochlorite may be used on synthetic fabrics despite a standing prejudice against using such bleaches on synthetic fabrics, as evidenced by warnings on labels of commercially available hypochlorite-containing compositions and clothes.
• a further advantage of the liquid bleaching compositions of the present invention is that said bleaching compositions are suitable for various laundry bleaching applications both when used in diluted conditions, e.g. as a detergent additive or a fully formulated laundry detergent composition, and when used in neat condition, e.g. as a liquid pretreater (spotter).
• hypochlorite-containing compositions like hypochlorite-containing compositions suitable for bleaching fabrics have been described in the art.
• EP-A-622 451 discloses compositions comprising hypochlorite, sodium hydroxide, a bleach stable perfume and as a buffering system whereby the pH of the diluted composition is buffered to a constant value throughout use, carbonate and/or silicate.
• no organic catalysts as defined herein are disclosed.
• EP-A-653 482, EP-A-668 345 and EP-A-688 857 disclose hypochlorite-containing compositions comprising a source of strong alkalinity, a pH buffering means and optionally other types of ingredients such as respectively radical scavengers, polycarboxylate acids of pyridine and periodates. However, no organic catalysts as described herein are disclosed.
• the present invention encompasses a bleaching composition for the bleaching of fabrics comprising a hypohalite bleach, and an organic catalyst according to the formulae: or a mixture thereof, wherein R1 is -COO - M + , or a saturated or unsaturated, linear or branched hydrocarbon chain being substituted by 1 to 20 carboxylic groups -COO - M + and M is H or an alkali metal, R2 is H, -COO - M + ', a substituted or unsubstituted, saturated or unsaturated, linear or branched hydrocarbon chain having from 1 to 20 carbon atoms or a saturated or unsaturated, linear or branched hydrocarbon chain being substituted by 1 to 20 carboxylic groups -COO - M + and M is H or an alkali metal, and wherein the phenyl groups each independently bare in one or more positions -H, -COO - M + , -Cl, -Br, -SO 3 M, -NO 2
• compositions of the present invention further comprise a pH buffering component.
• a pH buffering component in the compositions of the present invention further contributes to the effective whiteness performance and/or fabric safety of these compositions.
• the present invention also encompasses a method of bleaching fabrics wherein said fabrics are contacted with a bleaching composition according to the present invention.
• the present invention further encompasses the use of an organic catalyst as defined herein, in a hypohalite bleach-containing composition, to improve the fabric whiteness performance and/or fabric safety of said composition.
• compositions of the present invention are bleaching compositions that may be formulated either as solids or liquids.
• the compositions are formulated as solids for example as granules, tablets or powders, they are preferably applied on the fabrics to be bleached according to the present invention in a liquid form.
• the compositions are preferably but not necessarily formulated as aqueous compositions. Liquid compositions are preferred herein for convenience of use.
• Preferred liquid compositions of the present invention comprise water in an amount of from 60% to 98% by weight, more preferably of from 80% to 97% and most preferably 85% to 97% by weight of the total composition.
• compositions of the present invention comprise a hypohalite bleach or a mixture thereof.
• Hypohalite bleaches may be provided by a variety of sources, including beaches that are oxidative beaches and subsequently lead to the formation of positive halide ions as well as beaches that are organic based sources of halides such as chloroisocyanurates.
• Suitable hypohalite bleaches for use herein include the alkali metal and alkaline earth metal hypochlorites, hypobromites, hypoiodites, chlorinated trisodium phosphate dodecahydrates, potassium and sodium dichloroisocyanurates, potassium and sodium trichlorocyanurates, N-chloroimides, N-chloroamides, N-chloroamines and chlorohydantoins.
• the preferred hypohalite bleaches among the above described are the alkali metal and/or alkaline earth metal hypochlorites selected from the group consisting of sodium, potassium, magnesium, lithium and calcium hypochlorites, and mixtures thereof, more preferably the alkali metal sodium hypochlorite.
• the preferred hypohalite bleaches among the above described are the alkali metal and/or alkaline earth metal hypochlorites selected from the group consisting of lithium hypochlorites, calcium hypochlorites, chlorinated trisodium phosphate dodecahydrates, potassium dichloroisocyanurates, sodium dichloroisocyanurates, potassium trichlorocyanurates, sodium trichlorocyanurates, and mixtures thereof, more preferably sodium dichloroisocyanurates and/or calcium hypochlorite.
• the alkali metal and/or alkaline earth metal hypochlorites selected from the group consisting of lithium hypochlorites, calcium hypochlorites, chlorinated trisodium phosphate dodecahydrates, potassium dichloroisocyanurates, sodium dichloroisocyanurates, potassium trichlorocyanurates, sodium trichlorocyanurates, and mixtures thereof, more preferably sodium dichloroisocyanurates and/or calcium hypochlorite.
• the liquid compositions according to the present invention comprise said hypohalite bleach such that the content of active halide in the composition is of from 0.01% to 20% by weight, more preferably from 0.1% to 10% by weight, even more preferably from 0.5% to 7% and most preferably from 1% to 6% by weight of the composition.
• the solid compositions according to the present invention comprise said hypohalite bleach such that the content of active halide in the composition is of from 20% to 95% by weight, more preferably from 25% to 60% by weight of the composition.
• compositions according to the present invention comprise an organic catalyst as defined herein or a mixture thereof.
• Suitable organic catalysts for use herein are according to the formulae: or a mixture thereof, wherein R1 is -COO - M + , or a saturated or unsaturated, linear or branched hydrocarbon chain being substituted by 1 to 20 carboxylic groups -COO - M + and M is H or an alkali metal, R2 is H, -COO - M + ', a substituted or unsubstituted, saturated or unsaturated, linear or branched hydrocarbon chain having from 1 to 20 carbon atoms or a saturated or unsaturated, linear or branched hydrocarbon chain being substituted by 1 to 20 carboxylic groups -COO - M + and M is H or an alkali metal, and wherein the phenyl groups each independently bare in one or more positions -H, -COO - M + , -Cl, -Br, -SO 3 M, -NO 2 , -R f , -OR f wherein R f is
• R 1 is -COO - M + , or C 1 -C 20 alkyl-COO - M + , more preferably -COO - M + or C 1 -C 10 alkyl-COO - M + , most preferably -COO - M + or C 1 -C 5 alkyl-COO - M + , and M is H or an alkali metal, preferably sodium.
• R 2 is H, -COO - M + ', a substituted or unsubstituted, saturated or unsaturated, linear or branched hydrocarbon chain having from 1 to 10 carbon atoms, more preferably from 1 to 5 and most preferably from 1 to 3 or C 1 -C 20 alkyl-COO - M + , more preferably C 1 -C 10 alkyl-COO - M + , most preferably C 1 -C 5 alkyl-COO - M + , and M is H or an alkali metal, preferably sodium.
• the phenyl groups of the 3 classes of organic catalysts herein each independently are non-substituted or mono- or polysubstituted, i.e. that the carbon atoms of the phenyl group may bare each independently -H (if all the carbon atoms bare -H we call the phenyl groups herein non-substituted), -COO - M + , -Cl, -Br, -SO 3 M, -NO 2 , -R f , -OR f wherein R f is a substituted or unsubstituted, saturated or unsaturated, linear or branched hydrocarbon chain having from 1 to 20 carbon atoms, more preferably from 1 to 10, most preferably from 1 to 5.
• All the organic catalysts described above are the acidic form of the species, i.e. M is H. It is intended that the present invention also covers the salt derivatives of these species, i.e. M is an alkali metal, preferably sodium or potassium. In fact, since the pH of the compositions of the present invention is in the alkaline range, the organic catalysts of the present invention exist primarily as the ionized salt in the aqueous composition herein.
• the anhydrous derivatives of certain species described herein above can also be used in the present invention, e.g. diphenylacetic anhydride.
• Examples of preferred organic catalysts for use herein include diphenylacetic acid, phenyl acetic acid, phenyl malonic acid, phenyl succinic acid, triphenylmethane or a mixture thereof.
• Diphenyl acetic acid and salt thereof, like alkali metal diphenylacetate, have been found to be particularly suitable to use according to the present invention.
• sodium diphenyl acetate may be commercially available from Caffaro under its chemical name.
• the liquid compositions according to the present invention comprise from 0.001% to 10% by weight of the total composition of such an organic catalyst or a mixture thereof, more preferably from 0.01% to 5% by weight, more preferably from 0.01% to 2% and most preferably from 0.05% to 2%.
• the solid compositions according to the present invention comprise from 0.01% to 40% by weight of the total composition of such an organic catalyst or a mixture thereof, more preferably from 0.2% to 20% by weight, more preferably from 0.5% to 10% and most preferably from 0.5% to 5%.
• Cotton fabrics contain cellulose (i.e., (C 6 H 10 O 5 ) n ).
• a hypohalite bleach-containing composition e.g. hypochlorite-containing composition
• the bleach may react with the hydroxyl substituents of cellulose in position 6, 2, 3 and 5 of the cellulosic ring and thus may introduce new functional groups like carbonylic, aldehydic and/or carboxylic groups.
• Synthetic fabrics may be made of various synthetic materials like polyamide-elasthane that also comprise hydroxyl groups capable of being oxidized by bleach.
• improved fabric whiteness it is meant herein that the whiteness on fabric achieved by using the hypohalite bleach-containing compositions of the present invention (e.g., those containing hypochlorite) is improved, compared to the whiteness obtained by using the same compositions without the organic catalyst as described herein.
• hypohalite bleach-containing compositions of the present invention e.g., those containing hypochlorite
• the damage caused on fabric by using the hypohalite bleach-containing compositions of the present invention is reduced, compared to the damage caused by using the same compositions without the organic catalyst as described herein.
• the whitening effect i.e. the yellowing-prevention effect, and/or safety effect of the present invention can be evaluated by comparing the composition according to the present invention to the same composition without the organic catalyst.
• the degree of yellowing can be determined by both visual and instumental grading. Visually, the difference in yellowing between items treated with different compositions can be determined by a team of expert panelists. Instrumentally, the assessment can be determined with the help of Colorimeters such as Ganz Griesser® instruments (e.g., Datacolor® Spectraflash® SF 500, Machbet White-eye® 500) or a ZEISS ELREPHO® or others which are available for instance from Hunterlab® or Gardner®.
• Ganz Griesser® instruments e.g., Datacolor® Spectraflash® SF 500, Machbet White-eye® 500
• ZEISS ELREPHO® ZEISS ELREPHO®
• Fabric safety may be evaluated by different test methods including the degree of polymerisation test method according to UNI (Ente Nazionale Italiano di Unificazione) official method UNI 8282-Determinazione della viscosità intrinseca in soluée di cuprietilendiammina (CED).
• UNI Ente Nazionale Italiano di Unificacade
• CED cuprietilendiammina
• the pH of the liquid compositions according to the present invention is typically from 8 to 14 measured at 25°C, preferably from 10 to 13.5 and more preferably from 11 to 13.5.
• Solid compositions or liquid compositions of the invention have a pH of from 7.5 to 13, preferably from 8 to 12, more preferably from 8.5 to 11.5, when diluted into 1 to 500 times its weight of water. It is in this alkaline range that the optimum stability and performance of the hypohalite as well as fabric whiteness and/or safety are obtained.
• the pH range can suitably be provided by the pH buffering component mentioned hereinafter when present and the hypohalite bleach mentioned hereinbefore, which are alkalis. However, in addition to these components, a strong source of alkalinity may also optionally be used.
• Suitable sources of alkalinity are the caustic alkalis such as sodium hydroxide, potassium hydroxide and/or lithium hydroxide, and/or the alkali metal oxides such as sodium and/or potassium oxide.
• a preferred strong source of alkalinity is a caustic alkali, more preferably sodium hydroxide and/or potassium hydroxide.
• Typical levels of such caustic alkalis, when present, are of from 0.1% to 5% by weight, preferably from 0.3% to 2% and more preferably from 0.5% to 1.5% by weight of the composition.
• compositions according to the present invention further comprise a pH buffering component or a mixture thereof.
• the pH buffering component ensures that the pH of the composition is buffered to a pH value ranging from 7.5 to 13, preferably from 8 to 12, more preferably from 8.5 to 11.5 after the composition has been diluted into 1 to 500 times its weight of water.
• Suitable pH buffering components for use herein are selected from the group consisting of alkali metal salts of carbonates, polycarbonates, sesquicarbonates, silicates, polysilicates, boron salts, phosphates, stannates, alluminates and mixtures thereof.
• the preferred alkali metal salts for use herein are sodium and potassium.
• Suitable boron salts or mixtures thereof for use herein include alkali metal salts of borates and alkyl borates and mixtures thereof.
• Examples of boron salts include boric acid, alkali metal salts of metaborate, tetraborate, octoborate, pentaborate, dodecaboron, borontrifluoride and alkyl borate containing from 1 to 12 carbon atoms, preferably from 1 to 4.
• Suitable alkyl borate includes methyl borate, ethyl borate and propyl borate.
• Particularly preferred boron salts herein are the alkali metal salts of metaborate, such as sodium metaborate, potassium metaborate, and the alkali metal salts of borate, such as sodium borate, or mixtures thereof.
• Boron salts like sodium metaborate and sodium tetraborate are commercially available from Borax and Societa Chimica Larderello under the name sodium metaborate and Borax®.
• pH buffering components are selected from the group consisting of sodium carbonate, sodium silicate, sodium borate, sodium metaborate and mixtures thereof.
• the raw materials involved in the preparation of hypohalite bleaches usually contain by-products, e.g calcium carbonate resulting in an amount of up to 0.4% by weight of by-product within the hypohalite composition. However, at such amount, the by-product will not have the buffering action defined above.
• Liquid bleaching compositions herein will preferably contain an amount of pH buffering component of from 0.5% to 9% by weight, preferably from 0.5% to 5% by weight, and more preferably in an amount of from 0.6% to 3% by weight of the composition.
• Solid bleaching compositions herein will preferably contain an amount of pH buffering component of from 3% to 30% by weight, more preferably from 5% to 25% by weight, and most preferably in an amount of from 10% to 20% by weight of the composition.
• the buffering action of the pH buffering components allows to reduce the conversion of hypochlorite into hypochlorous acid, one of the species which are responsible for the fabric damage and/or fabric whiteness.
• the pH buffering components when added in a bleaching composition comprising a hypohalite bleach and such an organic catalyst, has a further action in addition to the one of said catalyst, allowing thereby to further improve the fabric whiteness and/or the fabric safety of fabrics bleached with said composition.
• compositions comprise an alkali metal salt of silicate and/or a boron salt and/or carbonate. Indeed it has been found that beside their buffering action these ingredients also have the ability to activate the organic catalyst and thereby further enhancing whiteness performance and/or fabric safety associated to this catalyst. It is speculated that this interaction may lead to an easier adsorption of the organic catalyst like diphenylacetic acid on the surface of the fabric thus allowing the organic acid to perform directly on the surface of the fabrics.
• compositions according to the present invention may further comprise other optional ingredients such as bleach-stable surfactants (e.g., nonionic surfactants, anionic surfactants, cationic surfactants and/or amphoteric surfactants), organic or inorganic alkalis, pigments, dyes, optical brighteners, solvents, builders, thickening agents, perfumes, chelating agents, radical scavengers, bleach activators and the like and mixtures thereof.
• bleach-stable surfactants e.g., nonionic surfactants, anionic surfactants, cationic surfactants and/or amphoteric surfactants
• organic or inorganic alkalis e.g., organic or inorganic alkalis, pigments, dyes, optical brighteners, solvents, builders, thickening agents, perfumes, chelating agents, radical scavengers, bleach activators and the like and mixtures thereof.
• the present invention further encompasses a method of bleaching fabrics which comprises the step of contacting said fabrics with a bleaching composition according to the present invention comprising a hypohalite bleach, and an organic catalyst.
• a bleaching composition according to the present invention comprising a hypohalite bleach, and an organic catalyst.
• the compositions used in said method of bleaching fabrics are liquid hypochlorite-containing compositions that may further comprise a pH buffering component as defined hereinbefore. Said method according to the present invention improves the fabric whiteness and/or the fabric safety.
• compositions according to the present invention are preferably contacted to fabrics in a liquid form.
• a liquid form it is meant herein the liquid compositions according to the present invention per se in neat or diluted form, as well as the granular or powder compositions or tablets according to the present invention that have been diluted with an appropriate solvent, typically water, before use, i.e., before being contacted to said fabrics.
• an appropriate solvent typically water
• compositions according to the present invention are typically used in diluted form in a laundry operation.
• in diluted form it is meant herein that the compositions for the bleaching of fabrics according to the present invention may be diluted by the user, preferably with water. Such dilution may occur for instance in hand laundry applications as well as by other means such as in a washing machine.
• Said compositions can be diluted up to 500 times, preferably from 5 to 200 times and more preferably from 10 to 80 times.
• the method of bleaching fabrics according to the present invention comprises the steps of first contacting said fabrics with a bleaching composition according to the present invention, in its diluted form, then allowing said fabrics to remain in contact with said composition, for a period of time sufficient to bleach said fabrics, typically 1 to 60 minutes, preferably 5 to 30 minutes, then rinsing said fabrics in water to remove said composition. If said fabrics are to be washed, i.e., with a conventional composition comprising at least one surface active agent, said washing may be conducted together with the bleaching of said fabrics by contacting said fabrics at the same time with a bleaching composition according to the present invention and said detergent composition, or said washing may be conducted before or after that said fabrics have been bleached.
• said method according to the present invention allows to bleach fabrics and optionally to wash fabrics with a detergent composition comprising at least one surface active agent before the step of contacting said fabrics with said bleaching composition and/or in the step where said fabrics are contacted with said bleaching composition and/or after the rinsing step when said bleaching composition has been removed from said fabrics.
• the method of bleaching fabrics comprises the step of contacting fabrics with a liquid bleaching composition according to the present invention, in its neat form, of allowing said fabrics to remain in contact with said bleaching composition for a period of time sufficient to bleach said fabrics, typically 5 seconds to 30 minutes, preferably 1 minute to 10 minutes and then rinsing said fabrics in water to remove the bleaching composition. If said fabrics are to be washed, i.e., with a conventional composition comprising at least one surface active agent, said washing may be conducted before or after that said fabrics have been bleached.
• the level of hypohalite bleach is from 0.01% to 5%, preferably from 0.1% to 3.5%, more preferably from 0.2% to 2% and most preferably from 0.2% to 1%.
• the present invention provides liquid hypohalite bleach-containing compositions that may be applied neat onto a fabric to bleach, despite a standing prejudice against using hypochlorite-containing compositions neat on fabrics.
• the bleaching pre-treatment operation may also be followed by the diluted bleaching method as described herein before either in bucket (hand operation) or in a washing machine.
• compositions which further illustrate the present invention were made by mixing the listed ingredients in the listed proportions: Compositions (weight %) I II III IV V VI VII Sodium hypochlorite 5.0 5.0 5.0 2.5 2.5 5.0 5.0 Sodium hydroxide 1.3 1.3 1.3 0.7 1.4 0.7 1.4 Sodium carbonate 1.2 1.2 1.2 1.0 1.2 1.2 1.2 Sodium silicate -- -- 0.5 -- -- 0.2 -- Sodium metaborate -- 0.5 -- -- -- -- -- -- -- Sodium diphenyl acetate 0.1 0.5 0.1 0.3 0.05 0.2 0.4 Minors and water balance up to 100% Compositions (weight %) VIII IX X XI XII XIII XIV Sodium hypochlorite 5.0 5.0 2.5 2.5 5.0 5.0 Sodium hydroxide 1.3 1.3 1.3 1.4 1.4 0.7 1.4 Sodium carbonate 1.2 1.2 1.2 -- 1.2 1.2 1.2 Sodium silicate -- -- 0.5 -- -- 0.2 -- Sodium diphenyl acetate 0.1 1.3
• compositions I to XIX and XXIV to XXVI are particularly suitable for use in diluted conditions as described herein.
• Compositions XX to XXIII are particularly suitable for use in neat conditions.

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Citations (5)

• 1998
  • 1998-02-23 EP EP98870036A patent/EP0937772A1/fr not_active Withdrawn
• 1999
  • 1999-02-22 ZA ZA9901406A patent/ZA991406B/xx unknown
  • 1999-02-23 WO PCT/IB1999/000326 patent/WO1999042552A1/fr active Application Filing
  • 1999-02-23 AR ARP990100719A patent/AR018105A1/es unknown
  • 1999-02-23 JP JP2000532493A patent/JP2002504591A/ja not_active Withdrawn
  • 1999-02-23 CA CA002321922A patent/CA2321922A1/fr not_active Abandoned
  • 1999-02-23 AU AU22962/99A patent/AU2296299A/en not_active Abandoned

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