CA2321922A1 - Bleaching compositions - Google Patents
Bleaching compositions Download PDFInfo
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- CA2321922A1 CA2321922A1 CA002321922A CA2321922A CA2321922A1 CA 2321922 A1 CA2321922 A1 CA 2321922A1 CA 002321922 A CA002321922 A CA 002321922A CA 2321922 A CA2321922 A CA 2321922A CA 2321922 A1 CA2321922 A1 CA 2321922A1
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- 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
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- 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
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- Oil, Petroleum & Natural Gas (AREA)
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Abstract
Bleaching compositions are disclosed which comprise a hypohalite bleach, and an organic catalyst according to any formulae (I) or (II) or (III) 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 rings each independently bare in one or more positions -H, -COO-M+, -Cl, -Br, -SO3M, -NO2, -Rf, -ORf wherein Rf is a substituted or unsubstituted, saturated or unsaturated, linear or branched hydrocarbon chain having from 1 to 20 carbon atoms. A method of treating fabrics with such a composition is also disclosed.
Description
BLEACHING COMPOSITIONS
Technical field 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.
Bac~round of the invention 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.
However, a problem encountered with the use of hypohalite bleach-containing compositions like hypochlorite-based compositions is the resulting damage andlor yellowing of the fabrics being bleached.
It is therefore an object of the invention to provide a hypohalite bleach-containing composition, suitable for use in laundry applications, which provides improved fabric whiteness to fabrics treated therewith.
It is another object of the invention to provide a hypohalite bleach-containing composition, suitable for use in laundry applications, which provides improved fabric safety to fabrics treated therewith.
Fabrics made of cotton andlor synthetic materials have free hydroxyl groups.
It is believed that the fabric damage andlor yellowing that may occur when bleaching a fabric may be due to the oxidation of the hydroxyl groups of the fabric by the bleach. For example, where a liquid hypochlorite-containing CONFIRMATION COPY
composition is applied on the fabric to bleach, either in its neat form or in its diluted form, 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.
This phenomenon is emphasised at lower pHs. Indeed, low pHs shift the chemical equilibrium between hypochlorite and hypochlorous acid to the latter, which has been found to contribute to fabric yellowing and fabric damage.
Also, it is further believed that at lower pHs these hydroxyl groups are more easily oxidised to form, for example, aldehyde groups which are responsible for the yellowing of the fabric.
tt is thus an object of the present invention to reduce or even limit the oxidizing of the hydroxyl groups of a fabric also occurring as a side effect of hypochlorite decomposition when bleaching a fabric with a hypochlorite bleach. More particularly it is an object of the present invention to provide hypohalite bleach-containing compositions, especially a hypochlorite-containing bleaching compositions, delivering improved fabric safety and/or whiteness.
It has been found that the previous objects can be met by formulating a composition 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 Biphenyl 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. In a preferred embodiment the compositions according to the present invention further comprise a ph buffering component, preferably an alkali metal salt of silicate andlor a boron salt to deliver further improved fabric whiteness andlor improved fabric safety on fabrics bleached with these compositions.
An advantage of the compositions of the present invention is that they 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. For example, 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).
Background art Hypohalite bleach-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 andlor silicate. However, no organic catalysts as defined herein are disclosed .
EP-A-653 482, EP-A-fi68 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.
Technical field 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.
Bac~round of the invention 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.
However, a problem encountered with the use of hypohalite bleach-containing compositions like hypochlorite-based compositions is the resulting damage andlor yellowing of the fabrics being bleached.
It is therefore an object of the invention to provide a hypohalite bleach-containing composition, suitable for use in laundry applications, which provides improved fabric whiteness to fabrics treated therewith.
It is another object of the invention to provide a hypohalite bleach-containing composition, suitable for use in laundry applications, which provides improved fabric safety to fabrics treated therewith.
Fabrics made of cotton andlor synthetic materials have free hydroxyl groups.
It is believed that the fabric damage andlor yellowing that may occur when bleaching a fabric may be due to the oxidation of the hydroxyl groups of the fabric by the bleach. For example, where a liquid hypochlorite-containing CONFIRMATION COPY
composition is applied on the fabric to bleach, either in its neat form or in its diluted form, 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.
This phenomenon is emphasised at lower pHs. Indeed, low pHs shift the chemical equilibrium between hypochlorite and hypochlorous acid to the latter, which has been found to contribute to fabric yellowing and fabric damage.
Also, it is further believed that at lower pHs these hydroxyl groups are more easily oxidised to form, for example, aldehyde groups which are responsible for the yellowing of the fabric.
tt is thus an object of the present invention to reduce or even limit the oxidizing of the hydroxyl groups of a fabric also occurring as a side effect of hypochlorite decomposition when bleaching a fabric with a hypochlorite bleach. More particularly it is an object of the present invention to provide hypohalite bleach-containing compositions, especially a hypochlorite-containing bleaching compositions, delivering improved fabric safety and/or whiteness.
It has been found that the previous objects can be met by formulating a composition 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 Biphenyl 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. In a preferred embodiment the compositions according to the present invention further comprise a ph buffering component, preferably an alkali metal salt of silicate andlor a boron salt to deliver further improved fabric whiteness andlor improved fabric safety on fabrics bleached with these compositions.
An advantage of the compositions of the present invention is that they 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. For example, 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).
Background art Hypohalite bleach-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 andlor silicate. However, no organic catalysts as defined herein are disclosed .
EP-A-653 482, EP-A-fi68 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.
Summary of the invention 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 or d~
H
/ \ ~ / \
H
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+, -CI, -Br, -S03M, -N02, -R,, -OR, wherein R, is a substituted or unsubstituted, saturated or unsaturated, linear or branched hydrocarbon chain having from 1 to 20 carbon atoms.
WO 99!42552 PCT/IB99100326 In a preferred embodiment the compositions of the present invention further comprise a pH buffering component. The presence of a pH buffering component in the compositions of the present invention further contributes to the effective whiteness performance andlor 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 andlor fabric safety of said composition.
Detailed Description of the invention The compositions of the present invention are bleaching compositions that may be formulated either as solids or liquids. In the case where 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. In liquid form including gel and pasty 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.
HYpohalite bleach:
As a first essential ingredient, the compositions of the present invention comprise a hypohalite bleach or a mixture thereof.
Hypohalite bleaches may be provided by a variety of sources, including bleaches that are oxidative bleaches and subsequently lead to the formation of positive halide ions as well as bleaches 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:
For liquid compositions, the preferred hypohalite bleaches among the above described are the alkali metal andlor 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.
For solid compositions, 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 trichiorocyanurates, sodium trichlorocyanurates, and mixtures thereof, more preferably sodium dichloroisocyanurates and/or calcium hypochlorite.
Preferably, 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.
Preferably, 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 fi0% by weight of the composition.
Or4anic catalyst:
As a second essential ingredient, the 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 or H
/ \ ~ / \
H
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', -CI, -Br, -S03M, -N02, -R,, -OR, wherein R, is a substituted or unsubstituted, saturated or unsaturated, linear or branched hydrocarbon chain having from 1 to 20 carbon atoms.
Preferably R, is -COO'M+, or C,-C~ alkyl-COO'M', more preferably -COO'Mi or C,-C,oalkyl-COO'M', most preferably -COO'M' or C,-CSalkyl-COO'M+, and M is H
or an alkali metal, preferably sodium.
Preferably R2 is H, -COO'Mi~, 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,-C~
alkyl-COO'M', more preferably C,-C,o alkyl-COO'M+, most preferably C,-CS 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+, -CI, -Br, -S03M, -N02, -Rf, -OR, wherein R, 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. biphenyl acetic acid and salt thereof, like alkali metal diphenylacetate, have been found to be particularly suitable to use according to the present invention.
Indeed, sodium diphenyl acetate may be commercially available from Caffaro under its chemical name.
Preferably, 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%.
Preferably, 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., (CgH1005)n). When a hypohalite bleach-containing composition, e.g. hypochlorite-containing composition, is used to bleach a cotton fabric, 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 andlor 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.
It has now been found that such organic catalysts in a hypohalite bleach-containing composition acts as a fabric protective agent when this composition is used to bleach fabrics. Indeed, it has been found that such organic catalysts are capable of reducing or even preventing the oxidation of the hydroxyl groups of a fabric and also the depolymerization of cellulose due to the oxidative attack of hypohalite bleach like hypochlorite, and thus- significantly improving the whiteness performance and/or the fabric safety profile of a hypohalite bleach-containing composition comprising them. This both when the liquid bleaching composition of the present invention is used in neat condition, e.g. as a pretreater, as well as in diluted conditions, e.g. typical dilution with water in conventional washing conditions. It is speculated that this oxidation of the hydroxyl groups of a fabric is one of the main mechanisms of fabric damage andlor fabric yellowing.
By "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.
By "improved fabric safety", it is meant herein that the damage caused on fabric by using the hypohalite bleach-containing compositions of the present invention (e.g., those containing hypochlorite) is reduced, compared to the damage caused by using the same compositions without the organic catalyst as described herein.
Indeed, the whitening effect, i.e. the yellowing-prevention effect, andlor 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. usually, the difference in yellowing between items treated with different compositions can be determined by a team of expert panellists. 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~l 500) or a ZEISS ELREPHO~ or others which are available for instance from Hunterlab~ or Gardner~.
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 delta viscosity intrinseca in soluzione di cuprietilendiammina (CED).
The pH of the liquid compositions according to the present invention, as is, 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 andlor safety are obtained. The pH range can suitably be provided by the pH buffering component mentioned hereinafter when present WO 99/42552 PC'T/IB99/00326 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 andlor lithium hydroxide, and/or the alkali metal oxides such as sodium andlor potassium oxide. A preferred strong source of alkalinity is a caustic alkali, more preferably sodium hydroxide andlor 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.
PH bufferin4 component:
In a preferred embodiment, the 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~.
Particularly preferred 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.
It has been found that 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 andlor fabric whiteness.
In other words, 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 andlor the fabric safety of fabrics bleached with said composition.
In a preferred embodiment herein the compositions comprise an alkali metal salt of silicate andlor 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 andlor 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.
Other optional components:
The 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 andlor 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.
Method of bleaching fabrics:
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. In a preferred embodiment, 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 andlor the fabric safety.
The compositions according to the present invention are preferably contacted to fabrics in a liquid form. Indeed, by "in a liquid form" it is meant herein the liquid compositions according to the present invention per se in neat or diluted form, 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.
The compositions according to the present invention are typically used in diluted form in a laundry operation. By "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.
WO 99/42552 PG"T/IB99100326 More specifically, 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 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. Accordingly, 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 andlor in the step where said fabrics are contacted with said bleaching composition andlor after the rinsing step when said bleaching composition has been removed from said fabrics.
In another embodiment of the present invention 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 minutes and then rinsing said fabrics in water to remove the bleaching composfion. 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. In the embodiment of the present invention wherein the liquid bleaching composition of the present invention, is contacted to the fabrics in its neat form, it is preferred that 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 %.
Advantageously, 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.
It is preferred to perform the bleaching methods herein before said fabrics are washed. Indeed, it has been observed that bleaching said fabrics with the compositions according to the present invention (diluted and/or neat bleaching methods) prior to washing them with a detergent composition provides superior whiteness and stain removal with less energy and detergent than if said fabrics are washed first, then bleached.
Alternatively instead of following the neat bleaching method as described herein above (pretreater application) by a rinsing step with water and/or a conventional washing step with a liquid or powder conventional detergent, 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.
Examples The following compositions which further illustrate the present invention were made by mixing the listed ingredients in the listed proportions:
Compositions I II III IV V VI VI1 (weight %) Sodium hypochlorite5.0 5.0 2.5 2.5 5.0 5.0 5.0 Sodium hydroxide 1.3 1.3 0.7 1.4 0.7 1.4 1.3 Sodium carbonate 1.2 1.2 1.0 1.2 1.2 1.2 1.2 Sodium silicate - 0.5 - -- 0.2 -S~ium metaborate 0.5 - -- - - ---Sodium Biphenyl 0.5 0.1 0.3 0.05 0.2 0.4 acetate 0.1 Minors and water ----balance up to 100°~-Compositions VIII IX X XI XII XIII XIV
(weight %) Sodium hypochlorite5.0 5.0 5.0 2.5 2.5 5.0 5.0 Sodium hydroxide1.3 1.3 1.3 1.4 1.4 0.7 1.4 Sodium carbonate1.2 1.2 1.2 -- 1.2 1.2 1.2 Sodium silicate- - 0.5 -- - 0.2 Sodium diphenyl0.1 0.4 0.1 0.2 0.05 0.2 0.3 acetate Minors and water ----balance up to 100%-Compositions XV XVI XVII XVIIIIX
(weight %) Sodium hypochlorite5.05.0 5.0 2.5 2.5 Sodium hydroxide1.31.3 1.3 0.7 1.4 Sodium carbonate1.21.2 1.2 1.0 1.2 Sodium silicate0.50.5 0.5 -Sodium phenyl 0.1- 0.05 - 0.1 acetate Sodium phenyl 0.1 - -succinate -Triphenylmethane- - 0.05 0.1 -Minors and -----balance ---water up to 100~-----Compositions XX XXIXXII XXIiIXXIV XXV XXVI
(weight %) Sodium hypochlorite1.0 1.01.0 2.5 3.5 2.5 5.0 Sodium carbonate1.2 1.21.2 1.2 1.2 1.2 1.2 Sodium metaborate-- -- 1.5 -- - --Sodium silicate- - - - - 0.2 -Surfactants 5.0 5.05.0 5.0 5.0 5:0 -Sodium diphenyi0.1 - 0.1 0.5 0.05 0.2 0.3 acetate sodium phenyl- 0.1- - - - _ acetate Minors and balance water up to Sodium hydroxide up to pH 12 All the above compositions provide excellent fabric safety and/or excellent whiteness to fabrics when used to treat fabrics. 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.
or or d~
H
/ \ ~ / \
H
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+, -CI, -Br, -S03M, -N02, -R,, -OR, wherein R, is a substituted or unsubstituted, saturated or unsaturated, linear or branched hydrocarbon chain having from 1 to 20 carbon atoms.
WO 99!42552 PCT/IB99100326 In a preferred embodiment the compositions of the present invention further comprise a pH buffering component. The presence of a pH buffering component in the compositions of the present invention further contributes to the effective whiteness performance andlor 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 andlor fabric safety of said composition.
Detailed Description of the invention The compositions of the present invention are bleaching compositions that may be formulated either as solids or liquids. In the case where 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. In liquid form including gel and pasty 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.
HYpohalite bleach:
As a first essential ingredient, the compositions of the present invention comprise a hypohalite bleach or a mixture thereof.
Hypohalite bleaches may be provided by a variety of sources, including bleaches that are oxidative bleaches and subsequently lead to the formation of positive halide ions as well as bleaches 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:
For liquid compositions, the preferred hypohalite bleaches among the above described are the alkali metal andlor 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.
For solid compositions, 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 trichiorocyanurates, sodium trichlorocyanurates, and mixtures thereof, more preferably sodium dichloroisocyanurates and/or calcium hypochlorite.
Preferably, 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.
Preferably, 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 fi0% by weight of the composition.
Or4anic catalyst:
As a second essential ingredient, the 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 or H
/ \ ~ / \
H
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', -CI, -Br, -S03M, -N02, -R,, -OR, wherein R, is a substituted or unsubstituted, saturated or unsaturated, linear or branched hydrocarbon chain having from 1 to 20 carbon atoms.
Preferably R, is -COO'M+, or C,-C~ alkyl-COO'M', more preferably -COO'Mi or C,-C,oalkyl-COO'M', most preferably -COO'M' or C,-CSalkyl-COO'M+, and M is H
or an alkali metal, preferably sodium.
Preferably R2 is H, -COO'Mi~, 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,-C~
alkyl-COO'M', more preferably C,-C,o alkyl-COO'M+, most preferably C,-CS 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+, -CI, -Br, -S03M, -N02, -Rf, -OR, wherein R, 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. biphenyl acetic acid and salt thereof, like alkali metal diphenylacetate, have been found to be particularly suitable to use according to the present invention.
Indeed, sodium diphenyl acetate may be commercially available from Caffaro under its chemical name.
Preferably, 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%.
Preferably, 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., (CgH1005)n). When a hypohalite bleach-containing composition, e.g. hypochlorite-containing composition, is used to bleach a cotton fabric, 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 andlor 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.
It has now been found that such organic catalysts in a hypohalite bleach-containing composition acts as a fabric protective agent when this composition is used to bleach fabrics. Indeed, it has been found that such organic catalysts are capable of reducing or even preventing the oxidation of the hydroxyl groups of a fabric and also the depolymerization of cellulose due to the oxidative attack of hypohalite bleach like hypochlorite, and thus- significantly improving the whiteness performance and/or the fabric safety profile of a hypohalite bleach-containing composition comprising them. This both when the liquid bleaching composition of the present invention is used in neat condition, e.g. as a pretreater, as well as in diluted conditions, e.g. typical dilution with water in conventional washing conditions. It is speculated that this oxidation of the hydroxyl groups of a fabric is one of the main mechanisms of fabric damage andlor fabric yellowing.
By "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.
By "improved fabric safety", it is meant herein that the damage caused on fabric by using the hypohalite bleach-containing compositions of the present invention (e.g., those containing hypochlorite) is reduced, compared to the damage caused by using the same compositions without the organic catalyst as described herein.
Indeed, the whitening effect, i.e. the yellowing-prevention effect, andlor 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. usually, the difference in yellowing between items treated with different compositions can be determined by a team of expert panellists. 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~l 500) or a ZEISS ELREPHO~ or others which are available for instance from Hunterlab~ or Gardner~.
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 delta viscosity intrinseca in soluzione di cuprietilendiammina (CED).
The pH of the liquid compositions according to the present invention, as is, 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 andlor safety are obtained. The pH range can suitably be provided by the pH buffering component mentioned hereinafter when present WO 99/42552 PC'T/IB99/00326 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 andlor lithium hydroxide, and/or the alkali metal oxides such as sodium andlor potassium oxide. A preferred strong source of alkalinity is a caustic alkali, more preferably sodium hydroxide andlor 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.
PH bufferin4 component:
In a preferred embodiment, the 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~.
Particularly preferred 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.
It has been found that 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 andlor fabric whiteness.
In other words, 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 andlor the fabric safety of fabrics bleached with said composition.
In a preferred embodiment herein the compositions comprise an alkali metal salt of silicate andlor 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 andlor 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.
Other optional components:
The 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 andlor 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.
Method of bleaching fabrics:
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. In a preferred embodiment, 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 andlor the fabric safety.
The compositions according to the present invention are preferably contacted to fabrics in a liquid form. Indeed, by "in a liquid form" it is meant herein the liquid compositions according to the present invention per se in neat or diluted form, 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.
The compositions according to the present invention are typically used in diluted form in a laundry operation. By "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.
WO 99/42552 PG"T/IB99100326 More specifically, 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 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. Accordingly, 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 andlor in the step where said fabrics are contacted with said bleaching composition andlor after the rinsing step when said bleaching composition has been removed from said fabrics.
In another embodiment of the present invention 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 minutes and then rinsing said fabrics in water to remove the bleaching composfion. 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. In the embodiment of the present invention wherein the liquid bleaching composition of the present invention, is contacted to the fabrics in its neat form, it is preferred that 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 %.
Advantageously, 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.
It is preferred to perform the bleaching methods herein before said fabrics are washed. Indeed, it has been observed that bleaching said fabrics with the compositions according to the present invention (diluted and/or neat bleaching methods) prior to washing them with a detergent composition provides superior whiteness and stain removal with less energy and detergent than if said fabrics are washed first, then bleached.
Alternatively instead of following the neat bleaching method as described herein above (pretreater application) by a rinsing step with water and/or a conventional washing step with a liquid or powder conventional detergent, 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.
Examples The following compositions which further illustrate the present invention were made by mixing the listed ingredients in the listed proportions:
Compositions I II III IV V VI VI1 (weight %) Sodium hypochlorite5.0 5.0 2.5 2.5 5.0 5.0 5.0 Sodium hydroxide 1.3 1.3 0.7 1.4 0.7 1.4 1.3 Sodium carbonate 1.2 1.2 1.0 1.2 1.2 1.2 1.2 Sodium silicate - 0.5 - -- 0.2 -S~ium metaborate 0.5 - -- - - ---Sodium Biphenyl 0.5 0.1 0.3 0.05 0.2 0.4 acetate 0.1 Minors and water ----balance up to 100°~-Compositions VIII IX X XI XII XIII XIV
(weight %) Sodium hypochlorite5.0 5.0 5.0 2.5 2.5 5.0 5.0 Sodium hydroxide1.3 1.3 1.3 1.4 1.4 0.7 1.4 Sodium carbonate1.2 1.2 1.2 -- 1.2 1.2 1.2 Sodium silicate- - 0.5 -- - 0.2 Sodium diphenyl0.1 0.4 0.1 0.2 0.05 0.2 0.3 acetate Minors and water ----balance up to 100%-Compositions XV XVI XVII XVIIIIX
(weight %) Sodium hypochlorite5.05.0 5.0 2.5 2.5 Sodium hydroxide1.31.3 1.3 0.7 1.4 Sodium carbonate1.21.2 1.2 1.0 1.2 Sodium silicate0.50.5 0.5 -Sodium phenyl 0.1- 0.05 - 0.1 acetate Sodium phenyl 0.1 - -succinate -Triphenylmethane- - 0.05 0.1 -Minors and -----balance ---water up to 100~-----Compositions XX XXIXXII XXIiIXXIV XXV XXVI
(weight %) Sodium hypochlorite1.0 1.01.0 2.5 3.5 2.5 5.0 Sodium carbonate1.2 1.21.2 1.2 1.2 1.2 1.2 Sodium metaborate-- -- 1.5 -- - --Sodium silicate- - - - - 0.2 -Surfactants 5.0 5.05.0 5.0 5.0 5:0 -Sodium diphenyi0.1 - 0.1 0.5 0.05 0.2 0.3 acetate sodium phenyl- 0.1- - - - _ acetate Minors and balance water up to Sodium hydroxide up to pH 12 All the above compositions provide excellent fabric safety and/or excellent whiteness to fabrics when used to treat fabrics. 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.
Claims (17)
1. A liquid or solid bleaching composition 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 rings each independently bare in one or more positions -H, -COO-M+, -Cl, -Br, -SO3M, -NO2, -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.
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 rings each independently bare in one or more positions -H, -COO-M+, -Cl, -Br, -SO3M, -NO2, -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.
2. A composition according to claim 1 wherein said hypohalite, based on active halide, is present in an amount of from 0.01 % to 20% by weight, preferably from 0.1% to 10% by weight of the liquid composition or in an amount of from 20% to 95% by weight, preferably from 25% to 60% by weight of the solid composition.
3. A composition according to any of the preceding claims wherein said hypohalite bleach is, for liquid bleaching compositions, an alkali metal sodium hypochlorite or, for solid compositions, sodium dichloroisocyanurate and/or calcium hypochlorite.
4. A composition according to any of the preceding claims wherein in said organic catalyst R1 is -COO-M+, or C1-C20 alkyl-COO-M+, more preferably C1-C10 alkyl-COO-M+, most preferably C1-C5 alkyl-COO-M+, wherein R2 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 C1-C20 alkyl-COO-M+, more preferably C1-C10 alkyl-COO-M+, most preferably C1-C5 alkyl-COO-M+, and M is H or an alkali metal, preferably sodium and wherein the phenyl groups each independently bare -H, -COO-M+, -Cl, -Br, -SO3M, - NO2, -R f, or -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.
5. A composition according to any of the preceding claims wherein said organic catalyst is diphenylacetic acid, phenyl acetic acid, phenyl malonic acid, phenyl succinic acid, triphenylmethane or a mixture thereof.
6. A composition according to any of the preceding claims wherein said organic catalyst is present in an amount of from 0.001% to 10% by weight, preferably from 0.01% to 5%, more preferably from 0.05% to 2% by weight of the liquid composition or in an amount of from 0.01% to 40% by weight, preferably from 0.2% to 20% by weight of the solid composition.
7. A bleaching composition according to any of the preceding claims, wherein said composition further comprises a pH buffering component which is preferably selected from the group consisting of alkali metal salts of carbonates, polycarbonates, sesquicarbonates, silicates, polysilicates, boron salts, phosphates, stannates, alluminates, and mixtures thereof.
8. A bleaching composition according to claim 7, wherein said pH buffering component is selected from the group consisting of sodium carbonate, sodium silicates, sodium borate, sodium metaborate and mixtures thereof and more preferably is sodium silicate and/or sodium borate.
9. A bleaching composition according to any of the claims 7 or 8, wherein said pH buffering component is in an amount of from 0.5% to 9% by weight, preferably 0.5% to 5% by weight of the liquid composition or in an amount of from 3% to 30% by weight, preferably from 5% to 25% by weight of the solid composition.
10. A bleaching composition according to any of the preceding claims, wherein said composition further comprises a strong source of alkalinity.
11. A composition according to any of the preceding claims wherein said composition is liquid and preferably aqueous.
12. A method of bleaching fabrics which comprises the step of contacting said fabrics with a bleaching composition according to any of the preceding claims, in its diluted form at a dilution level with water up to 500 times, preferably from 5 to 200 times and more preferably from 10 to 80 times.
13. A method of bleaching fabrics according to claim 12 which, after the step of contacting said fabrics with said bleaching composition, further comprises the steps of:
- allowing said fabrics to remain in contact with said bleaching composition for a period of time sufficient to bleach said fabrics, - then rinsing said fabrics in water to remove said bleaching composition.
- allowing said fabrics to remain in contact with said bleaching composition for a period of time sufficient to bleach said fabrics, - then rinsing said fabrics in water to remove said bleaching composition.
14. A method according to any of the claims 12 or 13 wherein said fabrics are washed 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.
15. A method of bleaching a fabric which comprises the step of contacting said fabric with a bleaching composition according to claim 11, in its neat form, allowing said fabric to remain in contact with said bleaching composition for a period of time sufficient to bleach said fabric, and then rinsing said fabric in water to remove said bleaching composition.
16. A method according to claim 15 wherein said fabric is washed with a detergent composition comprising at least one surface active agent before the step of contacting said fabric with said bleaching composition and/or after the rinsing step when said bleaching composition has been removed.
17. The use of an organic catalyst according to the formula:
or or 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, -SO3M, -NO2, -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, in a bleaching composition comprising a hypohalite bleach, to improve the fabric whiteness performance and/or fabric safety of said composition.
or or 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, -SO3M, -NO2, -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, in a bleaching composition comprising a hypohalite bleach, to improve the fabric whiteness performance and/or fabric safety of said composition.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP98870036A EP0937772A1 (en) | 1998-02-23 | 1998-02-23 | Bleaching compositions |
| EP98870036.5 | 1998-02-23 | ||
| PCT/IB1999/000326 WO1999042552A1 (en) | 1998-02-23 | 1999-02-23 | Bleaching compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2321922A1 true CA2321922A1 (en) | 1999-08-26 |
Family
ID=8236999
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002321922A Abandoned CA2321922A1 (en) | 1998-02-23 | 1999-02-23 | Bleaching compositions |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0937772A1 (en) |
| JP (1) | JP2002504591A (en) |
| AR (1) | AR018105A1 (en) |
| AU (1) | AU2296299A (en) |
| CA (1) | CA2321922A1 (en) |
| WO (1) | WO1999042552A1 (en) |
| ZA (1) | ZA991406B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0987315A1 (en) * | 1998-09-16 | 2000-03-22 | The Procter & Gamble Company | Bleaching compositions |
| DE102010038502A1 (en) * | 2010-07-27 | 2012-02-02 | Henkel Ag & Co. Kgaa | Stabilized liquid enzyme-containing surfactant preparation |
| EP3292173A1 (en) | 2015-05-04 | 2018-03-14 | Milliken & Company | Leuco triphenylmethane colorants as bluing agents in laundry care compositions |
| US20180119068A1 (en) * | 2016-11-01 | 2018-05-03 | The Procter & Gamble Company | Methods of using leuco colorants as bluing agents in laundry care compositions |
| ES2827831T3 (en) * | 2016-11-01 | 2021-05-24 | Procter & Gamble | Methods for using leuco dyes as blueing agents in laundry care compositions |
| US20180119056A1 (en) * | 2016-11-03 | 2018-05-03 | Milliken & Company | Leuco Triphenylmethane Colorants As Bluing Agents in Laundry Care Compositions |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0123400A3 (en) * | 1983-03-18 | 1987-09-09 | The Procter & Gamble Company | Fabric conditioning agents, compositions and processes |
| TR22733A (en) * | 1984-12-14 | 1988-05-24 | Clorox Co | MONTHED AND DIESTER PERASIT IPTIDAI SUBSTANCES |
| US4997590A (en) * | 1988-12-22 | 1991-03-05 | The Procter & Gamble Company | Process of coloring stabilized bleach activator extrudates |
| NZ242382A (en) * | 1991-07-11 | 1994-07-26 | Colgate Palmolive Co | Viscoelastic aqueous liquid automatic dishwasher detergent incorporating a benzoic acid (derivative) and a cross-linked polycarboxylate thickening agent |
| EP0668345B1 (en) * | 1994-02-22 | 2001-12-12 | The Procter & Gamble Company | Hypochlorite bleaching compositions |
-
1998
- 1998-02-23 EP EP98870036A patent/EP0937772A1/en not_active Withdrawn
-
1999
- 1999-02-22 ZA ZA9901406A patent/ZA991406B/en unknown
- 1999-02-23 AU AU22962/99A patent/AU2296299A/en not_active Abandoned
- 1999-02-23 AR ARP990100719A patent/AR018105A1/en unknown
- 1999-02-23 WO PCT/IB1999/000326 patent/WO1999042552A1/en active Application Filing
- 1999-02-23 JP JP2000532493A patent/JP2002504591A/en not_active Withdrawn
- 1999-02-23 CA CA002321922A patent/CA2321922A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| ZA991406B (en) | 1999-08-23 |
| JP2002504591A (en) | 2002-02-12 |
| AU2296299A (en) | 1999-09-06 |
| WO1999042552A1 (en) | 1999-08-26 |
| AR018105A1 (en) | 2001-10-31 |
| EP0937772A1 (en) | 1999-08-25 |
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