EP0635569A2 - Produits de nettoyage liquides - Google Patents

Produits de nettoyage liquides Download PDF

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Publication number
EP0635569A2
EP0635569A2 EP94201877A EP94201877A EP0635569A2 EP 0635569 A2 EP0635569 A2 EP 0635569A2 EP 94201877 A EP94201877 A EP 94201877A EP 94201877 A EP94201877 A EP 94201877A EP 0635569 A2 EP0635569 A2 EP 0635569A2
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EP
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Prior art keywords
weight
dye
particles
aqueous
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP94201877A
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German (de)
English (en)
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EP0635569B1 (fr
EP0635569A3 (fr
Inventor
Alan Don Unilever Res. Port Sunlight Lab. Barber
Cornelis B. Unilever Res. Vlaardingen Lab Donker
Philippus Unilever Research Van Der Hoeven
Andrew J. Unilever Research Perescott
Karl Unilever Res. Port Sunlight Lab. Burgess
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to EP19940201877 priority Critical patent/EP0635569B1/fr
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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
    • C11D3/40—Dyes ; Pigments
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0034—Fixed on a solid conventional detergent ingredient

Definitions

  • the present invention relates to substantially non-aqueous liquid cleaning products, especially detergent compositions and to a method of preparing such non-aqueous liquid cleaning products.
  • Non-aqueous liquid cleaning products are those containing little or no water.
  • Non-aqueous liquid detergent compositions are known in the art and have been described in quite a number of patent publications, e.g. in US-A-4,316,812, US-A-4,874,537 and EP-A-0,484,095.
  • the free water content of non-aqueous liquid detergent products is less than 5% by weight, preferably less than 3% by weight, more preferably less than 2% by weight, most preferably substantially nil.
  • Non-aqueous liquid detergent compositions provide a way of concentrating liquid detergents without giving in on washing performance.
  • Non-aqueous liquid detergent compositions normally comprise a non-aqueous liquid phase having incorporated therein as dispersion, solution or combination thereof, the usual detergent components and adjuncts depending on the purpose of use, primarily surfactants and builders.
  • the liquid phase often comprises a nonionic surfactant as major component, which apart from acting as carrier liquid for the other detergent components, usually and preferably also has detergent-active properties, thereby acting wholly or in part as the surfactant ingredient.
  • Adjuncts such as dyes are important ingredients incorporated in products, usually in small amounts to provide for certain desired properties.
  • Dye may be included in non-aqueous liquids to improve the product appearance, as a warning to consumers for toxic ingredients and/or to mask consumer-disliked colours of detergent ingredients.
  • GB-A-1,303,810 discloses clear liquid detergent compositions with a transparent aqueous or non-aqueous base comprising particles that are visually distinct and have a diameter size of at least 0.5 mm.
  • the formulation of these liquids is restricted as they must have a transparent liquid base and the suspending power of the liquid must be sufficiently high in order to stably suspend the particles with the large particle size, which may cause the product to have a high viscosity.
  • GB-A-2,194,793 discloses liquid detergent compositions having an aqueous base that comprise high electrolyte levels and suspended particles having a particle size of from 1 to 2000 ⁇ m, preferably up to 300 ⁇ m.
  • the aqueous liquids are prepared to have a mottled or speckled coloration appearance by using a pigment material and a carrier material for the suspended particles that are substantially insoluble and non-dispersible in the suspending aquoeus liquid.
  • Non-aqueous liquid cleaning compositions are among the most concentrated products in the art and the number of interactions between the ingredients of such products makes it in particular difficult to prepare compositions that are chemically stable, especially upon storage. This is not only true as compared with diluted aqueous liquids but also with powdered products in which components have a more or less fixed position in the product.
  • non-aqueous liquids comprising dye suffer from discolouring, i.e. fading and/or disappearance of the colour which leads to a worse product appearance, decreased effect of the warning function and less or no masking of consumer-disliked colours of ingredients of the non-aqueous liquid.
  • the present invention provides a non-aqueous liquid cleaning composition
  • a non-aqueous liquid cleaning composition comprising a non-aqueous phase with dispersed particles comprising a carrier material and dye material associated thereto wherein the particles have a D(3,2) particle size of from 50 ⁇ m to less than 500 ⁇ m.
  • a preferred embodiment of the invention provides a non-aqueous liquid comprising a non-aqueous phase and dispersed particles wherein the particles comprise a biopolymer as carrier material, and dye associated thereto.
  • a further embodiment of the invention provides a non-aqueous liquid comprising a non-aqueous phase and dispersed particles comprising a carrier material and dye material associated thereto, wherein the composition further comprises a bleach material.
  • a further embodiment of the invention provides a method of preparing a non-aqueous liquid cleaning composition having a non-aqueous phase with dispersed particles, said method comprising dispersing particles, comprising carrier material and dye material associated thereto, in the non-aqueous phase.
  • a further embodiment of the present invention provides a method of preparing a particle, comprising carrier material and dye material associated thereto, and suitable for use in a non-aqueous liquid cleaning composition, said method comprising dissolving of a biopolymer material in water, evaporating the water to an amount of lower than 15% by weight of the resulting material and before, during or after the evaporation step adding of dye material and subjecting the resulting material to milling and/or sieving.
  • the presently claimed invention not only overcomes colour fading of the dispersed particles but is believed also to provide a product with consumer preferred appearance as the resulting non-aqueous liquid will comprise coloured speckles suspended in the non-aqueous liquid phase.
  • dispersion of the particles with carrier material and dye material wherein the size of the particles is not smaller than 50 ⁇ m, in particular smaller than 90 ⁇ m, more particularly smaller than 100 ⁇ m leads to a better distinction of the particles from the rest of the formulation, the so-called non-aqueous base, which is the non-aqueous liquid cleaning composition without the dispersed particles of carrier and dye material.
  • the so-called non-aqueous base which is the non-aqueous liquid cleaning composition without the dispersed particles of carrier and dye material.
  • Preferably not more than 25% by weight of the particles, more preferably not more than 10% by weight, most preferably not more than 5% by weight of the particles have a size smaller than 50 ⁇ m, more preferably smaller than 90 ⁇ m, more preferably smaller than 100 ⁇ m. If smaller particles are used then the colour of the base of the liquid colour tends to become greyish, resulting in the dispersed particles not being distinct anymore, which may deteriorate one or more of the above mentioned effects.
  • dye material for particles enables preparation of non-aqueous cleaning compositions that can be formulated more flexibly, e.g. masking the undesired colours of other ingredients.
  • a bleach system in the non-aqueous liquid cleaning composition of the invention preferably a low temperature bleach system, i.e. a bleach system that is effective at temperatures of 60°C or lower, is a preferred embodiment of the invention.
  • a low temperature bleach system i.e. a bleach system that is effective at temperatures of 60°C or lower
  • the bleach system in the non-aqueous liquid cleaning composition of the invention will react with the dye material as soon as the dye and bleach are released in the wash liquor and this consequently prevents the dye from depositing on the material to be washed.
  • the dispersed particles according to the invention comprise carrier material and dye material.
  • the dye material can be present on the outside and/or in the inside of the particle.
  • association of dye to the carrier material reduces interaction of dye with other ingredients present in the non-aqueous liquids. It is preferred that the dye is present inside the particle to avoid substantially all interactions with other ingredients. This also reduces diffusion of the dye into the non-aqueous liquid phase upon storage. Particles with dye present on the outside of the particle, e.g. in a layer, can however be preferred for processing reasons, as manufacturing of such particles can take place at low costs, e.g. by simply rolling carrier material in a bed of dye material or by spaying the dye material on the carrier material.
  • the dye material can be associated to the carrier material by way of physical, e.g. Van der Waals forces or hydrogen bonding and also by way of chemical association, such as complexing and covalent bonding.
  • the particle size D(3,2) of the dispersed particles is at least 50 ⁇ m, more preferably at least 100 ⁇ m, most preferably at least 150 ⁇ m and particularly preferred at least 180 ⁇ m.
  • the particles have a particle size of less than 500 ⁇ m, preferably less than 300 ⁇ m, most preferably at most 250 ⁇ m.
  • references to the D(3,2) average particle diameter refer to the D(3,2) particle size, which is the average surface weighted, volume/weight mean diameter calculated as described by M. Alderliesten, Anal. Proc. Vol. 21, May, 1984, 167 to 172.
  • the particle size can for example be determined with a Malvern Mastersizer and preferably by using a sweep sieve.
  • the dispersed particles are present in the non-aqueous phase in a volume fraction of from 0.1 to 5.0% V/V of the total non-aqueous liquid cleaning composition, more preferably 0.3 to 3.0% V/V, most preferably 0.5 to 2.0% V/V.
  • the colour of the non-aqueous base as well as of the dispersed particles with carrier and dye material can be expressed in L, A and/or B values.
  • the L, A and B colour values are well-known in the art (ex CIE LAB, 1976).
  • the values represent colour intensity units.
  • the values for L, A and B are determined by using a Chromameter (ex Minolta) of the CR series, i.e. CR-300, CR-310, CR-321, CR-331 or CT-310 of which the CT-310 and in particular the CR-300 are preferred.
  • the manual of e.g. CR-310 contain a clear explanation as to the definition of the L, A and B colour values.
  • the L, A and B values for the non-aqueous base can be determined by measuring the L, A and B value of the non-aqueous base alone, i.e. the non-aqueous liquid cleaning composition without the dispersed particles comprising carrier and dye material.
  • the dispersed particles with carrier and dye material are measured in the non-aqueous phase, but for practical purposes the value can also be determined of the particles per se.
  • the difference between the intensity of the dispersed particles with carrier and dye material and the intensity of the non-aqueous base is such that the L, A and/or B units show a difference of 10 units or more, preferably 15 units or more, more preferably 20 units or more, i.e. the delta value is preferably higher than 10 and/or lower than -10, more preferably higher than 15 and/or lower than 15, most preferably higher than 20 and/or lower than -20.
  • the dispersed particles comprising carrier and dye material can have high as well as low density. Although still dependent on the particles size, for reasons of physical stability it is preferred that the density of the dispersed particle is at least 0.1 mg/l, more preferably at least 0.8 mg/l and most preferably at least 1.0 mg/l. Preferably the density is at most 1.8 g/ml, more preferably at most 1.5 g/ml, most preferably at most 1.3 g/ml.
  • the dispersed particles may be used in the composition at levels of up to 80% by weight of the composition, preferably of up to 40% by weight of the composition, more preferably of up to 20% by weight of the composition, particularly preferred of up to 10% by weight of the composition.
  • the lower level will generally be about 0.01% by weight of the composition, preferably 0.1% by weight of the composition, more preferably 0.2% by weight of the composition and most preferably 0.5% by weight of the composition.
  • dye material also covers pigment material.
  • the dye material is selected from red, orange, yellow, green, blue dyes and mixtures thereof such as pink. More preferably dyes are selected that have a colour selected from blue, green and pink.
  • the dye is chemically and physically stable in association with the specific carrier material in the non-aqueous liquid and preferably the dye does not cause spotting on articles in the wash cycle.
  • Dye material from any of the established dye classes can be selected.
  • the dye is selected from Disperse, Acid, Reactive, Direct, Sulphur, VAT and Azo type dyes. Pigments can be applied in a similar manner.
  • Disperse dyes are Dispersed Blue 69-0007 ex BASF (CI pigment Blue 15:1 CI constitution number 74160) and Patent Blue V80 (CI 42051).
  • the dye material is included in the product at levels of at least 10 ⁇ 6% by weight of the composition, more preferably at least 10 ⁇ 4% by weight of the composition, most preferably at least 10 ⁇ 2% by weight of the composition.
  • the level is at most 2% by weight of the composition, more preferably at most 1% by weight of the composition, more preferably at most 0.75% by weight of the composition.
  • the dye material can for example be included in levels of 0.0075% or of 0.025% by weight of the composition.
  • the level of dye by weight of the dispersed particle is at least 0.0001%, more preferred at least 0.001, most preferred at least 0.01% by weight; the level is preferably at most 5%, more preferably at most 1%, most preferably at most 0.5% by weight.
  • Carrier material can be selected from a wide range of material to which the dye is associated. It is however preferred that the carrier material does not affect the dye, i.e. is inert to the dye material.
  • Such carrier material can be selected from bleach, builder, clay, abrasive, enzyme and biopolymer material and mixtures thereof.
  • the carrier material comprises biopolymer material and the biopolymer material usable in the present invention may be selected from a wide variety of biopolymers.
  • biopolymers are polysaccharides and polypeptides.
  • biopolymers include starch, gelatin, pectin, casein, amylopectin (corn or potato) and custard.
  • starches are potato starch, wheat starch, corn starch, cereal starch, rice starch, tapioca starch and other modifications thereof, such as depolymerized starch.
  • biopolymer materials are amylose, substituted cellulose (tylose), whey proteins and zein, hemicelluloses, pentosans, chitin derived from shellfish, seaweed extracts such as alginates, carrageenans, agar and furcelleran, pectines from plants, and also gums from different sources such as gum arabic, arabic karya, tragacanth, locust bean, guar and xanthan.
  • tylose substituted cellulose
  • whey proteins and zein hemicelluloses
  • pentosans chitin derived from shellfish
  • seaweed extracts such as alginates, carrageenans, agar and furcelleran
  • pectines from plants
  • gums from different sources such as gum arabic, arabic karya, tragacanth, locust bean, guar and xanthan.
  • a preferred method for preparing the particle is as follows. A biopolymer material is dissolved in water, whereafter the water is allowed to evaporate which leaves a solid material having a water content of not more than about 15% by weight, preferably less than 12% by weight, more preferably less than 10% by weight. Optionally, the resulting material is subjected to milling and/or sieving.
  • the biopolymer material is mixed with water at a weight ratio of biopolymer material to water of from 1:99 to 35:65, preferably from 2:98 to 30:70, more preferably from 3:97 to 25:75, and thereafter heated as desired, e.g. by short boiling of the mixture to cause dissolution of the biopolymer material in the water.
  • the solution is then left to stand so as to allow the water to evaporate.
  • the temperature at which evaporation takes place will preferably be lower than 80°C, more preferably less than 50°C. The best results are obtained between 5°C and 50°C, although other methods of evaporation, such as freeze drying, microwave drying, vacuum drying or combinations thereof can also be applied.
  • the evaporation process may be carried out in less than 1 hour, though preferably at least 1 hour, more preferably at least 5 hours.
  • the resulting material can be subjected to higher temperatures at the beginning or at the end of the evaporation process, e.g. to eliminate any small water traces in a stove at 80°C or higher.
  • Milling can be carried out by means of a wide variety of size reduction equipment such as a mortar, a Janke & Kunkel Analysen Mühle A-10 at 20.000 rpm (rounds per minute), a ball-mill or a colloid mill.
  • size reduction equipment such as a mortar, a Janke & Kunkel Analysen Mühle A-10 at 20.000 rpm (rounds per minute), a ball-mill or a colloid mill.
  • the material can subsequently be sieved to the required particle size.
  • the temperature during milling should preferably be kept below the melting point of the material in order to avoid plasticising.
  • the dye can be added during the process as solution or dispersion in water.
  • a preferred method of preparation is to dissolve or disperse the dye in the water and use the solution or dispersion for the preparation of the biopolymer.
  • the dye can be added at several stages during the biopolymer preparation process, i.e. before, during or after the evaporation step. If the dye is however thermally unstable, it is preferably added to the biopolymer after the heating step, during the cooling step or during the evaporation process.
  • Another preferred method involves the agglomeration of particles of biopolymer that have been prepared by glueing them together using a dye solution as binder.
  • Particles comprising the biopolymer material with the associated dye can also be used as coating for a core material, e.g. with the purpose to mask the colour of the core material.
  • Other methods of preparing the dispersed particle are rolling the carrier material in a bed containing the dye material, or spraying the dye material on the carrier material.
  • Bleach, builder, clay, abrasive and enzyme can also be used as carrier material and are described hereunder.
  • the level of carrier material is at least 50% by weight of the dispersed particle, more preferably 60% by weight of the dispersed particle, most preferably at least 70% by weight of the dispersed particle.
  • the level of the carrier material is at most 99.9999% by weight of the dispersed particle, more preferably at most 99.999% by weight of the dispersed particle, most preferably 99.99% by weight of the dispersed particle.
  • Non-aqueous liquid cleaning compositions according to the invention comprise a non-aqueous base, i.e. the composition without the carrier-dye material.
  • This base comprises the non-aqueous liquid phase and may comprise a solid phase additional to the dispersed particles of carrier and dye material.
  • the non-aqueous liquid phase may comprise as liquid material surfactant material, solvent material, non-surfactant material, liquid bleach precursors, deflocculant material other liquid material and mixtures thereof.
  • the non-aqueous liquid phase is present in levels of from 10% to 90%, more preferably from 20% to 80% and most preferably from 30% to 65% by weight of the non-aqueous base.
  • This base may optionally comprise a solid phase additional to the dispersed particles of carrier and dye material.
  • the solid phase may preferably be from 10% to 90%, more preferably from 20% to 80% and most preferably from 30% to 65% by weight of the non-aqueous base.
  • Such solid dispersed phases may include e.g. one or more components selected from bleach materials, solid bleach activators, builders, abrasives, enzymes, solid surfactant material, minor ingredients such as fluorescers, other solid materials and mixtures thereof.
  • the particle size of the solid phase in terms of D(3,2) will be less than 100 ⁇ m, preferably not more than 30 ⁇ m, more preferably up to 10 ⁇ m and more than 0.1 ⁇ m, preferably from 1 ⁇ m and, most preferably, from 2.5 ⁇ m.
  • references to the D(3,2) average particle diameter refer to the D(3,2) particle size, which is an average surface weighted, volume/weight mean diameter determined as described by M Alderliesten, Anal., Proc. Vol. 21, May 1984, 167-172.
  • the particle size can for example, and preferably, be determined using a Malvern Mastersizer.
  • the base has a white colour.
  • the L, A and/or B values of the non-aqueous liquid base are compared with the values of the dispersed particles comprising carrier and dye material whereafter the difference between these values is determined (delta value). It is noted that to increase the delta value, the colour of the non-aqueous liquid base can also be changed. This can e.g. be done for a white coloured base by adding TiO2 or a similar whitening agent.
  • Nonionic detergent surfactants are well-known in the art. They normally consist of a water-solubilising polyalkoxylene or a mono- or di-alkanolamide group in chemical combination with an organic hydrophobic group derived from, for example, alkylphenols in which the alkyl group contains from about 6 to about 12 carbon atoms, dialkylphenols in which each alkyl group contains from 6 to 2 carbon atoms, primary, secondary or tertiary aliphatic alcohols (or alkyl-capped derivatives thereof), preferably having from 8 to 20 carbon atoms, monocarboxylic acids having from 10 to about 24 carbon atoms in the alkyl group and polyoxypropylenes.
  • Fatty acid mono- and dialkanolamides in which the alkyl group of the fatty acid radical contains from 10 to about 20 carbon atoms and the alkyloyl group having from 1 to 3 carbon atoms are also common.
  • polyalkoxylene moiety usually consists of an average of from 2 to 20 groups of ethylene oxide, propylene oxide groups or mixtures thereof.
  • the latter class includes those described in European Patent Specification EP-A-225 654, especially for use as all or part of the liquid phase.
  • ethoxylated nonionics which are condensation products of fatty alcohols with from 9 to 15 carbon atoms condensed with 3 to 7 moles of ethylene oxide.
  • condensation products of C11-13 alcohols with 3 or 7 moles of ethylene oxide may be used as the sole nonionic surfactant or in combination with those described in EP-A-225 654.
  • alkyl saccharides polyglycosides/oligosaccharides
  • suitable nonionics include the alkyl saccharides (polyglycosides/oligosaccharides) and, in particular those described in the following patent specifications, US 3 640 998; US 3 346 558; US 4 223 129; EP-A92 355; EP-A-99 183; EP-A-70 074; EP-A-70 075; EP-A-70 075; EP-A-70 076; EP-A-70 077; EP-A-75 994; EP-A-75 995 and EP-A-75 996.
  • alkyl saccharides polyglycosides/oligosaccharides
  • nonionic detergent surfactants may also be used.
  • Mixtures of nonionic detergent surfactants with other detergent surfactants such as anionic, cationic or ampholytic surfactants and soaps may also be used.
  • the level of nonionic surfactant is from 10 to 90% by weight of the composition, more preferably from 20 to 70% by weight of the composition and, most preferably, from 35 to 50% by weight of the composition.
  • nonionic surfactants are quite effective at removing oily and greasy stains
  • particulate soils such as clay soils may be more effectively removed by anionic surfactants. It may, therefore, be useful to use a combination of different surfactants.
  • Typical blends of surfactants include a nonionic and/or non-alkoxylated anionic and/or alkoxylated anionic surfactant.
  • Cationic, zwitterionic and amphoteric surfactants may also be present in minor amounts as desired.
  • the level of liquid precursors is preferably 0 to 20% by weight, more preferably 1 to 25 % by weight and, most preferably 2 to 10% by weight.
  • the level of solvents, other than nonionic surfactants, is preferably from 0 to 20% by weight, most preferably 0 to 15% and most preferably 0 to 10%.
  • any material may be used as a deflocculant provided it fulfils the deflocculation test described in European Patent Specification EP-A-266 199 (Unilever).
  • EP-A-266 199 Unilever
  • the capability of a substance to act as a deflocculant will partly depend on the solids/liquid phase combination. However, especially preferred are acids.
  • Deflocculants are preferably selected from Bronsted acids and Lewis acids. Examples thereof are transition metals, anhydrides, organic acids, inorganic mineral acids and salts, C8-C20 fatty acids and salts, C1-C10 alkanoic acids, substituted anhydrous alkali-metal aluminosilicate, alkyl, alkenyl aryl, aralkyl and aralkenyl sulphonic or carboxylic acids and salts and halogenated derivatives thereof, zwitterionic surfactants, anionic surfactants of the formula R-L-A-Y as defined in EP 266199 and compounds having an acidic P-OH group.
  • deflocculants in the acid form are used.
  • Deflocculant material if included, may be present at levels of from 0 to 15%, preferably at least 0.01 and most preferably at least 1% by weight. For most purposes, the amount of deflocculant material will be from 2 to 12 % by weight, preferably 4 to 10% by weight based on the final composition.
  • Suitable bleaches for inclusion in the detergent compositions of the invention include halogen, particularly chlorine bleaches such as are provided in the form of alkali-metal hypohalites, eg hypochlorites.
  • oxygen bleaches are preferred, for example, in the form of an inorganic persalt, preferably with a bleach precursor, or as a peroxy acid compound.
  • an activator or bleach precursor makes the bleaching more effective at lower temperatures, i.e. in the range from ambient temperature to about 60°C.
  • Such bleach systems are commonly known as low-temperature bleach systems.
  • the inorganic persalt such as sodium perborate, both the monohydrate and the tetrahydrate, acts to release active oxygen in solution, and the activator which is usually an organic compound having one or more reactive acyl residues which causes the formation of peroxy acids; the latter providing for more effective bleaching action at lower temperatures than the peroxybleach compound alone.
  • a commonly used precursor is tetraacetyl ethylene diamine (TAED).
  • the ratio of the peroxybleach compound to the activator is from 20:1 to about 1:1, preferably from about 10:1 to about 1.5:1.
  • the preferred level of the peroxybleach compound in the composition is from 0 to 30, more preferably 2 to 20 and most preferably 4 to 15% by weight.
  • the preferred level of activator is from 0 to 20, more preferably 1 to 10, most preferably 2 to 8% by weight of the composition.
  • Suitable peroxybleach compounds are alkali-metal perborates, both tetrahydrates and monohydrates, alkali metal percarbonates, persilicates and perphosphates, of which sodium perborate and sodium percarbonate are preferred.
  • a further class of bleach activators are hydrophobic peroxy acid bleach precursors such as sodium nonanoyl benzene sulphonate and sodium-3,5,5-trimethyl hexanoyloxy benzene sulphonate.
  • bleach catalysts and, in particular, transition metal catalysts.
  • Such catalyst optionally together with stabilisers, as hereinafter defined, can be used to activate peroxide compounds to make them more suitable for use for bleaching at lower temperatures, ie from 20-60°C.
  • Such catalysts may be incorporated in the form of a particulate product according to the invention.
  • a particularly suitable bleach catalyst usable herein in combination with an oxygen bleach in the form of an inorganic persalt with or without a bleach precursor or as a peroxyacid compound is a dinuclear manganese (III) - or Manganese (IV) complex as described in EP 458397 and EP 458398.
  • Preferred catalysts of this class are those referred to as having the following formulae: 1) [Mn IV 2(m-O)3(Me-TACN)2](PF6)2 2) [Mn IV 2(m-O)3(Me/Me-TACN)2](PF6)2 3) [Mn III 2(m-O)(m-OAc)2(Me-TACN)2](PF6)2 4) [Mn III 2(m-O)(m-OAc)2(Me/Me-TACN)2](PF6)2 Wherein Me-TACN is 1,4,7-trimethyl-1,4,7-triazacyclononane, and Me/Me-TACN is 1,2,4,7-tetramethyl-1,4,7-triazacyclononane.
  • These catalysts may be used in the present invention in an amount corresponding to a Manganese level of from about 0.0001 to about 1.0% by weight, preferably from about 0.0005 to about 0.5% by weight.
  • compositions may also be desirable to include in the compositions a stabiliser for the bleach or bleach system, for example hydroxyethylidene-1,1-diphosphonic acid, ethylene diamine tetramethylene phosphonate and diethylene triamine pentamethylene phosphonate or other appropriate organic phosphonates or salts thereof, such as the Dequest® range of materials.
  • a stabiliser for the bleach or bleach system for example hydroxyethylidene-1,1-diphosphonic acid, ethylene diamine tetramethylene phosphonate and diethylene triamine pentamethylene phosphonate or other appropriate organic phosphonates or salts thereof, such as the Dequest® range of materials.
  • the detergency builders are those materials which counteract the effects of calcium, or other ion, water hardness, either by precipitation or by an ion sequestering effect. They comprise both inorganic and organic builders.
  • the inorganic builders comprise the various phosphate-, carbonate-, silicate-, borate- and aluminosilicates-type materials, particularly the alkali-metal salt forms. Mixtures of these may also be used.
  • Examples of phosphorus-containing builders when present, include the water-soluble salts, especially alkali metal pyrophosphates, orthophosphates, polyphosphates and phosphonates.
  • Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, phosphates and hexametaphosphates.
  • non-phosphorus-containing inorganic builders when present, include water-soluble alkali metal carbonates, bicarbonates, borates, silicates, metasilicates, and crystalline and amorphous aluminosilicates.
  • specific examples include sodium carbonate (with or without calcite seeds), potassium carbonate, sodium and potassium bicarbonates, silicates such as sodium metasilicate and zeolites.
  • organic builders include the alkali metal, ammonium and substituted ammonium, citrates, succinates, malonates, fatty acid sulphonates, carboxymethoxy succinates, ammonium polyacetaes, carboxylates, polycarboxylates, aminopolycarboxylates, polyacetyl carboxylates and polyhydroxysulphonates.
  • Specific examples include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, melitic acid, benzene polycarboxylic acids and citric acid.
  • organic phosphonate type sequestering agents such as those sold by Monsanto under the tradename of the Dequest® range and alkanehydroxy phosphonates.
  • suitable organic builders include the higher molecular weight polymers and co-polymers known to have builder properties, for example appropriate polyacrylic acid, polymaleic acid and polyacrylic/polymaleic acid co-polymers and their salts, such as those sold by BASF under the Sokalan® Trade Mark. Polyacrylates or their derivatives may also be useful for their anti-ashing properties.
  • the level of builder materials is from 5-50% by weight of the composition, more preferably 10-40%, most preferably 15-35%.
  • HM materials hydrophobically modified dispersants
  • a dispersant material is a material, of which the main purpose is to stabilise the composition.
  • Hydrophobically modified dispersant materials are particulate materials, of which the outer surface has chemically been treated to reduce the hydrophilic nature thereof.
  • HM materials have a D(3,2) weight average particle size of from 0.005 to 5 micrometers, more preferred 0.01 to 3 micrometers, most preferred from 0.02 to 0.5 micrometer.
  • the amount of the HM material is preferably from 0.1 to 10 % by weight of the composition, more preferred 0.3 to 5 %, most preferred from 1.0 to 4 %.
  • the number of hydroxy- and/or acid- groups at the surface of the particles is reduced by the hydrophobic modification treatment.
  • Suitable reactions include esterification or etherification of the hydrophilic groups.
  • the hydrophobic modification treatment involves at least 10 % of the hydrophilic groups at the surface of the particle, more preferably from 40 to 95 %, most preferably from 50 to 90 %. Partial hydrophobing is preferred over complete hydrophobic modification.
  • HM silica containing dispersants are used.
  • the hydrophobic modification of the silica particles preferably involves the substitution of the free hydroxy-groups at the outer surface of the silica particles by a short alkyl or silyl group. More preferably the surface hydroxy-groups are substituted by methyl groups.
  • Preferred suspended metal oxides have a bulk density of 200 to 1,000 g/l, more preferred 250 to 800 g/l, especially preferably 300 to 700 g/l, most preferably from 400 to 650 g/l.
  • the metal oxide is selected from calcium oxide, magnesium oxide, silicon dioxide and aluminium oxide, most preferably magnesium oxide is used.
  • the weight average particle size of the metal oxide is preferably from 0.1 to 200 micrometers, more preferably from 0.5 to 100 micrometers, most preferably from 2 to 70 micrometers.
  • the level of metal oxide is preferably from 0.1 to 7 % by weight of the composition, more preferably from 0.5 to 5 %, most preferably from 1 to 4 %.
  • Appropriate clays may also be incorporated to fulfil this purpose and/or for fabric softening.
  • ingredients comprise those remaining ingredients which may be used in liquid cleaning products, such as fabric conditioning agents, abrasive material, enzymes, enzyme stabilising agents, fluorescer, perfumes (including deoperfumes), micro-biocides, soil-suspending agents (anti-redeposition agent), corrosion inhibitors, and lather depressants.
  • fabric softening materials such as fabric softening clays, quaternary ammonium salts, imidazolinium salts, fatty amines and cellulases.
  • Fabric softening clays are usually phyllosilicate clays with a 2:1 layer structure, which definition includes pyprophllite clays, smectite or montmorillonite clays, saponites, vermiculites and micas.
  • the clay is selected from Montomorillonite, Saponite clays and mixtures thereof. More preferred are smectite clays described in detail in US 3,959,155 and US 3936,537. Other suitable clays are disclosed in EP 26,528
  • Abrasive are particularly preferred for incorporation in hard suface cleaners (liuquid abrasive cleaners). These will inevitable be incorporated as particulate solid. They may be those of the kind which are water insoluble, for example calcite. Suitable materials of this kind are disclosed in teh applicatnts' patent specifications EP 50887, EP 80221, EP 140452, EP 214540 and EP 9942, which relate to such abrasives when suspended in aqueous media.
  • the abrasives may also be water soluble, especially in the form of particles of any solid water soluble salt hereinafter described, for example as an inorganic builder.
  • solidum sulphate e.g. solidum sulphate
  • Enzymes which can be used in liquids according to the present invention include proteolytic enzymes (protease), amylolytic enzymes (amylase), lipolytic enzymes (lipases) and cellulolytic enzymes (cellulase).
  • proteolytic enzymes proteolytic enzymes
  • amylolytic enzymes amylolytic enzymes
  • lipolytic enzymes lipases
  • cellulolytic enzymes cellulase
  • Various types of proteolytic enzymes and amylolytic enzymes are known in the art and are commercially available. They may be incorporated as “prills", “marumes” or suspensions.
  • enzymes are added as suspensions in a non-aqueous liquid surfactant.
  • the preferred level of enzyme materials is from 0.01 to 5% by weight of the composition.
  • the total amount of the fluorescent agent or agents used in a detergent composition is generally from 0.02-2% by weight.
  • anti-redepostion agents When it is desired to include anti-redepostion agents in the liquid cleaning products, the amount thereof is normally from about 0.1% to about 5% by weight, preferably from about 0.2% to about 2.5% by weight of the total liquid composition.
  • Preferred anti-redeposition agents include carboxy derivatives of sugars and celluloses, e.g. sodium carboxymethyl cellulose, anionic poly-electrolytes, especially polymeric aliphatic carboxylates, or organic phosphonates.
  • Composition in accordance with the present invention may be used for several detergency purposes, for example the cleaning of surfaces and the washing of fabrics.
  • an aqueous liquor containing 0.1 to 10 %, more preferably 0.2 to 2%, of the non-aqueous detergent composition of the invention is used.
  • the non-aqueous liquid During manufacture of the non-aqueous liquid, it is preferred that all raw materials should be dry and (in the case of hydratable salts) in a low hydration state, e.g. anhydrous phosphate builder, sodium perborate monohydrate and dry calcite abrasive, where these are employed in the composition.
  • a low hydration state e.g. anhydrous phosphate builder, sodium perborate monohydrate and dry calcite abrasive, where these are employed in the composition.
  • the dry, substantially anhydrous solids are blended with the liquid phase in a dry vessel. If deflocculant materials are used, these should preferably -at least partly- be mixed with the liquid phase, prior to the addition of the solids. In order to minimise the rate of sedimentation of the solids, this blend is passed through a grinding mill or a combination of mills, e.g.
  • a colloid mill a corundum disc mill, a horizontal or vertical agitated ball mill.
  • a preferred combination of such mills is a colloid mill followed by a horizontal ball mill since these can be operated under the conditions required to provide a narrow size distribution in the final product.
  • particulate material already having the desired particle size need not be subjected to this procedure and if desired, can be incorporated during a later stage of processing.
  • the particles comprising carrier material and dye material associated thereto, according to the invention can be prepared separately, as discussed above, whereafter they are dispersed in the non-aqueous phase of the non-aqueous cleaning product, e.g. by mixing using high shear or using a mill.
  • the D(3,2) particle size is of from 0.1 ⁇ m to 2000 ⁇ m in the non-aqueous phase.
  • a non-aqueous liquid was prepared by adding the following ingredients in the order listed.
  • the biopolymer material was starch and it contained 0.35% pigment paste (Dispersed Blue 69-0007 ex BASF); the D(3,2) particle size was 150 ⁇ m; it had a density of 1.3 and was prepared by solubilising starch with water and adding solutions of the bleach catalyst and paste.
  • the dispersed particles of carrier material and dye material had an excellent appearance in the non-aqueous base and the L, A as well as the B values showed a difference of more than 20 units, also after storage for 4 weeks at 37°C.
  • Particles of starch were prepared as in Example 1. The following distribution ws obtained. Particle size distribution: >500 ⁇ m 0 wt% >425 ⁇ m 0.1 wt% >355 ⁇ m 0.2 wt% >300 ⁇ m 0.4 wt% from 90 to 300 ⁇ m 87.6 wt% ⁇ 90 ⁇ m 10.1 wt% ⁇ 53 ⁇ m 1.6 wt%
  • the particles were distributed in a non-aqueous liquid of the following composition: INGREDIENTS % BY WEIGHT Nonionic 1) 21.91 Nonionic 2) 17.94 Solvent material 10.00 LAS acid 6.00 Solid Builder Material 24.00 Polymer 1.50 Hydrophobed silica 3.00 Perborate monohydrate 10.50 Minors 5.15 1) Vista 1012-62 2) Dobanol 25-3
  • the dispersed particles of carrier material and dye material had a good appearance in the non-aqueous base and the L, A as well as the B values showed a difference of more than 20 units.
  • Example 2 Similar results as in Example 2 were obtained with the starch particles with the following particle size distribution in a non-aqueous liquid with the same composition: >500 ⁇ m 0 wt% >425 ⁇ m 0 wt% >355 ⁇ m 0 wt% >300 ⁇ m 0.1 wt% from 90 to 300 ⁇ m 75.0 wt% ⁇ 90 ⁇ m 22.9 wt% ⁇ 53 ⁇ m 2.0 wt%
  • Example 2 Similar results as in Example 2 were obtained with the starch particles with the following particle size distribution in a non-aqueous liquid with the same composition: >500 ⁇ m 0 wt% >425 ⁇ m 0 wt% >355 ⁇ m 0 wt% >300 ⁇ m 0 wt% from 90 to 300 ⁇ m 78.7 wt% ⁇ 90 ⁇ m 19.4 wt% ⁇ 53 ⁇ m 1.9 wt%

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  • Engineering & Computer Science (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
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EP19940201877 1993-07-19 1994-06-30 Produits de nettoyage liquides Revoked EP0635569B1 (fr)

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EP93305720 1993-07-19
EP93305720 1993-07-19
EP19940201877 EP0635569B1 (fr) 1993-07-19 1994-06-30 Produits de nettoyage liquides

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EP0635569A2 true EP0635569A2 (fr) 1995-01-25
EP0635569A3 EP0635569A3 (fr) 1995-10-11
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0754749A1 (fr) * 1995-07-20 1997-01-22 The Procter & Gamble Company Adoucissants textiles contenant des colorants solubles dans l'eau à décoloration réduite
WO1999000477A1 (fr) * 1997-06-27 1999-01-07 The Procter & Gamble Company Compositions detergentes liquides non aqueuses renfermant des mouchetures
EP0897973A1 (fr) * 1997-08-18 1999-02-24 Clariant GmbH Agents de lavage et de nettoyage
WO1999029827A1 (fr) * 1997-12-11 1999-06-17 The Procter & Gamble Company Compositions de detergent liquide non aqueux contenant des composes d'argile d'amine quaternisee ethoxylee
WO2000047708A1 (fr) * 1999-02-10 2000-08-17 The Procter & Gamble Company Solides particulaires faible densite utilises dans les detergents pour lessive
WO2001088074A1 (fr) * 2000-05-15 2001-11-22 Unilever N.V. Composition detergente liquide
WO2008056324A1 (fr) * 2006-11-10 2008-05-15 The Procter & Gamble Company Composition de traitement de tissus à colorant direct pour tissus
WO2010031607A1 (fr) * 2008-09-18 2010-03-25 Henkel Ag & Co. Kgaa Produit de nettoyage contenant un agent de blanchiment

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2393846A1 (fr) * 1977-06-09 1979-01-05 Ici Ltd Composition detergente
GB2169613A (en) * 1984-12-31 1986-07-16 Colgate Palmolive Co Liquid detergent composition comprising liquid nonionic surfactants
GB2194793A (en) * 1987-10-15 1988-03-16 Unilever Plc Mottled liquid detergents
GB2208653A (en) * 1985-08-05 1989-04-12 Colgate Palmolive Co Phosphate free or low phosphate laundry detergent
US4874537A (en) * 1988-09-28 1989-10-17 The Clorox Company Stable liquid nonaqueous detergent compositions
EP0540089A1 (fr) * 1991-11-01 1993-05-05 Unilever N.V. Produits liquides nettoyants
WO1994012611A1 (fr) * 1992-12-03 1994-06-09 Unilever N.V. Produits liquides de nettoyage
WO1994012613A1 (fr) * 1992-12-03 1994-06-09 Unilever Plc Protection d'additifs

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2393846A1 (fr) * 1977-06-09 1979-01-05 Ici Ltd Composition detergente
GB2169613A (en) * 1984-12-31 1986-07-16 Colgate Palmolive Co Liquid detergent composition comprising liquid nonionic surfactants
GB2208653A (en) * 1985-08-05 1989-04-12 Colgate Palmolive Co Phosphate free or low phosphate laundry detergent
GB2194793A (en) * 1987-10-15 1988-03-16 Unilever Plc Mottled liquid detergents
US4874537A (en) * 1988-09-28 1989-10-17 The Clorox Company Stable liquid nonaqueous detergent compositions
EP0540089A1 (fr) * 1991-11-01 1993-05-05 Unilever N.V. Produits liquides nettoyants
WO1994012611A1 (fr) * 1992-12-03 1994-06-09 Unilever N.V. Produits liquides de nettoyage
WO1994012613A1 (fr) * 1992-12-03 1994-06-09 Unilever Plc Protection d'additifs

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0754749A1 (fr) * 1995-07-20 1997-01-22 The Procter & Gamble Company Adoucissants textiles contenant des colorants solubles dans l'eau à décoloration réduite
WO1999000477A1 (fr) * 1997-06-27 1999-01-07 The Procter & Gamble Company Compositions detergentes liquides non aqueuses renfermant des mouchetures
US6281187B1 (en) * 1997-06-27 2001-08-28 The Procter & Gamble Company Non-aqueous, speckle-containing liquid detergent compositions
EP0897973A1 (fr) * 1997-08-18 1999-02-24 Clariant GmbH Agents de lavage et de nettoyage
WO1999029827A1 (fr) * 1997-12-11 1999-06-17 The Procter & Gamble Company Compositions de detergent liquide non aqueux contenant des composes d'argile d'amine quaternisee ethoxylee
US6384008B1 (en) 1997-12-11 2002-05-07 The Procter & Gamble Company Non-aqueous liquid detergent compositions containing ethoxylated quaternized amine clay compounds
WO2000047708A1 (fr) * 1999-02-10 2000-08-17 The Procter & Gamble Company Solides particulaires faible densite utilises dans les detergents pour lessive
WO2001088074A1 (fr) * 2000-05-15 2001-11-22 Unilever N.V. Composition detergente liquide
WO2008056324A1 (fr) * 2006-11-10 2008-05-15 The Procter & Gamble Company Composition de traitement de tissus à colorant direct pour tissus
JP2010509513A (ja) * 2006-11-10 2010-03-25 ザ プロクター アンド ギャンブル カンパニー 布地直接染料を有する布地処理組成物
EP2316915A1 (fr) * 2006-11-10 2011-05-04 The Procter & Gamble Company Composition de traitement de tissus à colorant direct pour tissus
WO2010031607A1 (fr) * 2008-09-18 2010-03-25 Henkel Ag & Co. Kgaa Produit de nettoyage contenant un agent de blanchiment

Also Published As

Publication number Publication date
EP0635569B1 (fr) 2001-04-25
DE69427137T2 (de) 2001-08-16
ES2157950T3 (es) 2001-09-01
DE69427137D1 (de) 2001-05-31
EP0635569A3 (fr) 1995-10-11

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