WO1994001524A1 - Produits liquides de nettoyage - Google Patents

Produits liquides de nettoyage Download PDF

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Publication number
WO1994001524A1
WO1994001524A1 PCT/EP1993/001671 EP9301671W WO9401524A1 WO 1994001524 A1 WO1994001524 A1 WO 1994001524A1 EP 9301671 W EP9301671 W EP 9301671W WO 9401524 A1 WO9401524 A1 WO 9401524A1
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WO
WIPO (PCT)
Prior art keywords
polymer
composition
liquid phase
group
aqueous liquid
Prior art date
Application number
PCT/EP1993/001671
Other languages
English (en)
Inventor
Mark Phillip Houghton
Original Assignee
Unilever N.V.
Unilever Plc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Unilever N.V., Unilever Plc filed Critical Unilever N.V.
Priority to EP93915738A priority Critical patent/EP0649462A1/fr
Priority to JP6502897A priority patent/JPH07508781A/ja
Priority to PL93302678A priority patent/PL302678A1/xx
Priority to AU45614/93A priority patent/AU4561493A/en
Priority to CA002139674A priority patent/CA2139674A1/fr
Priority to BR9306692A priority patent/BR9306692A/pt
Priority to SK21-95A priority patent/SK2195A3/sk
Publication of WO1994001524A1 publication Critical patent/WO1994001524A1/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
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • 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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • 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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776—Heterocyclic compounds, e.g. lactam

Definitions

  • the present invention relates to substantially non-aqueous liquid cleaning products which comprise a non-aqueous liquid phase, optionally with a dispersed particulate solid material.
  • Non-aqueous liquids are those containing little or no water.
  • the non-aqueous liquid phase may comprise a liquid surfactant and/or a liquid non-surfactant suitable for use in a cleaning product.
  • particulate solids are those which have beneficial auxiliary effects in use, for example for fabrics washing, they may comprise detergency builders to counteract water hardness, as well as bleaches.
  • the solids could comprise abrasive particles.
  • EP 413 616 discloses non-aqueous liquids comprising carboxy-containing polymers to provide stability and improved water dispersibility.
  • EP 359 491 and EP 359 492 disclose non-aqueous liquids comprising respectively low and high molecular weight vinylpyrrolidone polymers.
  • EP 28 849 discloses non-aqueous liquids comprising a stabilising polymer that is an at least partially hydrolyzed copolymers of maleic anhydrride with ethylene or vinylmethy1ether.
  • GB 2,228,944 discloses non-aqueous liquids comprising polymeric materials that may comprise acrylamide monomers.
  • Non-pre-published EP 510 762 discloses non-aqueous liquids comprising polymers that may comprise 2-acrylamide-2 methyl propane sulphonic acid as monomer B.
  • Polymers according to the invention have the property that when added to the non-aqueous liquid phase in the absence of the solids, the viscosity of the liquid phase reduces with shear rate and when added to the same liquid phase in the presence of the solid material, still causes a contribution to viscosity reduction for a given change in shear rate which, at least over the shear thinning region (typically less than 400 s- 1 ) , is greater than for the liquid phase in the presence of the solids or polymer alone.
  • a substantially non-aqueous liquid cleaning product composition comprising a substantially non-aqueous liquid phase, the composition further comprising a polymer which (a) when added to the substantially non-aqueous liquid phase in the absence of the solid material causes the viscosity of said liquid phase to reduce with shear rate; and (b) when added to the substantially non-aqueous liquid phase in the presence of the solid material causes the viscosity of the liquid phase to reduce with shear rate but such that the gradient of the viscosity versus shear rate curve is greater than or equal to that in case (a) .
  • any solid may be suspended without sedimentation in a non-aqueous liqiuid phase if a strong enough structure is created in the liquid phase.
  • aqueous liquids can be made to suspend particulate solids, either by addition of a cross-linking thickening polymer, eg. of the "Carbopol" (Trade Mark) type, or else by creating an appropriate liquid crystalline phase using the functional ingredients of the composition themselves.
  • the structure must at least partially break-down or be modified under shear. In other words the visocity must reduce with increased shear rate.
  • the structure consists of multi-bilayer vescicles of surfactant molecules, it is only necessary for the vescicles to deform and "roll-over" each other to achieve this effect.
  • 7 suitable polymer materials are self-associative thickeners That is to say, when incorporated in the composition in an appropriate amount they increase its viscosity, without appreciable absorption onto the solid particles.
  • Such interactions could, for example, be strong due to cross-linking through co-valent bonding or be the result of weaker forces such a hydrogen bonding or van der Waal's interactions.
  • Cross-linking could be the direct result of reaction of functional groups present on pendant side-chains of the polymer molecules and/or the result of incorporation of specific cross-linking agents added for the purpose. Whils such cross-linking agents usually will have lower molecular weights than the molecular weights of the polymer(s) , they can still be relatively high (eg. >1000) .
  • the aforementioned requirement is primarily directed to selection of ingredients in advance, prior to formulation for the first time, of a specific new composition in accordance with the present invention. It i also desirable to have a test which will identify whether composition once prepared is in accordance with the presen invention.
  • the following is a non-limiting example of such a test. That is to say, if a non-aqueous solid-containing composition yields a positive result in such a test, it is a composition according to the present invention, although it is possible that a few compositions according to the present invention, particularly those with high volume fractions of solids (eg. >0.3), may give an equivocal or negative result in this test.
  • a given composition should be diluted with the same, or substantially the same component(s) of its liquid phase and either allowed to sediment over a period of time or else centrifuged gently. If the viscosity of the remnant clear layer decreases (typically more than 10 mPas) with increased shear rate (eg. somewhere in the range 0.01 to 200s- 1 ), and contains at least some of the polymer, then the polymer is a polymer as specified as a component of compositions according to the present invention.
  • Preferred polymers for use as the polymer ingredient of compositions according to the present invention are block co-polymers, that may be randomly ordered, containing at least one group soluble in the non-aqueous liquid phase which group is also capable of self-association with a like group of another polymer molecule when the polymer is dissolved in said liquid phase.
  • Examples of such soluble self-associating groups are amine, amide and C 10 _ 22 alkyl groups. Of these, amines and amides are especially preferred.
  • the polymers also contain at least one other group soluble in the non-aqueous liquid phase, which other group links two or more of the self-associating groups together and is substantially non-absorbent on the solid particles.
  • Typica other groups are homopolymers such as polyethylene oxide, polyvinyl pyrollidone and co-polymers made from commercially available vinyl monomers such as acrylic acid, maleic acid, vinyl pyrrolidone, vinyl alkyl ethoxylates, vinyl alcohol, vinyl alky, lates and vinyl ethoxy alkylates.
  • the mutually associating group(s) will constitute from 0.001% to 20% of the average polymer molecular weight, preferably from 0.01% to 10% and most preferably from 0.02 to 5%.
  • the polymer as a whole will usually be used at 0.1% to 10%, preferably from 0.1% to 5% and most preferably from 0.5% t 2% by weight of the total composition according to the present invention.
  • preferred polymers include those polymer that comprise:
  • More preferred polymers include those of formula (I)
  • y is 0 or else y is from 1 to 15;
  • A is a group which exhibits self-association when the polymer is dissolved in a non-aqueous liquid medium having a dielectric constant of from 1 to 20;
  • B is any monomeric or polymeric group soluble in the non-aqueous liquid phase.
  • y is less than 8, especially from 0 to 3.
  • x is from 20 to 200.
  • Preferred entities for group A include -NH 2 ,-CONR ⁇ -R 2 , wherein R 1 and R 2 are independently selected from hydrogen and alkyl groups have less than 20 carbon atoms, C 10 _ 22 alkyl groups (preferably C 10 _ 18 ) and mixtures thereof. More preferred entities for group A are -NH 2 and -CONR ⁇ -R 2 .
  • R 1 and R 2 are independently selected from hydrogen and C ⁇ -C ⁇ g alkyl, and more preferebly from hydrogen and C 1 -C 6 alkyl.
  • R 1 +R 2 in total contain less than 12 carbon atoms.
  • Preferred entities for group B include -(CH 2 -CH 2 0) n -, especially when n is from 20 to 200, vinylpyrrolidone, polyvinylpyrrollidone (i.e. [vinylpyrrolidone] n , wherein n is from 15 to 300), vinyl acetate, vinyl alcohol, acrylic acid, methacrylic acid, and half esters of maleic anhydride especially when co-polymerised with acrylic acid in a mole ratio of from 1:1 to 0.2:1.
  • the average molecular weight of the polymer material as determined by aqueous gel permeation chromatography using polyacrylate standards is preferably from 1000 to 100,000, more preferably from 2000 to 80,000, and most preferably from 5000 to 50,000.
  • the determination method is based on aqueous phosphate buffer eluant using Toya Soda and Polyme Laboratories aqueous GPC columns with an ultraviolet detector set at 215 nm. For polymers having no chromophore at 215 nm, a refractive index detector may be used.
  • the polymer prefferably be prepared in-situ in one or more or all of the component(s) of the non-aqueous liquid phase to be used as the non-aqueous liquid phase. This can be achieved using methods known in the art, for example as described in F. Billmeyer, Textbook of Polymer Science, Wiley Interscience.
  • the polymer may be prepared in isolation and subsequently pre-dissolved in the non-aqueou liquid phase before the solids are added.
  • Post dosing of separately prepared polymer, after incorporation of some or all of the solids in the non-aqueous liquid phase is also possible, especially if the Composition also contains a deflocculating agent (vide infra) .
  • a deflocculating agent vide infra
  • compositions according to the present invention are liquid cleaning products.
  • liquid cleaning products refer to those product materials which are liquid at 25°C at atmospheric pressure. They may be formulated in a very wide range of specific forms, according to the intended use. They may be formulated as cleaners for hard surfaces (with or without abrasive) or as agents for warewashing (cleaning of dishes, cutlery etc) either by hand or mechanical means, as well as in the form of specialised cleaning products, such as for surgical apparatus or artificial dentures.
  • compositions of the 3 invention are formulated as agents for washing and/or conditioning of fabrics.
  • compositions will contain at least one agent which promotes the cleaning and/or conditioning of the article(s) in question, selected according to the intended application.
  • this agent will be selected from surfactants, enzymes, bleaches, builders, buffers, microbiocides, (for fabrics) fabric softening agents and (in the case of hard surface cleaning) abrasives.
  • surfactants for fabrics
  • bleaches for fabrics
  • buffers for fabrics
  • microbiocides for fabrics
  • fabric softening agents in the case of hard surface cleaning
  • abrasives in many cases, more than one of these agents will be present, as well as other ingredients commonly used in the relevant product form.
  • compositions of the invention are fabric cleaning products they preferably contain a liquid phase containing nonionic surfactants and a solid phase dispersed in the liquid phase, said solid phase comprising one or more of the following ingredients bleaches, bleach activators, builders and solid surfactants.
  • compositions of the invention are intended for other uses, for example for mechanical warewashing, sometimes th liquid phase will comprise a solvent material other than nonionic surfactant such as for example glyceroltriacetate, paraffin, a low molecular weight polyethylene glycol or an ethoxylated polyethylene glycol.
  • th liquid phase will comprise a solvent material other than nonionic surfactant such as for example glyceroltriacetate, paraffin, a low molecular weight polyethylene glycol or an ethoxylated polyethylene glycol.
  • the solid phase of the product will then generally comprise one or more of builders, abrasive materials and solid surfactant materials.
  • surfactants are solids, they will usually be dissolved or dispersed in the liquid phase. Where they are liquids, they will usually constitute all or part of the liquid phase. However, in some cases the surfactants may undergo a phase change in the composition.
  • surfactants for use in the compositions of the invention may be chosen from any of the classes, sub-classes and specific materials described in "Surface Active Agents” Vol. I, by Schwartz & Perry, Interscience 1949 and "Surface Active Agents" Vol.
  • Nonionic detergent surfactants are well-known in the art.
  • They normally consist of a water-solubilizing polyalkoxylene or a mono- or di-alkanolamide group in chemical combination with an organic hydrophobic group derived, for example, from alkylphenols in which the alkyl group contains from about 6 to about 12 carbon atoms, dialkylphenols in which each alkyl group contains from 6 t 12 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.
  • an organic hydrophobic group derived, for example, from alkylphenols in which the alkyl group contains from about 6 to about 12 carbon atoms, dialkylphenols in which each alkyl group contains from 6 t 12 carbon atoms, primary, secondary or tertiary aliphatic alcohols (or alkyl-capped derivatives thereof)
  • 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.
  • 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.
  • the polyalkoxylene moiety preferably consists of an average of from 2 to 20 groups of ethylene oxide or of ethylene oxide and propylene oxide groups.
  • the latter class particularly preferred are those described in the applicants' published European specification EP-A-225,654, especially for use as all or part of the liquid phase.
  • those ethoxylated nonionics which are the condensation products of fatty alcohols with from 9 to 15 carbon atoms condensed with from 3 to 11 moles of ethylene oxide. Examples of these are the condensation products of Cll-13 alcohols with (say) 3 to 7 moles of ethylene oxide. These may be used as the sole nonionic surfactants or in combination with those of the described in the last-mentioned European specification, especially as all or part of the liquid phase.
  • Suitable nonionics comprise the alkyl polysaccharides (polyglycosides/oligosaccharides) such as described in any of specifications US 3,640,998; US 3,346,558; US 4,223,129; EP-A-92,355; EP-A-99,183; EP 70,074, '75, '76, '77; EP 75,994, '95, '96.
  • nonionic detergent surfactants may also be used.
  • detergency nonionics with non-detergency nonionics, for example mixtures of alkoxylated fatty alcohols containing 5-10 EO groups and alkoxylated alcohols containing 2-4 EO groups.
  • nonionic detergent surfactants with other detergent surfactants such as anionic, cationic or ampholytic detergent surfactants and soaps may also be used.
  • the level of nonionic surfactants in the composition is from 1 to 90 % by weight, more preferably 5 to 75 %, most preferably 20 to 60 %.
  • anionic detergent surfactants are alkali metal, ammonium or alkylolamine salts of alkylbenzene sulphonates or primary alkyl sulphates having from 10 to 18 carbon atoms in the alkyl group, alkyl and alkylether sulphates having from 10 to 24 carbon atoms in the alkyl group, the alkylether sulphates having from 1 to 5 ethylene oxide groups, and olefin sulphonates prepared by sulphonation of C10-24 alpha-olefins and subsequent neutralization and hydrolysis of the sulphonation reaction product and all stable free acid forms of such anionic surfactants.
  • the most suitable liquids to choose as the liquid phase are those organic materials having polar molecules.
  • those comprising a relatively lipophilic part and a relatively hydrophilic part, especially a hydrophilic part rich in electron lone pairs, tend to be well suited.
  • liquid surfactants especially polyalkoxylated nonionics, are one preferred class of material for the liquid phase.
  • Non-surfactants which are suitable for use as the liquid phase include those having the preferred molecular forms referred to above although other kinds may be used, especially if combined with those of the former, more preferred types.
  • the non-surfactant solvents can be used alone or with in combination with liquid surfactants.
  • Non-surfactant solvents which have molecular structures which fall into the former, more preferred category include ethers, polyethers, alkylamines and fatty amines, (especially di- and tri-alkyl- and/or fatty-N-substituted amines) , alkyl (or fatty) amides and mono- and di-N-alkyl substituted derivatives thereof, alky (or fatty) carboxylic acid lower alkyl esters, ketones, aldehydes, and glycerides.
  • ethers especially di- and tri-alkyl- and/or fatty-N-substituted amines
  • alkyl (or fatty) amides and mono- and di-N-alkyl substituted derivatives thereof alky (or fatty) carboxylic acid lower alkyl esters, ketones, aldehydes, and glycerides.
  • di-alkyl ethers examples include respectively, di-alkyl ethers, polyethylene glycols, alkyl ketones (such as acetone) and glyceryl trialkylcarboxylates (such as glyceryl tri-acetate, hereinafter referred to as GTA) , glycerol, propylene glycol, and sorbitol.
  • alkyl ketones such as acetone
  • GTA glyceryl trialkylcarboxylates
  • GTA glyceryl tri-acetate
  • the compositions of the invention contain the liquid phase (whether or not comprising liquid surfactant) in an amount of at least 10% by weight of the total composition.
  • the amount of the liquid phase present in the composition may be as high as about 90%, but in most cases the practical amount will lie between 20 and 70% and preferably between 35 and 60% by weight of the composition.
  • compositions of the invention may comprise a solid phase dispersed in the liquid phase.
  • solids is to be construed as referring to materials in the solid phase which are added to the composition and are dispersed therein in solid form, those solids which dissolve in the liquid phase and those in the liquid phase which solidify (undergo a phase change) in the composition, wherein they are then dispersed.
  • the solids content of the product may be within a very wide range, e.g. higher than 5%, for example from 10-90%, usually from 30-80% and preferably from 40-65% by weight of the final composition.
  • the solid phase should be in particulate form and have a D(3,2) weight average particle size of less than 300 microns, preferably less than 200 microns, more preferably less than 100 microns, especially less than 10 microns.
  • the particle size may even be of sub-micron size.
  • references to average particle diameter refer to the D(3,2) particle size, which is a surface, volume mean diameter calculated as described by M. Alderliesten, Anal. Proc. Vol. 21, May, 1984, 167-172.
  • any reference to average or mean particle size or diameter refers to the D(3,2) average unless explicitly stated to the contrary.
  • the proper particle size can be obtained by using materials of the appropriate size or by milling the total product in a suitable milling apparatus.
  • 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 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 0.5 to 3 %.
  • 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/1, more preferred 250 to 800 g/1, especially preferably 300 to 700 g/1, most / preferably from 400 to 650 g/1.
  • the metal oxide is selected from calcium oxide, magnesium oxide 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 %.
  • 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. They may also be sub-divided into the phosphorus-containing and non-phosphorus types, the latter being preferred when environmental considerations are important.
  • 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 inorganic 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 and zeolites.
  • organic builders include the alkali metal, ammonium and substituted ammonium, citrates, succinates, malonates, fatty acid sulphonates, carboxymethoxy succinates, ammonium polyacetates, carboxylates, polycarboxylates, a inopolycarboxylates, polyacetyl carboxylates and polyhydroxsulphonates.
  • 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.
  • level of builder materials is from 0-60%, more preferred 5-50, most preferred 10-40% by weight.
  • compositions of the invention also comprise one or more deflocculant materials.
  • 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, C 8 -C 20 fatty acids and salts, ⁇ -C ⁇ 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 and anionic surfactants of the formula R-L-A-Y as defined in EP 266199.
  • the acid form is preferably used.
  • deflocculants include the alkanoic acids such as acetic, propionic and stearic acids and their halogenated counterparts such as trichloracetic and trifluoracetic as well as the alkyl (e.g. methane) sulphonic acids and aralkyl (e.g. paratoluene) sulphonic acids.
  • alkanoic acids such as acetic, propionic and stearic acids and their halogenated counterparts such as trichloracetic and trifluoracetic as well as the alkyl (e.g. methane) sulphonic acids and aralkyl (e.g. paratoluene) sulphonic acids.
  • suitable inorganic mineral acids and their salts are hydrochloric, carbonic, sulphurous, sulphuric and phosphoric acids; potassium monohydrogen sulphate, sodium monohydrogen sulphate, potassium monohydrogen phosphate, potassium dihydrogen phosphate, sodium monohydrogen phosphate, potassium dihydrogen pyrophosphate, tetrasodium monohydrogen triphosphate.
  • organic acids may also be used as deflocculants, for example formic, lactic, amino acetic, benzoic, salicylic, phthalic, nicotinic, ascorbic, ethylenediamine tetraacetic, and a inophosphonic acids, as well as longer chain fatty carboxylates and triglycerides, such as oleic, stearic, lauric acid and the like.
  • Peracids such as percarboxylic and persulphonic acids may also be used.
  • the class of acid deflocculants further extends to the Lewis acids, including the anhydrides of inorganic and organic acids.
  • acetic anhydride maleic anhydride, phthalic anhydride and succinic anhydride, sulphur-trioxide, diphosphorous pentoxide, boron trifluoride, antimony pentachloride.
  • fatty anions are very suitable deflocculants, and a particularly preferred class of deflocculants comprises anionic surfactants.
  • anionics which are salts of alkali or other metals may be used, particularly preferred are the free acid forms of these surfactants (wherein the metal cation is replaced by an H+ cation, i.e. proton) .
  • These anionic surfactants include all those classes, sub-classes and specific forms described in the aforementioned general references on surfactants, viz, Schwartz & Perry, Schwartz Perry and Berch, McCutcheon's, Tensid-Taschenbuch; and the free acid forms of such surfactants. Many anionic surfactants have already been described hereinbefore. In the role of deflocculants, the free acid forms of these are generally preferred.
  • some preferred sub-classes and examples are the C10-C22 fatty acids and di ers thereof, the C8-C18 alkylbenzene sulphonic acids, the C10-C18 alkyl- or alkylether sulphuric acid monoesters, the C12-C18 paraffin sulphonic acids, the fatty acid sulphonic acids, the benzene-, toluene-, xylene- and cumene sulphonic acids and so on.
  • Particularly preferred are the linear C12-C18 alkylbenzene sulphonic acids.
  • zwitterionic-types can also be used as deflocculants. These may be any described in the aforementioned general surfactant references.
  • lecithin lecithin. n- 0
  • the level of the deflocculant material in the composition can be optimised by the means described in the aforementioned EP-A-266 199, but in very many cases is at least 0.01%, usually 0.1% and preferably at least 1% by weight, and may be as high as 15% by weight. For most practical purposes, the amount ranges from 2-12%, preferably from 4-10% by weight, based on the final composition. Surprisingly, however it has been found that for obtaining stability, in compositions of the invention generally the presence of the polymer material reduces the need for high levels of deflocculant material.
  • Bleaches include the halogen, particularly chlorine bleaches such as are provided in the form of alkalimetal hypohalites, e.g. hypochlorites.
  • the oxygen bleaches are preferred, for example in the form of an inorganic persalt, preferably with a bleach precursor, or as a peroxy acid compound.
  • the activator makes the bleaching more effective at lower temperatures, i.e. in the range from ambient temperature to about 60C, so that such bleach systems are commonly known as low-temperature bleach systems and are well-known in the art.
  • the inorganic persalt such as sodium perborate, both the monohydrate and the tetrahydrate, acts to release active oxygen in solution, and the activator is usually an organic compound having one or more reactive acyl residues, which cause the formation of peracids, the latter providin for a more effective bleaching action at lower temperature than the peroxybleach compound alone.
  • the ratio by weight of the peroxybleach compound to the activator is from abou 20:1 to about 2:1, preferably from about 10:1 to about 3.5:1. Whilst the amount of the bleach system, i.e. peroxybleach compound and activator, may be varied between about 5% and about 35% by weight of the total liquid, it i preferred to use from about 6% to about 30% of the ingredients forming the bleach system. Thus, the preferred level of the peroxybleach compound in the composition is between about 5.5% and about 27% by weight, while the preferred level of the activator is between about 0.5% and about 14%, most preferably between about 1% and about 7% by weight.
  • Suitable peroxybleach compounds are alkalimetal perborates, both tetrahydrates and monohydrates, alkali metal percarbonates, persilicates and perphosphates, of which sodium perborate is preferred.
  • a stabiliser for the bleach or bleach system for example ethylene diamine tetramethylene phosphonate and diethylene triamine pentamethylene phosphonate or other appropriate organic phosphonate or salt thereof, such as the Dequest range hereinbefore described.
  • These stabilisers can be used in acid or salt form, such as the calcium, magnesium, zinc or aluminium salt form.
  • the stabiliser may be present at a level of up to about 1% by weight, preferably between about 0.1% and about 0.5% by weight.
  • liquid bleach precursors such as glycerol triacetate and ethylidene heptanoate acetate, isopropenyl acetate and the like
  • liquid bleach precursors such as glycerol triacetate and ethylidene heptanoate acetate, isopropenyl acetate and the like
  • solid bleach precursors such as N, N, N 1 , N 1 -tetraacetyl ethylene diamine (TAED) may also be used.
  • ingredients comprise those remaining ingredients which may be used in liquid cleaning products, such as ⁇ 2 fabric conditioning agents, enzymes, perfumes (including deoperfumes) , micro-biocides, colouring agents, fluorescer ⁇ , soil-suspending agents (anti-redeposition agents) , corrosion inhibitors, enzyme stabilising agents, and lather depressants.
  • fabric conditioning agents which may be used, either in fabric washing liquids or in rinse conditioners, are fabric softening materials such as fabric softening clays, quaternary ammonium salts, imidazolinium salts, fatty amines and cellulases.
  • Enzymes which can be used in liquids according to the present invention include proteolytic enzymes, amylolytic enzymes and lipolytic enzymes (lipases) .
  • proteolytic enzymes amylolytic enzymes and lipolytic enzymes (lipases) .
  • lipolytic enzymes lipolytic enzymes
  • 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.
  • the fluorescent agents which can be used in the liquid cleaning products according to the invention are well known and many such fluorescent agents are available commercially. Usually, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts.
  • the total amount of the fluorescent agent or agents used in a detergent composition is generally from 0.02-2% by weight.
  • anti-redeposition agents When it is desired to include anti-redeposition 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 (SCMC) , anionic poly-electrolytes, especially polymeric aliphatic carboxylates, or organic phosphonates.
  • compositions are substantially non-aqueous, i.e. they contain little or no free water, preferably no more than 5%, preferably less than 3%, especially less than 1% by weight of the total composition. It has been found that the higher the water content, the more likely it is for the viscosity to be too high, or even for setting to occur.
  • 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.
  • 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.
  • 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, to achieve a particle size of 0.1 to 100 microns, preferably 0.5 to 50 microns, ideally 1 to 10 microns.
  • a grinding mill or a combination of mills e.g. a colloid mill, a corundum disc mill, a horizontal or vertical agitated ball mill, to achieve a particle size of 0.1 to 100 microns, preferably 0.5 to 50 microns, ideally 1 to 10 microns.
  • compositions which have a Bingham yield stress of 5 Pa. or more may be formulated with large particulate solids, for example speckles or balls included for endowing the composition with aesthetic appeal, or large functional solids such as abrasives if it is desired to formulate a liquid abrasive cleaner.
  • the aforementioned value of 5 Pa. as Bingham yield stress refers to that determined in the shear rate range of from 0.1 to 400 ⁇ - 1 at 25C after equilibration for one minute.
  • a preferred combination of such mills for achieving a particle size of 0.1 to 100 microns 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.
  • A NH 2
  • B ethylene oxide Ratio 2:1
  • Mw 8000 8 days
  • A -NH 2
  • A -NH 2
  • B ethylene oxide
  • Marlipal 013 materials are ethoxylated isotridecanol.
  • 013/30 contains 30% ethylene oxide and 013/60 60% ethylene oxide Ex Hoechst

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

Abstract

Composition d'un produit liquide sensiblement non aqueux de nettoyage. Elle comporte une phase liquide sensiblement non aqueuse ainsi qu'un certain type de polymère. La viscosité de la composition entière diminue en fonction de la vitesse de cisaillement. La composition équivalente exempte de matières solides présente également cette caractéristique, mais à un degré inférieur ou égal.
PCT/EP1993/001671 1992-07-08 1993-06-29 Produits liquides de nettoyage WO1994001524A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
EP93915738A EP0649462A1 (fr) 1992-07-08 1993-06-29 Produits liquides de nettoyage
JP6502897A JPH07508781A (ja) 1992-07-08 1993-06-29 液体洗浄製品
PL93302678A PL302678A1 (en) 1992-07-08 1993-06-29 Liquid cleaning agents
AU45614/93A AU4561493A (en) 1992-07-08 1993-06-29 Liquid cleaning products
CA002139674A CA2139674A1 (fr) 1992-07-08 1993-06-29 Produits de nettoyage liquides
BR9306692A BR9306692A (pt) 1992-07-08 1993-06-29 Composição de produto de limpeza líquido substancialmente não aquosa
SK21-95A SK2195A3 (en) 1992-07-08 1993-06-29 Liquid cleaning product

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP92202079.7 1992-07-08
EP92202079 1992-07-08

Publications (1)

Publication Number Publication Date
WO1994001524A1 true WO1994001524A1 (fr) 1994-01-20

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Country Status (11)

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EP (1) EP0649462A1 (fr)
JP (1) JPH07508781A (fr)
AU (1) AU4561493A (fr)
BR (1) BR9306692A (fr)
CA (1) CA2139674A1 (fr)
CZ (1) CZ2895A3 (fr)
HU (1) HUT70591A (fr)
PL (1) PL302678A1 (fr)
SK (1) SK2195A3 (fr)
WO (1) WO1994001524A1 (fr)
ZA (1) ZA934916B (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996005284A1 (fr) * 1994-08-16 1996-02-22 Henkel Kommanditgesellschaft Auf Aktien Produit liquide de lavage ou de nettoyage a pouvoir blanchissant
WO1996018716A1 (fr) * 1994-12-13 1996-06-20 Unilever N.V. Composition detergente
WO1997000936A1 (fr) * 1995-06-20 1997-01-09 The Procter & Gamble Company Compositions detergentes non aqueuses comprenant des polymeres capables d'enlever les salissures argileuses
US6699831B2 (en) 2000-06-07 2004-03-02 Kao Corporation Liquid detergent composition comprising aluminosilicate or crystalline silicate

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1256621B1 (fr) 2001-05-08 2011-07-13 Kao Corporation Composition de détergent liquide

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0028849A1 (fr) * 1979-11-09 1981-05-20 Unilever N.V. Composition détergente liquide non aqueuse contenant un adjuvant actif et procédé pour sa préparation
EP0359491A2 (fr) * 1988-09-12 1990-03-21 Unilever Plc Compositions liquides de nettoyage
GB2228944A (en) * 1989-03-08 1990-09-12 Unilever Plc Non-aqueous liquid cleaning composition
EP0413616A1 (fr) * 1989-08-18 1991-02-20 Colgate-Palmolive Company Composition détergente non-ionique non-aqueuse pour lavage intense
EP0510762A2 (fr) * 1991-04-23 1992-10-28 Unilever N.V. Produits détergents liquides

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0028849A1 (fr) * 1979-11-09 1981-05-20 Unilever N.V. Composition détergente liquide non aqueuse contenant un adjuvant actif et procédé pour sa préparation
EP0359491A2 (fr) * 1988-09-12 1990-03-21 Unilever Plc Compositions liquides de nettoyage
GB2228944A (en) * 1989-03-08 1990-09-12 Unilever Plc Non-aqueous liquid cleaning composition
EP0413616A1 (fr) * 1989-08-18 1991-02-20 Colgate-Palmolive Company Composition détergente non-ionique non-aqueuse pour lavage intense
EP0510762A2 (fr) * 1991-04-23 1992-10-28 Unilever N.V. Produits détergents liquides

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996005284A1 (fr) * 1994-08-16 1996-02-22 Henkel Kommanditgesellschaft Auf Aktien Produit liquide de lavage ou de nettoyage a pouvoir blanchissant
US5880083A (en) * 1994-08-16 1999-03-09 Henkel Kommanditgesellschaft Auf Aktien Liquid bleach-containing formulation for washing or cleaning
WO1996018716A1 (fr) * 1994-12-13 1996-06-20 Unilever N.V. Composition detergente
WO1997000936A1 (fr) * 1995-06-20 1997-01-09 The Procter & Gamble Company Compositions detergentes non aqueuses comprenant des polymeres capables d'enlever les salissures argileuses
US6699831B2 (en) 2000-06-07 2004-03-02 Kao Corporation Liquid detergent composition comprising aluminosilicate or crystalline silicate

Also Published As

Publication number Publication date
BR9306692A (pt) 1998-12-08
AU4561493A (en) 1994-01-31
HUT70591A (en) 1995-10-30
CZ2895A3 (en) 1995-08-16
PL302678A1 (en) 1994-08-22
JPH07508781A (ja) 1995-09-28
CA2139674A1 (fr) 1994-01-20
ZA934916B (en) 1995-01-09
EP0649462A1 (fr) 1995-04-26
HU9500037D0 (en) 1995-03-28
SK2195A3 (en) 1995-07-11

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