EP0225654A1 - Non-aqueous built liquid detergent composition - Google Patents

Non-aqueous built liquid detergent composition Download PDF

Info

Publication number
EP0225654A1
EP0225654A1 EP86201867A EP86201867A EP0225654A1 EP 0225654 A1 EP0225654 A1 EP 0225654A1 EP 86201867 A EP86201867 A EP 86201867A EP 86201867 A EP86201867 A EP 86201867A EP 0225654 A1 EP0225654 A1 EP 0225654A1
Authority
EP
European Patent Office
Prior art keywords
nonionic detergent
composition
ethylene oxide
aqueous
liquid detergent
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.)
Granted
Application number
EP86201867A
Other languages
German (de)
French (fr)
Other versions
EP0225654B1 (en
Inventor
Willem Michael Maria Möhlmann
Johannes Henricus Maria Rek
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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 PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0225654A1 publication Critical patent/EP0225654A1/en
Application granted granted Critical
Publication of EP0225654B1 publication Critical patent/EP0225654B1/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions

Definitions

  • the present invention relates to non-aqueous built liquid or pasty detergent compositions comprising a non-aqueous liquid medium which contains a nonionic detergent surfactant, and a builder suspended or dispersed in said liquid medium.
  • Non-aqueous built liquid detergent compositions of this type have already been proposed in the prior art, vide our British Patent Specifications l 205 7ll, l 270 040, and l 292 352. These prior proposals involve the use of a suspending agent for the builders. More recently, a non-aqueous built liquid detergent composition comprising a liquid nonionic detergent surfactant and being free from dispersants for the solids has been proposed in European Patent Application 0030096.
  • nonionic detergent surfactant can be of any type within the class of alkylene oxide condensation products with alcohols, alkylphenols, amides and so on.
  • non-aqueous built liquid detergent compositions on the basis of nonionic detergent surfactants do not always dissolve in an aqueous wash liquor sufficiently quickly, and although the rate of dissolution can be improved by inclusion of high levels of non-aqueous solvents, that may jeopardize the storage stability of the non-aqueous liquid composition and may undesirably increase the costs of such compositions.
  • the specific class of nonionic detergent surfactants of the invention consists of an organic hydrophobic group, such as C8-C18 alkylphenols, C8-C18 primary or secondary, linear or branched-chain alcohols, C8-­C18 fatty acid amides and so on, which has been condensed first with ethylene oxide (EO) and subsequently with propylene oxide (PO).
  • EO ethylene oxide
  • PO propylene oxide
  • the molar ratio of PO to EO in the condensation products is critical; too low a PO/EO ratio does not offer an advantage, and too high a PO/EO ratio influences the solubility negatively.
  • the molar ratio of PO to EO in the nonionic detergent surfactants of the invention should lie within the range of l:l7 to 2:l, preferably of 7:4 to l:2.
  • nonionic detergent surfactants of the invention should furthermore not form high viscosity liquid crystalline phases in the presence of water, and should have cloud points of above 5°C.
  • Suitable examples of nonionic detergent surfactants of the invention are C13-C15 primary alcohol, condensed with 7 moles of ethylene oxide and 4 moles of propylene oxide and C13-C15 alcohol, condensed with 4.9 moles of ethylene oxide and 2.7 moles of propylene oxide.
  • the nonionic detergent surfactants of the invention are low-foaming.
  • nonionic detergent surfactants of the invention with other detergent surfactants, such as anionic, cationic or ampholytic detergent surfactants, and soaps may also be used. If such mixtures are used, the mixture must be water-free and liquid at room temperature.
  • anionic detergent surfactants are alkali metal, ammonium or alkylolamine salts of alkylbenzene sulphonates having from l0 to l8 carbon atoms in the alkyl group, alkyl and alkylether sulphates having from l0 to 24 carbon atoms in the alkyl group and from l to 5 ethylene oxide groups, olefin sulphonates prepared by sulphonation of C10-­C24-olefins and subsequent neutralisation and hydrolysis of the sulphonation reaction product.
  • cationic detergent surfactants are aliphatic or aromatic higher alkyl di(lower alkyl) ammonium halides and examples of soaps are the alkali metal salts of C12-C24 fatty acids.
  • the composition of the invention contains the nonionic detergent surfactant in an amount of at least l0% by weight of the total composition.
  • the amount of nonionic detergent surfactant 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 20 and 50% by weight of the composition.
  • the builder which is used according to the present invention may be either a preferably anhydrous inorganic builder or an organic builder.
  • Suitable organic builders are the alkali metal salts of aminopolycarboxylic acids, such as ethylene diaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), diethylenetriamine pentacetic acid (DEPTA), hydroxythylaminodiacetic acid and the like; alkali metal salts of ethane hydroxyphosphonic acids, aminophosphonic acids and the like; polyelectrolytes such as alkali metal salts of hydrolysed copolymers of ethylene with maleic anhydride and alkali metal polyacrylates; alkali metal alkenylsuccinates and the like, and sodium phytate.
  • aminopolycarboxylic acids such as ethylene diaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), diethylenetriamine pentacetic acid (DEPTA
  • Suitable inorganic builder are zeolites, the alkaline ortho-, poly-, pyro- and metaphosphates, silicates, borates, carbonates and the like. Also mixtures of organic and inorganic builders may be used. The organic builders need not be anhydrous, but can be used in the hydrated form in which they are normally sold, for example NTA lH20, EDTA 2H20 and so on.
  • the amount of builder present in the composition may be from l to 70% by weight of the composition. For most commercial purposes the amount of builder is from about l0% to about 60% by weight of the composition.
  • the builder should have a particle size of less than 300 ⁇ , preferably less than 200 ⁇ .
  • the weight ratio of the nonionic detergent surfactant to builder should generally lie within the range of l0:l and l:4, and for most commercial purposes within the range of 4:l to l:4, the preferred ratio being about l:2.
  • the liquid detergent composition of the invention is substantially anhydrous, by which is to be understood that the final composition should contain not more than 5%, and preferably less than 2% by weight of water; this does not include any water of hydration.
  • the stability behaviour of the products may be further improved by the incorporation of a few per cent of an emulsifier or a thixotropic agent, such as lauric diethanolamide, ethoxylated lanolin, sodium dioctyl sulphosuccinate and the like.
  • an emulsifier or a thixotropic agent such as lauric diethanolamide, ethoxylated lanolin, sodium dioctyl sulphosuccinate and the like.
  • the viscosity of the composition will vary, depending upon its constituents. In order to ensure that the composition may be poured satisfactorily, it is preferred that the viscosity should be in the range of from l00 to 3,000 cP, although higher viscosities up to 60,000 cP can be satisfactory. If desired, the viscosity of the composition may be adjusted by the addition of amounts of up to 20% of a thinning agent, for example ethyl alcohol, hexane, heptane, benzene, xylene, toluene, tetrahydrofuran, dimethyl sulphoxide, and the like.
  • a thinning agent for example ethyl alcohol, hexane, heptane, benzene, xylene, toluene, tetrahydrofuran, dimethyl sulphoxide, and the like.
  • the composition may furthermore contain other materials which are considered normal and desirable additives in detergent compositions.
  • bleaching agents such as alkali metal perborates (either anhydrous or in one of their hydrate forms) may be incorporated in an amount of from about 5 to about 30% by weight of the composition.
  • enzymes such as amylases and proteases, lipases, colouring agents, fluorescers, bleaching agent precursors and activators, bleach stabilizers, perfumes, bactericides, soil suspending agents and corrosion-inhibitors.
  • bleach precursors such as tetraacetylethylene diamine are more stable in the non-aqueous detergent compositions of the present invention than in non-­aqueous liquid detergent compositions on the basis of nonionic detergents other than those according to the invention.
  • suspending agents such as highly voluminous metal oxides and metalloid oxides such as silica may also be included in an amount of l-5% by weight.
  • the rates of solution of the composition were measured by adding the non-aqueous liquid detergent at a concentration of6.5 g/l to tapwater of room temperature under constant stirring (l00 rpm) and measuring the conductivity of the resulting mixture. The time at which the conductivity does not change anymore is recorded as the dissolution time.
  • Example l using a C9-C15 primary alcohol mixture having an overall PO/EO molar ratio of l:l.6 (3.5 mol PO and 5.5 mol EO), with a cloud point of 3l°C, and a C9-C15 primary alcohol mixture having an overall PO/EO molar ratio of l:2.5 (2.3 mol PO and 5.7 mol EO), with a cloud point of 39°C, gave the following results:
  • TAED tetraacetylethylenediamine

Abstract

The present invention relates to a non-aqueous built liquid detergent composition on the basis of nonionic detergent surfactants and builders.
By using particular nonionic detergent surfactants, which contain ethylene oxide and propylene oxide in a molar ratio of l:l7 to 2:l (propylene oxide to ethylene oxide) instead of the known ethylene oxide condensation products, the rate of dissolution of the composition in the wash liquor is substantially improved.
Furthermore, a low temperature bleach activator such as tetraacetylethylenediamine is substantially much more stable in compositions containing the particular nonionic detergent surfactant than in compositions on the basis of the well-known ethylene oxide type nonionic detergent surfactants.

Description

  • The present invention relates to non-aqueous built liquid or pasty detergent compositions comprising a non-aqueous liquid medium which contains a nonionic detergent surfactant, and a builder suspended or dispersed in said liquid medium.
  • Non-aqueous built liquid detergent compositions of this type have already been proposed in the prior art, vide our British Patent Specifications l 205 7ll, l 270 040, and l 292 352. These prior proposals involve the use of a suspending agent for the builders. More recently, a non-aqueous built liquid detergent composition comprising a liquid nonionic detergent surfactant and being free from dispersants for the solids has been proposed in European Patent Application 0030096.
  • In all these prior proposals the nonionic detergent surfactant can be of any type within the class of alkylene oxide condensation products with alcohols, alkylphenols, amides and so on.
  • However, non-aqueous built liquid detergent compositions on the basis of nonionic detergent surfactants do not always dissolve in an aqueous wash liquor sufficiently quickly, and although the rate of dissolution can be improved by inclusion of high levels of non-aqueous solvents, that may jeopardize the storage stability of the non-aqueous liquid composition and may undesirably increase the costs of such compositions.
  • It has now been found that by using a specific class of nonionic detergent surfactants the rate of dissolution may be significantly improved in comparison with other nonionic surfactants, thereby obviating to a significant extent the use of non-aqueous solvents.
  • The specific class of nonionic detergent surfactants of the invention consists of an organic hydrophobic group, such as C₈-C₁₈ alkylphenols, C₈-C₁₈ primary or secondary, linear or branched-chain alcohols, C₈-­C₁₈ fatty acid amides and so on, which has been condensed first with ethylene oxide (EO) and subsequently with propylene oxide (PO). The molar ratio of PO to EO in the condensation products is critical; too low a PO/EO ratio does not offer an advantage, and too high a PO/EO ratio influences the solubility negatively. The molar ratio of PO to EO in the nonionic detergent surfactants of the invention should lie within the range of l:l7 to 2:l, preferably of 7:4 to l:2.
  • The nonionic detergent surfactants of the invention should furthermore not form high viscosity liquid crystalline phases in the presence of water, and should have cloud points of above 5°C. Suitable examples of nonionic detergent surfactants of the invention are C₁₃-C₁₅ primary alcohol, condensed with 7 moles of ethylene oxide and 4 moles of propylene oxide and C₁₃-C₁₅ alcohol, condensed with 4.9 moles of ethylene oxide and 2.7 moles of propylene oxide. Preferably, the nonionic detergent surfactants of the invention are low-foaming.
  • Mixtures of nonionic detergent surfactants of the invention with other detergent surfactants, such as anionic, cationic or ampholytic detergent surfactants, and soaps may also be used. If such mixtures are used, the mixture must be water-free and liquid at room temperature.
  • Examples of suitable anionic detergent surfactants are alkali metal, ammonium or alkylolamine salts of alkylbenzene sulphonates having from l0 to l8 carbon atoms in the alkyl group, alkyl and alkylether sulphates having from l0 to 24 carbon atoms in the alkyl group and from l to 5 ethylene oxide groups, olefin sulphonates prepared by sulphonation of C₁₀-­C₂₄-olefins and subsequent neutralisation and hydrolysis of the sulphonation reaction product. Examples of cationic detergent surfactants are aliphatic or aromatic higher alkyl di(lower alkyl) ammonium halides and examples of soaps are the alkali metal salts of C₁₂-C₂₄ fatty acids.
  • In general, the composition of the invention contains the nonionic detergent surfactant in an amount of at least l0% by weight of the total composition. The amount of nonionic detergent surfactant 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 20 and 50% by weight of the composition.
  • The builder which is used according to the present invention may be either a preferably anhydrous inorganic builder or an organic builder. Suitable organic builders are the alkali metal salts of aminopolycarboxylic acids, such as ethylene diaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), diethylenetriamine pentacetic acid (DEPTA), hydroxythylaminodiacetic acid and the like; alkali metal salts of ethane hydroxyphosphonic acids, aminophosphonic acids and the like; polyelectrolytes such as alkali metal salts of hydrolysed copolymers of ethylene with maleic anhydride and alkali metal polyacrylates; alkali metal alkenylsuccinates and the like, and sodium phytate. Suitable inorganic builder are zeolites, the alkaline ortho-, poly-, pyro- and metaphosphates, silicates, borates, carbonates and the like. Also mixtures of organic and inorganic builders may be used. The organic builders need not be anhydrous, but can be used in the hydrated form in which they are normally sold, for example NTA lH₂0, EDTA 2H₂0 and so on.
  • The amount of builder present in the composition may be from l to 70% by weight of the composition. For most commercial purposes the amount of builder is from about l0% to about 60% by weight of the composition. The builder should have a particle size of less than 300µ, preferably less than 200µ.
  • The weight ratio of the nonionic detergent surfactant to builder should generally lie within the range of l0:l and l:4, and for most commercial purposes within the range of 4:l to l:4, the preferred ratio being about l:2.
  • The liquid detergent composition of the invention is substantially anhydrous, by which is to be understood that the final composition should contain not more than 5%, and preferably less than 2% by weight of water; this does not include any water of hydration.
  • The stability behaviour of the products may be further improved by the incorporation of a few per cent of an emulsifier or a thixotropic agent, such as lauric diethanolamide, ethoxylated lanolin, sodium dioctyl sulphosuccinate and the like.
  • The viscosity of the composition will vary, depending upon its constituents. In order to ensure that the composition may be poured satisfactorily, it is preferred that the viscosity should be in the range of from l00 to 3,000 cP, although higher viscosities up to 60,000 cP can be satisfactory. If desired, the viscosity of the composition may be adjusted by the addition of amounts of up to 20% of a thinning agent, for example ethyl alcohol, hexane, heptane, benzene, xylene, toluene, tetrahydrofuran, dimethyl sulphoxide, and the like.
  • The composition may furthermore contain other materials which are considered normal and desirable additives in detergent compositions. For instance, bleaching agents such as alkali metal perborates (either anhydrous or in one of their hydrate forms) may be incorporated in an amount of from about 5 to about 30% by weight of the composition. Without substantially modifying the fundamental characteristics of the compositions of the invention, there can furthermore be incorporated enzymes, such as amylases and proteases, lipases, colouring agents, fluorescers, bleaching agent precursors and activators, bleach stabilizers, perfumes, bactericides, soil suspending agents and corrosion-inhibitors.
  • In this respect, it has surprisingly been found that bleach precursors such as tetraacetylethylene diamine are more stable in the non-aqueous detergent compositions of the present invention than in non-­aqueous liquid detergent compositions on the basis of nonionic detergents other than those according to the invention.
  • Optionally, suspending agents such as highly voluminous metal oxides and metalloid oxides such as silica may also be included in an amount of l-5% by weight.
  • The invention is illustrated by the following Examples in which the percentages are by weight.
  • The rates of solution of the composition were measured by adding the non-aqueous liquid detergent at a concentration of6.5 g/l to tapwater of room temperature under constant stirring (l00 rpm) and measuring the conductivity of the resulting mixture. The time at which the conductivity does not change anymore is recorded as the dissolution time.
    • Example l
  • The following formulations with different nonionic detergent surfactants as specified in Table A were prepared, and their cloud point, liquid crystalline (L.C.) phase formation and dissolution time were measured. The following results were obtained:
    Figure imgb0001
    Figure imgb0002
    • Example 2
  • Repeating Example l, using a C₉-C₁₅ primary alcohol mixture having an overall PO/EO molar ratio of l:l.6 (3.5 mol PO and 5.5 mol EO), with a cloud point of 3l°C, and a C₉-C₁₅ primary alcohol mixture having an overall PO/EO molar ratio of l:2.5 (2.3 mol PO and 5.7 mol EO), with a cloud point of 39°C, gave the following results:
    • l) no L.C. formation
    • 2) dissolution time: total dissolution in 2, respectively 3 minutes.
    Example 3
  • The following non-aqueous built liquid detergent was prepared:
    Figure imgb0003
  • The following nonionic detergent surfactants were used.
    • A. C₁₃-C₁₅ primary alcohol, condensed with 4.9 moles EO and 2.7 moles PO,
    • B. C₉-C₁₁ primary alcohol, condensed with 4 moles EO and l.5 moles PO,
    • C. C₉-C₁₁ primary alcohol, condensed with 5.5 moles EO and 0.5 moles PO, and
    • D. C₉-C₁₁ primary alcohol, condensed with 6 moles of EO.
  • The stability of tetraacetylethylenediamine (TAED) in each of these formulations was assessed by iodometric titration of the TAED which was left in the compositions after storage for l2 weeks at 37°C.
  • The following results were obtained:
    % TAED left in the non-aqueous liquid detergent after storage for l2 weeks at 37°C:
    with A: 79%
    with B: 69%
    with C: 45%
    with D: 30%

Claims (4)

1. A non-aqueous, built liquid detergent composition comprising a nonionic detergent surfactant and a builder, characterised in that the nonionic detergent surfactant consists of an organic hydrophobic group, which has been condensed first with ethylene oxide and subsequently with propylene oxide, whereby the molar ratio of propylene oxide to ethylene oxide in the nonionic detergent surfactant lies within the range of l:l7 to 2:l.
2. A composition according to claim l,
characterised in that the molar ratio lies within the range of 7:4 to l:2.
3. A composition according to claim l or 2,
characterised in that the organic hydrophobic group is a C₈-C₁₈ alkylphenol or a C₈-C₁₈ primary or secondary linear or branched-chain alcohol or a C₈-­C₁₈ fatty acid amide.
4. A composition according to any one of claims l-3, characterised in that it contains an alkali metal perborate and a low temperature bleach activator.
EP86201867A 1985-11-11 1986-10-24 Non-aqueous built liquid detergent composition Expired EP0225654B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8527772 1985-11-11
GB858527772A GB8527772D0 (en) 1985-11-11 1985-11-11 Non-aqueous built liquid detergent composition

Publications (2)

Publication Number Publication Date
EP0225654A1 true EP0225654A1 (en) 1987-06-16
EP0225654B1 EP0225654B1 (en) 1989-07-19

Family

ID=10588049

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86201867A Expired EP0225654B1 (en) 1985-11-11 1986-10-24 Non-aqueous built liquid detergent composition

Country Status (9)

Country Link
EP (1) EP0225654B1 (en)
JP (1) JPS62135599A (en)
AU (1) AU574590B2 (en)
BR (1) BR8605540A (en)
CA (1) CA1289434C (en)
DE (1) DE3664481D1 (en)
ES (1) ES2011249B3 (en)
GB (1) GB8527772D0 (en)
ZA (1) ZA868525B (en)

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0325100A2 (en) * 1988-01-21 1989-07-26 Colgate-Palmolive Company Acetylated sugar ethers as bleach activators and detergency boosters
US4874537A (en) * 1988-09-28 1989-10-17 The Clorox Company Stable liquid nonaqueous detergent compositions
US4919834A (en) * 1988-09-28 1990-04-24 The Clorox Company Package for controlling the stability of a liquid nonaqueous detergent
GB2196347B (en) * 1986-08-28 1991-05-15 Colgate Palmolive Co Liquid laundry bleach booster composition
EP0444858A1 (en) * 1990-02-26 1991-09-04 Unilever Plc Detergent composition
WO1992005235A1 (en) * 1990-09-20 1992-04-02 Henkel Kommanditgesellschaft Auf Aktien Non-ionic liquid surfactant combination with improved cold stability
US5209874A (en) * 1989-04-26 1993-05-11 Shell Oil Company Liquid surface active compositions
US5264147A (en) * 1991-05-17 1993-11-23 Unilever Patent Holdings B.V. Narrow range ethoxylate-based liquid nonionic surfactant blends
US5389284A (en) * 1986-10-30 1995-02-14 Lever Brothers Company, Division Of Conopco, Inc. Liquid cleaning products having improved storage capacity without settling
US5468418A (en) * 1990-02-26 1995-11-21 Lever Brothers Company, Division Of Conopco, Inc. Detergent composition containing mixture of hydratable and non-hydratable salts
US5872092A (en) * 1994-09-26 1999-02-16 The Procter & Gamble Company Nonaqueous bleach-containing liquid detergent compositions
US5916865A (en) * 1996-08-30 1999-06-29 Clariant Gmbh Liquid bleaching agent suspension
WO2001023274A1 (en) 1999-09-30 2001-04-05 The Procter & Gamble Company Detergent package with means to mask amine malodours
DE10011273A1 (en) * 2000-03-08 2001-09-20 Henkel Kgaa Non-aqueous liquid laundry and other detergents containing nonionic surfactant and/or anionic surfactant contain bleach activator in liquid form
WO2011088089A1 (en) 2010-01-12 2011-07-21 The Procter & Gamble Company Intermediates and surfactants useful in household cleaning and personal care compositions, and methods of making the same
WO2011120799A1 (en) 2010-04-01 2011-10-06 Unilever Plc Structuring detergent liquids with hydrogenated castor oil
WO2011120772A1 (en) 2010-03-31 2011-10-06 Unilever Plc Microcapsule incorporation in structured liquid detergents
WO2012112828A1 (en) 2011-02-17 2012-08-23 The Procter & Gamble Company Bio-based linear alkylphenyl sulfonates
EP2495300A1 (en) 2011-03-04 2012-09-05 Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House Structuring detergent liquids with hydrogenated castor oil
WO2012138423A1 (en) 2011-02-17 2012-10-11 The Procter & Gamble Company Compositions comprising mixtures of c10-c13 alkylphenyl sulfonates
WO2012146464A1 (en) 2011-04-25 2012-11-01 Unilever Nv Hard surface treatment composition
WO2013113541A1 (en) 2012-01-31 2013-08-08 Unilever N.V. A composition and method for treating substrates
WO2015101454A1 (en) 2013-12-30 2015-07-09 Unilever N.V. Detergent composition
WO2016184643A1 (en) 2015-05-20 2016-11-24 Unilever N.V. A composition and method for treating substrates
WO2023213524A1 (en) 2022-05-06 2023-11-09 Unilever Ip Holdings B.V. Detergent composition

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1551810A (en) * 1967-01-27 1968-12-27
GB1172931A (en) * 1966-02-14 1969-12-03 Marles Kuhlmann Wyandotte Improvements in or relating to Nonionic Condensation Products
DE2810703A1 (en) * 1977-03-16 1978-09-21 Mitsubishi Petrochemical Co NONIOGENIC SURFACTANT
EP0014980A1 (en) * 1979-02-22 1980-09-03 Henkel Kommanditgesellschaft auf Aktien Mechanically applicable combined dish washing and rinsing agent and process for simultaneously cleaning and rinsing dishes in dishwashing machines
EP0030096A1 (en) * 1979-12-04 1981-06-10 Imperial Chemical Industries Plc Detergent composition

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8308263D0 (en) * 1983-03-25 1983-05-05 Unilever Plc Aqueous liquid detergent composition
US4767558A (en) * 1985-08-05 1988-08-30 Colgate-Palmolive Company Low phosphate or phosphate free nonaqueous liquid nonionic laundry detergent composition and method of use

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1172931A (en) * 1966-02-14 1969-12-03 Marles Kuhlmann Wyandotte Improvements in or relating to Nonionic Condensation Products
FR1551810A (en) * 1967-01-27 1968-12-27
DE2810703A1 (en) * 1977-03-16 1978-09-21 Mitsubishi Petrochemical Co NONIOGENIC SURFACTANT
EP0014980A1 (en) * 1979-02-22 1980-09-03 Henkel Kommanditgesellschaft auf Aktien Mechanically applicable combined dish washing and rinsing agent and process for simultaneously cleaning and rinsing dishes in dishwashing machines
EP0030096A1 (en) * 1979-12-04 1981-06-10 Imperial Chemical Industries Plc Detergent composition

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2196347B (en) * 1986-08-28 1991-05-15 Colgate Palmolive Co Liquid laundry bleach booster composition
US5389284A (en) * 1986-10-30 1995-02-14 Lever Brothers Company, Division Of Conopco, Inc. Liquid cleaning products having improved storage capacity without settling
EP0325100A3 (en) * 1988-01-21 1991-04-24 Colgate-Palmolive Company Acetylated sugar ethers as bleach activators and detergency boosters
EP0325100A2 (en) * 1988-01-21 1989-07-26 Colgate-Palmolive Company Acetylated sugar ethers as bleach activators and detergency boosters
US4874537A (en) * 1988-09-28 1989-10-17 The Clorox Company Stable liquid nonaqueous detergent compositions
US4919834A (en) * 1988-09-28 1990-04-24 The Clorox Company Package for controlling the stability of a liquid nonaqueous detergent
US5209874A (en) * 1989-04-26 1993-05-11 Shell Oil Company Liquid surface active compositions
WO1991013139A1 (en) * 1990-02-26 1991-09-05 Unilever N.V. Detergent composition
EP0444858A1 (en) * 1990-02-26 1991-09-04 Unilever Plc Detergent composition
US5468418A (en) * 1990-02-26 1995-11-21 Lever Brothers Company, Division Of Conopco, Inc. Detergent composition containing mixture of hydratable and non-hydratable salts
WO1992005235A1 (en) * 1990-09-20 1992-04-02 Henkel Kommanditgesellschaft Auf Aktien Non-ionic liquid surfactant combination with improved cold stability
US5364552A (en) * 1990-09-20 1994-11-15 Henkel Kommanditgesellschaft Auf Aktien Liquid nonionic surfactant combination having improved low-temperaturestability
US5264147A (en) * 1991-05-17 1993-11-23 Unilever Patent Holdings B.V. Narrow range ethoxylate-based liquid nonionic surfactant blends
US5872092A (en) * 1994-09-26 1999-02-16 The Procter & Gamble Company Nonaqueous bleach-containing liquid detergent compositions
US5916865A (en) * 1996-08-30 1999-06-29 Clariant Gmbh Liquid bleaching agent suspension
WO2001023274A1 (en) 1999-09-30 2001-04-05 The Procter & Gamble Company Detergent package with means to mask amine malodours
DE10011273A1 (en) * 2000-03-08 2001-09-20 Henkel Kgaa Non-aqueous liquid laundry and other detergents containing nonionic surfactant and/or anionic surfactant contain bleach activator in liquid form
US8933131B2 (en) 2010-01-12 2015-01-13 The Procter & Gamble Company Intermediates and surfactants useful in household cleaning and personal care compositions, and methods of making the same
WO2011088089A1 (en) 2010-01-12 2011-07-21 The Procter & Gamble Company Intermediates and surfactants useful in household cleaning and personal care compositions, and methods of making the same
WO2011120772A1 (en) 2010-03-31 2011-10-06 Unilever Plc Microcapsule incorporation in structured liquid detergents
WO2011120799A1 (en) 2010-04-01 2011-10-06 Unilever Plc Structuring detergent liquids with hydrogenated castor oil
WO2012112828A1 (en) 2011-02-17 2012-08-23 The Procter & Gamble Company Bio-based linear alkylphenyl sulfonates
WO2012138423A1 (en) 2011-02-17 2012-10-11 The Procter & Gamble Company Compositions comprising mixtures of c10-c13 alkylphenyl sulfonates
US9193937B2 (en) 2011-02-17 2015-11-24 The Procter & Gamble Company Mixtures of C10-C13 alkylphenyl sulfonates
EP2495300A1 (en) 2011-03-04 2012-09-05 Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House Structuring detergent liquids with hydrogenated castor oil
WO2012146464A1 (en) 2011-04-25 2012-11-01 Unilever Nv Hard surface treatment composition
WO2013113541A1 (en) 2012-01-31 2013-08-08 Unilever N.V. A composition and method for treating substrates
WO2015101454A1 (en) 2013-12-30 2015-07-09 Unilever N.V. Detergent composition
WO2016184643A1 (en) 2015-05-20 2016-11-24 Unilever N.V. A composition and method for treating substrates
WO2023213524A1 (en) 2022-05-06 2023-11-09 Unilever Ip Holdings B.V. Detergent composition

Also Published As

Publication number Publication date
BR8605540A (en) 1987-08-11
ES2011249B3 (en) 1990-01-01
EP0225654B1 (en) 1989-07-19
GB8527772D0 (en) 1985-12-18
AU6488886A (en) 1987-05-14
JPS62135599A (en) 1987-06-18
ZA868525B (en) 1988-07-27
CA1289434C (en) 1991-09-24
AU574590B2 (en) 1988-07-07
DE3664481D1 (en) 1989-08-24

Similar Documents

Publication Publication Date Title
EP0225654B1 (en) Non-aqueous built liquid detergent composition
US4316812A (en) Detergent composition
EP0030096B2 (en) Detergent composition
US3630929A (en) Fast dissolving nonaqueous built liquid detergent compositions
EP0385521B1 (en) Liquid detergent products
CA1299052C (en) Nonaqueous liquid automatic dishwashing detergent composition with improved rinse properties and method of use
AU610833B2 (en) Nonaqueous liquid nonbuilt laundry detergent bleach booster composition
EP0038101B1 (en) Built liquid detergent compositions and method of preparation
US5413727A (en) Thixotropic aqueous compositions containing long chain saturated fatty acid stabilizers
US5094771A (en) Nonaqueous liquid automatic dishwasher detergent composition
IE861916L (en) Non gelling detergent
EP0266199A2 (en) Liquid cleaning products
JPH0463920B2 (en)
IE55461B1 (en) Liquid detergent compositions comprising coacervate mixture of alkylcellulose and carboxymethylcellulose and method for preparing them
CA1321339C (en) Liquid cleaning products
EP0256343B1 (en) Non aqueous liquid detergent product consisting of two separate base compositions
EP0001853B1 (en) Detergent compositions having improved bleaching effect
US4950424A (en) Non-aqueous liquid detergent compositions containing di-sulphonic acids as deflocculants
CA1292656C (en) Low phosphate or phosphate free laundry detergent
IE51245B1 (en) Granular detergent compositions
EP0460810B1 (en) Nonaqueous liquid automatic dishwasher detergent composition
EP0081908A1 (en) Low foaming liquid detergent compositions
AU694421B2 (en) Non-aqueuos liquid cleaing comosition containing modified silica
JP2583308B2 (en) Liquid detergent
EP0330060A2 (en) Automatic dishwashing detergent powder

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): CH DE ES FR GB IT LI NL SE

17P Request for examination filed

Effective date: 19870513

17Q First examination report despatched

Effective date: 19880226

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): CH DE ES FR GB IT LI NL SE

REF Corresponds to:

Ref document number: 3664481

Country of ref document: DE

Date of ref document: 19890824

ET Fr: translation filed
ITF It: translation for a ep patent filed

Owner name: JACOBACCI & PERANI S.P.A.

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
ITTA It: last paid annual fee
EAL Se: european patent in force in sweden

Ref document number: 86201867.8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19950913

Year of fee payment: 10

Ref country code: CH

Payment date: 19950913

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19950918

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19950920

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19950927

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 19951009

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19951128

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19961024

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19961025

Ref country code: ES

Free format text: LAPSE BECAUSE OF THE APPLICANT RENOUNCES

Effective date: 19961025

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19961031

Ref country code: CH

Effective date: 19961031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19970501

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19961024

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19970630

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19970501

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19970701

EUG Se: european patent has lapsed

Ref document number: 86201867.8

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 19991007

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20051024