EP0686691B1 - Emulsions aqueuses avec des azurants optiques - Google Patents

Emulsions aqueuses avec des azurants optiques Download PDF

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Publication number
EP0686691B1
EP0686691B1 EP94201667A EP94201667A EP0686691B1 EP 0686691 B1 EP0686691 B1 EP 0686691B1 EP 94201667 A EP94201667 A EP 94201667A EP 94201667 A EP94201667 A EP 94201667A EP 0686691 B1 EP0686691 B1 EP 0686691B1
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EP
European Patent Office
Prior art keywords
hydrophobic
emulsion
fabrics
brightener
hydrophilic
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.)
Expired - Lifetime
Application number
EP94201667A
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German (de)
English (en)
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EP0686691A1 (fr
Inventor
Raffaele Scoccianti
Stefano Scialla
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Procter and Gamble Co
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Procter and Gamble Co
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Filing date
Publication date
Priority to ES94201667T priority Critical patent/ES2158878T3/es
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to DE69427905T priority patent/DE69427905T2/de
Priority to EP94201667A priority patent/EP0686691B1/fr
Priority to CA002191569A priority patent/CA2191569A1/fr
Priority to AU25551/95A priority patent/AU704895B2/en
Priority to JP8502184A priority patent/JPH10501296A/ja
Priority to PCT/US1995/006482 priority patent/WO1995034621A1/fr
Publication of EP0686691A1 publication Critical patent/EP0686691A1/fr
Application granted granted Critical
Publication of EP0686691B1 publication Critical patent/EP0686691B1/fr
Priority to GR20010401214T priority patent/GR3036360T3/el
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • 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
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • 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
    • C11D3/42—Brightening agents ; Blueing agents
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/60—Optical bleaching or brightening
    • D06L4/614—Optical bleaching or brightening in aqueous solvents
    • D06L4/621—Optical bleaching or brightening in aqueous solvents with anionic brighteners
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the present invention relates to cleaning compositions. More particularly, the cleaning compositions according to the present invention are stable aqueous emulsions particularly suitable to be used in laundry applications for example as detergent compositions or as pre-wash treating compositions or as laundry additives to be used together with detergents.
  • a great variety of cleaning compositions have been described in the art.
  • a problem associated with common cleaning compositions is that they do not allow to deliver whitening performance which satisfactorily meet consumer's needs, when used in laundry application to treat different kind of fabrics, especially when used to treat synthetic fabrics such as polyesters, polyamides and the like.
  • compositions suitable for use in laundry application whereby the whiteness to synthetic fabrics is improved. It is a further object of the present invention to provide such compositions which can be satisfactorily used for treating various types of fabrics and clean various types of stains while providing at the same time also good fabric safety to the fabrics treated therewith. Also said compositions should provide improved whitening performance to synthetic fabrics under most common wash conditions including conditions under which the wash temperature is low, i.e. below 60° C.
  • aqueous compositions comprising a hydrophobic brightener wherein said hydrophobic brightener is emulsified in said compositions by a surfactant system comprising at least a hydrophobic surfactant having an HLB (Hydrophilic lipophilic balance) up to 9 and at least a hydrophilic surfactant having an HLB above 10.
  • HLB Hydrophilic lipophilic balance
  • compositions of the present invention allow to incorporate and to deliver hydrophobic brighteners into the wash solution, this under the most common wash conditions, e.g. below 60°C. Formulating such hydrophobic brighteners through liquid compositions being not emulsions or even through powder formulations does not allow to obtain the outstanding whitening performance associated with the present invention.
  • hydrophobic brighteners also contribute to the multi-cycle whitening of cotton fabrics. Indeed, after several wash cycles cotton fibers assume a partially hydrophobic character due for example of deposition of organic species on the fabric surface, i.e. a hydrophobic layer of soils tend to form onto aged fabrics, and thus they become sensitive to hydrophobic brighteners.
  • the hydrophobic brighteners may thus absorb onto said cotton fibers, adsorb UV light and retransmit visible blue light so providing superior whiteness.
  • compositions of the present invention are that in addition to their outstanding whitening action said compositions allow also good stain removal.
  • hydrophobic surfactants to emulsify said hydrophobic brighteners provides excellent hydrophobic soil removal and good grease cutting properties.
  • a further advantage of the present invention is that it allows for great flexibility in formulating and provides compositions being chemically and physically stable and suitable to be used in the most efficient manner by the consumer.
  • the preferred compositions therein comprise hydrogen peroxide.
  • compositions provide a means to formulate ingredients with very low water solubility, without the need for using alcoholic or solvent mixtures, which are usually undesirable for aesthetic (odor) and toxicity reasons.
  • Yet another advantage of the present invention is that hydrophobic brighteners, such as Tinopal SOP ® give to said compositions a perleascent color that improves the product aesthetics.
  • EP-A-598973 discloses a composition comprising hydrogen peroxide and as a surfactant, a fully nonionic system, i.e. at least one nonionic with an HLB above 15, at least one nonionic with an HLB of from 13 to 15, at least one nonionic with an HLB of from 9 to 13 and at least one nonionic with an HLB below 9.
  • This patent application further discloses the use of Tinopal CBS X® (4-4'-bis (2-2' styryl sulfonate) biphenyl) as an optical brightener.
  • Tinopal CBS X® also named Brightener 49®
  • Brightener 49® is a hydrophilic brightener having a solubility of 30 grams per liter at 25°C in deionized water.
  • EP-A-598170 discloses emulsions of at least one hydrophobic nonionic surfactant and at least one hydrophilic nonionic surfactant, said emulsions further comprise hydrogen peroxide, or a source thereof.
  • the invention disclosed in the '170 patent application allows to formulate compositions comprising H 2 O 2 and a hydrophobic bleach activator (ATC), wherein said bleach activator is kept separate from H 2 O 2 .
  • the pH of said emulsions is from 1 to 5.
  • This patent application further discloses the use of optical brighteners as optional ingredients and mentions Brightener 49® in an example. Brightener 49® is not a brightener being almost insoluble in water, i.e. a hydrophobic brightener whose solubility in water is lower than 5 grams per liter at 25°C .
  • the present invention is an aqueous emulsion comprising at least a hydrophilic surfactant having an HLB above 10 and at least a hydrophobic surfactant having an HLB up to 9, said aqueous emulsion further comprises a hydrophobic brightener whose solubility in water is lower than 5 grams per liter at 25 °C, or mixtures thereof.
  • the present invention also encompasses a method of bleaching or washing fabrics, especially fabrics having a hydrophobic character such as synthetic fabrics to improve fabrics whiteness.
  • the present invention also encompasses a process for the manufacture of said emulsions.
  • compositions according to the present invention are stable aqueous emulsions of surfactants which further comprise a hydrophobic brightener whose solubility in water is lower than 5 grams per liter at 25°C.
  • stable emulsion it is meant an emulsion which does not substantially separate into distinct layers, upon standing for at least two weeks at 50 °C.
  • compositions of the present invention comprise a surfactant system of at least two different surfactants, i.e. at least a hydrophobic surfactant having an HLB up to 9 and at least a hydrophilic surfactant having an HLB above 10 in order to emulsify the hydrophobic brightener.
  • said two different surfactants in order to form emulsions which are stable must have different HLB values (hydrophilic lipophilic balance), and preferably the difference in value of the HLBs of said two surfactants is at least 1, preferably at least 3.
  • HLB values hydrophilic lipophilic balance
  • Said surfactant system makes the compositions able to incorporate a hydrophobic brightener, i.e. a compound being almost insoluble in water medium, and to delivery it into the wash solution as a finely dispersed liquid.
  • a hydrophobic brightener i.e. a compound being almost insoluble in water medium
  • the present invention allows to exploit the benefits associated with a hydrophobic brightener otherwise not exploitable under common wash conditions, i.e. below 60°C, either through liquid or powder formulation.
  • compositions according to the present invention comprise from 2% to 50% by weight of the total composition of said hydrophilic and hydrophobic surfactants, preferably from 5% to 40% and more preferably from 8% to 30%.
  • compositions according to the present invention comprise at least from 0.1% by weight of the total composition of said hydrophobic surfactant, or mixtures thereof, preferably at least 3% and more preferably at least 5% and at least from 0.1% by weight of the total composition of said hydrophilic surfactant, or mixtures thereof, preferably at least 3% and more preferably at least 6%.
  • hydrophobic nonionic surfactants and hydrophilic nonionic surfactants are the hydrophobic nonionic surfactants and hydrophilic nonionic surfactants.
  • Said hydrophobic nonionic surfactants to be used herein have an HLB up to 9, preferably below 9, more preferably below 8 and said hydrophilic surfactants have an HLB above 10, preferably above 11, more preferably above 12.
  • the hydrophobic nonionic surfactants to be used herein have excellent grease cutting properties, i.e. they have a solvent effect which contributes to hydrophobic soils removal.
  • the hydrophobic surfactants act as carrier of the hydrophobic brighteners onto the fabrics allowing thereby said brighteners to work in close proximity with the fabrics surface since the beginning of the wash.
  • Suitable nonionic surfactants for use herein include alkoxylated fatty alcohols preferably, fatty alcohol ethoxylates and/or propoxylates. Indeed, a great variety of such alkoxylated fatty alcohols are commercially available which have very different HLB values (hydrophilic lipophilic balance).
  • HLB values of such alkoxylated nonionic surfactants depend essentially on the chain length of the fatty alcohol, the nature of the alkoxylation and the degree of alkoxylation. Hydrophilic nonionic surfactants tend to have a high degree of alkoxylation and a short chain fatty alcohol, while hydrophobic surfactants tend to have a low degree of alkoxylation and a long chain fatty alcohol.
  • Surfactants catalogues are available which list a number of surfactants including nonionics, together with their respective HLB values.
  • Suitable chemical processes for preparing the nonionic surfactants for use herein include condensation of corresponding alcohols with alkylene oxide, in the desired proportions. Such processes are well known to the man skilled in the art and have been extensively described in the art. As an alternative, a great variety of alkoxylated alcohols suitable for use herein is commercially available from various suppliers.
  • Preferred hydrophobic nonionic surfactants to be used in the compositions according to the present invention are surfactants having an HLB up to 9 and being according to the formula RO-(C 2 H 4 O) n (C 3 H 6 O) m H, wherein R is a C 6 to C 22 alkyl chain or a C 6 to C 28 alkyl benzene chain, and wherein n+m is from 0.5 to 5 and n is from 0 to 5 and m is from 0 to 5 and preferably n+m is from 0.5 to 4 and, n and m are from 0 to 4.
  • the preferred R chains for use herein are the C 8 to C 22 alkyl chains.
  • Dobanol R 23-3 or Dobanol R 23-2, Lutensol R TO3, or mixtures thereof.
  • These Dobanol R surfactants are commercially available from SHELL.
  • These Lutensol R surfactants are commercially available from BASF and these Tergitol R surfactants are commercially available from UNION CARBIDE.
  • hydrophobic nonionic surfactants to be used herein are non alkoxylated surfactants.
  • An example is Dobanol 23 (HLB ⁇ 3 ).
  • Preferred hydrophilic nonionic surfactants to be used in the compositions according to the present invention are surfactants having an HLB above 10 and being according to the formula RO-(C 2 H 4 O) n (C 3 H 6 O) m H, wherein R is a C 6 to C 22 alkyl chain or a C 6 to C 28 alkyl benzene chain, and wherein n+m is from 5 to 11 and n is from 0 to 11 and m is from 0 to 11, preferably n+m is from 6 to 10 and, n and m are from 0 to 10.
  • n and m refer to the average degree of the ethoxylation/propoxylation.
  • the preferred R chains for use herein are the C 8 to C 22 alkyl chains.
  • hydrophilic surfactants may further be used in the present invention such as anionic surfactants, in particular sulfonate and sulfate surfactants.
  • anionic surfactants are well-known in the art and have found wide application in commercial detergents.
  • anionic surfactants include C8-C22 alkyl benzene sulfonates (LAS), C8-C22 alkyl sulfates (AS), unsaturated sulfates such as oleyl sulfate, C10-C18 alkyl alkoxy sulfates (AES) and C10-C18 alkyl alkoxy carboxylates.
  • LAS C8-C22 alkyl benzene sulfonates
  • AS C8-C22 alkyl sulfates
  • unsaturated sulfates such as oleyl sulfate, C10-C18 alkyl alkoxy sulfates (AES) and C10-C18 alky
  • the neutralizing cation for the anionic synthetic sulfonates and/or sulfates is represented by conventional cations which are widely used in detergent technology such as sodium, potassium or alkanolammonium.
  • Preferred herein are the alkyl sulphate, or mixtures thereof, especially sodium alkyl sulphate having from 10 to 16 carbon atoms in the alkyl chain, preferably from 12 to 14 .
  • compositions according to the present invention may further comprise other surfactants which should however not significantly alter the weighted average HLB value of the overall composition.
  • compositions according to the present invention comprise a hydrophobic brightener, or mixtures thereof.
  • Brighteners are compounds which have the ability to fluorescent by absorbing ultraviolet wave-lengths of light and re-emitting visible light.
  • Brighteners also referred to as fluorescent whitening agent (FWA)
  • FWA fluorescent whitening agent
  • Said brighteners are substituted stilbenes and biphenyls such as but not limited to polycyclic oxazole derivatives, styryl stilbene derivatives, aryltriazole derivatives, or mixtures thereof.
  • hydrophobic brightener it is to be understood herein any brightener whose solubility in water is lower than 5 grams per liter at 25°C.
  • Said hydrophobic brighteners to be used herein preferably have a solubility in water being lower than 3 and more preferably being lower than 1.
  • solubility of a given compound it is to be understood herein the amount of said compound solubilized in deionized water at 25°C.
  • a compound having a solubility being lower than 5 grams per liter means that when less than 5 grams of said given compound is incorporated in deionized water at 25°C said compound is entirely dissolved in said water, i.e. a clear and stable solution is obtained.
  • incorporating 5 grams per liter or more of said given compound in water will result in a precipitation of said compound in said medium.
  • compositions according to the present invention comprise from 0.02% to 1% by weight of the total composition of said hydrophobic brightener, preferably from 0.05% to 0.5% and more preferably from 0.05% to 0.2%.
  • Preferred hydrophobic brighteners for use herein are styryl stilbene derivatives, or aryltriazole derivatives, or polycyclic oxazole derivatives such as benzo-oxazole derivatives, or mixtures thereof and particularly preferred herein are benzo-oxazole derivatives.
  • An example of such a brightener is benzoxazole,2,2'- (thiophenaldyl)bis having the following formula C18H10N2O2S, commercially available from Ciba-Geigy under the trade name Tinopal SOP®. This brightener is almost insoluble in water, i.e. it has a solubility being lower than 1 gram per liter.
  • compositions herein further comprise a hydrophilic brightener, or mixtures thereof.
  • hydrophilic brightener it is to be understood herein any brightener whose solubility in water is higher than 10 grams per liter at 25°C.
  • Said hydrophilic brighteners to be used herein preferably have a solubility in water being higher than 15 and more preferably being higher than 20.
  • the compositions according to the present invention comprise from 0% to 1% by weight of the total composition of said hydrophilic brightener, preferably from 0% to 0.5% and more preferably from 0% to 0.2%.
  • Such hydrophilic brighteners for use herein are the substituted stilbenes and biphenyls in general such as substituted stilbene 2,2'-disulfonic acid derivatives having a solubility in water higher than 10 grams per liter at 25°C.
  • An example of such a brightener is 4-4'-bis (2-2' styryl sulfonate) biphenyl, commercially available from Ciba-Geigy under the trade name Brightener 49 ®.
  • Other hydrophilic brighteners suitable to be used herein are for example Brightener 3® or Brightener 47®, also commercially available from Ciba-Geigy.
  • compositions according to the present invention are aqueous. Accordingly, the compositions according to the present invention may comprise from 10% to 95% by weight of the total composition of water, preferably from 30% to 90%, most preferably from 60% to 80%. Deionized water is preferably used.
  • the pH of the formulation influences its stability.
  • bleaching ingredients being optional but preferred ingredients of the compositions herein, it is of course necessary, for chemical stability purpose to formulate the compositions herein with bleaches at a pH as is of from 0 to 6, preferably of from 0.5 to 5 and more preferably from 0.5 to 4.
  • the pH of the composition can be trimmed by all means available to the man skilled in the art.
  • compositions according to the present invention comprise bleaches, i.e. hydrogen peroxide or a water-soluble source thereof.
  • Suitable water-soluble sources of hydrogen peroxide include perborate, percarbonate, persilicate and persulphate salts.
  • Hydrogen peroxide is most preferred to be used in the compositions according to the present invention.
  • the compositions according to the present invention comprise from 0.5% to 20% by weight of the total composition of hydrogen peroxide, preferably from 2% to 15%, most preferably from 3% to 10%.
  • compositions according to the present invention may further comprise a bleach activator.
  • bleach activator it is meant herein any compound which reacts with hydrogen peroxide to form a peracid.
  • hydrophobic bleach activators typically belong to the class of esters, amides, imides, or anhydrides.
  • a particular family of bleach activators of interest in the present invention were disclosed in WO 93/12067 claiming priority from the applicant's European patent application No 91870207.7. Particularly preferred in that family is acetyl triethyl citrate which was also disclosed in the context of bar soaps in FR 2 362 210.
  • Acetyl triethyl citrate has the advantages that it is environmentally friendly as it eventually degrades into citric acid and alcohol. Furthermore, acetyl triethyl citrate has a good hydrolytical stability in the product upon storage and it is an efficient bleach activator.
  • Other bleach activators to be used in the present invention are lactam derivatives. As used herein and unless otherwise specified, the term bleach activator includes mixtures of bleach activators.
  • compositions according to the present invention may further comprise the usual optional ingredients such as perfumes, dyes, builders, chelants, pigments, enzymes, dye transfer inhibitors, solvents, buffering agents and the like.
  • compositions comprise a hydrophobic brightener having a solubility in water being lower than 5 grams per liter, i.e. being almost insoluble in water
  • the surfactant system to be chosen to emulsify said hydrophobic brightener depends on the HLB value of said brightener.
  • a suitable way to proceed is to determine the HLB value of the hydrophobic ingredient (brightener), then select both the hydrophobic surfactants which have HLB values below said HLB value of said hydrophobic ingredient and the hydrophilic surfactants which have HLB values above said HLB value of said hydrophobic ingredient, wherein the difference in the HLB values of said hydrophobic and hydrophilic nonionic surfactants is at least 1, preferably at least 3.
  • an adequate nonionic surfactant system would comprise a hydrophobic nonionic surfactant with for instance an HLB of 6, such as a Dobanol R 23-2 and a hydrophilic nonionic surfactant with for instance an HLB of 15, such as a Dobanol R 91-10.
  • compositions of the present invention allow to achieve improved whitening performance on hydrophobic-type of fabrics, i.e. synthetic fabrics such as polyesters, polyamides and the like.
  • improved whitening performance it is meant herein that the whiteness on fabrics (synthetic) achieved by using a composition comprising a hydrophobic brightener emulsified by a surfactant system of at least one hydrophobic surfactant and at least one hydrophilic surfactant is improved, as compared to the whiteness obtained by using the same composition with a hydrophilic brightener instead of said hydrophobic one as herein defined.
  • the hydrophobic brightener is delivered into the wash as a finely dispersed liquid and thus is active at low temperature used in common wash conditions (below 60°C).
  • compositions of the present invention which further comprise a hydrophilic brightener as defined herein allow to achieve improved whitening performance on all kinds of fabrics (cotton natural fibers as well as synthetic and mixed fabrics) as compared- to the same compositions comprising only said hydrophilic brightener as the brightener.
  • compositions of the present invention comprising a hydrophobic brightener emulsified in a surfactant system as described herein is that said hydrophobic brightener may contribute to the multi-cycle whitening of cotton fibers even in absence of any hydrophilic brightener which are known to be particularly effective on cotton fabrics.
  • Aged cotton fabrics become partially hydrophobic, i.e. they are covered by thin hydrophobic layers of soils such as deposition of organic materials thus becoming sensitive to hydrophobic brighteners.
  • the present invention further encompasses a process for the manufacture of the composition described herein.
  • the process according to the present invention comprises at least three steps: In the first step, a hydrophobic mixture is prepared which comprises at least said hydrophobic nonionic surfactant and hydrophobic brightener. Said hydrophobic mixture may further comprises other hydrophobic ingredients which are to be formulated in the composition, such as perfumes, solvents, enzymes, bleach activators and polymers.
  • a hydrophilic mixture which comprises at least said water, and said hydrophilic nonionic surfactant.
  • Said hydrophilic mixture preferably further comprises other hydrophilic ingredients which are to be formulated in the composition such as dyes, hydrophilic optical brighteners, builders, chelants, hydrogen peroxide and buffering agents.
  • hydrogen peroxide when present is preferably added last, after said buffering agent has been added.
  • said first and said second steps can be performed in any order, i.e. second step first is also suitable.
  • said hydrophobic mixture and said hydrophilic mixture are mixed together.
  • compositions according to the present invention are particularly useful as laundry detergent or as laundry pretreaters, i.e. compositions which are dispensed and left to act onto fabrics before they are washed, or as laundry additives to be used together with detergents to boost their performance.
  • the compositions of the present invention are incorporated per se in detergents being in a liquid form.
  • the technologies used to incorporate the compositions of the present invention in a detergent being in a granular form are those commonly known to those skilled in the art like spraying and/or encapsulation.
  • the present invention further encompasses a method of bleaching and/or washing fabrics wherein a composition as defined hereinbefore is contacted with said fabrics. More specifically, in the preferred embodiment of the present invention where the compositions of the present invention comprise bleaches, the method of bleaching fabrics to improve fabric whiteness comprises the steps of first contacting said fabrics with a composition of the present invention, then allowing said fabrics to remain in contact with said composition, for a period of time sufficient to bleach said fabrics, typically 2 to 60 minutes, preferably 5 to 30 minutes, then rinsing said fabrics in water to remove said composition. If said fabrics are to be washed, i.e. with a conventional composition comprising at least one surface active agent, it is preferred to perform the method herein before said fabrics are washed.
  • said method according to the present invention further comprises a subsequent step where said fabrics are washed with a detergent composition comprising at least one surface active agent.
  • compositions are made which comprise the listed ingredients in the listed proportions (weight %).
  • Compositions I II III IV Dobanol R 45-7 6 6 6 6
  • Dobanol R 23-2 6 6 6 Hydrogen peroxide 7.5 7.5 7.5 7.5 Acetyl triethyl citrate 7.0 7.0 7.0 7.0 Brightener R 49 ---- ---- 0.1 0.1 Tinopal SOP R ---- 0.1 ---- 0.1 S,S-ethylene diamino disuccinic acid 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Poly(4-vinylpyridine-N-oxyde) 0.1 0.1 0.1 0.1 0.1 HOES R 3639 0.2 0.2 0.2 0.2 0.2 Silicon 0.2 0.2 0.2 0.2 0.2 Deionized water ---------------------------------------------------------------------------------------------- Citric acid up to pH 4
  • HOES R 3639 is a terephthalate based polymer commercially available from Hoechst.
  • Composition I is an emulsion taken as reference in the following test and comprises no brighteners at all.
  • compositions II and IV are representative of the present invention.
  • Composition II is an emulsion of nonionic surfactants comprising among other hydrogen peroxide, a bleach activator (ATC) and a hydrophobic brightener, Tinopal SOP®.
  • Composition IV differs from composition II in that it further comprises a hydrophilic brightener, Brightener 49®.
  • Composition III is a composition representative of the prior art, i.e. an emulsion of nonionic surfactants comprising hydrogen peroxide and a bleach activator (ATC) and as a brightener a hydrophilic brightener.
  • ATC bleach activator
  • a single tracer launderometer test was carried out by using said bleaching compositions mentioned above followed by the use of a detergent composition.
  • the test was performed in a stainless steel vessel. First 2 ml of each of the above bleaching compositions I to IV were diluted in 0.5 liters of tap water. The test was carried out at 18°C. The tracers, i.e. fabrics such as clothes, towels and the like, with standardized stains were added into the prepared solutions. The vessel was then kept under agitation for 20 minutes. At the end of the washing cycle the tracers were rinsed with water. Then, a detergent commercially available on the market (Dash Ultra®) was used to wash the tracers. 5g of the detergent were diluted into 0.5 liter of tap water. This solution was heated at 40°C. The vessel was then kept under agitation for 20 minutes with the tracers. At the end of the washing cycle the tracers were rinsed and dried. Then the tracers were evaluated by visual grading.
  • the tracers i.e. fabrics such as clothes, towels and the like, with standardized stains were added into the prepared solutions. The vessel was then kept under
  • compositions II and IV a hydrophobic brightener emulsified in a nonionic surfactant system
  • composition III a composition available on the market comprising only a hydrophilic brightener as the brightener
  • composition I* a hydrophilic brightener
  • composition IV shows that the emulsions of the present invention comprising a hydrophobic and a hydrophilic brightener provide fabric whiteness improvement on various types of fabrics, polyester alone, cotton alone or mixtures thereof as compared to the compositions available on the market (see composition IV versus composition III).
  • compositions according to the present invention are the following. These compositions are made comprising the listed ingredients in the listed proportions (weight %): Compositions I II III Dobanol R 45-7 6.7 6.0 6.0 Lutensol T03 8.3 --- ---- Na alkyl sulphate 2.0 --- ---- Dobanol R 23-2 ---- 6.0 6.0 Dobanol R 91-10 ---- 3.0 3.0 Hydrogen peroxide 7.5 7.5 7.5 Acetyl triethyl citrate 7.0 7.0 7.0 Brightener R 49 0.2 ---- ---- Brightener R 3 ---- 0.2 ---- Brightener R 47 ---- ---- 0.1 Tinopal SOP R 0.1 0.05 0.08 S,S-ethylene diamino disuccinic acid ---- 0.1 0.1 Diethylene triamine penta methylene phosphonic acid 1.0 --- ---- Poly(4-vinylpyridine-N-oxyde) 0.1 0.1 0.1 HOES R
  • a hydrophilic mixture is prepared which comprises the hydrophilic ingredients such as water, hydrophilic brightener, S,S-EDDS, poly(4-vinylpyridine-N-oxide), Dobanol R 45-7, Dobanol R 91-10, diethylene triamine penta methylene phosphonic acid or Na alkyl sulphate. Hydrogen peroxide is added in said hydrophilic mixture as last step.
  • a hydrophobic mixture is prepared which comprises acetyl triethyl citrate, Dobanol R 23-2, Lutensol T03, hydrophobic brightener, silicone or Hoes R 3639. Then said hydrophobic mixture is poured into said hydrophilic mixture, while mixing.
  • compositions according to the examples above are stable and provide excellent whitening performance and safety to the fabrics treated with them while being also efficient in removing stains. These advantages are observed when using said compositions as a laundry composition or as an additive or as a pre-bleach associated with a detergent composition.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Detergent Compositions (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

Claims (14)

  1. Emulsion aqueuse comportant au moins un tensioactif hydrophile ayant un HLB supérieur à 10 et au moins un tensioactif hydrophobe ayant un HLB allant jusqu'à 9, caractérisée en ce que ladite émulsion aqueuse comporte de plus un azurant hydrophobe dont la solubilité dans l'eau est inférieure à 5 grammes par litre à 25°C, ou des mélanges de ceux-ci.
  2. Emulsion selon la revendication 1, dans laquelle ledit azurant hydrophobe a une solubilité dans l'eau qui est inférieure à 3 grammes par litre, de préférence inférieure à 1 gramme par litre.
  3. Emulsion selon l'une quelconque des revendications précédentes, dans laquelle ledit azurant hydrophobe est un dérivé d'aryltriazole, un dérivé de stilbène styrylique, un dérivé d'oxazole polycyclique, ou des mélanges de ceux-ci, de préférence un dérivé benzo-oxazole et de manière plus préférée ledit benzo-oxazole est le benzoxazole,2,2'-(thiophénadyl)bis.
  4. Emulsion selon l'une quelconque des revendications précédentes, dans laquelle ladite émulsion comporte de 0,02 % à 1 % en poids de l'émulsion totale dudit azurant hydrophobe, de préférence de 0,05 % à 0,5 % et de manière plus préférée de 0,05 % à 0,2 %.
  5. Emulsion selon l'une quelconque des revendications précédentes, dans laquelle ladite émulsion comporte de 2 % à 5 % en poids de l'émulsion totale desdits tensioactifs hydrophobe et hydrophile, de préférence de 5 % à 40 % et de manière plus préférée de 8 % à 30 %.
  6. Emulsion selon l'une quelconque des revendications précédentes, dans laquelle ledit tensioactif hydrophobe est un tensioactif non-ionique, de préférence un tensioactif non-ionique hydrophobe ayant un HLB inférieur à 9, de préférence inférieur à 8, et dans laquelle ledit tensioactif hydrophile est un tensioactif non-ionique, de préférence un tensioactif non-ionique hydrophile ayant un HLB supérieur à 11, de préférence supérieur à 12.
  7. Emulsion selon l'une quelconque des revendications précédentes, dans laquelle ladite émulsion comporte de plus un tensioactif anionique ou des mélanges de celui-ci, de préférence un sulfate d'alkyle de sodium ayant de 10 à 16 atomes de carbone.
  8. Emulsion selon l'une quelconque des revendications précédentes, qui comporte de plus du peroxyde d'hydrogène, ou une source soluble dans l'eau de celui-ci, et un activateur de blanchiment, ledit activateur de blanchiment étant émulsifié par les tensioactifs.
  9. Emulsion selon la revendication 8, qui comporte de 0,5 % à 20 % en poids de l'émulsion totale dudit peroxyde d'hydrogène.
  10. Emulsion selon les revendications 8 et 9, dans laquelle ledit activateur de blanchiment est du citrate d'acétyle triéthyle.
  11. Emulsion selon l'une quelconque des revendications précédentes, qui comporte de plus un azurant hydrophile dont la solubilité dans l'eau est supérieure à 10 grammes par litre à 25°C, de préférence supérieure à 15 grammes par litre et de manière plus préférée supérieure à 20 grammes par litre.
  12. Composition détergente liquide comportant une émulsion selon l'une quelconque des revendications précédentes.
  13. Procédé de blanchiment ou de lavage de tissus, en particulier des tissus ayant un caractère hydrophobe tels que des tissus synthétiques, pour améliorer la blancheur des tissus, qui comporte les étapes consistant à :
    mettre en contact tout d'abord lesdits tissus avec une composition ou émulsion selon l'une quelconque des revendications précédentes,
    permettre alors auxdits tissus de rester en contact avec ladite composition ou émulsion pendant une période de temps suffisante pour blanchir ou laver lesdits tissus,
    rincer alors lesdits tissus dans de l'eau pour éliminer ladite composition ou émulsion.
  14. Procédé selon la revendication 13, qui comporte de plus une étape ultérieure où lesdits tissus sont lavés à l'aide d'une composition détergente comportant au moins un agent tensioactif.
EP94201667A 1994-06-10 1994-06-10 Emulsions aqueuses avec des azurants optiques Expired - Lifetime EP0686691B1 (fr)

Priority Applications (8)

Application Number Priority Date Filing Date Title
DE69427905T DE69427905T2 (de) 1994-06-10 1994-06-10 Wässrige Emulsionen mit Aufhellern
EP94201667A EP0686691B1 (fr) 1994-06-10 1994-06-10 Emulsions aqueuses avec des azurants optiques
ES94201667T ES2158878T3 (es) 1994-06-10 1994-06-10 Emulsiones acuosas con abrillantadores.
AU25551/95A AU704895B2 (en) 1994-06-10 1995-05-23 Aqueous emulsions containing a hydrophobic brightener, a hydrophilic surfactant and a hydrophobic surfactant
CA002191569A CA2191569A1 (fr) 1994-06-10 1995-05-23 Emulsions acqueuses contenant un agent de blanchiment hydrophobe, un tensio-actif hydrophile et un tensio-actif hydrophobe
JP8502184A JPH10501296A (ja) 1994-06-10 1995-05-23 疎水性ブライトナー、親水性界面活性剤および疎水性界面活性剤を含む水性エマルション
PCT/US1995/006482 WO1995034621A1 (fr) 1994-06-10 1995-05-23 Emulsions acqueuses contenant un agent de blanchiment hydrophobe, un tensio-actif hydrophile et un tensio-actif hydrophobe
GR20010401214T GR3036360T3 (en) 1994-06-10 2001-08-09 Aqueous emulsions with brighteners

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP94201667A EP0686691B1 (fr) 1994-06-10 1994-06-10 Emulsions aqueuses avec des azurants optiques

Publications (2)

Publication Number Publication Date
EP0686691A1 EP0686691A1 (fr) 1995-12-13
EP0686691B1 true EP0686691B1 (fr) 2001-08-08

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Country Status (8)

Country Link
EP (1) EP0686691B1 (fr)
JP (1) JPH10501296A (fr)
AU (1) AU704895B2 (fr)
CA (1) CA2191569A1 (fr)
DE (1) DE69427905T2 (fr)
ES (1) ES2158878T3 (fr)
GR (1) GR3036360T3 (fr)
WO (1) WO1995034621A1 (fr)

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EP2295531A1 (fr) 2009-09-14 2011-03-16 The Procter & Gamble Company Composition liquide de détergent pour linge
WO2011109319A1 (fr) 2010-03-01 2011-09-09 The Procter & Gamble Company Détergents de blanchisserie liquides double emploi
EP2365053A1 (fr) 2010-03-12 2011-09-14 The Procter & Gamble Company Compositions liquides de détergent comprenant des gélifiants amido à pH réglable et procédés de fabrication
EP2365051A1 (fr) 2010-03-12 2011-09-14 The Procter & Gamble Company Compositions liquides de détergent comprenant un gélifiant di-amido et procédés de fabrication
WO2011127102A1 (fr) 2010-04-06 2011-10-13 The Procter & Gamble Company Libération optimisée de systèmes de blanchiment dans des détergents de blanchisserie
EP2399978A1 (fr) 2010-06-24 2011-12-28 The Procter & Gamble Company Compositions liquides stables non aqueuses comprenant un polymère cationique sous forme particulaire
EP2399980A1 (fr) 2010-06-24 2011-12-28 The Procter & Gamble Company Compositions stables comprenant du polymère de cellulose cationique et de la cellulase
EP2399979A1 (fr) 2010-06-24 2011-12-28 The Procter & Gamble Company Articles à dose unitaire solubles comprenant un polymère cationique
WO2013039963A1 (fr) 2011-09-13 2013-03-21 The Procter & Gamble Company Compositions de microcapsule contenant des gélifiants di-amido sensibles au ph
EP2865742A1 (fr) 2013-10-28 2015-04-29 Dow Global Technologies LLC Compositions liquides stables non aqueuses comprenant un polymère cationique sous forme d'un particule
EP2865741A1 (fr) 2013-10-28 2015-04-29 Dow Global Technologies LLC Compositions liquides non aqueuses stables comprenant des ingrédients insolubles ou faiblement solubles
EP2899259A1 (fr) 2014-01-22 2015-07-29 The Procter and Gamble Company Compositions détergentes
EP3109306A1 (fr) 2015-06-22 2016-12-28 The Procter and Gamble Company Compositions de detergent liquide a faible teneur en solvant
EP3184619A1 (fr) 2015-12-22 2017-06-28 The Procter & Gamble Company Compositions détergentes structurées
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US5902354A (en) * 1994-04-12 1999-05-11 The Procter & Gamble Company Bleaching compositions
DE19635070A1 (de) * 1996-08-30 1998-03-05 Clariant Gmbh Flüssige Bleichmittelsuspension
DE19751860C1 (de) * 1997-11-22 1999-08-19 Henkel Ecolab Gmbh & Co Ohg Waschverfahren und Zubereitung zu seiner Durchführung
GB0418071D0 (en) * 2004-08-05 2004-09-15 Unilever Plc Fabric conditioning compositions
US20160168780A1 (en) * 2014-12-16 2016-06-16 Washing Systems, Llc Process to produce hygienically clean textile
EP3969553B1 (fr) 2019-05-16 2023-04-19 Unilever Global Ip Limited Composition de lessive

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US4559169A (en) * 1984-08-17 1985-12-17 The Procter & Gamble Company Stable liquid detergents containing anionic surfactant and monosulfonated brightener
US4909962A (en) * 1986-09-02 1990-03-20 Colgate-Palmolive Co. Laundry pre-spotter comp. providing improved oily soil removal
ES2029345T3 (es) * 1987-08-26 1992-08-01 Ciba-Geigy Ag Blanqueadores opticos de dispersion.
US4978475A (en) * 1988-02-26 1990-12-18 The Procter & Gamble Company Stable liquid detergents containing anionic surfactant and monosulfonated brightener
US5106523A (en) * 1989-06-16 1992-04-21 The Clorox Company Thickened acidic liquid composition with amine fwa useful as a bleaching agent vehicle
DE69224389T2 (de) * 1992-11-16 1998-08-13 The Procter & Gamble Co., Cincinnati, Ohio Reinigungs- und Bleichmittelzusammensetzungen
EP0598973A1 (fr) * 1992-11-26 1994-06-01 The Procter & Gamble Company Composition de nettoyage liquide pour tous usages

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WO2011031712A2 (fr) 2009-09-14 2011-03-17 The Procter & Gamble Company Composition de détergent à lessive fluide
WO2011109319A1 (fr) 2010-03-01 2011-09-09 The Procter & Gamble Company Détergents de blanchisserie liquides double emploi
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EP2365051A1 (fr) 2010-03-12 2011-09-14 The Procter & Gamble Company Compositions liquides de détergent comprenant un gélifiant di-amido et procédés de fabrication
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EP2399978A1 (fr) 2010-06-24 2011-12-28 The Procter & Gamble Company Compositions liquides stables non aqueuses comprenant un polymère cationique sous forme particulaire
EP2399980A1 (fr) 2010-06-24 2011-12-28 The Procter & Gamble Company Compositions stables comprenant du polymère de cellulose cationique et de la cellulase
EP2399979A1 (fr) 2010-06-24 2011-12-28 The Procter & Gamble Company Articles à dose unitaire solubles comprenant un polymère cationique
WO2011163428A1 (fr) 2010-06-24 2011-12-29 The Procter & Gamble Company Articles de type doses unitaires solubles comprenant un polymère cationique
WO2011163371A1 (fr) 2010-06-24 2011-12-29 The Procter & Gamble Company Compositions liquides non aqueuses stables comprenant un polymère cationique sous forme particulaire
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US9550962B2 (en) 2010-06-24 2017-01-24 The Procter & Gamble Company Stable non-aqueous liquid compositions comprising a cationic polymer in particulate form
US8889610B2 (en) 2010-06-24 2014-11-18 The Procter & Gamble Company Soluble unit dose articles comprising a cationic polymer
US8895493B2 (en) 2010-06-24 2014-11-25 The Procter & Gamble Company Stable non-aqueous liquid compositions comprising a cationic polymer in particulate form
WO2013039963A1 (fr) 2011-09-13 2013-03-21 The Procter & Gamble Company Compositions de microcapsule contenant des gélifiants di-amido sensibles au ph
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WO2015065805A1 (fr) 2013-10-28 2015-05-07 Dow Global Technologies Llc Compositions non aqueuses liquides stables contenant des ingrédients insolubles ou faiblement solubles
WO2015065809A1 (fr) 2013-10-28 2015-05-07 Dow Global Technologies Llc Compositions liquides non aqueuses stables contenant un polymère cationique sous forme particulaire
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WO2015112342A1 (fr) 2014-01-22 2015-07-30 The Procter & Gamble Company Procédé de fabrication de compositions de détergent comprenant des polymères
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Also Published As

Publication number Publication date
EP0686691A1 (fr) 1995-12-13
DE69427905T2 (de) 2002-04-04
JPH10501296A (ja) 1998-02-03
AU2555195A (en) 1996-01-05
CA2191569A1 (fr) 1995-12-21
WO1995034621A1 (fr) 1995-12-21
GR3036360T3 (en) 2001-11-30
DE69427905D1 (de) 2001-09-13
AU704895B2 (en) 1999-05-06
ES2158878T3 (es) 2001-09-16

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