EP0598693B1 - Stable aqueous emulsions of nonionic surfactants with a viscosity controlling agent - Google Patents

Stable aqueous emulsions of nonionic surfactants with a viscosity controlling agent Download PDF

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Publication number
EP0598693B1
EP0598693B1 EP93870134A EP93870134A EP0598693B1 EP 0598693 B1 EP0598693 B1 EP 0598693B1 EP 93870134 A EP93870134 A EP 93870134A EP 93870134 A EP93870134 A EP 93870134A EP 0598693 B1 EP0598693 B1 EP 0598693B1
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EP
European Patent Office
Prior art keywords
hydrophilic
hydrophobic
emulsion
ethylenediamine
nonionic surfactant
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EP93870134A
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German (de)
French (fr)
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EP0598693A1 (en
Inventor
Giulia Ottavia Bianchetti
Sergio Cardola
Stefano Scialla
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Procter and Gamble Co
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Procter and Gamble Co
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Priority claimed from EP92870188A external-priority patent/EP0598170B1/en
Priority claimed from EP93870104A external-priority patent/EP0629690B1/en
Priority claimed from SG1996002630A external-priority patent/SG52309A1/en
Priority to DE69322744T priority Critical patent/DE69322744T2/en
Priority to EP93870134A priority patent/EP0598693B1/en
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to AT93870134T priority patent/ATE174955T1/en
Priority to ES93870134T priority patent/ES2125322T3/en
Priority to PCT/US1993/010444 priority patent/WO1994011099A1/en
Priority to AU55891/94A priority patent/AU5589194A/en
Publication of EP0598693A1 publication Critical patent/EP0598693A1/en
Publication of EP0598693B1 publication Critical patent/EP0598693B1/en
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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
    • C11D1/825—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
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • 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
    • 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 of nonionic surfactants which comprise a viscosity control system.
  • such emulsions can be used to formulate products which do not contain hydrogen peroxide.
  • such emulsions can be useful because they allow to keep a given hydrophobic ingredient separate from the aqueous phase, with which said hydrophobic ingredient could react, e.g., by hydrolysis.
  • cleaning compositions be more or less viscous. Indeed, viscous compositions do not run like thin liquids, and their pouring, dispensing, i.e. their overall handling is therefore easier to control. This aspect is particularly important when cleaning compositions are used to clean hard surfaces, especially on inclined or vertical surfaces such as toilet bowls, or in the context of laundry. In those instances, the cleaning compositions must be thick enough for a controlled application onto fabrics, and for a good cling onto surfaces.
  • thickening compounds are available for this purpose.
  • thickening compounds it is meant herein compounds whose sole function is to thicken the compositions.
  • Such compounds typically polymers, are however rather undesirable for a variety of reasons. Indeed, they can significantly increase formula cost without participating to the overall cleaning performance, they may involve processing issues, they may affect product stability, particularly in extreme acidic conditions, and they may affect the cleaning performance of the compositions.
  • Another advantage of the present invention is that it is only required to use a very small amount of ethylenediamine-N,N'-disuccinic acid in order to obtain the desired effect, which makes the present invention particularly cost-efficient.
  • ethylenediamine-N,N'-disuccinic acid also acts as a builder in the compositions of the present invention.
  • ethylenediamine-N,N'-disuccinic acid plays has a dual function in the compositions of the present invention.
  • Yet another advantage of the present invention is that ethylenediamine-N,N'-disuccinic acid has been found to provide additional stability to the preferred compositions herein which may comprise hydrogen peroxide as an optional but preferred compound.
  • Yet another advantage of the present invention is that it allows to achieve a given viscosity target with a lower surfactant level, compared to a composition without ethylenediamine-N,N'-disuccinic acid.
  • US-A-4 704 233 discloses laundry detergent compositions comprising a surfactant, a detergent builder and ethylenediamine-N,N'-disuccinic acid or alkali metal, alkaline earth, ammonium or substituted ammonium salts thereof or mixtures thereof. No emulsions of hydrophilic and hydrophobic nonionic surfactants are disclosed.
  • EP-A-497 337 discloses stable aqueous suspensions of organic peracids containing surfactant mixtures consisting of C8-C22 fatty alcohol oxyethylated with 1-5 ethylene oxide (EO) units and C8-C22 fatty alcohol oxyethylated with 6-25 ethylene oxide units optionally together with other conventional component. No ethylenediamine-N,N'-disuccinic acid or alkali metal, alkaline earth, ammonium or substituted ammonium salts thereof or a mixture thereof is disclosed therein.
  • a stable aqueous emulsion comprising from 2% to 70% by weight of the total emulsion of a hydrophilic nonionic surfactant with an HLB (hydrophilic-lipophilic balance) above 11 and a hydrophobic nonionic surfactant with an HLB below 10, and from 10% to 95% by weight of water, said emulsion further comprising from 0,01% to 10% by weight of the total emulsion of ethylenediamine-N,N'-disuccinic acid, or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof or mixtures thereof.
  • HLB hydrophilic-lipophilic balance
  • compositions according to the present invention are aqueous. Accordingly, the compositions according to the present invention comprise from 10% to 95% by weight of the total composition of water, preferably from 30% to 90%, most preferably from 60% to 85%. Deionized water is preferably used.
  • compositions according to the present invention are emulsions of nonionic surfactants.
  • Said emulsions of nonionic surfactants comprise at least two nonionic surfactants.
  • said two nonionic surfactants In order to form emulsions which are stable, said two nonionic surfactants must have different HLB values (hydrophilic lipophilic balance), and the difference in value of the HLBs of said two surfactants is more than 1, preferably at least 3.
  • HLB values hydrophilic lipophilic balance
  • compositions according to the present invention comprise from 2 % to 70 % by weight of the total composition of said hydrophilic and hydrophobic nonionic surfactants, preferably from 3 % to 40 %, most preferably from 4 % to 30 %.
  • compositions according to the present invention further comprise as an essential element an ethylenediamine-N,N'-disuccinic acid.
  • compositions herein are not limited to any specific viscosity, and depending on the exact use envisioned, various viscosities may be achieved.
  • compositions according to the present invention comprise from 0.01 % to 10 % by weight of the total composition of ethylenediamine-N,N'-disuccinic acid, preferably from 0.01 % to 1 %.
  • Ethylenediamine-N,N'-disuccinic acid can be synthesised, for example, from readily available, inexpensive starting materials such as maleic anhydride and ethylenediamine as follows.
  • the magnesium complexes are the most preferred for inclusion in compositions according to the invention. These complexes may be added to the compositions as such, or they may be formed during the process for making the composition by the reaction of an inert magnesium salt such as MgCl 2 or Mg SO 4 with an ethylenediamine-N,N'-disuccinic acid compound added as either the acid, or as a salt or complex. Where the ethylenediamine-N,N'-disuccinic acid compound is added in the making process, together with the inert magnesium salt, it is preferred that the molar ratio of magnesium to ethylenediamine-N,N'-disuccinic acid should be greater than 1:1, preferably greater than 3:1, to ensure formation of the desired magnesium complexes.
  • 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 purposes to formulate the compositions herein with bleaches at a pH as is of from 0 to 6, preferably of from 0.5 to 5.
  • the pH of the 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 water-soluble sources thereof.
  • Suitable water-soluble sources of hydrogen peroxide include perborate, percarbonate and persilicate 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 as an optional ingredient.
  • bleach activator it is meant herein any compound which reacts with hydrogen peroxide to form a peracid.
  • Suitable bleach activators for use herein 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 EP-A-0 624 154. Particularly preferred in that family is acetyl triethyl citrate which was also disclosed in the context of bar soaps in FR-A-2 362 210.
  • Acetyl triethyl citrate has the advantages that it is environmentally friendly as it eventually degrades into citric acid and alcohol.
  • acetyl triethyl citrate has a good hydrolytical stability in the product upon storage and it is an efficient bleach activator.
  • the term bleach activator includes mixtures of bleach activators.
  • the nonionic surfactant system to be chosen to emulsify said bleach activator depends on the HLB value of said bleach activator. Accordingly, a suitable way to proceed is to determine the HLB value of the hydrophobic liquid ingredient (bleach activator), then select both the hydrophobic nonionic surfactants which have HLB values below said HLB value of said hydrophobic liquid ingredient and the hydrophilic nonionic surfactants which have HLB values above said HLB value of said hydrophobic liquid ingredient, wherein the difference in the HLB values of said hydrophobic and hydrophilic nonionic surfactants is preferably at least 3.
  • an adequate nonionic surfactant system would comprise a hydrophobic nonionic surfactant with an HLB from 1 to below 10, and a hydrophilic nonionic surfactant with an HLB of above 11.
  • a particularly suitable system comprises a hydrophobic nonionic surfactant with an HLB of 6, for instance a Dobanol @ 23-2 and a hydrophilic nonionic surfactant with an HLB of 15, for instance a Dobanol @ 91-10.
  • Another suitable nonionic surfactant system comprises a Dobanol @ 23-6.5 (HLB about 12) and a Dobanol @ 23 (HLB below 6). All these Dobanol @ surfactants are commercially available from Shell.
  • compositions according to the present invention may further comprise the usual optional ingredients such as perfumes, dyes, optical brighteners, builders and chelants, pigments, enzymes, dye transfer inhibitors, solvents, buffering agents and the like.
  • compositions according to the present invention are particularly useful 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, or as dishwashing compositions to be used either in the dishwashing machines or by hand, or as hard surface cleaners, or as toilet bowl cleaners, or as carpet cleaners to be used either by direct application onto the carpets or in carpet cleaning machines.
  • 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:
  • a hydrophobic mixture which comprises said hydrophobic nonionic surfactant, ethylenediamine-N,N'-disuccinic acid, together with other, optional, 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, optical brighteners, builders, chelants, hydrogen peroxide and buffering agents.
  • 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 are made which comprise the listed ingredients in the listed proportions (weigh %).

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  • 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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Colloid Chemistry (AREA)
  • Cosmetics (AREA)

Abstract

Stable aqueous emulsions are disclosed which comprise hydrophobic and hydrophilic nonionic surfactants and a ethylenediamine-N,N'-disuccinic acid. Ethylenediamine-N,N'-disuccinic acid builds viscosity in said emulsions.

Description

Technical field
The present invention relates to cleaning compositions. More particularly, the cleaning compositions according to the present invention are stable aqueous emulsions of nonionic surfactants which comprise a viscosity control system.
Background
A great variety of cleaning compositions have been described in the art. For instance, European Patent Application EP-A-598170, a particular type of cleaning compositions is described which are aqueous emulsions of a nonionic surfactant system. Such emulsions find a preferred application in the formulation of bleaching compositions comprising hydrogen peroxide or water soluble source thereof and a liquid hydrophobic bleach activator, or any other hydrophobic ingredient which needs to be separated from hydrogen peroxide.
Alternatively, such emulsions can be used to formulate products which do not contain hydrogen peroxide. In the latter case, such emulsions can be useful because they allow to keep a given hydrophobic ingredient separate from the aqueous phase, with which said hydrophobic ingredient could react, e.g., by hydrolysis.
It is also generally desirable that cleaning compositions be more or less viscous. Indeed, viscous compositions do not run like thin liquids, and their pouring, dispensing, i.e. their overall handling is therefore easier to control. This aspect is particularly important when cleaning compositions are used to clean hard surfaces, especially on inclined or vertical surfaces such as toilet bowls, or in the context of laundry. In those instances, the cleaning compositions must be thick enough for a controlled application onto fabrics, and for a good cling onto surfaces.
It is thus an object of the present invention to formulate thickened aqueous emulsions of nonionic surfactants.
A variety of thickening compounds are available for this purpose. By thickening compounds, it is meant herein compounds whose sole function is to thicken the compositions. Such compounds, typically polymers, are however rather undesirable for a variety of reasons. Indeed, they can significantly increase formula cost without participating to the overall cleaning performance, they may involve processing issues, they may affect product stability, particularly in extreme acidic conditions, and they may affect the cleaning performance of the compositions.
It is thus an object of the present invention to formulate such a thickened composition without having to use a thickening compound.
It has now been found that this object could be met by formulating ethylenediamine-N,N'-disuccinic acid in an aqueous emulsion of nonionic surfactant will significantly increase the formulation's viscosity.
Another advantage of the present invention is that it is only required to use a very small amount of ethylenediamine-N,N'-disuccinic acid in order to obtain the desired effect, which makes the present invention particularly cost-efficient.
Another advantage of the present invention is that ethylenediamine-N,N'-disuccinic acid also acts as a builder in the compositions of the present invention. Thus ethylenediamine-N,N'-disuccinic acid plays has a dual function in the compositions of the present invention.
Another advantage of the present invention is that it allows for the formulation of compositions which are thick and pseudoplastic, i.e. which are less viscous at higher shear stresses. Pseudoplasticity compositions achieve the multiple and somewhat contradictory objects of being easy to dispense, i.e. rather less viscous, and providing good cling onto surfaces, i.e. rather more viscous.
Yet another advantage of the present invention is that ethylenediamine-N,N'-disuccinic acid has been found to provide additional stability to the preferred compositions herein which may comprise hydrogen peroxide as an optional but preferred compound.
Yet another advantage of the present invention is that it allows to achieve a given viscosity target with a lower surfactant level, compared to a composition without ethylenediamine-N,N'-disuccinic acid.
The prior art is further illustrated by US-A-4 704 233 which discloses laundry detergent compositions comprising a surfactant, a detergent builder and ethylenediamine-N,N'-disuccinic acid or alkali metal, alkaline earth, ammonium or substituted ammonium salts thereof or mixtures thereof. No emulsions of hydrophilic and hydrophobic nonionic surfactants are disclosed.
EP-A-497 337 discloses stable aqueous suspensions of organic peracids containing surfactant mixtures consisting of C8-C22 fatty alcohol oxyethylated with 1-5 ethylene oxide (EO) units and C8-C22 fatty alcohol oxyethylated with 6-25 ethylene oxide units optionally together with other conventional component. No ethylenediamine-N,N'-disuccinic acid or alkali metal, alkaline earth, ammonium or substituted ammonium salts thereof or a mixture thereof is disclosed therein.
Summary of the invention
A stable aqueous emulsion comprising from 2% to 70% by weight of the total emulsion of a hydrophilic nonionic surfactant with an HLB (hydrophilic-lipophilic balance) above 11 and a hydrophobic nonionic surfactant with an HLB below 10, and from 10% to 95% by weight of water, said emulsion further comprising from 0,01% to 10% by weight of the total emulsion of ethylenediamine-N,N'-disuccinic acid, or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof or mixtures thereof.
Detailed description of the invention
The compositions according to the present invention are stable aqueous emulsions of nonionic surfactants. By stable emulsion it is meant an emulsion which does not substantially separate into distinct layers, upon standing for at least two weeks at 20 °C, preferably at least six months.
The compositions according to the present invention are aqueous. Accordingly, the compositions according to the present invention comprise from 10% to 95% by weight of the total composition of water, preferably from 30% to 90%, most preferably from 60% to 85%. Deionized water is preferably used.
The compositions according to the present invention are emulsions of nonionic surfactants. Said emulsions of nonionic surfactants comprise at least two nonionic surfactants. In order to form emulsions which are stable, said two nonionic surfactants must have different HLB values (hydrophilic lipophilic balance), and the difference in value of the HLBs of said two surfactants is more than 1, preferably at least 3. By appropriately combining at least two of said nonionic surfactants with different HLBs in water, emulsions according to the present invention will be formed.
One of said nonionic surfactants used herein is a nonionic surfactant with an HLB above 11 (herein referred to as hydrophilic nonionic surfactant), whereas the other one is a nonionic surfactant with an HLB below 10 (herein referred to as hydrophobic nonionic surfactant).
Suitable nonionic surfactants for use herein include alkoxylated fatty alcohols. Indeed, a great variety of such alkoxylated fatty alcohols are commercially available which have very different HLB values (hydrophilic lipophilic balance). The HLB values of such alkoxylated nonionic surfactants depend essentially on the alkoxylation and the degree of alkoxylation. Hydrophilic nonionic surfactants tend to have a higher degree of alkoxylation, while hydrophobic surfactants tend to have a lower degree of alkoxylation. Surfactants catalogs are available which list a number of surfactants including nonionics, together with their respective HLB values.
The compositions according to the present invention comprise from 2 % to 70 % by weight of the total composition of said hydrophilic and hydrophobic nonionic surfactants, preferably from 3 % to 40 %, most preferably from 4 % to 30 %.
The compositions according to the present invention may further comprise other nonionic surfactants which should however not significantly alter the weighted average HLB value of the overall composition.
The compositions according to the present invention further comprise as an essential element an ethylenediamine-N,N'-disuccinic acid.
The compositions herein are not limited to any specific viscosity, and depending on the exact use envisioned, various viscosities may be achieved.
The compositions according to the present invention comprise from 0.01 % to 10 % by weight of the total composition of ethylenediamine-N,N'-disuccinic acid, preferably from 0.01 % to 1 %.
The structure of the acid form of ethylenediamine-N,N'-disuccinic acid is as follows:
Figure 00070001
Ethylenediamine-N,N'-disuccinic acid can be synthesised, for example, from readily available, inexpensive starting materials such as maleic anhydride and ethylenediamine as follows.
Figure 00080001
A more complete disclosure of methods for synthesising ethylenediamine-N,N'-disuccinic acid from commercially available starting materials can be found in US Patent 3,158,635, Kezerian and Ramsay, issued November 24, 1964.
The synthesis of ethylenediamine-N,N'-disuccinic acid from maleic anhydride and ethylene diamine yields a mixture of three optical isomers, [R,R], [S,S], and [S,R], due to the two asymmetric carbon atoms. The biodegradation of ethylenediamine-N,N'-disuccinic acid is optical isomer-specific, with the [S,S] isomer degrading most rapidly and extensively, and for this reason the [S,S] isomer is most preferred for inclusion in the compositions of the invention.
The [S,S] isomer of ethylenediamine-N,N'-disuccinic acid can be synthesised from L-aspartic acid and 1,2-dibromoethane, as follows.
Figure 00080002
A more complete disclosure of the reaction of L-aspartic acid with 1,2-dibromoethane to form the [S,S] isomer of ethylenediamine-N,N'-disuccinic acid can be found in Neal and Rose, Stereospecific Ligands and Their Complexes of Ethylenediamine-discuccinic Acid, Inorganic Chemistry, Vol. 7 (1968), pp. 2405-2412.
Ethylenediamine-N,N'-disuccinic acid can be used in the compositions of the present invention in its acid form or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof. Preferred ethylenediamine-N,N'-disuccinic acid compounds for inclusion in the present compositions are the free acid form and the sodium or magnesium salt thereof. Examples of such preferred sodium salts of ethylenediamine-N,N'-disuccinic acid include Mg ethylenediamine-N,N'-disuccinic acid and Mg2 ethylenediamine-N,N'-disuccinic acid.
The magnesium complexes are the most preferred for inclusion in compositions according to the invention. These complexes may be added to the compositions as such, or they may be formed during the process for making the composition by the reaction of an inert magnesium salt such as MgCl2 or Mg SO4 with an ethylenediamine-N,N'-disuccinic acid compound added as either the acid, or as a salt or complex. Where the ethylenediamine-N,N'-disuccinic acid compound is added in the making process, together with the inert magnesium salt, it is preferred that the molar ratio of magnesium to ethylenediamine-N,N'-disuccinic acid should be greater than 1:1, preferably greater than 3:1, to ensure formation of the desired magnesium complexes.
It has been also found that the pH of the formulation influences its stability. Other than this, there are no other limitations in the pH of the composition. However, bleaching ingredients being optional but preferred ingredients of the compositions herein, it is of course necessary, for chemical stability purposes to formulate the compositions herein with bleaches at a pH as is of from 0 to 6, preferably of from 0.5 to 5. The pH of the can be trimmed by all means available to the man skilled in the art.
Accordingly, preferred compositions according to the present invention comprise bleaches, i.e. hydrogen peroxide or water-soluble sources thereof. Suitable water-soluble sources of hydrogen peroxide include perborate, percarbonate and persilicate salts. Hydrogen peroxide is most preferred to be used in the compositions according to the present invention. Typically, 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%.
The compositions according to the present invention may further comprise a bleach activator as an optional ingredient. By bleach activator, it is meant herein any compound which reacts with hydrogen peroxide to form a peracid. Suitable bleach activators for use herein 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 EP-A-0 624 154. Particularly preferred in that family is acetyl triethyl citrate which was also disclosed in the context of bar soaps in FR-A-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. As used herein and unless otherwise specified, the term bleach activator includes mixtures of bleach activators.
In the embodiment of the present invention, wherein the compositions comprise a bleach activator which is a hydrophobic liquid ingredient, the nonionic surfactant system to be chosen to emulsify said bleach activator depends on the HLB value of said bleach activator. Accordingly, a suitable way to proceed is to determine the HLB value of the hydrophobic liquid ingredient (bleach activator), then select both the hydrophobic nonionic surfactants which have HLB values below said HLB value of said hydrophobic liquid ingredient and the hydrophilic nonionic surfactants which have HLB values above said HLB value of said hydrophobic liquid ingredient, wherein the difference in the HLB values of said hydrophobic and hydrophilic nonionic surfactants is preferably at least 3.
In said embodiment comprising said bleach activator which is a hydrophobic ingredient, the emulsifying system meets the equation: HLB(X) = %A100 x HLB(A) + %B100 x HLB(B) and %A+%B = 100%; where X refers to the hydrophobic liquid ingredient to emulsify, A refers to one of said nonionic surfactants (hydrophilic or hydrophobic), and B refers to the other said nonionic surfactant (hydrophilic or hydrophobic).
In an embodiment of the present invention wherein the compositions comprise acetyl triethyl citrate with an HLB of about 10 as the bleach activator, an adequate nonionic surfactant system would comprise a hydrophobic nonionic surfactant with an HLB from 1 to below 10, and a hydrophilic nonionic surfactant with an HLB of above 11. A particularly suitable system comprises a hydrophobic nonionic surfactant with an HLB of 6, for instance a Dobanol@ 23-2 and a hydrophilic nonionic surfactant with an HLB of 15, for instance a Dobanol@ 91-10. Another suitable nonionic surfactant system comprises a Dobanol@ 23-6.5 (HLB about 12) and a Dobanol@ 23 (HLB below 6). All these Dobanol@ surfactants are commercially available from Shell.
The compositions according to the present invention may further comprise the usual optional ingredients such as perfumes, dyes, optical brighteners, builders and chelants, pigments, enzymes, dye transfer inhibitors, solvents, buffering agents and the like.
The compositions according to the present invention are particularly useful 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, or as dishwashing compositions to be used either in the dishwashing machines or by hand, or as hard surface cleaners, or as toilet bowl cleaners, or as carpet cleaners to be used either by direct application onto the carpets or in carpet cleaning machines.
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 said hydrophobic nonionic surfactant, ethylenediamine-N,N'-disuccinic acid, together with other, optional, hydrophobic ingredients which are to be formulated in the composition, such as perfumes, solvents, enzymes, bleach activators and polymers.
In the second step, a hydrophilic mixture is prepared 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, optical brighteners, builders, chelants, hydrogen peroxide and buffering agents.
Naturally, said first and said second steps can be performed in any order, i.e second step first is also suitable.
In the third step of the process according to the present invention, said hydrophobic mixture and said hydrophilic mixture are mixed together.
The present invention is further illustrated by the following examples:
Examples
Compositions are made which comprise the listed ingredients in the listed proportions (weigh %).
Example 1:
Dobanol@ 91-10 1.2
Dobanol@ 91-2.5 4.8
Citric acid 6
Hydrogen peroxide 6
S,S-EDDS 0.1
Perfume 0.5
Water and minors up to 100%
pH=1
Viscosity (12 rpm, 20°c, after 1 day): 630 cps (reference without S,S-EDDS: 470 cps).
Example 2:
Dobanol@ 91-10 1.2
Dobanol@ 91-2.5 4.8
Citric acid 6
S,S-EDDS 0.1
Perfume 0.5
Water and minors up to 100%
pH=1
Viscosity (12 rpm, 20°C, after 1day): 630 cps
Example 3:
Dobanol@ 91-10 1.2
Dobanol@ 91-2.5 4.8
Citric acid 6
Hydrogen peroxide 12
S,S-EDDS 0.1
Perfume 0.5
Water and minors up to 100%
pH=1
Viscosity (12 rpm, 20°C, after 1day): 650 cps
Example 4:
Dobanol@ 91-10 1.2
Dobanol@ 91-2.5 4.8
Citric acid 6
Hydrogen peroxide 6
S,S-EDDS 0.5
Perfume 0.5
Water and minors up to 100%
pH=1
Viscosity (12 rpm, 20°c, after 1 day): 700 cps
Example 5:
Dobanol@ 23-3 4.8
C8EO4 1.2
Citric acid 6
Hydrogen Peroxide 6
S,S-EDDS 0.1
Perfume 0.5
Water and minors up to 100%
pH=1
Viscosity (12 rpm, 20°C, after 1day): 570 cps

Claims (8)

  1. A stable aqueous emulsion comprising from 2% to 70% by weight of the total emulsion of a hydrophilic nonionic surfactant with an HLB (hydrophilic-lipophilic balance) above 11 and a hydrophobic nonionic surfactant with an HLB below 10 and from 10% to 95% by weight of water, characterized in that said emulsion further comprises from 0,01% to 10% by weight of the total emulsion of ethylenediamine-N,N'-disuccinic acid, or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof or mixtures thereof.
  2. An emulsion according to claim 1 which comprises 0.01% to 1% by weight of the total emulsion of ethylenediamine-N,N'-disuccinic acid, or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof or mixtures thereof.
  3. An emulsion according to any of the preceding claims wherein the nonionic surfactant amount is from 3% to 40% by weight of the total emulsion, preferably from 4% to 30%.
  4. An emulsion according to any of the preceding claims wherein the difference between the HLB values of the hydrophilic nonionic surfactants and the hydrophobic nonionic surfactants is of 3.
  5. An emulsion according to any of the preceding claims which further comprises from 0.5% to 20% of hydrogen peroxide.
  6. An emulsion according to claim 5 which further comprises a bleach activator.
  7. An emulsion according to claim 6 wherein said bleach activator is acetyl triethyl citrate.
  8. A process for the manufacture of a composition according to any of the preceding claims which comprises the steps of:
    Preparing a hydrophobic mixture comprising said hydrophobic nonionic surfactant, ethylenediamine-N,N'-disuccinic acid, or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof or mixtures thereof, together with other, optional, hydrophobic ingredients which are to be formulated in the composition, such as perfumes, solvents, enzymes, bleach activators and polymers;
    Preparing a hydrophilic mixture comprising at least said water, and said hydrophilic nonionic surfactant, and possibly other, optional, hydrophilic ingredients which are to be formulated in the composition such as dyes, optical brighteners, builders, chelants, hydrogen peroxide and buffering agents;
    Subsequently mixing said hydrophobic mixture and said hydrophilic mixture together.
EP93870134A 1992-11-16 1993-07-12 Stable aqueous emulsions of nonionic surfactants with a viscosity controlling agent Expired - Lifetime EP0598693B1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
ES93870134T ES2125322T3 (en) 1992-11-16 1993-07-12 STABLE AQUEOUS EMULSIONS OF NON-ION SURFACES WITH A VISCOSITY CONTROL AGENT.
AT93870134T ATE174955T1 (en) 1992-11-16 1993-07-12 STABLE, NON-IONIC SURFACTANT EMULSIONS CONTAINING VISCOSITY CONTROL AGENTS
DE69322744T DE69322744T2 (en) 1992-11-16 1993-07-12 Stable, nonionic surfactant emulsions that contain viscosity control agents
EP93870134A EP0598693B1 (en) 1992-11-16 1993-07-12 Stable aqueous emulsions of nonionic surfactants with a viscosity controlling agent
PCT/US1993/010444 WO1994011099A1 (en) 1992-11-16 1993-10-29 Stable aqueous emulsions of nonionic surfactants with a viscosity controlling agent
AU55891/94A AU5589194A (en) 1992-11-16 1993-10-29 Stable aqueous emulsions of nonionic surfactants with a viscosity controlling agent

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
EP92870188 1992-11-16
EP92870188A EP0598170B1 (en) 1992-11-16 1992-11-16 Cleaning and bleaching compositions
SG1996002630A SG52309A1 (en) 1993-06-09 1993-06-09 Stable aqueous emulsions of nonionic surfactants
SG1996008330A SG55157A1 (en) 1993-06-09 1993-06-09 Stable aqueous emulsions of nonionic surfactants
EP93870103 1993-06-09
EP93870103A EP0629691B1 (en) 1993-06-09 1993-06-09 Stable aqueous emulsions of nonionic surfactants
EP93870104 1993-06-09
EP93870104A EP0629690B1 (en) 1993-06-09 1993-06-09 Stable aqueous emulsions of nonionic surfactants
EP93870134A EP0598693B1 (en) 1992-11-16 1993-07-12 Stable aqueous emulsions of nonionic surfactants with a viscosity controlling agent

Publications (2)

Publication Number Publication Date
EP0598693A1 EP0598693A1 (en) 1994-05-25
EP0598693B1 true EP0598693B1 (en) 1998-12-23

Family

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Family Applications (1)

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EP93870134A Expired - Lifetime EP0598693B1 (en) 1992-11-16 1993-07-12 Stable aqueous emulsions of nonionic surfactants with a viscosity controlling agent

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AT (1) ATE174955T1 (en)
AU (1) AU5589194A (en)
DE (1) DE69322744T2 (en)
ES (1) ES2125322T3 (en)
WO (1) WO1994011099A1 (en)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996006908A1 (en) * 1994-08-26 1996-03-07 The Procter & Gamble Company Ethylenediamine disuccinate as detergent builder
US5928384A (en) * 1994-11-10 1999-07-27 The Procter & Gamble Company Method of cleaning carpets
CA2204631C (en) * 1994-11-10 2001-02-06 Stefano Scialla Method of cleaning carpets
US5905065A (en) * 1995-06-27 1999-05-18 The Procter & Gamble Company Carpet cleaning compositions and method for cleaning carpets
US5733858A (en) * 1995-08-30 1998-03-31 The Dow Chemical Company Succinic acid derivative degradable chelants, uses and compositions thererof
WO1997008288A1 (en) * 1995-08-30 1997-03-06 The Dow Chemical Company Succinic acid derivative degradable chelants, uses and compositions thereof
EP0779357A1 (en) * 1995-12-16 1997-06-18 The Procter & Gamble Company Stable emulsions comprising a hydrophobic liquid ingredient
WO1999000478A1 (en) * 1997-06-27 1999-01-07 The Procter & Gamble Company Non-aqueous liquid detergent compositions containing enzyme particles
EP0906950A1 (en) * 1997-10-03 1999-04-07 The Procter & Gamble Company Peroxygen bleach-containing compositions comprising a particular chelating agent system
DE19961659A1 (en) * 1999-12-21 2001-07-12 Henkel Kgaa Agents for the treatment of substrates
EP1233055A1 (en) * 2001-02-15 2002-08-21 Givaudan SA Bleaching composition
DE60235068D1 (en) † 2001-03-20 2010-03-04 Procter & Gamble HAIR TREATMENT COMPOSITIONS CONTAINING COMPLEX THINKERS AND METHODS OF REDUCING OXIDATIVE HAIR DAMAGE
KR101615431B1 (en) 2014-05-15 2016-04-25 코오롱인더스트리 주식회사 Polyimide and Film thereof

Citations (4)

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Publication number Priority date Publication date Assignee Title
EP0497337A2 (en) * 1991-02-01 1992-08-05 Hoechst Aktiengesellschaft Aqueous suspensions of peroxycarboxylic acids
EP0598170A1 (en) * 1992-11-16 1994-05-25 The Procter & Gamble Company Cleaning and bleaching compositions
EP0629690A1 (en) * 1993-06-09 1994-12-21 The Procter & Gamble Company Stable aqueous emulsions of nonionic surfactants
EP0629691A1 (en) * 1993-06-09 1994-12-21 The Procter & Gamble Company Stable aqueous emulsions of nonionic surfactants

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Publication number Priority date Publication date Assignee Title
US4704233A (en) * 1986-11-10 1987-11-03 The Procter & Gamble Company Detergent compositions containing ethylenediamine-N,N'-disuccinic acid
DE3907131A1 (en) * 1989-03-06 1990-09-13 Henkel Kgaa BLEACH SUSPENSION

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0497337A2 (en) * 1991-02-01 1992-08-05 Hoechst Aktiengesellschaft Aqueous suspensions of peroxycarboxylic acids
EP0598170A1 (en) * 1992-11-16 1994-05-25 The Procter & Gamble Company Cleaning and bleaching compositions
EP0629690A1 (en) * 1993-06-09 1994-12-21 The Procter & Gamble Company Stable aqueous emulsions of nonionic surfactants
EP0629691A1 (en) * 1993-06-09 1994-12-21 The Procter & Gamble Company Stable aqueous emulsions of nonionic surfactants

Also Published As

Publication number Publication date
DE69322744D1 (en) 1999-02-04
EP0598693A1 (en) 1994-05-25
WO1994011099A1 (en) 1994-05-26
AU5589194A (en) 1994-06-08
DE69322744T2 (en) 1999-07-22
ATE174955T1 (en) 1999-01-15
ES2125322T3 (en) 1999-03-01

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