WO1994012599A1 - Cleaning compositions with combined highly hydrophilic and highly hydrophobic nonionic surfactants - Google Patents

Cleaning compositions with combined highly hydrophilic and highly hydrophobic nonionic surfactants Download PDF

Info

Publication number
WO1994012599A1
WO1994012599A1 PCT/US1993/011293 US9311293W WO9412599A1 WO 1994012599 A1 WO1994012599 A1 WO 1994012599A1 US 9311293 W US9311293 W US 9311293W WO 9412599 A1 WO9412599 A1 WO 9412599A1
Authority
WO
WIPO (PCT)
Prior art keywords
hlb
nonionic surfactant
weight
compositions
composition
Prior art date
Application number
PCT/US1993/011293
Other languages
French (fr)
Inventor
Peter Rosalia Joannes Geboes
Louise Gail Scott
Original Assignee
The Procter & Gamble Company
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=27442487&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO1994012599(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from EP92870191A external-priority patent/EP0598973A1/en
Priority claimed from EP93870050A external-priority patent/EP0616028A1/en
Priority to KR1019950702134A priority Critical patent/KR950704462A/en
Priority to CA002149227A priority patent/CA2149227C/en
Priority to US08/432,154 priority patent/US5559091A/en
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to JP6513290A priority patent/JPH08505413A/en
Priority to BR9307515-4A priority patent/BR9307515A/en
Priority to AU56149/94A priority patent/AU681365B2/en
Publication of WO1994012599A1 publication Critical patent/WO1994012599A1/en
Priority to NO952058A priority patent/NO952058L/en
Priority to FI952540A priority patent/FI952540A/en

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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2079—Monocarboxylic acids-salts thereof
    • 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
    • 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
    • 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
    • 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
    • C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains
    • 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
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C11D1/8305—Mixtures of non-ionic with anionic compounds containing a combination of non-ionic compounds differently alcoxylised or with different alkylated chains
    • 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
    • C11D1/831—Mixtures of non-ionic with anionic compounds of sulfonates with ethers of polyoxyalkylenes without phosphates
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2068—Ethers
    • 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
    • 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
    • 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
    • C11D1/143—Sulfonic 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
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups

Definitions

  • the present invention relates to cleaning compositions. Although the present invention applies primarily to hard surface cleaning compositions, it may also be of interest for other cleaning compositions including dishwashing and laundry detergent compositions.
  • compositions which can be used in diluted form are known in the art.
  • the technical problem lies in sustaining upon dilution an efficient cleaning performance.
  • Such compositions for dilute cleaning are described for instance in the European Patent EP-A- 0 503 219.
  • the dilute cleaning performance is obtained by using alkanolamines.
  • This '219 patent application also mentions the use of nonionic surfactants among which ethoxylated fatty alcohols are listed.
  • Hard surface cleaning compositions comprising various surfactants, including highly ethoxylated nonionic surfactants, which can be used in diluted form are also known in the art. Representative of this prior art are the compositions described in European Patent Application EP 92870045.9.
  • cleaning compositions comprising a specific nonionic surfactant system. Indeed, it has been found that cleaning compositions comprising at least a first nonionic surfactant with an HLB of at least 12(hydrophilic-lipophilic balance) and at least a second nonionic surfactant with an HLB below 10 and at least 4 less than the HLB of said first surfactant exhibit a great flexibility in the soils it may clean. These compositions unexpectedly exhibit outstanding cleaning performance upon dilution, compared to compositions comprising typical nonionic surfactants while the cleaning performance of the neat, i.e. undiluted compositions is similar, regardless of the presence of said nonionic surfactant system.
  • the cleaning compositions comprising a nonionic surfactant system of at least a first surfactant with an HLB of at least 12 and at least a second surfactant with an HLB below 10 and at least 4 less than the HLB of said first surfactant exhibit outstanding cleaning performance when used both neat and diluted.
  • compositions according to the present invention are especially effective on greasy soils, both when used in hard water and also when used in soft water.
  • a particular advantage of the present invention is robustness to different usage conditions, e.g. variations in water hardness used for diluting the product.
  • This invention is also particularly useful as it allows to formulate compositions with reduced levels of other ingredients, yet retaining optimal cleaning performance, due to said combination of at least a first nonionic surfactant with an HLB of at least 12 and at least a second nonionic surfactant with an HLB below 10 and at least 4 less than the HLB of said first surfactant; also, the user needs less product to achieve the same task.
  • This advantage is particularly valuable in terms of environmental compatibility.
  • the present invention encompasses an aqueous cleaning composition comprising from 0.5 % to 30 % by weight of the total composition of a nonionic surfactant system, whereby said nonionic surfactant system comprises: at least 0.1 % by weight of the total composition of a first surfactant with an HLB of at least 12; at least 0.1 % by weight of the total composition of a second surfactant with an HLB below 10 and at least 4 less than the HLB of said first surfactant.
  • the present invention encompasses both neat compositions as described hereinabove and diluted compositions.
  • Diluted compositions are obtained by diluting in water the above neat compositions comprising from 0.5 % to 30 % by weight of the total composition of a nonionic surfactant system.
  • Said diluted compositions comprise from 0.001 % to 5 % by weight of the total composition of said nonionic surfactant system.
  • the present invention also encompasses a method of cleaning hard surfaces wherein a composition comprising a nonionic surfactant system, whereby said nonionic surfactant system comprises at least 0.1 % by weight of the total composition of a first surfactant with an HLB of at least 12 and at least 0.1 % by weight of the total composition of a second surfactant with an HLB below 10 and at least 4 less than the HLB of said first surfactant, is diluted in water and subsequently applied to said hard surface.
  • compositions according to the invention comprise, as an essential ingredient, a nonionic surfactant system comprising at least a nonionic surfactant with an HLB of at least 12, hereinafter referred to as highly hydrophilic surfactant and at least a nonionic surfactant with an HLB below 10 and at least 4 less than that of said highly hydrophilic surfactant, hereinafter referred to as highly hydrophobic surfactant.
  • Suitable nonionic surfactants for the implementation of said surfactant system are alkoxylated alcohols or alkoxylated phenylalcohols which are commercially available with a variety of alcohol chain lengths and a variety of alkoxylation degrees.
  • alkoxylated alcohols or alkoxylated phenylalcohols can be obtained with different HLB values. It is to be understood to those ordinarily skilled in the art that the HLB value of any specific compound is available from the literature.
  • Suitable chemical processes for preparing the highly hydrophilic and highly hydrophobic 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.
  • the highly hydrophilic nonionic surfactants for use in the present invention have an HLB of at least 12, preferably above 14 and most preferably above 15. Those highly hydrophilic nonionic surfactants have been found to be particularly efficient for a rapid wetting of typical hard surfaces covered with greasy soils and to provide effective soil suspension.
  • the highly hydrophobic nonionic surfactants for use in the present invention have an HLB below 10, preferably below 9 and most preferably below 8.5. Those highly hydrophobic nonionic surfactants have been found to provide excellent grease cutting and emulsification properties.
  • Preferred highly hydrophilic nonionic surfactants to be used in the compositions according to the present invention are surfactants having an HLB from 12 to 20 and being according to the formula RO-(C 2 H4 ⁇ ) n( C 3 H 6 ⁇ ) ⁇ n H, wherein R is a C 8 to C2 2 alkyl chain or a Cg to C 28 alkyl benzene chain, and wherein n+m is from 6 to 100 and n is from 0 to 100 and m is from 0 to 100, preferably n+m is from 21 to 50 and, n and m are from 0 to 50, and more preferably n+m is from 21 to 35 and, n and m are from 0 to 35.
  • n and m refer to the average degree of the ethoxylation/propoxylation.
  • the preferred R chains for use herein are the Cg to C22 alkyl chains.
  • Preferred highly hydrophobic nonionic surfactants to be used in the compositions according to the present invention are surfactants having an HLB of from 2 to 10 and being according to the formula RO-(C2H 4 ⁇ ) n( C 3 H 6 ⁇ ) m H, wherein R is a Cg to C22 alkyl chain or a Cg to C2 8 alkyl benzene chain, and wherein n+m is from 0.5 to 5 and n is from 0 to 5 and is from 0 to 5, preferably n+m is from 0.5 to 4 and, n and are from 0 to 4, more preferably n+m is from 1 to 4 and, n and m are from 0 to 4.
  • the preferred R chains for use herein are the Cg to C22 alkyl chains.
  • aqueous cleaning compositions according to the present invention comprise from 0.5% to 30% by weight of the total composition of said nonionic surfactant system, preferably from 2 % to 25 %, more preferably from 4 % to 20 %.
  • compositions according to the present invention comprise said highly hydrophilic nonionic surfactant in an amount of at least 0.1 %, preferably of at least 0.5 %, more preferably of at least 2 %, and said highly hydrophobic nonionic surfactant in an amount of at least 0.1%, preferably of at least 0.5 %, more preferably of at least 2 %.
  • said highly hydrophilic and highly hydrophobic nonionic surfactants may be used in a weight ratio from one to another of from 0.1:1 to 1:0.1, preferably of from 0.2:1 to 1:0.2.
  • the present invention further encompasses diluted compositions which are obtainable by diluting the compositions described hereinabove, and said diluted compositions comprise from 0.001 % to 5 % by weight of the total composition of the nonionic surfactant mixture described hereinabove, preferably from 0.01 % to 0.5 %.
  • compositions according to the present invention further comprise an anionic surfactant.
  • anionic surfactants including alkyl benzene sulfates and sulfonate ⁇ , alkyl ether sulfates, paraffin sulfonates, sulfonates of fatty acids and of fatty acid esters, sulpho succinates, sarcosinates, all of which are suitable for use herein.
  • Said anionic surfactants can also be used in the form of their salts, including sodium, potassium, magnesium, ammonium and alkanol/alkyl ammonium salts.
  • the preferred anionic surfactants for use herein are paraffin sulfonates or alkyl sulfates, preferably in the form of their sodium or ammonium salt.
  • the aqueous cleaning compositions according to the present invention comprise up to 15% by weight of the total neat composition of anionic surfactant, preferably from 2 % to 6 %.
  • the cleaning compositions according to the present invention may further comprise additional surfactants, including other nonionic surfactants, amphoteric and zwitterionic surfactants and mixtures thereof. Typical of these are amine oxides, betaines, sulphobetaines and the like, which are well-known in the detergency art.
  • compositions according to the present invention may further comprise an alkanola ine, or mixtures thereof, in amounts ranging from 0.1% to 10% by weight of the total neat composition, preferably from 0.5% to 5%, most preferably from 0.8% to 3%.
  • the alkanolamine has a buffering effect for alkaline products in the undiluted product, as well as an unexpected boosting effect on the cleaning performance of the diluted compositions.
  • Suitable alkanolamines for use in the compositions according to the present include monoalkanolamines, dialkanolamines, trialkanolamines, alkylalkanolamines, dialkylalkanolamines and alkoxyalkanolamines.
  • Preferred alkanolamines to be used according to the present invention include monoethanolamine, triethanolamine, aminoethylpropanediol, 2-aminomethyl propanol, and ethoxyethanolamine. Particularly preferred are monoethanolamine, triethanolamine and ethoxyethanolamine.
  • compositions according to the present invention may further comprise builders.
  • Suitable builders for use herein include nitrilotriacetates (NTA) , polycarboxylates, dipicolinates, citrates, water-soluble phosphates such as tri-polyphosphate and sodium ortho-and pyro-phosphates, silicates, ethylene diamine tetraacetate (EDTA) , amino- polyphosphonates (DEQUEST) , ether carboxylate builders such as in EP-A-286 167, phosphates, iminodiacetic acid derivatives such as described in EP-A-317 542, EP-262 112 and EP-A-399 133, and mixtures thereof.
  • NTA nitrilotriacetates
  • polycarboxylates such as tri-polyphosphate and sodium ortho-and pyro-phosphates
  • silicates ethylene diamine tetraacetate (EDTA)
  • EDTA ethylene diamine tetraacetate
  • Preferred builders/sequestrants for use herein are selected from tetrapotassium pyrophosphate and citric acid.
  • the aqueous cleaning compositions according to the present invention may comprise up to 15% by weight of the total neat composition of a builder, preferably from 1% to 10%.
  • compositions according to the present invention may further comprise solvents.
  • suitable solvents for- use herein include propylene glycol derivatives such as n- butoxypropanol or n- butoxypropoxypropanol, water-soluble CARBITOL R solvents or water-soluble CELLOSOLVE R solvents; water-soluble CARBITOL R solvents are compounds of the 2- (2-alkoxyethoxy)ethanol class wherein the alkoxy group is derived from ethyl, propyl or butyl; a preferred water- soluble carbitol is 2-(2-butoxyethoxy)ethanol also known as butyl carbitol.
  • Water-soluble CELLOSOLVE R solvents are compounds of the 2-alkoxyethoxy ethanol class, with 2- butoxyethoxyethanol being preferred.
  • Other suitable solvents include benzyl alcohol, and diols such as 2-ethyl- 1, 3-hexanediol and 2,2,4-trimethyl-l,3-pentanediol and mixtures thereof.
  • Preferred solvents for use herein are n- butoxypropoxypropanol, BUTYL CARBITOL R and mixtures thereof.
  • the compositions according to the present invention comprise up to 15% by weight of the total neat composition of a solvent, preferably from 3% to 10%.
  • compositions according to the present invention may also comprise minor ingredients to provide aesthetic or additional product performance benefits.
  • Typical minor ingredients include perfumes, dyes, optical brighteners, soil suspending agents, detersive enzymes, gel-control agents, thickeners, freeze-thaw stabilizers, bactericides, preservatives, hydrotopes like sodium cumene sulfonate and the like.
  • an aqueous cleaning composition comprising from 0.5 % to 30 % by weight of the total composition of a nonionic surfactant system, whereby said nonionic surfactant system comprises at least 0.1 % by weight of the total composition of a first surfactant with an HLB of at least 12 and at least 0.1 % by weight of the total composition of a second surfactant with an HLB below 10 and at least 4 less than said first surfactant's HLB, is diluted in water so as to obtain from 0.001 % to 5 % by weight of the total composition of said nonionic surfactant system and subsequently applied to said hard surface.
  • said composition is diluted into 10 to 200 times its weight of water, more preferably 50 to 150 times, before it is applied to said hard surface.
  • Example I The present invention is further illustrated by the following examples.
  • Example I The present invention is further illustrated by the following examples.
  • compositions were tested for their cleaning performance when used diluted on greasy soil.
  • compositions were made by mixing the listed ingredients in the listed proportions:
  • compositions are Compositions:
  • compositions were evaluated for their grease removal efficiency.
  • a high index is correlated to a high performance.
  • (1) is an ethoxylate nonionic surfactant representative of the prior art with an HLB of 12.
  • Compounds (2) and (3) are ethoxylate nonionic surfactants according to the present invention.
  • (2) is a highly hydrophilic nonionic surfactant with an HLB of 17, wherein R is a mixture of C13 and C15 alkyl chains and n is 30.
  • (3) is a highly hydrophobic nonionic surfactant with an HLB of 8, wherein R is a mixture of C13 and C15 alkyl chains and alkyl chains and n is 3.
  • compositions 1-3 described hereinabove can be used neat or diluted. In the present cleaning performance test these compositions are diluted in 64 times their weight of water and subsequently applied to a hard surface.
  • composition #1 which comprises a nonionic surfactant with an moderate HLB (12) gets a cleaning index of 100 and is used as a reference.
  • compositions #2 and #3 which comprise a nonionic surfactant system comprising alcohol ethoxylate 30EO (an highly hydrophilic nonionic surfactant) and alcohol ethoxylate 3E0 (an highly hydrophobic nonionic surfactant) exhibit outstanding cleaning performance upon dilution both in hard and soft water. Indeed, when used with hard water the compositions #2 and #3 are almost four times more efficient than the composition #1 and when used with soft water the compositions #2 and #3 are two times more efficient than the composition #1.
  • a nonionic surfactant system comprising alcohol ethoxylate 30EO (an highly hydrophilic nonionic surfactant) and alcohol ethoxylate 3E0 (an highly hydrophobic nonionic surfactant) exhibit outstanding cleaning performance upon dilution both in hard and soft water. Indeed, when used with hard water the compositions #2 and #3 are almost four times more efficient than the composition #1 and when used with soft water the compositions #2 and #3 are two times more efficient than the composition #1.
  • a concentrated composition is prepared with the following composition:
  • Neodol 23-3 (C 12 -C 13 E 3 ) 4.0
  • This composition provides good performance while requiring less packaging.

Abstract

The present invention encompasses cleaning compositions comprising a nonionic surfactant system containing a mixture of highly hydrophilic and highly hydrophobic nonionic surfactants. The present invention also encompasses a method of cleaning wherein said compositions are diluted in water before they are used to clean hard surfaces. The present invention also encompasses the diluted cleaning composition obtained in the method according to the present invention.

Description

CLEANING COMPOSITIONS WITH COMBINED HIGHLY HYDROPHILIC AND HIGHLY HYDROPHOBIC NONIONIC SURFACTANTS
Technical field
The present invention relates to cleaning compositions. Although the present invention applies primarily to hard surface cleaning compositions, it may also be of interest for other cleaning compositions including dishwashing and laundry detergent compositions.
Background
Compositions which can be used in diluted form are known in the art. In such compositions, the technical problem lies in sustaining upon dilution an efficient cleaning performance. Such compositions for dilute cleaning are described for instance in the European Patent EP-A- 0 503 219. In these compositions, the dilute cleaning performance is obtained by using alkanolamines. This '219 patent application also mentions the use of nonionic surfactants among which ethoxylated fatty alcohols are listed. Hard surface cleaning compositions comprising various surfactants, including highly ethoxylated nonionic surfactants, which can be used in diluted form are also known in the art. Representative of this prior art are the compositions described in European Patent Application EP 92870045.9.
There is a constant strive for the development of cleaning compositions with better performance in several respects. Better cleaning on all soils, including greasy soils and soap scum is of course a principal object, both for neat and diluted compositions which are often used in the cleaning of for instance hard surfaces. Such greasy soils are commonly brought by cooking with oils and fatty foods, and by simple contact with human skin, thus they are present on most surfaces, particularly in bathrooms and kitchens.
It is thus an object of the present invention to provide cleaning compositions which can be effectively used in diluted form, on various surfaces as well as in laundry applications, to clean various soils and stains. More specifically, it is a further object of the present invention to provide satisfactory shine performance and surface safety when used, as hard surface cleaners.
It has now been found that this object can be efficiently met by formulating cleaning compositions comprising a specific nonionic surfactant system. Indeed, it has been found that cleaning compositions comprising at least a first nonionic surfactant with an HLB of at least 12(hydrophilic-lipophilic balance) and at least a second nonionic surfactant with an HLB below 10 and at least 4 less than the HLB of said first surfactant exhibit a great flexibility in the soils it may clean. These compositions unexpectedly exhibit outstanding cleaning performance upon dilution, compared to compositions comprising typical nonionic surfactants while the cleaning performance of the neat, i.e. undiluted compositions is similar, regardless of the presence of said nonionic surfactant system.
In other words, it has now been found that the cleaning compositions comprising a nonionic surfactant system of at least a first surfactant with an HLB of at least 12 and at least a second surfactant with an HLB below 10 and at least 4 less than the HLB of said first surfactant exhibit outstanding cleaning performance when used both neat and diluted.
Specifically, the compositions according to the present invention are especially effective on greasy soils, both when used in hard water and also when used in soft water. Indeed, a particular advantage of the present invention is robustness to different usage conditions, e.g. variations in water hardness used for diluting the product.
This invention is also particularly useful as it allows to formulate compositions with reduced levels of other ingredients, yet retaining optimal cleaning performance, due to said combination of at least a first nonionic surfactant with an HLB of at least 12 and at least a second nonionic surfactant with an HLB below 10 and at least 4 less than the HLB of said first surfactant; also, the user needs less product to achieve the same task. This advantage is particularly valuable in terms of environmental compatibility.
Summary of the invention
The present invention encompasses an aqueous cleaning composition comprising from 0.5 % to 30 % by weight of the total composition of a nonionic surfactant system, whereby said nonionic surfactant system comprises: at least 0.1 % by weight of the total composition of a first surfactant with an HLB of at least 12; at least 0.1 % by weight of the total composition of a second surfactant with an HLB below 10 and at least 4 less than the HLB of said first surfactant.
The present invention encompasses both neat compositions as described hereinabove and diluted compositions. Diluted compositions are obtained by diluting in water the above neat compositions comprising from 0.5 % to 30 % by weight of the total composition of a nonionic surfactant system. Said diluted compositions comprise from 0.001 % to 5 % by weight of the total composition of said nonionic surfactant system.
The present invention also encompasses a method of cleaning hard surfaces wherein a composition comprising a nonionic surfactant system, whereby said nonionic surfactant system comprises at least 0.1 % by weight of the total composition of a first surfactant with an HLB of at least 12 and at least 0.1 % by weight of the total composition of a second surfactant with an HLB below 10 and at least 4 less than the HLB of said first surfactant, is diluted in water and subsequently applied to said hard surface.
Detailed description of the invention
The compositions according to the invention comprise, as an essential ingredient, a nonionic surfactant system comprising at least a nonionic surfactant with an HLB of at least 12, hereinafter referred to as highly hydrophilic surfactant and at least a nonionic surfactant with an HLB below 10 and at least 4 less than that of said highly hydrophilic surfactant, hereinafter referred to as highly hydrophobic surfactant. Suitable nonionic surfactants for the implementation of said surfactant system are alkoxylated alcohols or alkoxylated phenylalcohols which are commercially available with a variety of alcohol chain lengths and a variety of alkoxylation degrees. By simply varying the length of the chain of the alcohol and/or the degree of alkoxylation, alkoxylated alcohols or alkoxylated phenylalcohols can be obtained with different HLB values. It is to be understood to those ordinarily skilled in the art that the HLB value of any specific compound is available from the literature.
Suitable chemical processes for preparing the highly hydrophilic and highly hydrophobic 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.
The highly hydrophilic nonionic surfactants for use in the present invention have an HLB of at least 12, preferably above 14 and most preferably above 15. Those highly hydrophilic nonionic surfactants have been found to be particularly efficient for a rapid wetting of typical hard surfaces covered with greasy soils and to provide effective soil suspension.
The highly hydrophobic nonionic surfactants for use in the present invention have an HLB below 10, preferably below 9 and most preferably below 8.5. Those highly hydrophobic nonionic surfactants have been found to provide excellent grease cutting and emulsification properties.
Preferred highly hydrophilic nonionic surfactants to be used in the compositions according to the present invention are surfactants having an HLB from 12 to 20 and being according to the formula RO-(C2H4θ)n(C3H6θ)ιnH, wherein R is a C8 to C22 alkyl chain or a Cg to C28 alkyl benzene chain, and wherein n+m is from 6 to 100 and n is from 0 to 100 and m is from 0 to 100, preferably n+m is from 21 to 50 and, n and m are from 0 to 50, and more preferably n+m is from 21 to 35 and, n and m are from 0 to 35. Throughout this description n and m refer to the average degree of the ethoxylation/propoxylation. The preferred R chains for use herein are the Cg to C22 alkyl chains. Examples of highly hydrophilic nonionic surfactants for use herein are LUTENSOL R A030 (HLB=17; R is a mixture of C13 and C15 alkyl chains, n is 30 and m is 0) commercially available from BASF, CETALOX R 50 (HLB= 18 ; R is a mixture of C16 and C^8 alkyl chains, n is 50 and.m is 0) commercially available from WITCO Alfonic R and 810-60 (HLB=12; R is a mixture of Cg and C^Q alkyl chains, n is 6 and m is 0) ; and
MARLIPAL R 013/400 (HLB= 18; R is a mixture of C12 and c 14, n is 40 and m is 0) commercially available from HULS.
Preferred highly hydrophobic nonionic surfactants to be used in the compositions according to the present invention are surfactants having an HLB of from 2 to 10 and being according to the formula RO-(C2H4θ)n(C3H6θ)mH, wherein R is a Cg to C22 alkyl chain or a Cg to C28 alkyl benzene chain, and wherein n+m is from 0.5 to 5 and n is from 0 to 5 and is from 0 to 5, preferably n+m is from 0.5 to 4 and, n and are from 0 to 4, more preferably n+m is from 1 to 4 and, n and m are from 0 to 4. The preferred R chains for use herein are the Cg to C22 alkyl chains. Examples of highly hydrophobic nonionic surfactants for use herein are DOBANOL R 91-2.5 (HLB= 8.1; R is a mixture of C9 and C-n alkyl chains, n is 2.5 and m is 0) commercially available from SHELL, LUTENSOL R A03 (HLB=8; R is a mixture of C13 and C15 alkyl chains, n is 3 and m is 0) commercially available from BASF; Neodol 23-3 (HLB=7.9; R is a mixture of C12 and
C13 alkyl chains, n is 3 and m is 0) and TERGITOL R 25L3 (HLB= 7.7; R is in the range of C12 to ci5 alkyl chain length, n is 3 and m is 0) commercially available from UNION CARBIDE.
It is possible to use for each category of nonionic surfactants (highly hydrophilic or highly hydrophobic) either one of the nonionic surfactant belonging to said category or mixtures thereof.
The aqueous cleaning compositions according to the present invention comprise from 0.5% to 30% by weight of the total composition of said nonionic surfactant system, preferably from 2 % to 25 %, more preferably from 4 % to 20 %.
The compositions according to the present invention comprise said highly hydrophilic nonionic surfactant in an amount of at least 0.1 %, preferably of at least 0.5 %, more preferably of at least 2 %, and said highly hydrophobic nonionic surfactant in an amount of at least 0.1%, preferably of at least 0.5 %, more preferably of at least 2 %.
In the compositions according to the present invention, said highly hydrophilic and highly hydrophobic nonionic surfactants may be used in a weight ratio from one to another of from 0.1:1 to 1:0.1, preferably of from 0.2:1 to 1:0.2.
The present invention further encompasses diluted compositions which are obtainable by diluting the compositions described hereinabove, and said diluted compositions comprise from 0.001 % to 5 % by weight of the total composition of the nonionic surfactant mixture described hereinabove, preferably from 0.01 % to 0.5 %.
In a preferred embodiment of the present invention the compositions according to the present invention further comprise an anionic surfactant. The prior art extensively describes anionic surfactants, including alkyl benzene sulfates and sulfonateε, alkyl ether sulfates, paraffin sulfonates, sulfonates of fatty acids and of fatty acid esters, sulpho succinates, sarcosinates, all of which are suitable for use herein. Said anionic surfactants can also be used in the form of their salts, including sodium, potassium, magnesium, ammonium and alkanol/alkyl ammonium salts. The preferred anionic surfactants for use herein are paraffin sulfonates or alkyl sulfates, preferably in the form of their sodium or ammonium salt. The aqueous cleaning compositions according to the present invention comprise up to 15% by weight of the total neat composition of anionic surfactant, preferably from 2 % to 6 %.
The cleaning compositions according to the present invention may further comprise additional surfactants, including other nonionic surfactants, amphoteric and zwitterionic surfactants and mixtures thereof. Typical of these are amine oxides, betaines, sulphobetaines and the like, which are well-known in the detergency art.
The compositions according to the present invention may further comprise an alkanola ine, or mixtures thereof, in amounts ranging from 0.1% to 10% by weight of the total neat composition, preferably from 0.5% to 5%, most preferably from 0.8% to 3%. At such levels, the alkanolamine has a buffering effect for alkaline products in the undiluted product, as well as an unexpected boosting effect on the cleaning performance of the diluted compositions. Suitable alkanolamines for use in the compositions according to the present include monoalkanolamines, dialkanolamines, trialkanolamines, alkylalkanolamines, dialkylalkanolamines and alkoxyalkanolamines. Preferred alkanolamines to be used according to the present invention include monoethanolamine, triethanolamine, aminoethylpropanediol, 2-aminomethyl propanol, and ethoxyethanolamine. Particularly preferred are monoethanolamine, triethanolamine and ethoxyethanolamine.
The compositions according to the present invention may further comprise builders. Suitable builders for use herein include nitrilotriacetates (NTA) , polycarboxylates, dipicolinates, citrates, water-soluble phosphates such as tri-polyphosphate and sodium ortho-and pyro-phosphates, silicates, ethylene diamine tetraacetate (EDTA) , amino- polyphosphonates (DEQUEST) , ether carboxylate builders such as in EP-A-286 167, phosphates, iminodiacetic acid derivatives such as described in EP-A-317 542, EP-262 112 and EP-A-399 133, and mixtures thereof. Preferred builders/sequestrants for use herein are selected from tetrapotassium pyrophosphate and citric acid. The aqueous cleaning compositions according to the present invention may comprise up to 15% by weight of the total neat composition of a builder, preferably from 1% to 10%.
The compositions according to the present invention may further comprise solvents. Suitable solvents for- use herein include propylene glycol derivatives such as n- butoxypropanol or n- butoxypropoxypropanol, water-soluble CARBITOL R solvents or water-soluble CELLOSOLVE R solvents; water-soluble CARBITOL R solvents are compounds of the 2- (2-alkoxyethoxy)ethanol class wherein the alkoxy group is derived from ethyl, propyl or butyl; a preferred water- soluble carbitol is 2-(2-butoxyethoxy)ethanol also known as butyl carbitol. Water-soluble CELLOSOLVE R solvents are compounds of the 2-alkoxyethoxy ethanol class, with 2- butoxyethoxyethanol being preferred. Other suitable solvents include benzyl alcohol, and diols such as 2-ethyl- 1, 3-hexanediol and 2,2,4-trimethyl-l,3-pentanediol and mixtures thereof. Preferred solvents for use herein are n- butoxypropoxypropanol, BUTYL CARBITOL R and mixtures thereof. The compositions according to the present invention comprise up to 15% by weight of the total neat composition of a solvent, preferably from 3% to 10%.
The compositions according to the present invention may also comprise minor ingredients to provide aesthetic or additional product performance benefits. Typical minor ingredients include perfumes, dyes, optical brighteners, soil suspending agents, detersive enzymes, gel-control agents, thickeners, freeze-thaw stabilizers, bactericides, preservatives, hydrotopes like sodium cumene sulfonate and the like.
The present invention further encompasses a method for the cleaning of hard surfaces. According to the present invention, an aqueous cleaning composition comprising from 0.5 % to 30 % by weight of the total composition of a nonionic surfactant system, whereby said nonionic surfactant system comprises at least 0.1 % by weight of the total composition of a first surfactant with an HLB of at least 12 and at least 0.1 % by weight of the total composition of a second surfactant with an HLB below 10 and at least 4 less than said first surfactant's HLB, is diluted in water so as to obtain from 0.001 % to 5 % by weight of the total composition of said nonionic surfactant system and subsequently applied to said hard surface.
In the method according to the present invention, said composition is diluted into 10 to 200 times its weight of water, more preferably 50 to 150 times, before it is applied to said hard surface.
The present invention is further illustrated by the following examples. Example I
The following compositions were tested for their cleaning performance when used diluted on greasy soil.
The following compositions were made by mixing the listed ingredients in the listed proportions:
Compositions:
Ingredients:
Sodium paraffin sulfonate
Alcohol ethoxylate 7E0 (1)
Alcohol ethoxylate 30EO (2)
Alcohol ethoxylate 3E0 (3)
Sodium Citrate
Butylcarbitol R
Triethanolamine water & minors
Figure imgf000013_0001
These compositions were evaluated for their grease removal efficiency. A high index is correlated to a high performance.
Dilute cleaning performance (index)
Compositions Hard water Soft water
Figure imgf000013_0002
In the examples hereinabove, (1) is an ethoxylate nonionic surfactant representative of the prior art with an HLB of 12. Compounds (2) and (3) are ethoxylate nonionic surfactants according to the present invention. (2) is a highly hydrophilic nonionic surfactant with an HLB of 17, wherein R is a mixture of C13 and C15 alkyl chains and n is 30. (3) is a highly hydrophobic nonionic surfactant with an HLB of 8, wherein R is a mixture of C13 and C15 alkyl chains and alkyl chains and n is 3.
Compositions 1-3 described hereinabove can be used neat or diluted. In the present cleaning performance test these compositions are diluted in 64 times their weight of water and subsequently applied to a hard surface.
Typical dilute grease cleaning results obtained for such compositions are given for the examples hereinabove. Composition #1 which comprises a nonionic surfactant with an moderate HLB (12) gets a cleaning index of 100 and is used as a reference.
According to the present invention, the compositions #2 and #3 which comprise a nonionic surfactant system comprising alcohol ethoxylate 30EO (an highly hydrophilic nonionic surfactant) and alcohol ethoxylate 3E0 (an highly hydrophobic nonionic surfactant) exhibit outstanding cleaning performance upon dilution both in hard and soft water. Indeed, when used with hard water the compositions #2 and #3 are almost four times more efficient than the composition #1 and when used with soft water the compositions #2 and #3 are two times more efficient than the composition #1.
The above results surprisingly show that the use of diluted compositions according to the present invention provides a significant benefit in grease cleaning compared to the composition comprising only nonionic surfactant with a moderate HLB (for example 12) , both in hard and soft water. Example II
A concentrated composition is prepared with the following composition:
Ingredients Weight %
Alfonic 810-60 (Cg-C10 E6) 20.0
Neodol 23-3 (C12-C13 E3) 4.0
Coconut fatty acid 0.6
Monoethanolamine 1.o
Sodium cumene sulfonate 1.5
Minors and water Balance
This composition provides good performance while requiring less packaging.

Claims

What is claimed is:
1. An aqueous cleaning composition comprising from 0.5 % to 30 % by weight of the total composition of a nonionic surfactant system, characterized in that said nonionic surfactant system comprises:
at least 0.1 % by weight of the total composition of a first highly hydrophilic surfactant with an HLB of at least 12; at least 0.1 % by weight of the total composition of a second highly hydrophobic surfactant with an HLB below 10 and at least 4 less than the HLB of said first surfactant.
2. A composition according to claim 1 wherein in said nonionic surfactant system said highly hydrophilic surfactants have an HLB above 14, preferably above 15, and said highly hydrophobic surfactants have an HLB below 9, preferably below 8.5.
3. A composition according to any of the preceding claims wherein the amount of. said highly hydrophilic nonionic surfactant in the total composition is at least 0.5 % by weight, preferably at least 2 %, and the amount of said highly hydrophobic nonionic surfactant in the total composition is at least 0.5 % by weight, preferably at least 2 %.
4. A composition according to any of the preceding claims wherein the weight ratio of said highly hydrophilic nonionic surfactant to said highly hydrophobic nonionic surfactant is from 0.1:1 to 1:0.1, preferably from 0.2:1 to 1:0.2.
5. A composition according to any of the preceding claims wherein the highly hydrophilic nonionic surfactant is a nonionic of the formula RO-(C2H4)n(c 3 H4)mH wherein R is a C8 to C22 alkyl chain or a Cg to C2g alkyl benzene chain, and wherein n+m is from 6 to 100 and n and m are from 0 to 100, preferably n+m is from 21 to 50 and n and m are from 0 to 50, most preferably n+m is from 21 to 35 and n and m are from 0 to 35.
6. A composition according to any of the preceding claims wherein the highly hydrophobic nonionic surfactant is a nonionic of the formula
Figure imgf000017_0001
wherein R is a Cg to C22 alkyl chain or a Cg to C2g alkyl benzene chain, and wherein n+m is from 0.5 to 5 and n and m are from 0 to 5, preferably n+m is from 0.5 to 4 and n and m are from 0 to 4, and most preferably n+m is from 1 to 4 and n and m are from 0 to 4.
7. A composition according to any of the preceding claims which further comprises up to 15% by weight of the total composition of an anionic surfactant.
8. A composition according to claim 7, wherein said anionic surfactant is a paraffin sulfonate in the form of its sodium salt.
9. A method for the cleaning of a hard surface wherein a cleaning composition according to any of the preceding claims is diluted in water and subsequently applied to said hard surface.
10. A method according to claim 9, wherein said composition is diluted into 10 to 200 times its weight of water, more preferably 50 to 150 times, before it is subsequently applied to said hard surface.
11. A diluted hard surface cleaning composition obtainable by diluting in water a composition according to claims 1 to 8, comprising from 0.001 % to 5 %, preferably from 0.01 % to 0.5 % by weight of the total composition of said nonionic surfactants.
PCT/US1993/011293 1992-11-26 1993-11-19 Cleaning compositions with combined highly hydrophilic and highly hydrophobic nonionic surfactants WO1994012599A1 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
AU56149/94A AU681365B2 (en) 1992-11-26 1993-11-19 Cleaning compositions with combined highly hydrophilic and highly hydrophobic nonionic surfactants
BR9307515-4A BR9307515A (en) 1992-11-26 1993-11-19 Cleaning compositions with highly hydrophilic and highly hydrophobic non-ionic surfactants combined
JP6513290A JPH08505413A (en) 1992-11-26 1993-11-19 Cleaning composition combining high hydrophilicity and high hydrophobicity nonionic surfactant
CA002149227A CA2149227C (en) 1992-11-26 1993-11-19 Cleaning compositions with combined highly hydrophilic and highly hydrophobic nonionic surfactants
US08/432,154 US5559091A (en) 1992-11-26 1993-11-19 Alkaline cleaning compositions with combined highly hydrophilic and highly hydrophobic nonionic surfactants
KR1019950702134A KR950704462A (en) 1992-11-26 1993-11-19 CLEANING COMPOSITIONS WITH COMBINED HIGHLY HYDROPHILIC AND HIGHLY HYDROPHOBIC NONIONIC SURFACTANTS
NO952058A NO952058L (en) 1992-11-26 1995-05-24 Purification mixtures with combined high hydrophilic and high hydrophobic nonionic surfactants
FI952540A FI952540A (en) 1992-11-26 1995-05-24 Cleaning compositions with both highly hydrophilic and surface residual hydrophobic non-ionic surfactants

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
EP92870191A EP0598973A1 (en) 1992-11-26 1992-11-26 Multi-purpose liquid cleaning composition
EP92870191.1 1992-11-26
EP93870050A EP0616028A1 (en) 1993-03-19 1993-03-19 Cleaning compositions with short chain nonionic surfactants
EP93870050.7 1993-03-19
EP93201757 1993-06-18
EP93201757.7 1993-06-18
EP93870181.0 1993-08-31
EP93870181A EP0600847B2 (en) 1992-11-26 1993-08-31 Cleaning compositions with combined highly hydrophilic and highly hydrophobic nonionic surfactants

Publications (1)

Publication Number Publication Date
WO1994012599A1 true WO1994012599A1 (en) 1994-06-09

Family

ID=27442487

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1993/011293 WO1994012599A1 (en) 1992-11-26 1993-11-19 Cleaning compositions with combined highly hydrophilic and highly hydrophobic nonionic surfactants

Country Status (17)

Country Link
EP (1) EP0600847B2 (en)
JP (1) JPH08505413A (en)
KR (1) KR950704462A (en)
AT (1) ATE172234T1 (en)
AU (1) AU681365B2 (en)
BR (1) BR9307515A (en)
CA (1) CA2149227C (en)
DE (1) DE69321562T3 (en)
DK (1) DK0600847T3 (en)
EG (1) EG20373A (en)
ES (1) ES2124778T5 (en)
FI (1) FI952540A (en)
MA (1) MA23039A1 (en)
NO (1) NO952058L (en)
NZ (1) NZ258466A (en)
TR (1) TR28413A (en)
WO (1) WO1994012599A1 (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5634979A (en) * 1994-12-22 1997-06-03 Henkel Corporation Composition and method for degreasing metal surfaces
WO1999009121A1 (en) * 1997-08-20 1999-02-25 Colgate-Palmolive Company Microemulsion all purpose liquid cleaning compositions
US7153493B2 (en) 1999-03-12 2006-12-26 Warner-Lambert Company Llc Clear oral compositions containing potassium salt
WO2009143510A1 (en) * 2008-05-23 2009-11-26 Colgate-Palmolive Company All-purpose cleaning compositions
WO2013107579A1 (en) * 2012-01-18 2013-07-25 Henkel Ag & Co. Kgaa Washing, cleaning or pre-treatment agent with increased cleaning power
US20170253833A1 (en) * 2016-03-04 2017-09-07 S.C. Johnson & Son, Inc. Neutral floor cleaner compositions
EP2625256B1 (en) * 2010-10-08 2017-11-22 Ecolab USA Inc. Laundry detergent composition for low temperature washing and disinfection

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0598973A1 (en) * 1992-11-26 1994-06-01 The Procter & Gamble Company Multi-purpose liquid cleaning composition
EP0616027A1 (en) * 1993-03-19 1994-09-21 The Procter & Gamble Company Concentrated cleaning compositions
JP3556806B2 (en) * 1996-07-24 2004-08-25 サンスター株式会社 Detergent composition
GB0004769D0 (en) * 2000-03-01 2000-04-19 Reckitt & Colmann Prod Ltd Improvements in or relating to organic compositions
CA2632934A1 (en) * 2005-12-20 2007-07-05 Novozymes Biologicals, Inc. Surfactants systems for surface cleaning

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5145850A (en) * 1990-03-01 1992-09-08 Takeda Chemical Industries, Ltd. Imidazopyridazines, their production and use

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1792066A1 (en) * 1968-07-18 1971-10-14 Henkel & Cie Gmbh Low-foaming stain treatment agent for textiles
DK132960A (en) * 1970-03-31
GB2011944B (en) * 1978-01-09 1982-06-09 Unilever Ltd Liquid detergent composition
US5076954A (en) † 1986-05-21 1991-12-31 Colgate-Palmolive Company Stable microemulsion cleaning composition
US4764302A (en) * 1986-10-21 1988-08-16 The Clorox Company Thickening system for incorporating fluorescent whitening agents
DE3818062A1 (en) * 1988-05-27 1989-12-07 Henkel Kgaa FOAMING ALKYL POLYGLYCOLETHER FOR CLEANING AGENT (I)
US5008030A (en) * 1989-01-17 1991-04-16 Colgate-Palmolive Co. Acidic disinfectant all-purpose liquid cleaning composition
GB8914602D0 (en) * 1989-06-26 1989-08-16 Unilever Plc Liquid detergent composition
JPH078991B2 (en) * 1989-07-18 1995-02-01 花王株式会社 Neutral liquid detergent composition
DE3928600A1 (en) * 1989-08-30 1991-03-07 Henkel Kgaa FOAM-ABSORBING MULTI-MATERIAL MIXTURES WITH TENSIDE CHARACTER FOR MACHINE CLEANING AND BOTTLE CLEANING
DE4028138A1 (en) * 1990-09-05 1992-03-12 Huels Chemische Werke Ag VISCOSE ACIDIC DETERGENTS
TW291496B (en) * 1991-02-01 1996-11-21 Hoechst Ag
EP0503219A1 (en) * 1991-03-11 1992-09-16 THE PROCTER & GAMBLE COMPANY Method and diluted cleaning composition for the cleaning of hard surfaces
DE69224389T2 (en) * 1992-11-16 1998-08-13 Procter & Gamble Detergent and bleach compositions

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5145850A (en) * 1990-03-01 1992-09-08 Takeda Chemical Industries, Ltd. Imidazopyridazines, their production and use

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5634979A (en) * 1994-12-22 1997-06-03 Henkel Corporation Composition and method for degreasing metal surfaces
WO1999009121A1 (en) * 1997-08-20 1999-02-25 Colgate-Palmolive Company Microemulsion all purpose liquid cleaning compositions
US7153493B2 (en) 1999-03-12 2006-12-26 Warner-Lambert Company Llc Clear oral compositions containing potassium salt
US7435409B2 (en) 1999-03-12 2008-10-14 Mcneil-Ppc, Inc. Compositions comprising a potassium salt active ingredient, including oral compositions for reducing dental nerve and dentin sensitivity comprising a non-menthol flavoring
US8618041B2 (en) 2008-05-23 2013-12-31 Colgate-Palmolive Company All-purpose cleaning compositions
WO2009143510A1 (en) * 2008-05-23 2009-11-26 Colgate-Palmolive Company All-purpose cleaning compositions
EP3219780A1 (en) * 2008-05-23 2017-09-20 Colgate-Palmolive Company All-purpose cleaning compositions
EP2625256B1 (en) * 2010-10-08 2017-11-22 Ecolab USA Inc. Laundry detergent composition for low temperature washing and disinfection
WO2013107579A1 (en) * 2012-01-18 2013-07-25 Henkel Ag & Co. Kgaa Washing, cleaning or pre-treatment agent with increased cleaning power
US20170253833A1 (en) * 2016-03-04 2017-09-07 S.C. Johnson & Son, Inc. Neutral floor cleaner compositions
WO2017152063A1 (en) * 2016-03-04 2017-09-08 S.C.Johnson & Son, Inc. Neutral floor cleaner compositions
US11046913B2 (en) 2016-03-04 2021-06-29 S. C. Johnson & Son, Inc. Neutral floor cleaner compositions
AU2017228372B2 (en) * 2016-03-04 2021-08-19 S.C. Johnson & Son, Inc. Neutral floor cleaner compositions
US11866674B2 (en) 2016-03-04 2024-01-09 S.C. Johnson & Son, Inc. Neutral floor cleaner compositions

Also Published As

Publication number Publication date
TR28413A (en) 1996-06-14
AU5614994A (en) 1994-06-22
ES2124778T5 (en) 2002-05-01
DK0600847T3 (en) 1999-06-23
CA2149227C (en) 1999-05-11
BR9307515A (en) 1999-08-31
ATE172234T1 (en) 1998-10-15
FI952540A0 (en) 1995-05-24
KR950704462A (en) 1995-11-20
DE69321562T2 (en) 1999-06-02
NO952058D0 (en) 1995-05-24
CA2149227A1 (en) 1994-06-09
AU681365B2 (en) 1997-08-28
NZ258466A (en) 1997-05-26
JPH08505413A (en) 1996-06-11
DE69321562T3 (en) 2002-04-18
MA23039A1 (en) 1994-07-01
NO952058L (en) 1995-07-24
FI952540A (en) 1995-05-24
ES2124778T3 (en) 1999-02-16
EP0600847B1 (en) 1998-10-14
DE69321562D1 (en) 1998-11-19
EP0600847B2 (en) 2001-10-31
EP0600847A1 (en) 1994-06-08
EG20373A (en) 1999-01-31

Similar Documents

Publication Publication Date Title
US5559091A (en) Alkaline cleaning compositions with combined highly hydrophilic and highly hydrophobic nonionic surfactants
EP0527625B1 (en) Glass cleaning composition
EP0126545B1 (en) Liquid scouring cleansers containing solvent system
US7786068B2 (en) Cleaning composition comprising a ternary surfactant system in combination with dipropyl or diisopropyl adipate solvent
CA2158541C (en) Cleaning compositions with short chain nonionic surfactants
US20060211593A1 (en) Enhanced solubilization using extended chain surfactants
CA2625073C (en) Acidic cleaning compositions
AU681365B2 (en) Cleaning compositions with combined highly hydrophilic and highly hydrophobic nonionic surfactants
EP3015540B1 (en) Hard surface cleaners comprising ethoxylated alkoxylated nonionic surfactants
CA2063219A1 (en) Method and diluted cleaning composition for the cleaning of hard surfaces
JP7274494B2 (en) Aqueous cleaning formulation
EP0561103B1 (en) Dilutable compositions and method for cleaning of hard surfaces
GB2179669A (en) Liquid laundry detergent compositions
US9957467B2 (en) Hard surface cleaners comprising ethoxylated alkoxylated nonionic surfactants
US20170369817A1 (en) Hard surface cleaning compositions
US5981455A (en) Cleaning compositions with short chain nonionic surfactants
IE920774A1 (en) Method and diluted cleaning composition for the cleaning of¹hard surfaces
EP0815188A1 (en) Alkaline detergent having high contents of nonionic surfactant and complexing agent, and use of an amphoteric compound as solubiliser
NZ242077A (en) Diluted cleaning compositions containing an alkanolamine : method for cleaning hard surfaces

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU BB BG BR BY CA CZ FI HU JP KP KR KZ LK LV MG MN MW NO NZ PL RO RU SD SK UA US UZ VN

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BF BJ CF CG CI CM GA GN ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 08432154

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 258466

Country of ref document: NZ

WWE Wipo information: entry into national phase

Ref document number: 2149227

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 952540

Country of ref document: FI