EP0106266A2 - Mélange terpène-solvant utilisable pour la préparation de compositions détergentes liquides - Google Patents
Mélange terpène-solvant utilisable pour la préparation de compositions détergentes liquides Download PDFInfo
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- EP0106266A2 EP0106266A2 EP83109923A EP83109923A EP0106266A2 EP 0106266 A2 EP0106266 A2 EP 0106266A2 EP 83109923 A EP83109923 A EP 83109923A EP 83109923 A EP83109923 A EP 83109923A EP 0106266 A2 EP0106266 A2 EP 0106266A2
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- EP
- European Patent Office
- Prior art keywords
- alkyl
- terpene
- acid
- compositions
- carbon atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- 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
- C11D3/164—Organic compounds containing a carbon-carbon triple bond
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- 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
- C11D3/18—Hydrocarbons
- C11D3/188—Terpenes
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- 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
- C11D3/2003—Alcohols; Phenols
- C11D3/2006—Monohydric alcohols
- C11D3/2037—Terpenes
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- 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
- C11D3/43—Solvents
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- 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
- C11D3/2003—Alcohols; Phenols
- C11D3/2006—Monohydric alcohols
- C11D3/2034—Monohydric alcohols aromatic
Definitions
- This invention relates to liquid detergent compositions.
- it relates to aqueous detergent compositions suitable for use as general purpose household cleaning . compositions.
- Powdered cleaning compositions consist mainly of builder or buffering-salts such as phosphates, carbonates, silicates etc., and although such compositions may display good inorganic soil removal, they are generally deficient in cleaning ability on organic soils such as the grease/fatty/oily soils typically found in the domestic environment.
- Liquid cleaning compositions on the other hand, have the great advantage that they can be applied to hard surfaces in neat or concentrated form so that a relatively high level of surfactant material is delivered directly to the soil. Moreover, it is a rather more straightforward task to incorporate high concentrations of anionic or nonionic surfactant in a liquid rather than a granular composition. For both these reasons, therefore, liquid cleaning compositions have the potential to provide superior grease and oily soil removal over powdered cleaning compositions.
- liquid cleaning compositions still suffer a number of drawbacks which can limit their consumer acceptability.
- they generally contain little or no detergency builder salts and consequently they tend to have. poor cleaning performance on particulate soil and also lack "robustness" under varying water hardness levels.
- they can suffer problems of product form, in particular, inhomogeneity, lack of clarity, or inadequate viscosity characteristics for consumer use.
- the higher in- product and in-use surfactant concentration necessary for improved grease handling raises problems of extensive suds formation requiring frequent rinsing and wiping on behalf of the consumer.
- oversudsing may be controlled to some extent by incorporating a suds-regulating material such as hydrophobic silica and/or silicone or soap, this in itself can raise problems of poor product stability and homogeneity and also problems associated with deposition of insoluble particulate or soap residues on the items or surfaces being cleaned, leading to filming, streaking and spotting.
- a suds-regulating material such as hydrophobic silica and/or silicone or soap
- terpenes herein specified are valuable in regulating the sudsing behavious of the instant compositions in both hard and soft water and under both diluted and neat or concentrated usage, while terpenes of the terpene alcohol class are also valuable for providing effective control of product viscosity characteristics.
- Terpenes are, of course, well-known components of perfume compositions and are often incorporated into detergent compositions at low levels via the perfume. Certain terpenes have also been included in detergent compositions at higher levels; for instance, German patent application 2,113,732 discloses the use of aliphatic and alicyclic terpenes as anti-microbial agents in washing compositions, while British Patent 1,308,190 teaches the use of dipentene in a thixotropic liquid detergent suspension base composition. German patent application 2,709,690 teaches the use of pine oil (a mixture mainly of terpene alcohols) in liquid hard surface cleaning compositions. There has apparently been no disclosure, however, of the combined use of a terpene cleaning agent with a polar solvent of low-water solubility.
- the present invention thus provides liquid detergent compositions which are stable homogeneous fluent liquids having excellent suds control across the range of usage and water hardness conditions and which provide excellent shine performance together with improved cleaning characteristics both on greasy/oily soils and on inorganic particulate soils with little tendency to cause filming or streaking on washed surfaces.
- Preferred terpenes are mono- and bicyclic monoterpenes, especially those of the hydrocarbon class, which can be selected from terpinenes, terpinolenes, limonenes and pinenes. Highly preferred materials of this type include d-limonene, dipentene, a-pinene, ⁇ -pinene and the mixture of terpene hydrocarbons obtained from the essence of oranges (eg. cold-pressed orange terpenes and orange terpene oil phase ex fruitjuice).
- Terpene alcohols, aldehydes and ketones can also be used, however, the alcohols, in particular, providing valuable but unexpected improvements in viscosity regulation when incorporated in the compositions of the invention at a level, preferably, of from about 1% to about 3%, more preferably from about 1.5% to about 2.5%.
- the terpene is used in combination with a polar solvent (i.e. containing at least one hydrophilic group) having a solubility in water of from about 0.2% to about 10% by weight (g/100 g solution), preferably from about 0.5% to about 6% by weight, for example benzyl alcohol.
- compositions of the invention also preferably contain from about 0.005% to about 2%, more preferably from about 0.05% to about 0.7% of an alkali metal, ammonium or alkanolammonium soap of a C13-C24, especially C 13 -C 18 , fatty acid.
- the fatty acid is fully saturated, for example, by hydrogenation of naturally occurring fatty acids. Addition of the soap, particularly to compositions containing terpene hydrocarbons, is found to provide significant.synergistic enhancement in the suds-suppression effectiveness of the system.
- a calcium sequestrant is also desirable in the present compositions, providing not only cleaning advantages on particulate soil, but also, surprisingly, advantages in terms of product homogeneity and stability.
- the sequestrant component is a water-soluble inorganic or organic polyanionic sequestrant having a calcium ion stability constant at 25°C of at least about 2,0, preferably at least about 3.0, the weight ratio of surfactant:sequestrant preferably lying in the range from about 5:1 to about 1:3, especially about 3:1 to about 1:1.
- the sequestrant has an anion valence of at least 3 and is incorporated at a level of from about 0.5% to about 13% by weight.
- the composition itself preferably has a pH in 1% aqueous solution of at least about 8.0.
- the sequestrant can be selected from the. water-soluble salts of polyphosphates, polycarboxylates, aminopolycarboxylates, polyphosphonates and amino polyphosphonates and added at a level in the range from 1 to 9%, especially 2 to 8%, more especially 3 to 7% by weight of the composition. Adjustment of the sequestrant level and surfactant:sequestrant ratio within the above specified ranges is important for providing compositions of optimum stability.
- a notable feature of the instant compositions is the suds-suppression effectiveness of the terpenes in liquid compositions based on ampholytic or zwitterionic surfactants.
- ampholytic or zwitterionic surfactants are notoriously difficult to control the sudsing behaviour of these surfactants in a cost-effective manner using conventional suppression agents such as soaps, waxes etc.
- the terpenes are thus particularly valuable in this respect.
- anionic, nonionic, zwitterionic and amphoteric surfactants can be used in the present compositions.
- a typical listing of the classes and species of these sur- . factants is given in U.S. Patent 3,663,961 issued to Norris on May 23, 1972 and incorporated herein by reference.
- These surfactants can be used singly or in combination at levels in the range from about 1% to about 20%, preferably at levels from about 3% to about 10% by weight of the compositions.
- Suitable anionic non-soap "surfactants are water-soluble salts of alkyl benzene sulfonates, alkyl sulfates, alkyl polyethoxy ether sulfates, paraffin sulfonates, alpha-olefin sulfonates, alpha-sulfocarboxylates and their esters, alkyl glyceryl ether sulfonates, fatty acid monoglyceride sulfates and sulfonates, alkyl phenol polyethoxy ether sulfates, 2- acyloxy-alkane-l-sulfonate, and beta-alkyloxy alkane sulfonate.
- the paraffin sulfonates are highly preferred.
- a particularly suitable class of anionic detergents includes water-soluble salts, particularly the alkali metal, ammonium and alkanolammonium salts of organic sulfuric reaction products having in their molecular structure an alkyl or alkaryl group containing from about 8 to about 22, especially from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
- alkyl is the alkyl portion of acyl groups.
- Examples of this group of synthetic detergents which form part of the detergent compositions of the present invention are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C 8 -C 18 ) carbon atoms produced by reducing the glycerides of tallow or coconut oil and sodium and potassium alkyl benzene sulfonates, in which the alkyl group contains from about 9 to about 15, especially about 11 to about 13, carbon atoms, in straight chain or branched chain configuration, e.g.
- anionic detergent compounds herein include the sodium C 10 -C 18 alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride r sulfonates and sulfates; and sodium or potassium salts of alkyl phenol ethylene oxide ether sulfate containing about 1 :o about 10 units of ethylene oxide per molecule and wherein the alkyl groups contain about 8 to about 12 carbon atoms.
- Other useful anionic detergent compounds herein include the water-soluble salts or esters of ⁇ -sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-l-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from'about 9 to about 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing from about 10 to 18, especially about 12 to 16, carbon atoms in the alkyl group and from about 1 to 12, especially 1 to 6, more especially 1 to 4 moles of ethylene oxide; water-soluble salts of olefin sulfonates containing from about 12 to 24, preferably about 14 to 16, carbon atoms, especially those made by reaction with sulfur trioxide followed by neutralization under conditions such that any sultones present are hydrolysed to the corresponding hydroxy alkane sulfon
- alkane chains of the foregoing non-soap anionic surfactants can be derived from natural sources such as coconut oil or tallow, or can be made synthetically as for example using the Ziegler or_Oxo processes.
- Water solubility can be achieved by using alkali metal, ammonium or alkanol- ammoniiun cations; sodium is preferred.
- Magnesium and calcium are preferred cations under circumstances described by Belgian patent 843,636 invented by Jones et al, issued December 30, 1976.
- a preferred mixture contains alkyl benzene sulfonate having 11 to 13 carbon atoms in the alkyl group or paraffin sulfonate having 14 to 18 carbon atoms and either an alkyl sulfate having 8 to 18, preferably 12 to 18, carbon atoms in the alkyl group, or an alkyl polyethoxy alcohol sulfate having 10 to 16 carbon atoms in the alkyl group and an average degree of ethoxylation of 1 to 6.
- Suitable nonionic surfactants include alkoxylated nonionic surfactants and also those of a semi-polar character.
- Alkoxylated nonionic surfactant materials can be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
- Suitable nonionic surfactants include:
- alkoxylated nonionic surfactants having an average HLB in the range from about 9.5 to 13.5, especially 10 to 12.5.
- Highly suitable nonionic surfactants of this type are ethoxylated primary or secondary Cg-15 alcohols having an average degree of ethoxylation from about 3 to 9, more preferably from about 5 to 8.
- Suitable semi-polar surfactants are water-soluble amine oxides containing one alkyl moiety of from about 10 to 28 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to about 3 carbon atoms, and especially alkyl dimethyl amine oxides wherein the alkyl group contains from about 11 to 16 carbon atoms; water-soluble phosphine oxide detergents containing one alkyl moiety of about 10 to 28 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to 3 carbon atoms; and water-soluble sulfoxide detergents containing one alkyl moiety of from about 10 to 28 carbon atoms an a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from 1 to 3 carbon atoms.
- Suitable ampholytic surfactants are water-soluble derivatives of aliphatic secondary and tertiary amines in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water-solubilizing group, e.g. carboxy, sulfonate, sulfate, phosphate, or phosphonate.
- Suitable zwitterionic surfactants are water soluble derivatives of aliphatic quaternary ammonium phosphonium and sulfonium cationic compounds in which the aliphatic moieties can be straight chain or branched, and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water-solubilizing group.
- Preferred amphoteric and zwitterionic surfactants have the general formula:- wherein X is CO 2 or SO 3 , R1 is alkyl or alkenyl group having 8 to 22 carbon atoms, possibly interrupted by amide, ester or ether linkages, R 2 is a methylene, ethylene, propylene, isopropylene or isobutylene radical, R 3 and R 4 are independently selected from hydrogen, C 1-3 alkyl or -R 2 -X, whereby one of the substituents R 3 and R 4 is hydrogen if the other one is represented by the group -R 2 X, n is an integer from 1 to 6, and A is an equivalent amount of a neutralizing anion, except that amphoteric surfactants include amine salts of the above formula and also the corresponding free amines.
- Highly preferred surfactants include N-alkyl-2-aminopropionic acid, N-alkyl-2 - imino-diacetic acid, N-alkyl-2-iminodipropionic acid, N-alkyl-2-amino-2-methyl-propionic acid, N-alkyl-propylenediamine- propionic acid, N-alkyl-dipropylenetriamine-propionic acid, N-alkyl-dipropylenetriamine dipropionic acid, N-alkylglycine, N-alkyl-amino-succinic acid, N-amidoalkyl- N'-carboxymethyl-N',N'-dimethyl-ammonio -ethylene diamine, N-alkyl-aminoethane-sulfonic acid, N-alkyl-N,N-dimethyl-ammonio-hydroxy- propene-sulfonic acid and salts thereof, wherein alkyl
- Armeen Z (marketed by Armour), Amphosol AA and SP (marketed by I.C.V.), Amphoram CP1, Diamphoram CP1, Triamphoram CP1, Triamphoram C 2 P 1 and Polyamphorams CP1, C 2 P 1 and C 3 Pl (marketed by Pierrefitte-Auby) and Deriphat 170C and Deriphat 154 (marketed by General Mills).
- compositions comprise as the single or major surfactant component, surfactants selected from the anionic, amphoteric and zwitterionic classes.
- the nonionic surfactants when present are preferably included in only a minor amount, i.e. at a level of about 5 to about 50% by weight of the surfactant system.
- the sequestrant can be selected from the water-soluble salts of polyphosphates, polycarboxylates, aminopolycarboxylates, polyphosphonates and aminopolyphosphonates having a logarithmic calcium ion stability constant (pK Ca ++) of about 2 or greater and preferably an anion valence of at least 3.
- the stability constant is defined as follows:- where and An is the ionic species of sequestrant which predominates at the in-use pH of the composition (defined as the pH of a 1% aqeuous solution of the composition) and n is at least 3.
- the sequestrant has a pK Ca ++ in the range from about 2 to about 11, especially from about 3 to about 8.
- Literature values of stability constants are taken where possible (see Stability Constants of Metal-Ion Complexes, Special Publication No. 25, The Chemical Society, London); where doubt arises, the stability constant is defined at 25°C and at zero ionic strength using a glass electrode method of measurement as described in Complexation in Analytical Chemistry by Anders Ringbom (1963).
- Suitable polyphosphates include pyrophosphates such as tetrasodium pyrophosphate decahydrate, and tetrapotassium pyrophosphate; tripolyphosphates such as pentapotassium tripolyphosphate; and higher polyphosphates and metaphosphates such as sodium pentapolyphosphate and sodium hexametaphosphate.
- the carboxylate-type sequestrants can be described as monomeric polycarboxylate materials or oligomers or polymers derived from carboxylate or polycarboxylate monomers.
- the sequestrants can be acyclic, alicyclic or aromatic in nature.
- Suitable polycarboxylates include the salts of citric acid, aconitic acid, citraconic acid, carboxymethyloxy succinic acid, lactoxysuccinic acid, and 2-oxa-1,1,3-propane tricarboxylic acid; oxydisuccinic acid, 1,1,2,2-ethane tetra carboxylic acid, 1,1,3,3-propane tetracarboxylic acid and 1,1, 2,3-propane tetracarboxylic acid; cyclopentane-cis, cis, cis-tetracarboxylic acid, cyclopenta dienide penta- carboxylic acid, 2,3,4,5-tetrahydrofuran-cis, cis, cis- carboxylic acid, 2,5-tetrahydrofuran-cis-dicarboxylic acid, 1,2,3,4,5,6-hexane-hexacarboxylic acid, mellitic acid, pyromelli
- Suitable polymeric polycarboxylates include homo- and copolymers of polycarboxyl monomers such as maleic acid, citraconic acid, aconitic acid, fumaric acid, mesaconic acid, phenyl maleic acid, benzyl maleic acid, itaconic acid and methylene malonic acid; homo- and copolymers of acrylic monomers such as acrylic acid, methacrylic acid or d-hydroxy acrylic acid; or copolymers of one or more of the above polycarboxyl and acrylic monomers with another unsaturated polymerizable monomer, such as vinyl ethers, acrylic esters, olefins, vinyl pyrrolidones and styrenes.
- polycarboxyl monomers such as maleic acid, citraconic acid, aconitic acid, fumaric acid, mesaconic acid, phenyl maleic acid, benzyl maleic acid, itaconic acid and methylene malonic acid
- acrylic monomers such
- Suitable aminopolycarboxylates include especially the amino polyacetates, e.g. sodium, potassium, ammonium and alkanolammonium ethylenediamine tetraacetates, diethylene triamine pentaacetates and nitrilotriacetates.
- Polyphosphonate and aminopolyphosphonate materials suitable for use herein can be exemplified by nitrilo tri(methylene phosphonic acid), ethylenediamine tetra (methylene phosphonic acid), diethylenetriamine penta (methylenephosphonic acid) and the water-soluable salts thereof.
- the terpene component of the instant compositions belongs to the class of mono- or sesquiterpenes or mixtures thereof and can be acyclic or preferably monocyclic or bicyclic in structure. It is preferably liquid at room temperature (25 C).
- Preferred terpenes belong to the class of terpene hydrocarbbns and terpene alcohols.
- Examples of acyclic terpene hydrocarbons suitable for use herein include 2-methyl-6-methylene-2, 7-octadiene and 2,6-dimethyl-2,4,6-octadiene.
- Preferred monocyclic terpene hydrocarbons belong to the terpinene, terpinolene and limonene classes, for example, the ⁇ , ⁇ andr-terpinenes, the d and Z-limonenes and dipentene (essentially a limonene racemate).
- the limonenes occur naturally in certain fruit and vegetable essences and a preferred source of limonene is the essence of orange and other citrus fruits.
- Preferred bicyclic terpene hydrocarbons include ⁇ and ⁇ -pinene. The terpene is added at a level of about 0.5% to about 10%, preferably 1% to about 5% by weight of the composition.
- the terpene alcohol can be a primary, secondary or tertiary alcohol derivative of a cyclic or acyclic terpene hydrocarbon.
- Suitable tertiary alcohols include terpineol, usually sold commercially as a mixture of ⁇ , ⁇ and ⁇ isomers and linalool;
- suitable secondary alcohols include borneol;
- suitable primary alcohols include geraniol.
- Complex mixtures of terpene alcohols are also suitable, especially the mixture of alcohols manufactured by distilling the oils extracted from pine wood, cones and needles and sold commercially as "pine oils”.
- the terpene alcohol is preferably added at a level in the range from about 1% to about 3%, more preferably from about 1.5% to about 2.5% by weight of the compositions in order to provide optimum control of product viscosity characteristics.
- Preferably such compositions have a-viscosity in the range from about 80 to 200 cp (0.08 to 0.2 Pa.s) measured in a Brookfield viscometer, using Spindle No. 2 at 60 r.p.m. and at 21 0 C.
- the polar solvent component of the present compositions has a solubility in water at 25°C in the range from about 0.2% to about 10%, preferably from about 0.5% to about 6%.
- the solvent contains at least one hydrophilic group and is liquid at room temperature.
- the solvent can be at a level of about 0.5% to about 10% especially 1% to about 5%, by weight of the composition and at a weight ratio of terpene:solvent in the range from about 5:1 to 1:5, especially 2:1 to 1:2.
- Highly preferred materials include aromatic alcohols such as benzyl alcohol, polyethoxylated phenols containing from 2 to 6 ethoxy groups and phenylethyl alcohol; esters of C 1 -C 6 fatty acids with C 1 -C 6 alcohols containing a total of from 5 to 9 carbon atoms, et, n-butyl butyrate, n-butyl propionate and n-propyl acetate; and mono C 6 -C 9 and di-C 4 -C 9 alkyl or aryl ethers of ethylene glycol such as hexyl, benzyl and phenyl Cellosolves (Registered Trade Mark) and ethyleneglycol dibutyl ether.
- aromatic alcohols such as benzyl alcohol, polyethoxylated phenols containing from 2 to 6 ethoxy groups and phenylethyl alcohol
- compositions of the invention can be supplemented by all manner of detergent components compatible with a fluent, liquid system.
- Anon-aqueous solvent is a particularly suitable additional ingredient, especially water miscible or highly soluble (at least 20%w/w) aliphatic mono-, di- and tri alcohols.
- water miscible or highly soluble (at least 20%w/w) aliphatic mono-, di- and tri alcohols are particularly suitable.
- Specific examples are ethanol, propanol, isopropanol, and propane-1,3-diol.
- Suitable solvents are ethylene-, propylene-, diethylene- and dipropylene glycol and the mono-C 1-4 alkyl ether and C 1-4 ester derivatives thereof such as the ethylene glycol monomethyl-, monoethyl-and monobutyl ethers, propylene glycol propyl ether, dipropylene glycol methyl ether, ethylene glycol mono acetate and ethylene glycol monoethyl ether acetate,
- the nonaqueous solvent can be added in amounts up to about 10%, preferably 6% by weight of the composition.
- Hydrotropes such as urea, monoethanolamine, diethanolamine, triethanolamine and the sodium, potassium, ammonium and alkanol ammonium salts of xylene-, toluene-, ethylbenzene-, isopropyl- benzene sulfonates, can also be added to the compositions of the present invention in amounts up to about 10% by weight. It is a feature of the present invention, however, that stable, homogenous formulations can be prepared without the need for hydrotropic materials of this kind, or with only very minor levels (i.e. less than about 4% by weight).
- pH buffering materials such as alkali metal and ammonium carbonates, bicarbonates, metasilicates and ortho phosphates. These can be added, if appropriate, at levels up to about 10% by weight to provide a compositional pH equal to or greater than about pH 8, preferably greater than about pH9 and more preferably greater than about pHlO.
- Dyes perfumes enzymes, chlorine-releasing agents, polypeptides and protein hydrolysates, soil suspending agents such as carboxy methylcellulose, hydroxymethyl cellulose and polyethylene glycols having a molecular weight of about 400 to about 10,000
- fluorescers such as disodium 4,4'-bis(2-morpholino-4-anilino- s-triazin-6-yl amino) stilbene-2,2'-disulfonate
- preservatives such as Preventol ON marketed by Bayer
- thickeners such as xanthan gum
- additional suds regulants such as tributylphosphate and silicone oil can all be included in the instant compositions.
- a germicide such as o-phenyl phenate can also be added to the present compositions, providing excellent hard surface germicidal activity.
- compositions were homogenous fluent liquids having good stability, excellent surface-shine and cleaning characteristics on both inorganic particulate soils and oily/greasy soils with controlled sudsing in both dilute and concentrated usage under both hard and soft water conditions.
- compositions were homogenous fluent liquids having good stability, excellent surface shine and cleaning characteristics on both inorganic particulate soils and oily/greasy soils with controlled sudsing in both dilute and concentrated usage under both hard and soft water conditions.
- compositions were homogeneous fluent liquids having good stability, excellent cleaning characteristics on both inorganic particulate soils and oily/greasy soils with controlled sudsing in both dilute and concentrated usage under both hard and soft water conditions.
- compositions were homogeneous, fluent liquids having good stability at both normal and low temperatures, as well as excellent germicidal activity, surface shine and cleaning performance on both inorganic particulate soils and oily/greasy soils.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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AT83109923T ATE32608T1 (de) | 1980-05-27 | 1981-05-20 | Terpen-loesungsmittelgemisch verwendbar zur herstellung fluessiger reinigungsmittelzusammensetzungen. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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GB8017364 | 1980-05-27 | ||
GB8017364 | 1980-05-27 |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP81200540.3 Division | 1981-05-20 |
Publications (3)
Publication Number | Publication Date |
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EP0106266A2 true EP0106266A2 (fr) | 1984-04-25 |
EP0106266A3 EP0106266A3 (en) | 1984-07-25 |
EP0106266B1 EP0106266B1 (fr) | 1988-02-24 |
Family
ID=10513677
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP83109923A Expired EP0106266B1 (fr) | 1980-05-27 | 1981-05-20 | Mélange terpène-solvant utilisable pour la préparation de compositions détergentes liquides |
EP81200540A Expired EP0040882B1 (fr) | 1980-05-27 | 1981-05-20 | Compositions détergentes liquides |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP81200540A Expired EP0040882B1 (fr) | 1980-05-27 | 1981-05-20 | Compositions détergentes liquides |
Country Status (7)
Country | Link |
---|---|
EP (2) | EP0106266B1 (fr) |
AT (1) | ATE32608T1 (fr) |
CA (1) | CA1174551A (fr) |
DE (1) | DE3168593D1 (fr) |
FI (1) | FI66903C (fr) |
GR (1) | GR75605B (fr) |
IE (1) | IE51294B1 (fr) |
Cited By (31)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0137616A1 (fr) * | 1983-08-11 | 1985-04-17 | The Procter & Gamble Company | Détergents liquides avec un solvant |
FR2564105A1 (fr) * | 1984-05-10 | 1985-11-15 | Saint Marc Lessives | Composition detergente liquide et procede pour sa preparation. |
EP0164467A1 (fr) * | 1984-04-07 | 1985-12-18 | The Procter & Gamble Company | Composition de nettoyage avec un solvant |
GB2175003A (en) * | 1985-05-16 | 1986-11-19 | Nakanishi Kaken Kabushiki Kais | Rapidly dissolving detergent composition |
AT385769B (de) * | 1986-06-12 | 1988-05-10 | Henkel Austria Ges Mbh | Fluessige allzweckreinigungsmittel |
EP0351810A1 (fr) * | 1988-07-21 | 1990-01-24 | E.I. Du Pont De Nemours And Company | Composition de nettoyage contenant un composé terpénique et un ester dibasique |
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GB2243842A (en) * | 1990-04-12 | 1991-11-13 | Electrolube Limited | Circuit board cleaning |
WO1994014945A1 (fr) * | 1992-12-22 | 1994-07-07 | Henkel-Ecolab Gmbh & Co. Ohg | Nettoyant liquide neutre (i) |
US5336445A (en) * | 1990-03-27 | 1994-08-09 | The Procter & Gamble Company | Liquid hard surface detergent compositions containing beta-aminoalkanols |
US5342549A (en) * | 1990-01-29 | 1994-08-30 | The Procter & Gamble Company | Hard surface liquid detergent compositions containing hydrocarbyl-amidoalkylenebetaine |
US5454983A (en) * | 1992-01-23 | 1995-10-03 | The Procter & Gamble Company | Liquid hard surface detergent compositions containing zwitterionic and cationic detergent surfactants and monoethanolamine and/or beta-aminoalkanol |
WO1996016158A1 (fr) * | 1994-11-22 | 1996-05-30 | Alliedsignal Inc. | Agent nettoyant au terpene et a l'alcool tetrahydrofurfurylique |
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US5540864A (en) * | 1990-12-21 | 1996-07-30 | The Procter & Gamble Company | Liquid hard surfce detergent compositions containing zwitterionic detergent surfactant and monoethanolamine and/or beta-aminoalkanol |
DE19617278A1 (de) * | 1996-04-30 | 1997-11-13 | Hubert Dr Christ | Universalreiniger, Verfahren zur Herstellung und seiner Verwendung |
WO1998001524A1 (fr) * | 1996-07-03 | 1998-01-15 | Unilever Plc | Compositions detergentes antimicrobiennes contenant des alcools ou phenols aromatiques |
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US20120201902A1 (en) * | 2009-06-30 | 2012-08-09 | The Trustees Of Columbia University In The City Of New York | Antimicrobial/preservative compositions comprising botanicals |
EP2780439B1 (fr) | 2011-11-18 | 2016-11-16 | Colgate-Palmolive Company | Composition nettoyante |
US9687429B2 (en) | 2007-06-20 | 2017-06-27 | The Trustees Of Columbia University In The City Of New York | Antimicrobial compositions containing low concentrations of botanicals |
US9968101B2 (en) | 2011-11-03 | 2018-05-15 | The Trustees Of Columbia University In The City Of New York | Botanical antimicrobial compositions |
US9981069B2 (en) | 2007-06-20 | 2018-05-29 | The Trustees Of Columbia University In The City Of New York | Bio-film resistant surfaces |
US10542760B2 (en) | 2007-06-20 | 2020-01-28 | The Trustees Of Columbia University In The City Of New York | Skin and surface disinfectant compositions containing botanicals |
US10806144B2 (en) | 2011-11-03 | 2020-10-20 | The Trustees Of Columbia University In The City Of New York | Composition with sustained antimicrobial activity |
Families Citing this family (45)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1178160A (fr) * | 1981-09-10 | 1984-11-20 | Donald B. Compton | Produit liquide pour le nettoyage de surfaces dures |
EP0080749B1 (fr) * | 1981-11-12 | 1986-04-16 | THE PROCTER & GAMBLE COMPANY | Compositions détergentes liquides |
GB2134132A (en) * | 1983-01-14 | 1984-08-08 | Unilever Plc | Vehicle cleaning compositions |
GR79860B (fr) * | 1983-04-19 | 1984-10-31 | Procter & Gamble | |
DE3316988C2 (de) * | 1983-05-10 | 1986-07-17 | Jürgen 6926 Kirchardt Rohrmoser | Verfahren zum Reinigen von Vorrichtungen und Maschinen der Papier-, Pappe- und Zellstoff-Industrie |
GB8314710D0 (en) * | 1983-05-27 | 1983-07-06 | Optikon Ltd | Cleaning compositions |
EP0137615B1 (fr) * | 1983-08-11 | 1988-01-27 | The Procter & Gamble Company | Compositions de nettoyage de tissus pour enlever des taches |
US4613340A (en) * | 1984-01-09 | 1986-09-23 | Polar Molecular Corp. | Residual oil sludge dispersant |
GB8409054D0 (en) * | 1984-04-07 | 1984-05-16 | Procter & Gamble | Stabilized oil-in-water cleaning microemulsions |
JPH0647677B2 (ja) * | 1984-10-02 | 1994-06-22 | ライオン株式会社 | 液体洗浄剤組成物 |
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EP0261718B1 (fr) * | 1986-09-22 | 1991-03-06 | The Procter & Gamble Company | Compositions de nettoyage crémeuses |
EP0261874A3 (fr) * | 1986-09-22 | 1989-01-25 | The Procter & Gamble Company | Compositions détergentes concentrées pour surfaces dures |
US5202050A (en) * | 1987-04-06 | 1993-04-13 | The Procter & Gamble Company | Method for cleaning hard-surfaces using a composition containing organic solvent and polycarboxylated chelating agent |
US5108643A (en) * | 1987-11-12 | 1992-04-28 | Colgate-Palmolive Company | Stable microemulsion cleaning composition |
US4954286A (en) * | 1988-04-14 | 1990-09-04 | Lever Brothers Company | Fabric pretreatment cleaning compositions |
FR2640637A1 (fr) * | 1988-12-19 | 1990-06-22 | Derives Resiniques Terpenique | Nettoyant liquide pour surfaces solides a base de derives terpeniques et procede pour sa fabrication |
US5080831A (en) * | 1989-06-29 | 1992-01-14 | Buckeye International, Inc. | Aqueous cleaner/degreaser compositions |
GR1000541B (el) * | 1989-11-02 | 1992-08-25 | Colgate Palmolive Co | Σταθερη συνθεσις καθαρισμου υπο μορφην μικρογαλακτωματος. |
CA2070679A1 (fr) * | 1989-12-19 | 1991-06-20 | Donald N. Vaneenam | Compositions d'emulsion aqueuse nettoyante-degraissante |
US5540865A (en) * | 1990-01-29 | 1996-07-30 | The Procter & Gamble Company | Hard surface liquid detergent compositions containing hydrocarbylamidoalkylenebetaine |
DE4025039A1 (de) * | 1990-08-07 | 1992-02-13 | Bernd Neumann Malermeister Gmb | Verfahren zum reinigen und regenerieren von verschmutzten flaechen- und fasergebilden und hierzu geeignetes mittel |
CA2062075A1 (fr) * | 1991-05-06 | 1992-11-07 | Patrizia Barone | Composition de nettoyage sans danger pour les aliments |
US5447575A (en) * | 1991-05-31 | 1995-09-05 | The Dow Chemical Company | Degradable chelants having sulfonate groups, uses and compositions thereof |
DE4119116C2 (de) * | 1991-06-10 | 1997-08-07 | Boehme Chem Fab Kg | Biologisch leicht eliminierbare Entschäumer für wäßrige Systeme |
JP2521630B2 (ja) * | 1992-12-10 | 1996-08-07 | 花王株式会社 | 硬質表面用洗浄剤組成物 |
GB9302869D0 (en) * | 1993-02-12 | 1993-03-31 | Rogers Neil | Cleaning |
NZ260144A (en) * | 1993-04-12 | 1995-10-26 | Colgate Palmolive Co | Cleaning composition; contains three liquid phases which merge at a tricritical point; use for removing tar or grease from articles |
US6221823B1 (en) * | 1995-10-25 | 2001-04-24 | Reckitt Benckiser Inc. | Germicidal, acidic hard surface cleaning compositions |
JP3005050B2 (ja) | 1996-02-14 | 2000-01-31 | ステパン カンパニー | 残留物の少ないヒドロトロープを含む硬質表面洗浄剤 |
US5922665A (en) * | 1997-05-28 | 1999-07-13 | Minnesota Mining And Manufacturing Company | Aqueous cleaning composition including a nonionic surfactant and a very slightly water-soluble organic solvent suitable for hydrophobic soil removal |
GB2331703B (en) * | 1997-11-28 | 2002-01-23 | Reckitt & Colman Inc | Disinfectant compositions |
GB2331760B (en) * | 1997-11-28 | 2002-05-15 | Reckitt & Colman Inc | Hard surface cleaning compositions |
US6849589B2 (en) | 2001-10-10 | 2005-02-01 | 3M Innovative Properties Company | Cleaning composition |
GB2405639A (en) * | 2003-09-08 | 2005-03-09 | R Mc Power Recovery Ltd | Metal cleaning compositions |
GB2408051A (en) * | 2003-11-14 | 2005-05-18 | Reckitt Benckiser Inc | Hard surface cleaning compositions |
WO2008157092A1 (fr) | 2007-06-20 | 2008-12-24 | The Trustees Of Columbia University In The City Of New York | Surfaces résistantes à la formation de biofilm |
TW201330856A (zh) | 2011-12-06 | 2013-08-01 | Univ Columbia | 廣效性的天然防腐組成物 |
EP2727991A1 (fr) * | 2012-10-30 | 2014-05-07 | The Procter & Gamble Company | Compositions détergente liquides nettoyant et désinfectant pour laver la vaisselle à la main |
EP3399013B1 (fr) | 2017-05-05 | 2022-08-03 | The Procter & Gamble Company | Compositions de détergent à lessive présentant une meilleure élimination de graisse |
BR112021003676A2 (pt) * | 2018-09-05 | 2021-05-18 | Unilever Ip Holdings B.V. | composição de tratamento de tecido, método para tratar um tecido e uso da composição |
WO2020106847A1 (fr) * | 2018-11-20 | 2020-05-28 | Emerald Kalama Chemical, Llc | Alcools aromatiques multifonctionnels pour soins d'hygiène personnelle, soins à domicile et compositions industrielles et institutionnelles |
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GB1237874A (en) * | 1967-07-19 | 1971-06-30 | Unilever Australia Proprietary | Detergent composition |
US3634338A (en) * | 1970-07-10 | 1972-01-11 | Grace W R & Co | Method and composition for cleaning aluminum magnesiumand alloys thereof |
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GB1308190A (en) * | 1970-06-26 | 1973-02-21 | Unilever Ltd | Suspending liquids |
DE2113732A1 (de) * | 1971-03-22 | 1972-09-28 | Henkel & Cie Gmbh | Antimikrobielle Wirkstoffe enthaltende Wasch- und Waschhilfsmittel |
DE2709690B1 (de) * | 1977-03-05 | 1978-05-11 | Henkel Kgaa | Fluessiges Reinigungsmittel |
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1981
- 1981-05-20 AT AT83109923T patent/ATE32608T1/de not_active IP Right Cessation
- 1981-05-20 EP EP83109923A patent/EP0106266B1/fr not_active Expired
- 1981-05-20 DE DE8181200540T patent/DE3168593D1/de not_active Expired
- 1981-05-20 EP EP81200540A patent/EP0040882B1/fr not_active Expired
- 1981-05-21 GR GR65028A patent/GR75605B/el unknown
- 1981-05-26 CA CA000378298A patent/CA1174551A/fr not_active Expired
- 1981-05-26 IE IE1166/81A patent/IE51294B1/en unknown
- 1981-05-26 FI FI811612A patent/FI66903C/fi not_active IP Right Cessation
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GB1237874A (en) * | 1967-07-19 | 1971-06-30 | Unilever Australia Proprietary | Detergent composition |
US3634338A (en) * | 1970-07-10 | 1972-01-11 | Grace W R & Co | Method and composition for cleaning aluminum magnesiumand alloys thereof |
USRE29649E (en) * | 1975-02-07 | 1978-05-30 | Cleaning composition | |
GB1603047A (en) * | 1977-07-05 | 1981-11-18 | Dotolo V | Cleaners containing d-limonene |
GB2033421A (en) * | 1978-10-06 | 1980-05-21 | Scheidel Georg Gmbh | Cleansing Composition |
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Cited By (38)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0137616A1 (fr) * | 1983-08-11 | 1985-04-17 | The Procter & Gamble Company | Détergents liquides avec un solvant |
EP0164467A1 (fr) * | 1984-04-07 | 1985-12-18 | The Procter & Gamble Company | Composition de nettoyage avec un solvant |
FR2564105A1 (fr) * | 1984-05-10 | 1985-11-15 | Saint Marc Lessives | Composition detergente liquide et procede pour sa preparation. |
GB2175003A (en) * | 1985-05-16 | 1986-11-19 | Nakanishi Kaken Kabushiki Kais | Rapidly dissolving detergent composition |
AT385769B (de) * | 1986-06-12 | 1988-05-10 | Henkel Austria Ges Mbh | Fluessige allzweckreinigungsmittel |
US4790951A (en) * | 1986-06-12 | 1988-12-13 | Henkel Kommanditgesellschaft Auf Aktien | Liquid all-purpose cleaning preparations containing terpene and hydrogenated naphthalene as fat dissolving agent |
EP0351810A1 (fr) * | 1988-07-21 | 1990-01-24 | E.I. Du Pont De Nemours And Company | Composition de nettoyage contenant un composé terpénique et un ester dibasique |
EP0354027A2 (fr) * | 1988-08-04 | 1990-02-07 | Envirosolv Inc. | Composition de solvants biodégradable, non toxique et non dangereuse |
EP0354027A3 (fr) * | 1988-08-04 | 1991-02-06 | Envirosolv Inc. | Composition de solvants biodégradable, non toxique et non dangereuse |
US5342549A (en) * | 1990-01-29 | 1994-08-30 | The Procter & Gamble Company | Hard surface liquid detergent compositions containing hydrocarbyl-amidoalkylenebetaine |
US5336445A (en) * | 1990-03-27 | 1994-08-09 | The Procter & Gamble Company | Liquid hard surface detergent compositions containing beta-aminoalkanols |
GB2243842A (en) * | 1990-04-12 | 1991-11-13 | Electrolube Limited | Circuit board cleaning |
GB2243842B (en) * | 1990-04-12 | 1993-09-22 | Electrolube Limited | Method and compositions for circuit board cleaning using ether-containing terpenoid compounds |
US5540864A (en) * | 1990-12-21 | 1996-07-30 | The Procter & Gamble Company | Liquid hard surfce detergent compositions containing zwitterionic detergent surfactant and monoethanolamine and/or beta-aminoalkanol |
US5454983A (en) * | 1992-01-23 | 1995-10-03 | The Procter & Gamble Company | Liquid hard surface detergent compositions containing zwitterionic and cationic detergent surfactants and monoethanolamine and/or beta-aminoalkanol |
US5536451A (en) * | 1992-10-26 | 1996-07-16 | The Procter & Gamble Company | Liquid hard surface detergent compositions containing short chain amphocarboxylate detergent surfactant |
WO1994014945A1 (fr) * | 1992-12-22 | 1994-07-07 | Henkel-Ecolab Gmbh & Co. Ohg | Nettoyant liquide neutre (i) |
US5536450A (en) * | 1993-11-12 | 1996-07-16 | The Procter & Gamble Comany | Liquid hard surface detergent compositions containing amphoteric detergent surfactant and perfume |
US5531933A (en) * | 1993-12-30 | 1996-07-02 | The Procter & Gamble Company | Liquid hard surface detergent compositions containing specific polycarboxylate detergent builders |
US5534198A (en) * | 1994-08-02 | 1996-07-09 | The Procter & Gamble Company | Glass cleaner compositions having good filming/streaking characteristics and substantive modifier to provide long lasting hydrophilicity |
WO1996016158A1 (fr) * | 1994-11-22 | 1996-05-30 | Alliedsignal Inc. | Agent nettoyant au terpene et a l'alcool tetrahydrofurfurylique |
US5679631A (en) * | 1994-11-22 | 1997-10-21 | Alliedsignal, Inc. | Limonene and tetrahydrofurfurly alcohol cleaning agent |
DE19617278A1 (de) * | 1996-04-30 | 1997-11-13 | Hubert Dr Christ | Universalreiniger, Verfahren zur Herstellung und seiner Verwendung |
WO1998001524A1 (fr) * | 1996-07-03 | 1998-01-15 | Unilever Plc | Compositions detergentes antimicrobiennes contenant des alcools ou phenols aromatiques |
EP0834550A1 (fr) * | 1996-10-01 | 1998-04-08 | The Procter & Gamble Company | Compositions détergentes pour le linge |
EP0855439A1 (fr) * | 1997-01-24 | 1998-07-29 | The Procter & Gamble Company | Compositions détergentes liquides antibactériennes pour le lavage de vaisselle |
EP0855440A1 (fr) * | 1997-01-24 | 1998-07-29 | The Procter & Gamble Company | Compositions détergents liquides antibactériennes pour le lavage de la vaisselle |
EP0971995A1 (fr) * | 1997-01-24 | 2000-01-19 | The Procter & Gamble Company | Compositions antibacteriennes liquides de detergent de lavage de vaisselle |
EP0971995A4 (fr) * | 1997-01-24 | 2000-11-02 | Procter & Gamble | Compositions antibacteriennes liquides de detergent de lavage de vaisselle |
WO2008153961A1 (fr) * | 2007-06-08 | 2008-12-18 | S. C. Johnson & Son, Inc. | Compositions de nettoyage contenant un parfum hydrophile |
CN101679920B (zh) * | 2007-06-08 | 2012-03-28 | S.C.约翰逊父子公司 | 含有亲水性香料的清洁组合物 |
US9687429B2 (en) | 2007-06-20 | 2017-06-27 | The Trustees Of Columbia University In The City Of New York | Antimicrobial compositions containing low concentrations of botanicals |
US9981069B2 (en) | 2007-06-20 | 2018-05-29 | The Trustees Of Columbia University In The City Of New York | Bio-film resistant surfaces |
US10542760B2 (en) | 2007-06-20 | 2020-01-28 | The Trustees Of Columbia University In The City Of New York | Skin and surface disinfectant compositions containing botanicals |
US20120201902A1 (en) * | 2009-06-30 | 2012-08-09 | The Trustees Of Columbia University In The City Of New York | Antimicrobial/preservative compositions comprising botanicals |
US9968101B2 (en) | 2011-11-03 | 2018-05-15 | The Trustees Of Columbia University In The City Of New York | Botanical antimicrobial compositions |
US10806144B2 (en) | 2011-11-03 | 2020-10-20 | The Trustees Of Columbia University In The City Of New York | Composition with sustained antimicrobial activity |
EP2780439B1 (fr) | 2011-11-18 | 2016-11-16 | Colgate-Palmolive Company | Composition nettoyante |
Also Published As
Publication number | Publication date |
---|---|
EP0040882A1 (fr) | 1981-12-02 |
EP0106266A3 (en) | 1984-07-25 |
GR75605B (fr) | 1984-08-01 |
IE51294B1 (en) | 1986-11-26 |
FI66903B (fi) | 1984-08-31 |
EP0106266B1 (fr) | 1988-02-24 |
FI811612L (fi) | 1981-11-28 |
CA1174551A (fr) | 1984-09-18 |
EP0040882B1 (fr) | 1985-01-30 |
DE3168593D1 (en) | 1985-03-14 |
FI66903C (fi) | 1984-12-10 |
IE811166L (en) | 1981-11-27 |
ATE32608T1 (de) | 1988-03-15 |
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