EP0040882A1 - Liquid detergent compositions - Google Patents
Liquid detergent compositions Download PDFInfo
- Publication number
- EP0040882A1 EP0040882A1 EP81200540A EP81200540A EP0040882A1 EP 0040882 A1 EP0040882 A1 EP 0040882A1 EP 81200540 A EP81200540 A EP 81200540A EP 81200540 A EP81200540 A EP 81200540A EP 0040882 A1 EP0040882 A1 EP 0040882A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- terpene
- composition according
- alkyl
- acid
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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
- C11D3/164—Organic compounds containing a carbon-carbon triple bond
-
- 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
-
- 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
-
- 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
-
- 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 .
- 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 C 13 -C 24 , 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 surfactants 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-1-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 (C8-C18) 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 sulfonates and sulfates: and sodium or potassium salts of alkyl phenol ethylene oxide ether sulfate containing about 1 to 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 trioxi.de followed,by neutralization under conditions such that any sultones present are hydrolysed to the corresponding hydroxy alkane s
- 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 alkanolammonium 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 lO to 12.5.
- Highly suitable nonionic surfactants of this type are ethoxylated primary or secondary C 9-15 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 - , R l 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 al
- Armeen Z (marketed by Armour), Amphosol AA and SP (marketed by T.C.V.) , Amphoram CP1, Diamphoram CP1, Triamphoram CP1, Triamphoram C 2 P 1 and Polyamphorams CPl, C 2 P 1 and C 3 P 1 (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 A n- 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 elcctrode 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-l,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, pyrom
- 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 ⁇ -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 hydrocarbons 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.
- 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.
- 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 (0.0.8 to 0.2 Pa.s) measured in a Brookfield viscometer, using Spindle No. 2 at 60 r.p.m. and at 21°C:
- the polar solvent component of the present compositions has a solubility in water at 25 0 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 l -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.
- a non-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 additional ingredient, especially water miscible or highly soluble (at least 20%w/w) aliphatic mono-, di- and tri alcohols.
- 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 non-aqueous 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.
Abstract
Description
- This invention relates to liquid detergent compositions. In particular, it relates to aqueous detergent compositions suitable for use as general purpose household cleaning compositions.
- General purpose household cleaning compositions for hard surfaces such as metal, glass, ceramic, plastic and linoleum surfaces, are commercially available in both powdered and liquid form. 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.
- Nevertheless, liquid cleaning compositions still suffer a number of drawbacks which can limit their consumer acceptability. Thus, 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. In addition, they can suffer problems of product form, in particular, inhomogeneity,lack of clarity, or inadequate viscosity characteristics for consumer use. Moreover, 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. Although 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.
- It has now been discovered, however, that these defects of prior art liquid cleaning composition can be minimized or overcome through the incorporation therein of a specified level of mono- or sesquiterpene material in combination with a polar solvent of specified water-solubility characteristics. "Although the terpenes, as a class, have limited water-solu- ―.-―- bility, it has now been found that they can be incorporated into liquid cleaning compositions in homogeneous form, even under "cold" processing conditions, with the ability to provide excellent cleaning characteristics across the range of water hardness on grease/oily soils and inorganic particulate soils, as well as on shoe polish, marker ink, bath tub soil etc, and excellent shine performance with low soil redeposition and little or no propensity to cause filming, streaking or spotting on surfaces washed therewith. Moreover, the terpenes herein specified, and in particular those of the hydrocarbon class, 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.
- According to the present invention there is provided an aqueous liquid detergent composition characterized by:
- (a) from about 1% to about 20% of a synthetic anionic, nonionic, amphoteric or zwitterionic surfactant or mixture thereof,
- (b) from about 0.5% to about 10% of a mono- or sesquiterpene or mixture thereof, the weight ratio of surfactant: terpene lying in the range 5:1 to 1:3 and
- (c) from about 0.5 to about 10% of a polar solvent having a solubility in water at 25°C in the range from about 0.2% to about 10%.
- 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, β-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. The 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. Preferably, 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. In preferred embodiments 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.
- Suitably, 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. Thus, it is 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.
- We will now discuss the individual components of the present compositions in more detail.
- A wide range of anionic, nonionic, zwitterionic and amphoteric surfactants can be used in the present compositions.. A typical listing of the classes and species of these surfactants 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-1-sulfonate, and beta-alkyloxy alkane sulfonate. Of all the above, 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. (Included in the term "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 (C8-C18) 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. those of the type described in USP 2,220,099 and 2,477,383 and those prepared from alkylbenzenes obtained by alkylation with straight chain chloroparaffins (using aluminium trichloride catalysis) or straight chain olefins (using hydrogen fluoride catalysis). Especially valuable are linear straight chain alkyl benzene sulfonates in which the average of the alkyl group is about 11.8 carbon atoms, abbreviated as C11.8LAS.
- Other anionic detergent compounds herein include the sodium C10-C18 alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates: and sodium or potassium salts of alkyl phenol ethylene oxide ether sulfate containing about 1 to 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 α-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 trioxi.de followed,by neutralization under conditions such that any sultones present are hydrolysed to the corresponding hydroxy alkane sulfonates; water-soluble salts of paraffin sulfonates containing from about 8 to 24, especially 14 to 18 carbon atoms, and β-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the-alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
- The 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 alkanolammonium 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. Mixtures of anionic surfactants are contomplated by this invention; 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.
- Examples of suitable nonionic surfactants include:
- 1. The polyethylene oxide condensates of alkyl phenol, e.g. the condensation products of alkyl phenols having an alkyl group containing from 6 to 12 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to 5 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds may be derived, for example, from polymerised propylene, diisobutylene, octene and nonene. Other examples include dodecylphenol condensed with 12 moles of ethylene oxide per mole of phenol; dinonylphenol condensed with 15 moles of ethylene oxide per mole of phenol; nonylphenol and di-iso- isooctylphenol condensed with 15 moles of ethylene oxide.
- 2. The condensation product of primary or secondary aliphatic alcohols havinq from 8 to 24 carbon atoms, in either straight chain or branched chain configuration, with from 1 to about 30 moles of alkylene oxide per mole of alcohol. Preferably,. the aliphatic alcohol comprises between 9 and 15 carbon atoms and .is ethoxylated with between 2 and 12, desirably between 3 and 9 moles of ethylene oxide per mole of aliphatic alcohol. Such nonionic surfactants are e preferred from the point of view of providing good to excellent detergency performance on fatty and greasy soils, and in the presence of hardness sensitive anionic surfactants such as alkyl benzene sulfonates. The preferred surfactants are prepared from primary alcohols which are either linear (such as those derived from natural fats or, prepared by the Ziegler process from ethylene, e.g. myristyl, cetyl, stearyl alcohols), or partly branched such as the Dobanols and Neodols which have about 25% 2-methyl branching (Dobanol and Neodol being Trade Names of Shell) or Synperonics, which are understood to have about 50% 2-methyl branching (Synperonic is a Trade Name of I.C.I.) or the primary alcohols having more than 50% branched chain structure sold under the Trade Name Lial by Liquichimica. Specific examples of nonionic surfactants falling within the scope of the invention include Dobanol 45-4, Dobanol 45-7, Dobanol 45-9, Dobanol 91-3, Dobanol 91-6, Dobanol 91-8, Synperonic 6, Synperonic 14, the condensation products of coconut alcohol with an average of between 5 and 12 moles of ethylene oxide per mole of alcohol, the coconut alkyl portion having from 10 to 14 carbon atoms, and the condensation products of tallow alcohol with an average of between 7 and 12 moles of ethylene oxide per mole of alcohol, the tallow portion comprising essentially between 16 and 22 carbon atoms. Secondary linear alkyl ethoxylates are also suitable in the present compositions, especially those ethoxylates of the Tergitol series having from about 9 to 15 carbon atoms in the alkyl group and up to about 11, especially from about 3 to 9, ethoxy residues per molecule.
- 3. The compounds formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with either propylene glycol or ethylene diamine. Such synthetic nonionic detergents are available on the market under the Trade Names of "Pluronic" and "Tetronic" respectively supplied by Wyandotte Chemicals Corporation.
- Of the above, highly preferred are alkoxylated nonionic surfactants having an average HLB in the range from about 9.5 to 13.5, especially lO to 12.5. Highly suitable nonionic surfactants of this type are ethoxylated primary or secondary C9-15 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:-
- Highly preferred surfactants according to the above formula, 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 represents a Cato C18 alkyl group, especially coconut alkyl, lauryl and tallow alkyl. Specific examples include Armeen Z (marketed by Armour), Amphosol AA and SP (marketed by T.C.V.) , Amphoram CP1, Diamphoram CP1, Triamphoram CP1, Triamphoram C2P1 and Polyamphorams CPl, C2P1 and C3P1 (marketed by Pierrefitte-Auby) and Deriphat 170C and Deriphat 154 (marketed by General Mills).
- Of all the above surfactants, highly preferred 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 (pKCa++) of about 2 or greater and preferably an anion valence of at least 3. The stability constant is defined as follows:-
- Preferably, the sequestrant has a pKCa++ 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 elcctrode 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-l,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, pyromellitic acid and the phthalic acid derivatives disclosed in British Patent No. 1,425,343.
- 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 α-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.
- 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 hydrocarbons 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 α,β 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 αand β-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 α, β and α 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 (0.0.8 to 0.2 Pa.s) measured in a Brookfield viscometer, using Spindle No. 2 at 60 r.p.m. and at 21°C:
- The polar solvent component of the present compositions has a solubility in water at 250C 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 C1-C6 fatty acids with Cl-C6 alcohols containing a total of from 5 to 9 carbon atoms, et, n-butyl butyrate, n-butyl propionate and n-propyl acetate; and mono C6-C9 and di-C4-C9 alkyl or aryl ethers of ethylene glycol such as hexyl, benzyl and phenyl Cellosolves (Registered Trade Mark) and ethyleneglycol dibutyl ether.
- The compositions of the invention can be supplemented by all manner of detergent components compatible with a fluent,.liquid system.
- A non-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. Specific examples are ethanol, propanol, isopropanol, and propane-1,3-diol. Other suitable solvents are ethylene-, propylene-, diethylene- and dipropylene glycol and the mono-C1-4 alkyl ether and C1-4 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 non-aqueous 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).
- Other suitable ingredients of the present compositions include 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, and 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.
- In the examples which follow, the abbreviations used have the following descriptions:-
- PS : Sodium C13 to C16 paraffin sulfonate marketed by Hoechst under Trade Name Hostapur SAS.
- LAS . : Sodium salt of linear C11.8 alkyl benzene sulfonate.
- AE3S : Sodium linear C12-14 alcohol sulfate including 3 ethylene oxide moieties.
- Dobanol 91-8 : A C9-11 oxo-alcohol with 8 moles of ethylene oxide, marketed by Shell.
- Dobanol 45-7 : A C14-15 oxo-alcohol with 7 moles of ethylene oxide, marketed by Shell.
- Pluronic L-42 : A condensation product of ethylene oxide and propylene oxide, marketed by BASF-Wyandotte.
- Deriphat 170C : N-C12-14 alkyl-β-amino propionic acid marketed by General Mills.
- Amphoram CP1 : N-cocoyl-β-amino propionic acid marketed by Pierrefitte-Auby.
- Deriphat 154 : Disodium-N-tallow-β-amino propionate marketed by General Mills.
- Ethylan HB-4 : Phenol ethoxylated with 4 moles of ethylene oxide, marketed by Diamond Shamrock.
- HT Soap : Sodium soap prepared from hydrogenated tallow.
- CN Soap : Monoethanolamine soap of coconut fatty acids.
- TEA : Triethanolamine.
- CS : Sodium cumene sulfonate.
- TPP : Tetrasodium pyrophosphate.
- EDTA : Tetrasodium salt of ethylenediamine tetraacetic acid.
- NTA : Trisodium salt of nitrilotriacetic acid.
- Dequest 2060 : Diethylenetriamine penta(methylene phosphonic acid), marketed by Monsanto.
- Dequest 2041 : Ethylenediamine tetra(methylene phosphonic acid) marketed by Monsanto.
-
- The above 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.
-
-
-
Claims (10)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT81200540T ATE11565T1 (en) | 1980-05-27 | 1981-05-20 | LIQUID DETERGENT COMPOSITIONS. |
DE8383109923T DE3176660D1 (en) | 1980-05-27 | 1981-05-20 | Terpene-solvent mixture useful for making liquid detergent compositions |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8017364 | 1980-05-27 | ||
GB8017364 | 1980-05-27 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP83109923.9 Division-Into | 1981-05-20 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0040882A1 true EP0040882A1 (en) | 1981-12-02 |
EP0040882B1 EP0040882B1 (en) | 1985-01-30 |
Family
ID=10513677
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP81200540A Expired EP0040882B1 (en) | 1980-05-27 | 1981-05-20 | Liquid detergent compositions |
EP83109923A Expired EP0106266B1 (en) | 1980-05-27 | 1981-05-20 | Terpene-solvent mixture useful for making liquid detergent compositions |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP83109923A Expired EP0106266B1 (en) | 1980-05-27 | 1981-05-20 | Terpene-solvent mixture useful for making liquid detergent compositions |
Country Status (7)
Country | Link |
---|---|
EP (2) | EP0040882B1 (en) |
AT (1) | ATE32608T1 (en) |
CA (1) | CA1174551A (en) |
DE (1) | DE3168593D1 (en) |
FI (1) | FI66903C (en) |
GR (1) | GR75605B (en) |
IE (1) | IE51294B1 (en) |
Cited By (55)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0080749A1 (en) * | 1981-11-12 | 1983-06-08 | THE PROCTER & GAMBLE COMPANY | Liquid detergent compositions |
EP0105063A1 (en) * | 1981-09-10 | 1984-04-11 | THE PROCTER & GAMBLE COMPANY | Liquid hard-surface cleaner |
GB2134132A (en) * | 1983-01-14 | 1984-08-08 | Unilever Plc | Vehicle cleaning compositions |
DE3316988A1 (en) * | 1983-05-10 | 1984-11-15 | Jürgen 6926 Kirchardt Rohrmoser | MEANS FOR CLEANING MACHINES AND DEVICES AND PARTS THEREOF |
EP0126545A1 (en) * | 1983-04-19 | 1984-11-28 | The Procter & Gamble Company | Liquid scouring cleansers containing solvent system |
EP0129987A1 (en) * | 1983-05-27 | 1985-01-02 | Optikon Limited | Cleaning compositions |
EP0137615A1 (en) * | 1983-08-11 | 1985-04-17 | The Procter & Gamble Company | Fabric cleaning compositions for clay-based stains |
EP0137616A1 (en) * | 1983-08-11 | 1985-04-17 | The Procter & Gamble Company | Liquid detergents with solvent |
EP0160762A1 (en) * | 1984-04-07 | 1985-11-13 | The Procter & Gamble Company | Stabilized oil-in-water cleaning microemulsions |
JPS6185498A (en) * | 1984-10-02 | 1986-05-01 | ライオン株式会社 | Liquid detergent composition |
GB2174984A (en) * | 1985-05-10 | 1986-11-19 | Polar Molecular Corp | Residual oil sludge dispersant |
DE3716526A1 (en) * | 1986-05-21 | 1987-11-26 | Colgate Palmolive Co | STABLE MICROEMULSION |
EP0261874A2 (en) * | 1986-09-22 | 1988-03-30 | The Procter & Gamble Company | Concentrated hard-surface cleaning compositions |
EP0261718A2 (en) * | 1986-09-22 | 1988-03-30 | The Procter & Gamble Company | Creamy scouring compositions |
AT385769B (en) * | 1986-06-12 | 1988-05-10 | Henkel Austria Ges Mbh | LIQUID ALL-PURPOSE CLEANER |
EP0164467B1 (en) * | 1984-04-07 | 1988-06-29 | The Procter & Gamble Company | Cleaning compositions with solvent |
US4758377A (en) * | 1985-09-24 | 1988-07-19 | The Proctor & Gamble Company | Viscous phase stable liquid scouring cleansers containing solvent |
EP0316726A2 (en) * | 1987-11-12 | 1989-05-24 | Colgate-Palmolive Company | Stable microemulsion cleaning composition |
EP0368146A2 (en) * | 1988-11-07 | 1990-05-16 | Colgate-Palmolive Company | Stable microemulsion cleaning composition |
FR2640637A1 (en) * | 1988-12-19 | 1990-06-22 | Derives Resiniques Terpenique | LIQUID CLEANER FOR SOLID SURFACES BASED ON TERPENIC DERIVATIVES AND METHOD FOR MANUFACTURING THE SAME |
US4954286A (en) * | 1988-04-14 | 1990-09-04 | Lever Brothers Company | Fabric pretreatment cleaning compositions |
US5082584A (en) * | 1986-05-21 | 1992-01-21 | Colgate-Palmolive Company | Microemulsion all purpose liquid cleaning composition |
DE4025039A1 (en) * | 1990-08-07 | 1992-02-13 | Bernd Neumann Malermeister Gmb | Aq. compsn. for cleaning soiled surfaces and fibrous articles - contains fatty acid, oil, pref. plant oil, hydrocarbon solvent and opt. polishing agent |
EP0479908A1 (en) * | 1989-06-29 | 1992-04-15 | Buckeye Int | Improved aqueous cleaner/degreaser compositions. |
GR1000541B (en) * | 1989-11-02 | 1992-08-25 | Colgate Palmolive Co | Stable microemulsion cleaning composition |
EP0506744A1 (en) * | 1989-12-19 | 1992-10-07 | Buckeye International, Inc. | Aqueous cleaner/degreaser emulsion compositions |
EP0512328A1 (en) * | 1991-05-06 | 1992-11-11 | Miles Inc. | Food safe cleaning composition |
WO1992022369A1 (en) * | 1991-06-10 | 1992-12-23 | Dr. Th. Böhme KG Chem. Fabrik GmbH & Co. | Readily biodegradable anti-foaming agent for aqueous systems |
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 |
GB2273300A (en) * | 1992-12-10 | 1994-06-15 | Kao Corp | Hard surface cleaning compositions |
US5336445A (en) * | 1990-03-27 | 1994-08-09 | The Procter & Gamble Company | Liquid hard surface detergent compositions containing beta-aminoalkanols |
WO1994018300A2 (en) * | 1993-02-12 | 1994-08-18 | Neil Rogers | Cleaning |
US5342549A (en) * | 1990-01-29 | 1994-08-30 | The Procter & Gamble Company | Hard surface liquid detergent compositions containing hydrocarbyl-amidoalkylenebetaine |
EP0620270A2 (en) * | 1993-04-12 | 1994-10-19 | Colgate-Palmolive Company | Cleaning compositions |
WO1995013345A1 (en) * | 1993-11-12 | 1995-05-18 | The Procter & Gamble Company | Liquid hard surface detergent compositions containing amphoteric detergent surfactant and perfume |
US5447575A (en) * | 1991-05-31 | 1995-09-05 | The Dow Chemical Company | Degradable chelants having sulfonate groups, uses and compositions thereof |
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 |
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 |
US5536451A (en) * | 1992-10-26 | 1996-07-16 | The Procter & Gamble Company | Liquid hard surface detergent compositions containing short chain amphocarboxylate detergent surfactant |
US5540865A (en) * | 1990-01-29 | 1996-07-30 | The Procter & Gamble Company | Hard surface liquid detergent compositions containing hydrocarbylamidoalkylenebetaine |
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 |
WO1998001524A1 (en) * | 1996-07-03 | 1998-01-15 | Unilever Plc | Antimicrobial cleaning compositions containing aromatic alcohols or phenols |
WO1998054277A1 (en) * | 1997-05-28 | 1998-12-03 | Minnesota Mining And Manufacturing Company | Cleaning composition and method of use |
EP0904343A1 (en) * | 1995-10-25 | 1999-03-31 | Reckitt & Colman Inc. | Germicidal acidic hard surface cleaning compositions |
GB2331760A (en) * | 1997-11-28 | 1999-06-02 | Reckitt & Colman Inc | Hard surface cleaning composition |
US6075002A (en) * | 1997-11-28 | 2000-06-13 | Reckitt & Colman Inc. | Biphenyl based solvents in blooming type germicidal hard surface cleaners |
US6281178B1 (en) | 1996-02-14 | 2001-08-28 | Stepan Company | Reduced residue hard surface cleaner comprising hydrotrope |
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 |
EP2727991A1 (en) * | 2012-10-30 | 2014-05-07 | The Procter & Gamble Company | Cleaning and disinfecting liquid hand dishwashing detergent compositions |
EP3399013A1 (en) | 2017-05-05 | 2018-11-07 | The Procter & Gamble Company | Laundry detergent compositions with improved grease removal |
WO2020048679A1 (en) * | 2018-09-05 | 2020-03-12 | Unilever Plc | A quick and easy cleaning formulation |
EP3883524A4 (en) * | 2018-11-20 | 2022-09-07 | Emerald Kalama Chemical, LLC | Multifunctional aromatic alcohols for personal care, home care and industrial and institutional compositions |
Families Citing this family (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2564105B1 (en) * | 1984-05-10 | 1987-09-11 | Saint Marc Lessives | LIQUID DETERGENT COMPOSITION AND PROCESS FOR ITS PREPARATION. |
JPS61275396A (en) * | 1985-05-16 | 1986-12-05 | 中西化研株式会社 | Detergent |
US4867800B1 (en) * | 1988-07-21 | 1995-02-14 | Du Pont | Cleaning composition of terpene compound and dibasic ester |
EP0354027A3 (en) * | 1988-08-04 | 1991-02-06 | Envirosolv Inc. | Biodegradable, non-toxic, nonhazardous solvent composition |
GB2243842B (en) * | 1990-04-12 | 1993-09-22 | Electrolube Limited | Method and compositions for circuit board cleaning using ether-containing terpenoid compounds |
DE4243468A1 (en) * | 1992-12-22 | 1994-06-23 | Henkel Ecolab Gmbh & Co Ohg | Neutral liquid detergent (I) |
US5514294A (en) * | 1994-11-22 | 1996-05-07 | Alliedsignal Inc. | Limonene and tetrahydrofurfuryl alcohol cleaning agent |
DE19617278A1 (en) * | 1996-04-30 | 1997-11-13 | Hubert Dr Christ | Biodegradable universal cleaning agents for e.g. cleaning equipment used to make paper, board or pulp |
EP0834550A1 (en) * | 1996-10-01 | 1998-04-08 | The Procter & Gamble Company | Laundry detergent compositions |
EP0855439A1 (en) * | 1997-01-24 | 1998-07-29 | The Procter & Gamble Company | Antibacterial liquid dishwashing detergent compositions |
EP0855440A1 (en) * | 1997-01-24 | 1998-07-29 | The Procter & Gamble Company | Antibacterial liquid dishwashing detergent compositions |
US20080305978A1 (en) * | 2007-06-08 | 2008-12-11 | S.C. Johnson & Son, Inc. | Cleaning compositions containing a hydrophilic fragrance |
EP2166840B1 (en) | 2007-06-20 | 2017-01-11 | The Trustees of Columbia University in the City of New York | Bio-film resistant surfaces |
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 |
US9511040B2 (en) | 2007-06-20 | 2016-12-06 | The Trustees Of Columbia University In The City Of New York | Skin and surface disinfectant compositions containing botanicals |
US9981069B2 (en) | 2007-06-20 | 2018-05-29 | The Trustees Of Columbia University In The City Of New York | Bio-film resistant surfaces |
MX2012000105A (en) * | 2009-06-30 | 2012-03-14 | Univ Columbia | Antimicrobial/preservative compositions comprising botanicals. |
ES2762405T3 (en) | 2011-11-03 | 2020-05-25 | Univ Columbia | Composition with sustained antimicrobial activity |
US9968101B2 (en) | 2011-11-03 | 2018-05-15 | The Trustees Of Columbia University In The City Of New York | Botanical antimicrobial compositions |
AU2011381063B2 (en) | 2011-11-18 | 2014-07-31 | Colgate-Palmolive Company | Cleaning composition |
TW201330856A (en) | 2011-12-06 | 2013-08-01 | Univ Columbia | Broad spectrum natural preservative composition |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2130808A1 (en) * | 1970-06-26 | 1972-01-13 | Unilever Nv | Suspending fluids |
DE2113732A1 (en) * | 1971-03-22 | 1972-09-28 | Henkel & Cie Gmbh | Anti-microbial washing composns - contg terpenes as bactericides and optical brighteners |
DE2709690C2 (en) * | 1977-03-05 | 1979-01-11 | Henkel Kgaa, 4000 Duesseldorf |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
US3933674A (en) * | 1975-02-07 | 1976-01-20 | Farnsworth Albert M | Cleaning composition |
JPS5414406A (en) * | 1977-07-05 | 1979-02-02 | Dotolo V | Deterging compositions |
DE2843764C3 (en) * | 1978-10-06 | 1982-01-14 | Georg Scheidel Jr. Gmbh, 8606 Hirschaid | cleaning supplies |
-
1981
- 1981-05-20 EP EP81200540A patent/EP0040882B1/en not_active Expired
- 1981-05-20 DE DE8181200540T patent/DE3168593D1/en not_active Expired
- 1981-05-20 AT AT83109923T patent/ATE32608T1/en not_active IP Right Cessation
- 1981-05-20 EP EP83109923A patent/EP0106266B1/en not_active Expired
- 1981-05-21 GR GR65028A patent/GR75605B/el unknown
- 1981-05-26 CA CA000378298A patent/CA1174551A/en not_active Expired
- 1981-05-26 IE IE1166/81A patent/IE51294B1/en unknown
- 1981-05-26 FI FI811612A patent/FI66903C/en not_active IP Right Cessation
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2130808A1 (en) * | 1970-06-26 | 1972-01-13 | Unilever Nv | Suspending fluids |
FR2099966A5 (en) * | 1970-06-26 | 1972-03-17 | Unilever Nv | |
GB1308190A (en) * | 1970-06-26 | 1973-02-21 | Unilever Ltd | Suspending liquids |
DE2113732A1 (en) * | 1971-03-22 | 1972-09-28 | Henkel & Cie Gmbh | Anti-microbial washing composns - contg terpenes as bactericides and optical brighteners |
DE2709690C2 (en) * | 1977-03-05 | 1979-01-11 | Henkel Kgaa, 4000 Duesseldorf | |
US4175062A (en) * | 1977-03-05 | 1979-11-20 | Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) | Aqueous cleanser compositions |
Cited By (84)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0105063A1 (en) * | 1981-09-10 | 1984-04-11 | THE PROCTER & GAMBLE COMPANY | Liquid hard-surface cleaner |
EP0080749A1 (en) * | 1981-11-12 | 1983-06-08 | THE PROCTER & GAMBLE COMPANY | Liquid detergent compositions |
GB2134132A (en) * | 1983-01-14 | 1984-08-08 | Unilever Plc | Vehicle cleaning compositions |
US4767563A (en) * | 1983-04-19 | 1988-08-30 | The Procter & Gamble Company | Liquid scouring cleansers containing solvent system |
EP0126545A1 (en) * | 1983-04-19 | 1984-11-28 | The Procter & Gamble Company | Liquid scouring cleansers containing solvent system |
DE3316988A1 (en) * | 1983-05-10 | 1984-11-15 | Jürgen 6926 Kirchardt Rohrmoser | MEANS FOR CLEANING MACHINES AND DEVICES AND PARTS THEREOF |
EP0178340A1 (en) * | 1983-05-10 | 1986-04-23 | Jürgen Rohrmoser | Means for cleaning machines and apparatuses as well as their parts |
EP0129987A1 (en) * | 1983-05-27 | 1985-01-02 | Optikon Limited | Cleaning compositions |
EP0137615A1 (en) * | 1983-08-11 | 1985-04-17 | The Procter & Gamble Company | Fabric cleaning compositions for clay-based stains |
EP0137616A1 (en) * | 1983-08-11 | 1985-04-17 | The Procter & Gamble Company | Liquid detergents with solvent |
EP0164467B1 (en) * | 1984-04-07 | 1988-06-29 | The Procter & Gamble Company | Cleaning compositions with solvent |
EP0160762A1 (en) * | 1984-04-07 | 1985-11-13 | The Procter & Gamble Company | Stabilized oil-in-water cleaning microemulsions |
JPS6185498A (en) * | 1984-10-02 | 1986-05-01 | ライオン株式会社 | Liquid detergent composition |
GB2174984A (en) * | 1985-05-10 | 1986-11-19 | Polar Molecular Corp | Residual oil sludge dispersant |
GB2174984B (en) * | 1985-05-10 | 1989-10-25 | Polar Molecular Corp | Residual oil sludge dispersant |
US4758377A (en) * | 1985-09-24 | 1988-07-19 | The Proctor & Gamble Company | Viscous phase stable liquid scouring cleansers containing solvent |
DE3716526A1 (en) * | 1986-05-21 | 1987-11-26 | Colgate Palmolive Co | STABLE MICROEMULSION |
DE3716526C2 (en) * | 1986-05-21 | 2001-03-15 | Colgate Palmolive Co | Stable oil-in-water microemulsion |
US5082584A (en) * | 1986-05-21 | 1992-01-21 | Colgate-Palmolive Company | Microemulsion all purpose liquid cleaning composition |
US5076954A (en) * | 1986-05-21 | 1991-12-31 | Colgate-Palmolive Company | Stable microemulsion cleaning composition |
US5075026A (en) * | 1986-05-21 | 1991-12-24 | Colgate-Palmolive Company | Microemulsion all purpose liquid cleaning composition |
AT385769B (en) * | 1986-06-12 | 1988-05-10 | Henkel Austria Ges Mbh | LIQUID ALL-PURPOSE CLEANER |
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 |
EP0261874A2 (en) * | 1986-09-22 | 1988-03-30 | The Procter & Gamble Company | Concentrated hard-surface cleaning compositions |
EP0261874A3 (en) * | 1986-09-22 | 1989-01-25 | The Procter & Gamble Company | Concentrated hard-surface cleaning compositions |
EP0261718A2 (en) * | 1986-09-22 | 1988-03-30 | The Procter & Gamble Company | Creamy scouring compositions |
EP0261718A3 (en) * | 1986-09-22 | 1989-01-25 | The Procter & Gamble Company | Creamy scouring compositions |
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 |
EP0316726A2 (en) * | 1987-11-12 | 1989-05-24 | Colgate-Palmolive Company | Stable microemulsion cleaning composition |
EP0316726A3 (en) * | 1987-11-12 | 1989-10-04 | Colgate-Palmolive Company | Stable microemulsion cleaning composition |
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 |
EP0368146A3 (en) * | 1988-11-07 | 1990-08-29 | Colgate-Palmolive Company | Stable microemulsion cleaning composition |
EP0368146A2 (en) * | 1988-11-07 | 1990-05-16 | Colgate-Palmolive Company | Stable microemulsion cleaning composition |
EP0375474A1 (en) * | 1988-12-19 | 1990-06-27 | Les Derives Resiniques Et Terpeniques | Liquid cleaning agent based on terpene derivatives for hard surfaces, and process for its preparation |
FR2640637A1 (en) * | 1988-12-19 | 1990-06-22 | Derives Resiniques Terpenique | LIQUID CLEANER FOR SOLID SURFACES BASED ON TERPENIC DERIVATIVES AND METHOD FOR MANUFACTURING THE SAME |
EP0479908A1 (en) * | 1989-06-29 | 1992-04-15 | Buckeye Int | Improved aqueous cleaner/degreaser compositions. |
EP0479908A4 (en) * | 1989-06-29 | 1992-06-17 | Buckeye International, Inc. | Improved aqueous cleaner/degreaser compositions |
GR1000541B (en) * | 1989-11-02 | 1992-08-25 | Colgate Palmolive Co | Stable microemulsion cleaning composition |
EP0506744A4 (en) * | 1989-12-19 | 1993-09-22 | Buckeye International, Inc. | Aqueous cleaner/degreaser emulsion compositions |
EP0506744A1 (en) * | 1989-12-19 | 1992-10-07 | Buckeye International, Inc. | Aqueous cleaner/degreaser emulsion compositions |
US5540865A (en) * | 1990-01-29 | 1996-07-30 | The Procter & Gamble Company | Hard surface liquid detergent compositions containing hydrocarbylamidoalkylenebetaine |
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 |
DE4025039A1 (en) * | 1990-08-07 | 1992-02-13 | Bernd Neumann Malermeister Gmb | Aq. compsn. for cleaning soiled surfaces and fibrous articles - contains fatty acid, oil, pref. plant oil, hydrocarbon solvent and opt. polishing agent |
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 |
EP0512328A1 (en) * | 1991-05-06 | 1992-11-11 | Miles Inc. | Food safe cleaning composition |
US5447575A (en) * | 1991-05-31 | 1995-09-05 | The Dow Chemical Company | Degradable chelants having sulfonate groups, uses and compositions thereof |
WO1992022369A1 (en) * | 1991-06-10 | 1992-12-23 | Dr. Th. Böhme KG Chem. Fabrik GmbH & Co. | Readily biodegradable anti-foaming agent for aqueous systems |
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 |
GB2273300A (en) * | 1992-12-10 | 1994-06-15 | Kao Corp | Hard surface cleaning compositions |
GB2273300B (en) * | 1992-12-10 | 1997-03-26 | Kao Corp | Detergent composition for hard surfaces |
WO1994018300A3 (en) * | 1993-02-12 | 1994-11-24 | Neil Rogers | Cleaning |
WO1994018300A2 (en) * | 1993-02-12 | 1994-08-18 | Neil Rogers | Cleaning |
EP0620270A3 (en) * | 1993-04-12 | 1995-07-26 | Colgate Palmolive Co | Cleaning compositions. |
EP0620270A2 (en) * | 1993-04-12 | 1994-10-19 | Colgate-Palmolive Company | Cleaning compositions |
US5536450A (en) * | 1993-11-12 | 1996-07-16 | The Procter & Gamble Comany | Liquid hard surface detergent compositions containing amphoteric detergent surfactant and perfume |
WO1995013345A1 (en) * | 1993-11-12 | 1995-05-18 | The Procter & Gamble Company | 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 |
EP0904343A1 (en) * | 1995-10-25 | 1999-03-31 | Reckitt & Colman Inc. | Germicidal acidic hard surface cleaning compositions |
EP0904343A4 (en) * | 1995-10-25 | 1999-03-31 | ||
US6281178B1 (en) | 1996-02-14 | 2001-08-28 | Stepan Company | Reduced residue hard surface cleaner comprising hydrotrope |
WO1998001524A1 (en) * | 1996-07-03 | 1998-01-15 | Unilever Plc | Antimicrobial cleaning compositions containing aromatic alcohols or phenols |
WO1998054277A1 (en) * | 1997-05-28 | 1998-12-03 | Minnesota Mining And Manufacturing Company | Cleaning composition and method of use |
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 |
GB2331760A (en) * | 1997-11-28 | 1999-06-02 | Reckitt & Colman Inc | Hard surface cleaning composition |
US6075002A (en) * | 1997-11-28 | 2000-06-13 | Reckitt & Colman Inc. | Biphenyl based solvents in blooming type germicidal hard surface cleaners |
US6100231A (en) * | 1997-11-28 | 2000-08-08 | Reckitt & Colman Inc. | Biphenyl based solvents in blooming type hard surface cleaners |
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 |
GB2421736B (en) * | 2003-09-08 | 2007-02-28 | R Mc Power Recovery Ltd | Method and composition for cleaning metals |
GB2408051A (en) * | 2003-11-14 | 2005-05-18 | Reckitt Benckiser Inc | Hard surface cleaning compositions |
EP2727991A1 (en) * | 2012-10-30 | 2014-05-07 | The Procter & Gamble Company | Cleaning and disinfecting liquid hand dishwashing detergent compositions |
WO2014070643A1 (en) * | 2012-10-30 | 2014-05-08 | The Procter & Gamble Company | Cleaning and disinfecting liquid hand dishwashing detergent compositions |
US8846591B2 (en) | 2012-10-30 | 2014-09-30 | The Procter & Gamble Company | Cleaning and disinfecting liquid hand dishwashing detergent compositions |
US8993500B2 (en) | 2012-10-30 | 2015-03-31 | The Procter & Gamble Company | Cleaning and disinfecting liquid hand dishwashing detergent comprising a benzyl alcohol/ethanol mixture |
EP3399013A1 (en) | 2017-05-05 | 2018-11-07 | The Procter & Gamble Company | Laundry detergent compositions with improved grease removal |
WO2018204559A1 (en) | 2017-05-05 | 2018-11-08 | The Procter & Gamble Company | Laundry detergent compositions with improved grease removal |
WO2020048679A1 (en) * | 2018-09-05 | 2020-03-12 | Unilever Plc | A quick and easy cleaning formulation |
CN112673082A (en) * | 2018-09-05 | 2021-04-16 | 联合利华知识产权控股有限公司 | Fast and easy cleaning formulation |
EP3883524A4 (en) * | 2018-11-20 | 2022-09-07 | Emerald Kalama Chemical, LLC | Multifunctional aromatic alcohols for personal care, home care and industrial and institutional compositions |
Also Published As
Publication number | Publication date |
---|---|
DE3168593D1 (en) | 1985-03-14 |
CA1174551A (en) | 1984-09-18 |
EP0040882B1 (en) | 1985-01-30 |
GR75605B (en) | 1984-08-01 |
IE811166L (en) | 1981-11-27 |
FI66903C (en) | 1984-12-10 |
ATE32608T1 (en) | 1988-03-15 |
IE51294B1 (en) | 1986-11-26 |
EP0106266B1 (en) | 1988-02-24 |
FI66903B (en) | 1984-08-31 |
EP0106266A3 (en) | 1984-07-25 |
EP0106266A2 (en) | 1984-04-25 |
FI811612L (en) | 1981-11-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4414128A (en) | Liquid detergent compositions | |
EP0040882B1 (en) | Liquid detergent compositions | |
EP0126545B1 (en) | Liquid scouring cleansers containing solvent system | |
EP0080749B1 (en) | Liquid detergent compositions | |
US5281354A (en) | Liquid cleanser composition | |
AU596244B2 (en) | Aqueous detergent compositions containing diethyleneglycol monohexyl ether solvent | |
EP0377261B1 (en) | Detergent composition | |
EP0160762B1 (en) | Stabilized oil-in-water cleaning microemulsions | |
US4581161A (en) | Aqueous liquid detergent composition with dicarboxylic acids and organic solvent | |
US5075026A (en) | Microemulsion all purpose liquid cleaning composition | |
US6281178B1 (en) | Reduced residue hard surface cleaner comprising hydrotrope | |
EP2245128B1 (en) | Degreasing all purpose cleaning compositions and methods | |
US5082584A (en) | Microemulsion all purpose liquid cleaning composition | |
US5376298A (en) | Hard surface detergent compositions | |
US4758377A (en) | Viscous phase stable liquid scouring cleansers containing solvent | |
US4576738A (en) | Hard surface cleaning compositions containing pianane | |
AU604648B2 (en) | Improved viscous phase stable liquid scouring cleansers containing solvent | |
EP0344847A2 (en) | Improved liquid cleaners | |
US5763386A (en) | Microemulsion all purpose liquid cleaning compositions comprising ethoxylated polyhydric alcohols with at least partial esters thereof, and optional dralkyl sulfosuccinate | |
IE890278L (en) | Hard-surface cleaning compositions | |
EP0200263A2 (en) | Homogeneous concentrated liquid detergent compositions containing ternary surfactant system | |
EP0164467A1 (en) | Cleaning compositions with solvent | |
USH1467H (en) | Detergent formulations containing a surface active composition containing a nonionic surfactant component and a secondary alkyl sulfate anionic surfactant component | |
EP0212723B1 (en) | Built liquid detergents | |
EP1268738B1 (en) | Microemulsion cleaning compositions |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Designated state(s): AT BE CH DE FR GB IT LI NL SE |
|
17P | Request for examination filed |
Effective date: 19820515 |
|
ITF | It: translation for a ep patent filed |
Owner name: ING. C. GREGORJ S.P.A. |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Designated state(s): AT BE CH DE FR GB IT LI NL SE |
|
REF | Corresponds to: |
Ref document number: 11565 Country of ref document: AT Date of ref document: 19850215 Kind code of ref document: T |
|
REF | Corresponds to: |
Ref document number: 3168593 Country of ref document: DE Date of ref document: 19850314 |
|
ET | Fr: translation filed | ||
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
GBPC | Gb: european patent ceased through non-payment of renewal fee | ||
GBDL | Gb: delete "european patent ceased" from journal |
Free format text: 5263 PAGE 288 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19900509 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19900510 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 19900511 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 19900515 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 19900528 Year of fee payment: 10 |
|
ITTA | It: last paid annual fee | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19900531 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 19900601 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19900629 Year of fee payment: 10 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Effective date: 19910520 Ref country code: AT Effective date: 19910520 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Effective date: 19910521 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Effective date: 19910531 Ref country code: CH Effective date: 19910531 Ref country code: BE Effective date: 19910531 |
|
BERE | Be: lapsed |
Owner name: PROCTER & GAMBLE EUROPEAN TECHNICAL CENTER Effective date: 19910531 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Effective date: 19911201 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee | ||
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Effective date: 19920131 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Effective date: 19920303 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
EUG | Se: european patent has lapsed |
Ref document number: 81200540.3 Effective date: 19911209 |