IE51294B1 - Liquid detergent compositions - Google Patents
Liquid detergent compositionsInfo
- Publication number
- IE51294B1 IE51294B1 IE1166/81A IE116681A IE51294B1 IE 51294 B1 IE51294 B1 IE 51294B1 IE 1166/81 A IE1166/81 A IE 1166/81A IE 116681 A IE116681 A IE 116681A IE 51294 B1 IE51294 B1 IE 51294B1
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/164—Organic compounds containing a carbon-carbon triple bond
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/18—Hydrocarbons
- C11D3/188—Terpenes
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2006—Monohydric alcohols
- C11D3/2037—Terpenes
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/43—Solvents
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2006—Monohydric alcohols
- C11D3/2034—Monohydric alcohols aromatic
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Emergency Medicine (AREA)
- Health & Medical Sciences (AREA)
- Detergent Compositions (AREA)
- Measuring Pulse, Heart Rate, Blood Pressure Or Blood Flow (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
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Abstract
Liquid detergent compositions, particularly for use as hard surface cleaners, comprising 1%-20% surfactant, 0.5%-10% mono- or sesquiterpenes, and 0.5%-10% of a polar solvent having a solubility in water of from 0.2% to 10%, preferably benzyl alcohol. The compositions provide excellent cleaning of both greasy and particulate soils, improved surface appearance, excellent formulation homogeneity, stability and viscosity characteristics as well as good suds control.
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 sui'faces 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 deficie.nt in cleaning ability on organic soils such as the grease/fatty/oilv soils typically found in the domestic environment, Ijiquid 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 ?0 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 composi25 tions.
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 inproduct 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, a3 a class, have limited water-solubility, 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, tire valuable in regulating the sudsing behavious of the instant compositions in both hard and soft water and under 51394 - 4 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 5 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, DE-A2,113,732 discloses the use of aliphatic and alicyclic ter10 penes as anti-microbial agents in washing compositions, while Patent Specification No. 35833 teaches the use of dipentene in a thixotropic liquid detergent suspension base DE-A-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 vzith little tendency to cause filming or streaking on washed surfaces.
According to the present invention there is provided a liquid detergent canpositian canprising a water base together with: (a) from 1% to 20% by weight of a synthetic anionic, nonionic, amphoteric or zwitterionic surfactant or mixture thereof, (b) from 0.5% to 10% by weight of a mono- or sesquiterpene or mixture thereof, the weight ratio of surfactant: terpene lying in the range ?; 5:1 tc 1:3 and - 5 (c) from 0.5 to 10% by weight of a polar solvent having a solubility in water at 25°C in the range from 0.2% to 10% by weight (g/lOOg solution), containing at least one hydrophilic group, and being liquid at room temperature.
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, o-pinene, 0-pinene and the mixture of terpene hydrocarbons obtained from the essence of oranges (eg. coldpressed 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 1% to 3%, more preferably from 1.5% to 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 0.2% to 10% by weight (g/100 g solution), preferably from 0.5% to 6% by weight, for example benzyl alcohol. The compositions of the invention also preferably contain from 0.005% to 2%, more preferably from 0.05% to 0.7% of an alkali metal, ammonium or alkanolammonium soap of a especially ^33-^3, 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 2.0, preferably at least 3.0, the - 6 weight ratio of surfactant:sequestrant preferably lying ir, the range from 5:1 to 1:3, especially j 3:1 to 1:1. In preferred embodiments the sequestrant j has an anion valence of at least 3 and is incorporated at a : level of from 0.5% to 13% by weight. The compo- , sition itself preferably has a pH in 1% aqueous solution of at least 8.0. ‘ i Suitably, the sequestrant can be selected from the I water-soluble salts of polyphosphates, polycarboxylates, i aminopolycarboxylates, polyphosphonates and amino polyphos- | phonates 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. i A notable feature of the present compositions is the I suds-suppression effectiveness of the terpenes in liquid ί compositions based on ampholytic or zwitterionic surfactants. ; Thus, it is notoriously difficult to control the sudsing ί behaviour of these surfactants in a cost-effective manner ! using conventional suppression agents such as soaps, waxes ί etc. The terpenes are thus particularly valuable in this j respect. i Vie will new discuss the individual components of the , present compositions in more detail. i A wide range of anionic, nonionic, zwitterionic and ί amphoteric surfactants can be used in the present compositions. ' Λ typical listing of the classes and species of these sur- | I factants is given in US-A-3,663,961. ; These surfactants can be used singly or in combina- i tion at levels in the range from 1% to 20%, preferably ί at levels from 3% to 10% by weight of the compositions, j Suitable anionic non-soap surfactants are water-soluble salts of alkyl benzene sulfonates, alkyl sulfates, alkyl polyethoxy ether sulfates, paraffin sulfonates, alpha-olefin - 7 sulfonates, alpha-sulfocarboxylates and their esters, alkyl glyceryl ether sulfonates, fatty acid inonoglyceride sulfates and sulfonates, alkyl phenol polyethoxy ether sulfates, 2acyloxy-alkane-l-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 8 to 22, especially from 10 to 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 (Cg-C^g) 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 9 to 15, especially to 13, carbon atoms, in straight chain or branched chain configuration, e.g. those of the typo described in US-A-2,220,099 and US-A-2,477,383 and those prepared from alkyIbenzenes 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 gl.AS.
Other anionic detergent compounds herein include the sodium cj0-cpg 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 - 8 alkyl phenol ethylene oxide ether sulfate containing about 1 to about 10 uni l.s of ethylene oxide per molecule and wherein the alkyl groups contain 8 to 12 carbon atoms.
Other useful anionic detergent compounds herein include 5 the water-soluble salts or esters of&<-sulfonated fatty acids containing from 6 to 20 carbon atoms in the fatty acid group and from 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-lsulfonic acids containing from 2 to 9 carbon atoms in the acyl group and from 9 to 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing from 10 to 18, especially 12 to 16, carbon atoms in the alkyl group and from 1 to 12, especially 1 to 6, jsoie especially 1 to 4 moles of ethylene oxide; water15 so-luble salts of olefin sulfonates containing from to 24, preferably 14 to 16, carbon atoms, especially those made by reaction witli sulfur trioxide followed by neutralization under conditions such that any sulfones present are hydrolysed to the corresponding hydroxy alkane sulfonates; water-soluble salts of paraffin sulfonates containing from 8 to 24, especially 14 to 18 carbon atoms, andβ> -alkyloxy alkane sulfonates containing to 3 carbon atoms in the alkyl group and from 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 alkanol30 ammonium cations; sodium is preferred. Magnesium and calcium are preferred cations under circumstances described by BE-A-843,636. Mixtures of anionic surfactants are contemplated by this invention; a preferred mixture contain» alkyl benzene sulfonate having 11 to 13 carbon atoms in the - 9 eilkyl qroup 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 whicli 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-isoisooctylphenol condensed with 15 moles of ethylene oxide. I 2, The condensation product of primary or secondary ! aliphatic alcohols having from 8 to 24 carbon atoms, in ; either straight chain or branched chain configuration, with frcm 1 to 30 moles of alkylene oxide per mole of i ! i 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 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 (Dobanol and Neodol are Trade Marks) vhich have about 25% 2-methyl branching (Eobanol and Neodol being Trade Names of Shell) or Synperonics, (Synperonic is a Trade Mark), which are understood to have about 50% 2-methyl branching (Synperonic is a Trade Name of X.C.I.) or the primary alcohols having more than 50% branched chain structure sold under the Trade Name Lial (Trade Mark) hy Liguichimica. Specific examples of ncnionic 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 (Trade Mark) series having from 9 to 15 carbon atoms in the alkyl group and up to 11, especially from 3 to 9, ethoxy residues per molecule. - 11 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. (Pluronic and Tetronic are Trade Marks.) Of the above, highly preferred are alkoxylated nonionic surfactants having an average HLB in the range about 9.5 to 13.5, especially 10 to 12.5. Highly suitable nonionic surfactants of this type are ethoxylated primary or secondary C9-15 alc°hols having an average degree of ethoxylation from 3 to 9, more preferably from 5 to 8.
Suitable semi-polar surfactants are water-soluble amine oxides containing one alkyl moiety of from 10 to 28 carbon atoms and 2 moieties selected from alkyl groups and hydroxyalkyl groups containing from 1 to 3 carbon atoms, and especially alkyl dimethyl amine oxides wherein the alkyl group contains from 11 to 16 carbon atoms; water-soluble phosphine oxide detergents containing one alkyl moiety of 10 to 28 carbon atoms and 2 moieties selected from alkyl groups and hydroxyalkyl groups containing from 1 to 3 carbon atoms; and water-soluble sulfoxide detergents containing one alkyl moiety of from 10 to 28 carbon atoms and- a moiety selected from alkyl and hydroxyalkyl moieties of from 1 to 3 carbon atoms.
Suitable arapholytic 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 8 to 18 carbon atoms and one contains an anionic watersolubilizing group, e.g. carboxy, sulfonate, sulfate, phosphate, or phosphonate. 1294 - 12 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 8 to 18 carbon atoms and one contains an anionic water-solubilizing group.
Preferred amphoteric and zwitterionic surfactants have the general formula:-X A wherein X is COg" or SOg", Rg is an alkyl or alkenyl group having 8 to 22 carbon atoms, possibly interrupted by amide, ester or ether linkages, Rg is a methylene, ethylene, propylene, isopropylene or isobutylene radical, Rg and R.^ are independently selected from hydrogen, Cg_g alkyl or -RgX, whereby one of the substituents Rg and R^ is hydrogen if the other one is represented by the group -RgX, 4.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 according to the above formula, Include N-alkyl-2-aminopropionic acid, N-alkyl-2 imino-diacetic acid, N-alkyl-2-·iminodipropionic acid, Nalkyl-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- N1-carboxymethylN1,N1-dimethy1-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 Cgto Cgg alkyl group, especially coconut alkyl, lauryl and tallow alkyl. Specific exanples include Armeen (Trade Marie) Z - 13 (marketed by Armour), Amphosol (Trade Mark) AA and SP (marketed by I.C.V.), Amphoram (Trade Mark) CPI, Diamphoram (Trade Mark) CPI, Triamphoram (Trade Mark) CPI, Triamphoram and Polyamphorams (Trade Mark) CPI, C2P1 and C^P^ (marketed by PierrefitteAuby) and Deriphat (Trade Mark) 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 5 to 50% by weight of the surfactant system.
The sequestrant can be selected from the water-soluble salts of polyphosphates, polycarboxylates, arainopolycarboxylates, polyphosphonates and aminopolyphosphonates having a logarithmic calcium ion stability constant (ρΚθ&++) of about 2 or greater and preferably an anion valence of at least 3. The stability constant is defined as follows :pKca.-+ = log10KCa++ where w·.= [ Ca++ A(n"2)·] FIT and An is the ionic species of sequestrant which predominates at the in-use pH of the composition (defined as the pH of a 1% aqeuous solution of the composition) and n is at least 3.
Preferably, the sequestrant has a pK,, ++ in the range Ltl from 2 to 11, especially from 3 to 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 «-,i: ionic strength us.ing .-i glass electrode method of measurement as described in Complcxation in Analytical Chemistry by Anders ltfngbom (3.963) . 51394 - 14 Suitable polyphosphates include pyrophosphates such as tetresodium pyrophosphate decahydrate, and tetrapotassium pyrophosphate;' tripolyphosphates such as pentapotassium tripolyphosphate; and higher polyphosphates and metaphos5 phates such as sodium pentapolyphosphate and sodium hexameta phosphate.
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, aconit.ic 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 pentacarboxylic acid, 2,3,4,5-tetrahydrofuran-cis, cis, ciscarboxyiic acid, 2,5-tetrahydrofuran-cis-dicarboxylic acid, 2.0 1,2,3,4,5,6-hexane-hexacarboxylic acid, mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in GB-A-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 add; 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.
Suitable aminopolycarboxylates include especially the amino polyacetates, e.g. sodium, potassium, ammonium and alkanolammonium ethylenediamine tetraacetates, diethylene triaminc pentaaertates ana nitrilotriacetates. - 15 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-soluble salts thereof.
The terpene component of the present compositions belongs to the class of mono- or sesquiterpenes or mixtures thereof and can be acyclic or preferably mono10 cyclic 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 β and y-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 otandβ-pinene. The terpene is added at a level of 0.5% to 10%, preferably 1% to 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 oi, β and isomers and linalool; suitable secondary alcohols include borneol; suitable primary alcohols include geraniol. Complex mixtures of terpene alcohols are also suitable, especially the mixture of alcohols manufactured by distilling the oils extracted from pine wpod, cones and needles and sold commercially as pine oils. The terpene alcohol is preferably added at a level in the range from 1% to 3%, more 31294 - 16 preferably from 1.5% to 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 80 to 200 cp (0.08 to 0.2 Pa.s) measured in a Brookfield viscometer, using Spindle No. 2 at 60 r.p.m. and at 2l°C.
The polar solvent component of the present compositions has a solubility in water at 25°C in the range from 0.2% to 10%, preferably from 0.5% to 6%. The solvent contains at least one hydrophilic group and is liquid at room temperature. The solvent can be at a level of 0.5% to 10% especially 1% to 5%, by weight of the composition and at a weight ratio of terpene: solvent in the range from 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^-Cg fatty acids with C,-C, alcohols containing a total of from 5 to 9 carbon 1 o atoms, e.g. n-butyl butyrate, n-butyl propionate and n-propyl acetate; and mono Cg-Cg and di-C4"Cg alkyl or aryl ethers of ethylene glycol such as hexyl, benzyl and phenyl Cellosolves (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 C^_4 ester derivatives thereof such as the ethylene glycol monomethyl-, monoethyland monobutyl ethers, propylene glycol propyl ether, dipropylene glycol methyl ether, ethylene glycol mono aceta'te - 17 and ethylene glycol monoethyl ethex- acetate, The nonaqueous solvent can be added in amounts up to 10%, preferably 65 by weight of the composition. : Hydrotropes such as urea, monoethanolamine, J diethanolamine, triethanolamine and the sodium, potassium, j ammonium and alkanol ammonium salts of xylene-, toluene-, : ethylbenzene-, isopropyl- benzene sulfonates, can also J be added to the compositions of the present invention in I amounts up to 10% by weight. It is a feature of the i present invention, however, that stable, homogeneous formu- ! lations can be prepared without the need for hydrotropic ; materials of this kind, or with only very minor levels j (i.e. less than 4% by weight). i ί Other suitable ingredients of the present compositions | include pH buffering materials such as alkali metal and j ammonium carbonates, bicarbonates, metasilicates and ortho j phosphates. These can be added, if appropriate, at levels j up to 10% by weight to provide a compositional pH equal i to or greater than pH 8, preferably greater than ί pH9 and more preferably greater than pH 10. Dyes, perfumes ϊ f enzymes, chlorine-releasing agents, polypeptides and protein j hydrolysates, soil suspending agents such as carboxy methyl- I cellulose, hydroxymethyl cellulose and polyethylene glycols having a molecular weight of 400 to 10,000, fluorescers such as disodium 4,4'-bis(2-morpholino-4-anilinos-triazxn-6-yl amino) stilbene-2,2'-disulfonate, preservatives such as Preventol (Trade Mark) ON marketed by Bayer, thickeners such as xanthan gum, and additional suds regulants such as tributylphosphate ana silicone oil can all be included in the present compositions.
A germicide such as o-phenyl phenate can also be added to the present compositions, providing excellent hard surface germicidal activity.
I i - 18 In the examples the following descrij PS I.AS ae^s Dobanol 91-8 Dobanol 45-7 Pluronic L-42 Deriphat 170C Amphoram CPI : Deriphat 154 : Ethylan (Trade Mark) : HB-4 HT Soap ; CN Soap ; TE?· ; CS : TPP : EDTA : NTA : Dequest (Trade Mark) : 2060 Deque’t 2041 which follow, the abbreviations used h,ave 'tions :Sodium C., to C.., paraffin sulfonate marketedoy Hoecnst under Trade Name IJostapur SAS.
Sodium salt of linear C^ θ alkyl benzene sulfonate.
Sodium linear c^9-14 alco^°l sulfate including 3 ethylene oxide moieties.
A Cg,. oxo-alcohol with 8 moles of ethylene oxide, marketed by Shell.
A C.oxo-alcohol with 7 moles of ethylene oxide, marketed by Shell.
A condensation product of ethylene oxide and propylene oxide, marketed by BASF-Wyandotte.
N-C,2_3(, alkyl-/?-amino propionic acid marketed by General Mills.
N-cocoyl-(?-amino propionic acid marketed by Pierrefitte-Auby.
Disodium-N-tallow-β-amino propionate marketed by General. Mills.
Phenol ethoxylated with 4 moles of ethylene oxide, marketed by Diamond Shamrock.
Sodium soap prepared from hydrogenated tallow.
Monoethanolamine soap of coconut fatty acids.
Triethanolamine.
Sodium cumene sulfonate.
Tetrasodium pyrophosphate.
Tetrasodium salt of ethylenediamine tetraacetic acid.
Trisodium salt of nitrilotriacetic acid.
Diethylenetriamine penta(methylene phosphonic acid), marketed by Monsanto.
Ethylenediamine tetra(methylene phosphonic acid) 'marketed by Monsanto.
S1394 - 19 EXAMPLES 1 TO 7 The following liquid compositions were prepared by mixing the ingredients in water :- 1 2 3 4 5 6 7 5 PS 4.5 4.0 - 8.0 5.0 - 6.0 LAS - - 4.0 - - 4.0 - Dobanol 91-8 2.0 - - - - 2.0 0.5 TPP - - - - 3.0 - - Sodium citrate .2^0 3.5 3.5 - - - - 8.0 10 Sodium metasilicate - - - 3.0 - - 1.0 Sodium carbonate 3.0 3.0 2.5 - - - - EDTA - - - 2.5 - - - NTA - - 3.0 - - 6.0 - Orange terpenes 2.0 2.0 - - - - - 15 Dipentene - - 2.0 - - - - D-limonene - - - 6.0 - - -· tf -pinene - - - - 2.0 - - ji -pinene - - - - - 3.0 - Terpinolene - - - - · - 2.0 20 Benzyl alcohol 2.0 - 2.0 G.O - 1.5 - Hexyl Cellosolve - 3.0 - - - - 2.0 Ethylan HB-4 - - - 1.0 - - Ethanol - - - 2.0 - - - Xanthan gum - - - - 0.5 - - 25 CS Water, Perfume & minors 2.0 2.0 2.0 3.0 •To 100 3.5 2.0 2.0 The above compositions were bcnogeneous fluent liquids having good stability, excellent surface-shine and cleaning character!sties on both inorganic particulate j soils and oily/greasy soils with controlled sudsing in i both dilute and concentrated usage under both hard ‘ and soft water conditions. - 20 EXAMPLES P TO 13 8 2 10 11 12 1_3 PS 4.5 8.0 4.0 - 5.0 - LAS - - - 5.0 - 6.0 Dobanol 91-8 2.0 - - 1.5 2.0 0.5 TPP - - - 6.0 - - Sodium citrate .21^0 3.5 - 3.0 - - 3.0 Sodium metasilicate - 3.0 - 1.0 - - Sodium carbonate 3.0 - 3.0 - - - EDTA - 2.5 - - -- 0.5 NTA - - - - 6.0 - Orsmge terpene - - 2.0 - - - Dipentene - 6.0 - - - - D-limonene 4.0 - - - - - ot. -pinene - - -- 2.0 - - p-pinene - - - - - 4.0 Terpinolene - - - - 3.0 - n-Butyl butyrate 3.0 - -- 2.0 Benzyl alcohol - 6.0 1.5 - - - Benzyl Cellosolve - - - 3.0 - 2.0 CM Soap 1.5 .1.5 0.3 0.05 - - HT Soap - - - - 0.1 0.5 Xanthan gum - - 0.5 - - - Ethanol - 2 - - - 1.5 TEA 1.0 3.0 - - - 2.0 CS - - 2.0 - - 1.0 Water, Perfume & minors —To 100- The above compositions were hanogeneous 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 conoen'- rated usage under both hard and soft water conditions. - 21 EX&Mi;1,ES 14 TO 20 ii 15 16 17 18 19 20 PS - - - - 2.0 - - LAS - - - - - 1.0 - Dobanol Sl~8 2.7 2.0 3.2 2.0 1.0 - - Deriphat 170C - 5.0 - 2.5 - - - Amphoram CPI 3.2 - 3.2 - - - 5.0 Deriphat 154 - - - 1.0 2.0 4.0 - CN Soap - - - - - 0.5 - Sodium citrate .2Π20 - - .. 6.0 8.0 - Sodium carbonate 3.0 - 2.0 - - - - Sodium nietasilicate - - -- - 1.0 - 2.0 TPP - 4 .0 - - - - - EDTA - - 2.5 - - - - NTA 3.0 - - - - - 4.0 Dequest 2060 - - - - 0.5 - - Ethylene glyco.l dibutyl, ether 1.5 - - - 1.0 - - Benzyl alcohol - 2.0 - 3.0 - 2.0 - Ethylan HB-4 - - 1.0 - - - 2.0 CS - 5.0 - 7.0 - 2.0 - Orange terpenes - - 1.0 - - 2.5 - D.i pen tone - - - -- 2.0 - - D-limonene 3.0 - - - - - -- v/~p.ibcno - 2.0 - - - - f’-pincnc .. - - - - - 2.0 Terpinolene - - - 5.0 - - - Ethanol - - 1.0 2.0 - - - Water, Perf lane & minors ---To 100- The above compositions were homogeneous fluent i liquids having good stability, excellent cleaning J characteristics on both inorganic particulate soils and j oily/grcasy soils vzith controlled sudsing in both dilute j and concentrated usage under both hard and soft water I conditions - 22 EX.AUPT.ES 21 TO 24 PS LAB Dobanol 91-8 CN Soap Sodium citrate .2J-J„Q £.
Sodium carbonate Pine oil o; -terpineol Linalool Geraniol Benzyl alcohol Phenyl ethyl alcohol ρ-Phenyl phenate CS Water, Perfume and minors 21 22 23 24 4.5 5.0 1.0 3.0 - - 2.0 - - - 0.5 3.0 - - - 0.5 3.5 3.5 - 6.0 3.0 2 6.0 1.0 2.0 - - - - 1.8 - - - - 2.2 - - - - 2.5 1.5 1.5 · 4.0 - - - - 2.5 1.3 1.5 1.3 1.3 1.4 i.5 1.0 2.0 To • 100.
Tha above 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.
Claims (13)
1. A liquid detergent composition comprising a water base together with: (a) from 1% to 20% by weight of a synthetic anionic, nonionic, amphoteric or zwitterionic surfactant or mixture thereof, (b) from 0.5% to 10% by weight 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 0.5 to 10% by weight of a polar solvent having a solubility in water at 25°C in the range from 0,2% to 10% by weight (g/lOOg solution), containing at least one hydrophilic group, and being liquid at room temperature.
2. A composition according to Claim 1, wherein the terpene is a mono- or bicyclic monoterpene selected from terpinenes, terpinolenes, limonenes, and pinenes and mixtures thereof.
3. A composition according to Claim 1 or 2, wherein the terpene is selected from d-limonene, dipentene, a-pinene, β-pinene and orange terpenes.
4. A composition according to Claim 1, wherein the terpene is a terpene alcohol, terpene aldehyde or terpene ketone.
5. A composition according to Claim 4, wherein the terpene is a terpene alcohol present in a level of from 1% to 3% by weight.
6. A composition according to Claim 5, wherein the terpene alcohol is present in a level of from 1.5% to 2.5% by Weight.
7. A composition according to any one of Claims 1 to 6, wherein the polar solvent is selected from benzyl alcohol polyethoxylated phenols containing from 2 to 6 ethoxy groups, phenylethyl alcohol, mono-Cg—C g alkyl ethers of ethylene glycol and di-C^—C g alkyl ethers of ethylene glycol. - 24
8. A composition according to Claim 1, wherein the terpene is selected from orange terpenes and the polar solvent is benzyl alcohol.
9. A composition according to any one of Claims 1 to 8, 5 wherein the weight ratio of mono- or sesquiterpene to polar solvent is in the range from 5:1 to 1:5.
10. A composition according to any one of Claims 1 to 9 having a pH in 1% aqueous solution of at least 8.0, comprising from 0.5% to 13% by weight of a water-soluble inorganic or 10 organic polyanionic sequestrant having a calcium ion stability constant at 25°C of at least 2.0, the weight ratio of surfactant:sequestrant lying in the range from 5:1 to 1:3.
11. A composition according to Claim 10, wherein the 15 sequestrant is selected from the water-soluble salts of polyphosphates, polycarboxylates, amino polycarboxylates, polyphosphonates and aminopolyphosphonates, the weight ratio of the surfactant:sequestrant lying in the range 3:1 to 1:1.
12. A composition according to any one of Claims 1 to 11, 20 which comprises from 0.005 to 2% of an alkali metal, ammonium or alkanolammonium soap of a C^g to Cg 4 fatty acid.
13. A liquid detergent composition according to Claim 1, substantially as hereinbefore described with particular reference to the accompanying Examples.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8017364 | 1980-05-27 |
Publications (2)
Publication Number | Publication Date |
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IE811166L IE811166L (en) | 1981-11-27 |
IE51294B1 true IE51294B1 (en) | 1986-11-26 |
Family
ID=10513677
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
IE1166/81A IE51294B1 (en) | 1980-05-27 | 1981-05-26 | 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) |
Families Citing this family (76)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1178160A (en) * | 1981-09-10 | 1984-11-20 | Donald B. Compton | Liquid hard-surface cleaner |
DE3270670D1 (en) * | 1981-11-12 | 1986-05-22 | Procter & Gamble | Liquid detergent compositions |
GB2134132A (en) * | 1983-01-14 | 1984-08-08 | Unilever Plc | Vehicle cleaning compositions |
DE3465496D1 (en) * | 1983-04-19 | 1987-09-24 | Procter & Gamble | Liquid scouring cleansers containing solvent system |
DE3316988C2 (en) * | 1983-05-10 | 1986-07-17 | Jürgen 6926 Kirchardt Rohrmoser | Process for cleaning devices and machines in the paper, cardboard and pulp industry |
GB8314710D0 (en) * | 1983-05-27 | 1983-07-06 | Optikon Ltd | Cleaning compositions |
EP0137615B1 (en) * | 1983-08-11 | 1988-01-27 | The Procter & Gamble Company | Fabric cleaning compositions for clay-based stains |
DE3469037D1 (en) * | 1983-08-11 | 1988-03-03 | Procter & Gamble | Liquid detergents with solvent |
US4613340A (en) * | 1984-01-09 | 1986-09-23 | Polar Molecular Corp. | Residual oil sludge dispersant |
GB8409054D0 (en) * | 1984-04-07 | 1984-05-16 | Procter & Gamble | Stabilized oil-in-water cleaning microemulsions |
GB8409055D0 (en) * | 1984-04-07 | 1984-05-16 | Procter & Gamble | Cleaning compositions |
FR2564105B1 (en) * | 1984-05-10 | 1987-09-11 | Saint Marc Lessives | LIQUID DETERGENT COMPOSITION AND PROCESS FOR ITS PREPARATION. |
JPH0647677B2 (en) * | 1984-10-02 | 1994-06-22 | ライオン株式会社 | Liquid detergent composition |
JPS61275396A (en) * | 1985-05-16 | 1986-12-05 | 中西化研株式会社 | Detergent |
US4758377A (en) * | 1985-09-24 | 1988-07-19 | The Proctor & Gamble Company | Viscous phase stable liquid scouring cleansers containing solvent |
US5075026A (en) * | 1986-05-21 | 1991-12-24 | Colgate-Palmolive Company | Microemulsion all purpose liquid cleaning composition |
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 |
AT385769B (en) * | 1986-06-12 | 1988-05-10 | Henkel Austria Ges Mbh | LIQUID ALL-PURPOSE CLEANER |
EP0261718B1 (en) * | 1986-09-22 | 1991-03-06 | The Procter & Gamble Company | Creamy scouring compositions |
EP0261874A3 (en) * | 1986-09-22 | 1989-01-25 | The Procter & Gamble Company | Concentrated hard-surface cleaning 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 |
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 |
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 |
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 |
US5080831A (en) * | 1989-06-29 | 1992-01-14 | Buckeye International, Inc. | 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 |
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 |
GB2243842B (en) * | 1990-04-12 | 1993-09-22 | Electrolube Limited | Method and compositions for circuit board cleaning using ether-containing terpenoid compounds |
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 |
CA2062075A1 (en) * | 1991-05-06 | 1992-11-07 | Patrizia Barone | 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 |
DE4119116C2 (en) * | 1991-06-10 | 1997-08-07 | Boehme Chem Fab Kg | Biologically easily removable defoamers for aqueous systems |
JPH07503271A (en) * | 1992-01-23 | 1995-04-06 | ザ、プロクター、エンド、ギャンブル、カンパニー | Liquid hard surface detergent composition containing a zwitterionic detergent surfactant, a cationic detergent surfactant, and monoethanolamine and/or β-aminoalkanol. |
US5536451A (en) * | 1992-10-26 | 1996-07-16 | The Procter & Gamble Company | Liquid hard surface detergent compositions containing short chain amphocarboxylate detergent surfactant |
JP2521630B2 (en) * | 1992-12-10 | 1996-08-07 | 花王株式会社 | Cleaning composition for hard surfaces |
DE4243468A1 (en) * | 1992-12-22 | 1994-06-23 | Henkel Ecolab Gmbh & Co Ohg | Neutral liquid detergent (I) |
GB9302869D0 (en) * | 1993-02-12 | 1993-03-31 | Rogers Neil | Cleaning |
NZ260144A (en) * | 1993-04-12 | 1995-10-26 | Colgate Palmolive Co | Cleaning composition; contains three liquid phases which merge at a tricritical point; use for removing tar or grease from articles |
CA2173437C (en) * | 1993-11-12 | 1999-08-31 | Ronald Anthony Masters | 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 |
US5514294A (en) * | 1994-11-22 | 1996-05-07 | Alliedsignal Inc. | Limonene and tetrahydrofurfuryl alcohol cleaning agent |
US6221823B1 (en) * | 1995-10-25 | 2001-04-24 | Reckitt Benckiser Inc. | Germicidal, acidic hard surface cleaning compositions |
AU728470B2 (en) | 1996-02-14 | 2001-01-11 | Stepan Company | Reduced residue hard surface cleaner comprising hydrotrope |
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 |
GB9613967D0 (en) * | 1996-07-03 | 1996-09-04 | Unilever Plc | Improvements relating to antimicrobial cleaning compositions |
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 |
US5922665A (en) * | 1997-05-28 | 1999-07-13 | Minnesota Mining And Manufacturing Company | Aqueous cleaning composition including a nonionic surfactant and a very slightly water-soluble organic solvent suitable for hydrophobic soil removal |
GB2331703B (en) * | 1997-11-28 | 2002-01-23 | Reckitt & Colman Inc | Disinfectant compositions |
GB2331760B (en) * | 1997-11-28 | 2002-05-15 | Reckitt & Colman Inc | Hard surface cleaning compositions |
US6849589B2 (en) | 2001-10-10 | 2005-02-01 | 3M Innovative Properties Company | Cleaning composition |
GB2405639A (en) * | 2003-09-08 | 2005-03-09 | R Mc Power Recovery Ltd | Metal cleaning compositions |
GB2408051A (en) * | 2003-11-14 | 2005-05-18 | Reckitt Benckiser Inc | Hard surface cleaning compositions |
US20080305978A1 (en) * | 2007-06-08 | 2008-12-11 | S.C. Johnson & Son, Inc. | Cleaning compositions containing a hydrophilic fragrance |
US9981069B2 (en) | 2007-06-20 | 2018-05-29 | The Trustees Of Columbia University In The City Of New York | Bio-film resistant surfaces |
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 |
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 |
WO2008157092A1 (en) | 2007-06-20 | 2008-12-24 | The Trustees Of Columbia University In The City Of New York | Bio-film resistant surfaces |
JP2012532141A (en) * | 2009-06-30 | 2012-12-13 | ザ トラスティース オブ コロンビア ユニバーシティ イン ザ シティ オブ ニューヨーク | Antimicrobial / preservative composition containing plant components |
US9968101B2 (en) | 2011-11-03 | 2018-05-15 | The Trustees Of Columbia University In The City Of New York | Botanical antimicrobial compositions |
EP2773334B1 (en) | 2011-11-03 | 2019-08-28 | The Trustees of Columbia University in the City of New York | Composition with sustained antimicrobial activity |
MX340821B (en) | 2011-11-18 | 2016-07-26 | Colgate Palmolive Co | Cleaning composition. |
WO2013086094A1 (en) | 2011-12-06 | 2013-06-13 | The Trustees Of Columbia University In The City Of New York | Broad spectrum natural preservative composition |
EP2727991A1 (en) | 2012-10-30 | 2014-05-07 | The Procter & Gamble Company | Cleaning and disinfecting liquid hand dishwashing detergent compositions |
EP3399013B1 (en) | 2017-05-05 | 2022-08-03 | The Procter & Gamble Company | Laundry detergent compositions with improved grease removal |
US20210395647A1 (en) * | 2018-09-05 | 2021-12-23 | Conopco, Inc., D/B/A Unilever | A quick and easy cleaning formulation |
WO2020106847A1 (en) * | 2018-11-20 | 2020-05-28 | Emerald Kalama Chemical, Llc | Multifunctional aromatic alcohols for personal care, home care and industrial and institutional compositions |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1237874A (en) * | 1967-07-19 | 1971-06-30 | Unilever Australia Proprietary | Detergent composition |
GB1308190A (en) * | 1970-06-26 | 1973-02-21 | Unilever Ltd | Suspending liquids |
US3634338A (en) * | 1970-07-10 | 1972-01-11 | Grace W R & Co | Method and composition for cleaning aluminum magnesiumand alloys thereof |
DE2113732A1 (en) * | 1971-03-22 | 1972-09-28 | Henkel & Cie Gmbh | Anti-microbial washing composns - contg terpenes as bactericides and optical brighteners |
US3933674A (en) * | 1975-02-07 | 1976-01-20 | Farnsworth Albert M | Cleaning composition |
DE2709690B1 (en) * | 1977-03-05 | 1978-05-11 | Henkel Kgaa | Liquid detergent |
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 AT AT83109923T patent/ATE32608T1/en not_active IP Right Cessation
- 1981-05-20 EP EP81200540A patent/EP0040882B1/en not_active Expired
- 1981-05-20 EP EP83109923A patent/EP0106266B1/en not_active Expired
- 1981-05-20 DE DE8181200540T patent/DE3168593D1/en not_active Expired
- 1981-05-21 GR GR65028A patent/GR75605B/el unknown
- 1981-05-26 IE IE1166/81A patent/IE51294B1/en unknown
- 1981-05-26 CA CA000378298A patent/CA1174551A/en not_active Expired
- 1981-05-26 FI FI811612A patent/FI66903C/en not_active IP Right Cessation
Also Published As
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EP0106266A3 (en) | 1984-07-25 |
EP0106266B1 (en) | 1988-02-24 |
FI66903C (en) | 1984-12-10 |
GR75605B (en) | 1984-08-01 |
EP0040882B1 (en) | 1985-01-30 |
IE811166L (en) | 1981-11-27 |
ATE32608T1 (en) | 1988-03-15 |
DE3168593D1 (en) | 1985-03-14 |
FI811612L (en) | 1981-11-28 |
EP0106266A2 (en) | 1984-04-25 |
FI66903B (en) | 1984-08-31 |
EP0040882A1 (en) | 1981-12-02 |
CA1174551A (en) | 1984-09-18 |
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