CA1174551A

CA1174551A - Liquid detergent compositions

Info

Publication number: CA1174551A
Application number: CA000378298A
Authority: CA
Inventors: Pierre C.E. Goffinet
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1980-05-27
Filing date: 1981-05-26
Publication date: 1984-09-18
Also published as: ATE32608T1; EP0106266A2; EP0106266A3; GR75605B; FI66903C; DE3168593D1; EP0040882B1; EP0040882A1; FI811612L; EP0106266B1; FI66903B; IE51294B1; IE811166L

Abstract

LIQUID DETERGENT COMPOSITIONS

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

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LI~UID DETERGENT COMPOSITIONS

This inven-tion relates to liquid detergent compositions.
In particular, it relates to aqueous detergent compositions suitable for use as general purpose household cleaning compositions.
Gene~al 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 buf~ering salts such as phosph~tes, carbonates, silicates etc., and although such composi-tions 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.
Li~uid cleaning compositions, on the other hand, have the great advantage that they can be applied to hard surfaces in neat or concentrated form so tha-t a relatively high level o~ ~uractant material is delivered directl~ -to the soil~ Moreover, it ls a xather m~re straightEorward kask to incorporake hi~h concentrations oE anionic or ~onionic sur~ac~ant in a lic~uicl rather than a granular composltion. For both these reasons, thereEore, liquid cleaniny compos.i-tion~ have the potenk.ial to provide superior grease ancl oil~ soil removal ovcr powdered cleaning composi-tions, ~

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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 for~, in particular, inhomogeneity, lack of clarity, or inadequate viscosity characteristics for consumer use D 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 behal~ 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-solubility, it has now been found that they can be incorpor-ated into liquid cleaning compositions in homogeneous form, even under cold processing conditions, with the ability to provide excellent cleaning characteristics across the ran~e o~ water hardness on grease/oil~ soild and inorganic par-tlcula-te soils, as well as on shoe polish, marker ink, bath tub soil etc, and excellent shine per~ormance with low soil redeposltion and little or no propensity to cause ~llm-ing, ~treAking or spottin~ on sur~aces washed therewith.
Moreover, the terpenes herein specified, and in particular those o~ the h~drocarbon class, are valuable in regulating the sudsing behaviour of the instant compositions in both hard and soft water and under both diluted and neat ' , ~ ~'7~-~S~

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 deter-gent compositions at low levels via the perfume. Certain terpenes have also been included in detergent compositions at higher levels; for instance, German Patent Specification ~o. 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 Specification No. 2,709,690 teaches the use of pine oil (a mixture mainly of terpene alcohols) in liquid hard surface cleaning co~positions. 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 haviny 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 characteri~ed by:
~a) from about }~ to about 20~ of a synthetic anionlc, nonionic, amphoteric or zwitterionic sur~actarlt or mixture thereoE, ~b) ~rom 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 -~t~ ~ 5 ~

(c) from about 0.5 to about 10~ of a polar solvent having a solubility in water at 25C in the range ~rom about 0.2% to abo~t 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,~ -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 ~ruit-juice).
Terpene alcohols, aldehydes and ketones can also be used, however, the alcohols/ in particular/ providing valuable but unexpected improvements in viscosity regulation when incorpor-ated 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 pre~erably 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 C13-C18, fatty acid. Preferably, the fatty acid is fully saturated, for example, by hydrogenation of naturally occurring fatty acids. Additon o~ the soap, particularly to compositions containing terpene hydrocarbons, is found to provide slgnificant synergistic enhancement in the suds~
suppression effectiveness o~ the system.
~ calcium sequestrant is also desirable in the present compositions, providing not only cleaning advantages on partiaulate 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 25C
of at least about 2.0 preferably at least about 3.0, the .

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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 a~ a level of from about 0.5% to about 13~ by weight. The compo-sition itself preferably has a pH in 1% aqueous solution of at least about 8Ø
Suitably, the sequestrant can be selected from the water-soluble salts of polyphosphates, polycarboxylates, 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.
A notable feature of the instant composi~ions 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, switterionic and amphoteric surfactants can be used in the present compositions.
~ typical listing of the classes and species of these sur-~actants ls glven ln U.S. Patent 3,663,961 issued to Norris on May 23, 1972. These sur~actants can be used singly or in aombination at levels in the range from about 1% to about 20~r pre~erably at levels ~rom about 3~ to about 10% b~ weight of the compositions.
Suitable anionic non soap sur~actants are water-soluble salts of alkyl benzene sulfonates, alkyl sulfates, alkyl polyethoxy ether sulfates, parafin sulfonates, alpha-olefin , .

L~ ~ S 'l sulfonates, alpha-sulfocarboxylates and their esters, alkyl glyceryl ether sulfonates, fatty acid monoglyceride sulfates and sulfonates, alkyl phenol polyethoxy ether sulfates, 2~
acyloxy-alkane-l-sulfonate, and beta-alkyloxy alkane sul-i-onate. 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 sul~ates, especially those obtained by sulfating the highest 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 9ulfonates in which the average of the alkyl group is about 11.8 carbon atoms, abbr~viated as Cl1 8LAS.
~th~r anionic detergent compounds herein include the sodium C10-Cl8 alkyl glyceryl ether sulEonates, especially those others of higher alcohols dexived from tallow and coconut oil sodium coconut oil ~atty acid monoglyceride sulfonates and sulfates; and sodium or ptoassium salts of X

5~

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 containiny 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-1-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about g 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 ~o 16, carbon atoms, especially those made by reaction with sulfur trioxide followed by neutralization under conditions such that any sultones present are hydrolysed to the corresponding hydroxy alkane sulfonates; water-soluble salts of paraffin sulfonates containing from about 8 to 24, especially 14 to 18 carbon atoms, and ~-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 alkanol-ammonium cations; sodium is pre~erred. Magnesium and calcium are preferred cations under circumstances described by ~el~ian patent 843,636 invented by Jones et al, issued December 30, 1976. Mixtures of anionic surfactants a.re contemp.1ated by this invention; a pre~erred mixture contains alkyl benzene sulfonate having 11 to 13 carbon atoms in the ~.t7~SS~

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 ~oles of ethylene oxide per mole of alkyl 2S phenol. The alkyl substituent in such compounds may be derived~ for example, rom polymerised propylene, disobutylene, octene and nonene. Other examples include dodecylphenol condensed with 12 moles of ethylene oxide per mole of phenol;
dinonylphenol condensed with 15 moles o~ ethylene oxide per mol~ o phenol; nonylphenol and di-isoisooctylphenol condensed wlth 15 moles of ethylene oxide.

2. The condensation product o primary or secondary aliphatic alcohols having rom 8 to 24 carbon atoms, in either stral~ht chain or branched chain confi~uration, with from 1 to about 30 moles o~ alkylene oxide per mole of ~ .
.

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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 which have about 25% 2~methyl branching(<~Dobanol and aNeodol>> being Trade Marks of Shell) or Synperonics, which are understood to have about 50% 2-methyl branching (Synperonic is a Trade Mark of I.C.I.~ or the primary alcohols having more than 50% branched chain structure sold under the Trade Mark ~Lial by Liquichimica. Specific examples of nonionic surfactants falling within the scope of the inven-tion include Dobanol 45-4, Dobanol 45-7, Dobanol 45-9, Dobanol 91-3, aDobanol 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 compris-ing 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, etlloxy xesidues per molecule.

*Trademar]c g ~7 .~

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3. The compounds formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of pxopylene oxide with either propylene glycol or ethylene ciia~ine.
Such synthetic nonionic detergents are available on the i market under the Trade Marks o "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 10 to 12.5. Highly suitable nonionic 0 surfactants of this type are ethoxylated primary or secondary Cg 15 alcohols having an average degree of ethoxylation from about 3 to 9, more preferably from about 5 to 8.
Suitable semi-polar surfactants are water-soluble amine oxides containing one alkyI moiety of from about 10 to 28 carbon atoms and 2 moieties selec~ed from the group consisting o alkyl groups and hydroxyalkyl groups containing from 1 to about 3 carbon atoms, an~ especially alkyl dimethyl amine oxides wherein the alkyl group contains from about 11 ~o 16 carbon atoms; water-soluble phosphine oxide detergents ~o containing one alkyl moiety o 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 con-taining one alkyl moiety of from about 10 to 28 carbon atoms an a moiety selected from the group consisting o~ alkyl and hydroxyalkyl moieties oE from 1 to 3 carbon atoms.
Suitable amp}lol~tic surfactants are water-soluble d~rivatives o~ allphatic secondary and tertiary amines in Which the aliphatic moiety can be straight chain or branched o and whereln one o~ the aliphatic substituents con~ains ~rom about 8 to 18 carbon atoms and one contains an Ani~nic water-solubilizing cJroup/ e.g. carboxy, sulfonate, sulate, phosphate, or phosphonate.

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Suitable zwitterionic surfactants are water soluble d~rivatives 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 ampho~eric and zwitterionic surfactants have the general formula:-1 T ~ X A

wherein X is C02 or S03 , Rl is alkyl or alkenyl grouphaving 8 to 22 carbon atoms, possibly interrupted by amide, ester or ether linkages, R2 is a methylene, ethylene, propylene, isopropylene or isobutylene radical, R3 and R4 .
are independently selected from hydrogen, Cl 3 alkyl or -R2-X, whereby one of the substituents R3 and R4 is hydrogen if the other one is represented by the group -R2X, ~.is an integer from 1 to 6, and A is ~n equivalent amount of a neutralizing anion, except that amphoteric surfactants include amine salts of the above formula and also the corre-sponding free amines.
Highly preferr~d surfactants according to the aboveformula, include N-alkyl-2-aminopropionic acid, N-alkyl-2 -imino-diacetic acid, N-alkyl-2-iminodipropionic acid, N-alkyl~ mino-~-methyl-propionic acid, N-alkyl-propylenediamine-propionic acid, N-alkyl-dipropylenetriamine-propionic acid, N~alkyl-dlpropylenetriamino dipropionic aci.d, N-alkylglycine, N-alkyl-amino-succinic acid, N-amidoalkyl- N'-carboxymethyl-N',N'-dimethyl-ammonio -e~hylene diamlne, N-alkyl-c~mino-othane-sulonic acid, N-a~kyl-N,N-dimethyl-ammonio-hydroxy-propene-sulonic acid and salts thereo~, wherein alkyl represents a C8to C18 alkyl group, especially coconut alkyl, lauryl and tallow alkyl. Speci~ic examples include"Armeen Z"

* Trademark .

C~, l !- , ~'7~-~5 (marketed by Armour),"Amphos~ol"AA and SP ~marketed by I.C.V.), "~mphoram CP~', Diamphoram CPl,"Triamphora~ CPl~"Triamphoram C2Pl and~olyamphorams CPl, C2Pl an~ C3Pi" (marketed by Pierrefitte-Auby) and"Deriphat 170C and~Deriphat 15~"
(marketed by General ~lills).
Of all the above surfactants, highly preferred composi-tions comprise as the single or major sur~c~ant component, surfactants selected from the anionic, amphoteric and zwitterionic classes. The nonionic surfactants ~hen present are preferab-y 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
The sequestrant can be selected from ~he water-soluble salts of polyphosphates, polycarboxylates, aminopolycarboxy-lates, polyphosphonates and aminopolyphosphonates having a logarithmic calcium ion stability constant (pKCa++) of about 2 or greater and an anion valence o~ at least 3. The stability constant is defined as follows:-pKCa++ = log10 KCa wh~re Ca + = ~ A~ 2)-~

and An is the ionic species of sequestrant which predomina~esat the in-use pH of the composition ~defined as the pH of a 1% a~euous solutlon o~ the composition) and n ls at least 3.
Pre~erabl~, the se~uestrant has a pKCa~ in the ran~e ~om about 2 to about 11, especially from about 3 to about 8.
Literatu~e v~lues of stability constan~s are taken where possible ~see ~abiliky Constants of Metal-Ion Complexes, Special Publi~ation No. 25, The Chemical Society, London);
wh~re dQubt ~ises, the stability constant is defined at 25C and at ~e~o ionic strength using a glass electrode method o~ meagurement as described in Complexation in ~nalytical Chemistry by Anders Rlngbom (1963).
1-8 inclusive. The terms bearing these superscript numerals are trademarks.

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Suitable polyphosphates include ~yrophosphates such as tetrasodium pyrophosphate decahydrate, and tetrapotassiwn pyrophosphate; tripolyphosphates such as pentapotassium tripolyphosphate; and higher polyphosphates and metaphos-phates such as sodium pentapolyphosphate and sodium hexameta-phospha~e.
The carhoxylate-type sequestrants can be described as monomeric polycarboxyla-te materials or oligomers or polymers derived from carboxylate or polycarboxylate monomers. The se~uestrants can be acyclic, alicyclic or aromatic in na-ture.
Suitable polycarboxylates include the salts of citric acid, aconitic acid, citraconic aci~, carboxymethyloxy succinic acid, lac~oxysuccinic acid, and 2-oxa-1,1,3-propane tricarboxylic acid; oxydisuccinic acid, l,1,2,2-ethane tetra carboxylic acid, 1,lr3,3-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 pol~meric polycarbox-ylates include homo- and copolymers o~ 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 suh as acrylic acid, methacrylic acid or ~-hydroxy acrylic acid; or copolymer.s o~ one or more o~ the above pol~carboxyl. and acryllc monomers with another unsaturated polymerizable monomer, such as vinyl ethe~s, acrylic esters, ole~ins, vln~l pyrrolidones and styrenes.
Suikable aminopolycarboxylates include especially the amino polyacetates, e.g sodium, potassium, ammonium and alkanolammonium ethylenediamine tetraacetates, d~ethylene triamine pentaacetates and nitrilotriacetates.

Polyphosphonate and aminopolyphosphonate materials suitable for use herein can be exemplified by nitrilo tri-(~ethylenephosphonic acid), ethylenediamine tetra(methylene-phosphonic acid), diethylenetriamine penta(methylenephosphonic acid) and the water-soluble 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 ~25C). Preferred terpenes belong to the class of terpene hydrocarbons ~nd 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, ~-octadiene. Preferred monocyclic terpene hydrocarbons belong to the terpinene, terpinolene and limonene classes, for example, the ~ , ~ and ~-terpinenes, the d and 2 -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 or 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 borneQl;
suit~ble primary alcohols include geraniol. Complex mixtures 3~ oP kerpene alcohols are also suitable, especially the mixture o alcohols manufactured by distilling the oils extracted from pine wood, cones and needles and 801d commercially as pine oils>). The terpene alcohol ~.s preferably added at a level in the range from abou-t 1% to abou-t 3~, more 3~

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preferably~from about 1.5~ to about 2.5% by weight o~ the compositions in order to provide optimum control of product viscosity characteristics. Preferably such compositions have L
a viscosity in the range from about 80 to 200 cp (0.08 to 0.2 Pa.s) measured in a Brookfield viscometer, using Spindle No.
2 at 60 r.p.m. and at 21C.
The polar solvent component of the present compositions has a solubility in water at 25C 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, polye~hoxylated phenols containing from 2 to 6 ethoxy groups and phenylethyl alcohol; esters of Cl-C6 fatty acids with Cl-C6 alcohols containing a total of from 5 to 9 carbon atoms, eq, n-butyl butyrate, n-butyl propionate and n-propyl acetate; and mono C6~Cg and di-C4-Cg alkyl or aryl ethers of ethylene glycol such as hexyl, benzyl and phenyl <~Cellosolves)> (Registered Trade Mark) and ethylene-glycol 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 a~ditional ingredient, especially water miscible or high}y soluble (at least 20~w/w) aliphatic mono-, di- and tri alcohols.
Speci~lc examples are e~hanol, propanol, lsopropanol, ancl propane-1,3-dlol. Other suitable solvents are ethylene-, propylene-, diethylene- and dipropylene glycol and the mono-alkyl ether and Cl 4 ester derivatives thereo such as the ethylene glycol monomethyl-, monoethyl- and monobutyl ethers, propylene glycol propyl ether, dipxopylene glycol methyl ether, ethylene glycol mono acetate `

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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 sul~onates, 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, homogeneous formulations can be prepared without the need for hydrotropic materials of this kind, or with only very minor levels li.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 prefer-ably greater than about pH10. Dyes, perfumes,enzymes, chlorine-releasing agents, polypeptides and protein hydrolysates, soil suspending agents such as carboxy methyl- cellulose, hydroxy-methyl 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 addition-al suds regulants such as tributylphosphate and silicone oil can all be included in~-the instant compositions.
~ ~ germicide such as o-phenyl phenate can also be added ~o the present composltions, providing excellent hard surface germiaidal activity.

*Trademark )~ - 16 -~ 7~ ~3~

In the examples which follow, the abbreviations used have the following descriptions:-PS : Sodium Cl to Cl paraffin sulfonate marketed by Hoec~st under Trade Mark Hostapur SAS.
LAS Sodium salt of linear Cll 8 alkyl benzene sulfonate.
3 Sodium linear Cl 14 alcohol sulfate including 3 ethy~ene oxide moieties.
Dobanol 91-8 : A C 11 oxo-alcohol with 8 moles of ethylene oxide, marketed by Shell.
~Dobanol 45-7 : A Cl -15 oxo-alcohol with 7 moles of ethy~ene oxide, marketed by Shell.
aPluronic L-42 : A condensation product of ethylene - oxide and propylene oxide, marketed by BASF-Wyandotte.
Deriphat 170C : N-C 2 1 alkyl-~ -amino propionic acid mar~ete~ by General Mills.
Amphoram CPl : N-cocoyl- ~-amino propionic acid marketed ~y Pierrefitte-Auby.
Deriphat 154 : Disodium-N-tallow- ~-amino propionate marketed by General Mills.
Ethylan HB-4 : Phenol ethoxylated with 4 moles of ethylene oxide, marketed by Diamond Shamroc~..
HT Soap : Sodium soap prepared from hydrogenated tallow.
CN Soap : Monoethanolamine soap of coconut fatty acids.
TEA : Triethanolamine.
CS : Sodium cumene sulfona,te.
TPP : Tetrasodium pyrophosphate.
~DTA : Tetrasodium salt o~ ethylenediamine tetraacetic acid.
NTA : Trisodium salt of nitrilotriacetic acid.
~Dequest 2060 : Dlethylenetriamlne penta(methylene phosphonic acid), marketed by Monsanto.
~Dequest 20~1 : Ethylenediamine tetra(methylene phosphonic acid) marketed by Monsanto.

* Trademark ** Trademark *** Trzdemark -~7~

The following liquid compositions were prepared by mixing the ingredients in water:-~ _ _ _ _ _ _ PS 4.54.0 - 8.0 5.0 - 6.0 LAS - - 4.0 - - 4.0 Dobanol 91-8 2.0 - - - - 2.00.5 TP2 - - - - 3.0 Sodium citrate .2H2O 3.5 3.5 - - - - 8.0 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 Dipentene - - 2.0 D-limonene - - - 6.0 - - -~-pinene - - - - 2.0 ~-pinene - - - - ~ 3.0 Terpinolene - - - - - - 2.0 Benzyl alcohol 2.0 - 2.06.0 - 1.5 Hexyl <~Cellosolve - 3.0 - - - - 2.0 Ethylan HB-4 - - - - 1.0 Ethanol - - - 2.0 Xanthan gum - - - - 0.5 CS 2.0 2.02.0 3.0 3.5 2.0 2.0 Water, Perfume &
minors To 100 The above compositions were hono~eneous fluent liquids having good stability, excellent surface-shine and cleaning characteri~tics on both inoryanic particulate soils and olly/greasy soils with oontrolled sudsing in both dilute and concentrated usage under both hard and sof t water conditions.

~ .

~l~7~

PS g.5 8.0 4.0 - 5.0 LAS - - - 5.0 - 6.0 Dobanol 91-8 2.0 - - l. 5 2.0 0.5 TPP - - - 6.0 Sodium citrate .2H2O3.5 - 3.0 - - 3.0 Sodium metasilicate - 3.0 - 1.0 Sodium carbonate 3.0 - 3.0 - - -EDTA - 2.5 - - 0.5 NTA - - - - 6.0 Orange terpene - - 2.0 Dipentene - 6.0 - - - -D-limonene 4.0 - - - - -15 ~-pinene - - - 2.0 -pinene - - - - - 4.0 Terpinolene - - - - 3.0 n-Butyl butyrate 3.0 - - - 2.0 Benzyl alcohol - 6.0 l. 5 Benzyl Cellosolve - - - 3.0 - 2.0 CN 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 &
mlnors --- - To 100 - - -- -~he above compositions were homoqenous fluent liqu:Lds having good stability, excellent surface shine and cleaning characteristics on both inorganic particula-te soils and ol.ly/greasy soils with con-trolled sudsing in both dllute and concent.rated usage under both hard and soft water conditions.

:~7455~

PS ~ 2.0 -LAS ~ 1.0 <~Dobanol 91-8 2.7 2.0 3.2 2.0 1.0 - -<~Deriphat 170C - 5.0 - 2.5 Amphoram CPl 3.2 - 3.2 - - - 5.0 Deriphat 154)> - - - 1.0 2.0 4.0 CN Soap - - - - - 0.5 Sodium citrate .2H2O - - - - 6.0 8.0 Sodium carbonate 3.0 - 2.0 - - - -Sodium metasilicate - - - - 1.0 - 2.0 TPP - 4.0 EDTA - - 2.5 NTA 3.0 - - - ~ 4-0 <~Dequest 2060 - - - ~ 0-5 Ethylene glycol 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 Dipentene - - - - 2.0 - -D-limonene 3.0 - - - - - -a-pinene - 2.0 - - - - -~-pinene - - - - - - 2.0 T~rpinolene - - - 5,0 Ethanol - - 1.0 2.0 Water, Per~ume &
minors ~ -To 100 The above compositions were homogeneous ~luent liquids having good stability, excellent cleaning characteristics on both inorganic particulate soils and oily/greasy soils with controlled sudsing in both d:ilute and concentrated usage under both hard and soft water.

: , ~7~5~

PS 4.5 5.0 4.03.0 LAS - - 2 . 0 Dobanol 91-8 - - O. 5 3 0 CN Soap ~ ~ ~ 0 5 Sodium Citrate 3 . 5 3 . 5 - 6.0 . 2H20 Sodium carbonate 3 . 0 2 6 . 01. 0 Pine oil 2 . 0 ~-terpineol - 1.8 Linalool - - 2 . 2 Geraniol - - - 2 . 5 Benzyl alcohol 1.5 1.5 4.0 Phenyl ethyl alcohol- - - 2 . 5 o-Phenyl phenate1.3 1.5 1. 3 1. 3 CS 1.4 1.5 1.0 2.0 Water, Perfume and minors To 100 The 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.

,.
'J

Claims

1. An aqueous liquid detergent composition characterized by:-(a) from 1% to 20% of a synthetic anionic, nonionic, amphoteric or zwitterionic surfactant or mixture thereof, (b) from 0.5% to 10% of a mono- or sesquiterpene or mixtures thereof, the weight ratio of surfactants:
terpene lying in the range 5:1 to 1:3 and (c) from 0.5 to 10% of a polar solvent having a solubility in water at 25°C in the range from 0.2% to 10%.

2. A composition according to Claim 1 characterized in that the terpene is a mono- or bicyclic monoterpene selected from the terpinenes, terpinolenes, limonenes, and pinenes and mixtures thereof.

3. A composition according to Claim 1 characterized in that the terpene is selected from d-limonene, dipentene, .alpha.-pinene and .beta.-pinene.

4. A composition according to Claim 1 characterized in that 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%, preferably from 1.5% to 2.5%.

6. A composition according to any of Claims 1 to 3, characterized in that the polar solvent is benzyl alcohol.

7. A composition according to any of Claims 1 to 3 chara-cterized in that the weight ratio of mono- or sesquiterpene to polar solvent is in the range from 5:1 to 1:5.

8. A composition according to any of Claims 1 to 3 having a pH in 1% aqueous solution of at least 8.0, characterized by from 0.5% to 13% of a water-soluble inorganic or 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.

9. A composition according to any of Claims 1,2, or 3 having a pH in 1% aqueous solution of at least 8.0, characterized by from 0.5% to 13% of a water-soluble inorganic or 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 3:1 to 1:1, wherein the sequestrant is selected from the group consisting of the water-soluble salts of polyphosphates, polycarboxylates, aminopolycarboxylates, polyphosphonates and aminopolyphosphonates.

10. A composition according to any of Claims 1 to 3 characterized in that it comprises from 0.005 to 2% of an alkali metal, ammonium or alkanolammonium soap of a C13 to C24 fatty acid.