CA2247902A1 - Liquid crystal detergent compositions - Google Patents

Abstract

This invention relates to an acidic liquid crystal composition comprising an ethoxylated nonionic surfactant, an aliphatic carboxylic acid, an ethoxylated alkyl ether sulfate surfactant or sodium lauryl sulfate, a weak base, a water-insoluble organic compound selected from perfumes, essential oils and hydrocarbons, a cosurfactant, a magnesium salt and water.

Description

W O 97t32968 PCT~US97/04065 LIQUID CRYSTAL DETERGENT COMPOSITIONS
Field of the Invention This invention relates to an acidic liquid crystal detergent composition. More 5 specifically, it is of an acidic liquid detergent composition in a liquid crystal state which when brought into contact with oily soil is superior to other liquid detergent compositions in detergency and in other physical properties.
~ck~round of the Invention Liquid aqueous synthetic organic detergent compositions have long been 10 employed for human hair shampoos and as dishwashing detergents for hand washing of dishes (as distinguished from automatic dishwashing machine washing of dishes).
Liquid detergent compositions have also been employed as hard surface c~eaners, as in pine oil liquids, for cleaning floors and walls. More recently they have proven successful as laundry detergents too, apparently because they are convenient to use, 15 are instantly soluble in wash water, and may be employed in "pre-spotting" applications to facilitate removals of soils and stains from laundry upon subsequent washing. Liquid detergent compositions have comprised anionic, cationic and nonionic surface active agents, builders and adjuvants, including, as adjuvants, lipophilic materials which can act as solvents for lipophilic soils and stains. The various liquid aqueous synthetic 20 organic detergent compositions mentioned serve to emulsify lipophilic materials, including oily soils, in aqueous media, such as wash water, by forming micellar dispersions and emulsions.
Although emulsification is a mechanism of soil removal, it has been only comparatively recently that it was discovered how to make microemulsions which are 25 much more effective than ordinary emulsions in removing lipophilic materials from substrates. Such microemulsions are described in British Patent Specification No.

2,1gO,681 and in U.S. Patents 5,075,026; 5,076,954 and 5,082,584 and 5,108,643, most of which relate to acidic microemulsions useful for cleaning hard surfaced items, such as bathtubs and sinks which microemulsions are especially effective in removing SUBSTITUTE SHEET (~ULE 26) ' ~ U J. ~ ' Ur~ v L~ ~ . . L ' soap scum an~ lime scal~ frQm them. ~owever, as in U.S. Patent No. 4,919,839 themicroemulsions may be essentially neutral and such are also taught to be effective for micro~mulsifying lipophilic soils from s~sl,~:te~. In U.S. Patent application Serial ~o.
71313,664 there is des~ribed a li~m duty l"icroe,i,LIlsion liquid deter~ent cor"~osilion which is useful for washin~ dishss and remo~ring gr~asy deposits from them in both neat and dilllted forms. Such cornposilions includa compl~xes of anionic and cationic detergents as su~fa~e active components of the microernulsions.
The various ~nicr~en~ulsions referred to include a llp~Jhile, which may be a hydrocarbon, a surFactant, wh;~h m~y be an anionic and/or a nonionic dotr rgent~s), a co-surfactant, which may be a poly-lower alkylene ~Iycol lower alkyl ether, e.g., tripropylene ~Iycol monomethyl ether! and w~ter.
Aithou~h the man~f~ e and use of i~t~r~nt compositions in microsmulsion form sisnTficantly impro~d cleaning power and ~reasy soil rQmo~fal. comparsd to the usual emulsions, the pr~sent invention improves them still furth~r and also ;n~reases the capaclty of the deter~ent compositi~ns to adher~ to surfac~s to which they have been applied. Thus, they drop or run c~bst~nUally less than cleanin~ composiUons of "similat" cieaning power which are in microemulsion or normal liquicl datergant torm.
Also, ~e~ s~ they forrn l"icroer"ulsions with lipophilic soil or stain material spontaneously, wlth essentiaily no requirement for addit~on of any ener~y, eith~r thermal or me-;l,ani~', they are more etf~ctiYe cleaners at room ~~ er~lure and at higher and lower t~""Je,~tures that are normally employed in olsaning op6r~lions than are otdinary liquid detergents, ~ncl are also more effective than deter~ent compositions in microemulsion form.
Th~ pr~s~nt llquid crystal ~lel~ent compositions may be either ~lear or somQwhat ctoudy or milky (or~lescent) in appearance but both farms thereof ar~ stable on stor~ge and components thoreo~ do n~t seKle out or b~come ine~e-,1i./e, even on storage at somewhat eleYated temp~ratures t~r periods as long as six months and up i~ .r~ NDED SHEET
- IP~A/EP

.... .. , ~ , . ~ .. .

' - CA 02247902 1998-08-28 to a y~ar. The presence of the cosurtactallt in the liquid crystal detergent compositions he,~ps to make such cc mpositions resist ~reezin~ at low temperatures.

~.r~ ) SHEET
5r ~.; 1tP
.. ,, .. .. ... ~ ~ .. . . . .. . . . . . . ..

W O 97/32968 PCT~US97/0406 In accordance with the present invention an acidic liquid detergent composition,suitable at room temperature or colder, for pre-treating and cleaning materials soiled with lipophilic soil and soap scum, is in liquid crystal form and comprises synthetic organic surface active agent, a cosurfactant, an organic acid, a solvent for the soil, and 5 water. The invention also relates to processes for treating items and materials soiled with soap scum and/or lipophilic soil with compositions of this invention to loosen or remove such soil, by applying to the locus of such soil on such material a soil loosening or removing amount of an invented composition. In another aspect of the invention lipophilic soil is absorbed from the soiled surface into the liquid crystal.
In recent years all-purpose liquid detergents have become widely accepted for cleaning hard surfaces, e.g., painted woodwork and panels, tiled walls, wash bowls, bathtubs, linoleum or tile floors, washable wall paper, etc.. Such all-purpose liquids comprise clear and opaque aqueous mixtures of water-soluble synthetic organic detergents and water-soluble detergent builder salts. In order to achieve comparable 15 cleaning efficiency with granular or powdered all-purpose cleaning compositions, use of water-soluble inorganic phosphate builder salts was favored in the prior art all-purpose liquids. For example, such early phosphate-containing compositions are described in U.S. Patent Nos. 2,560,839; 3,234,138; 3,350,31~; and British Patent No. 1,223,739.
In view of the environmentalist's efforts to reduce phosphate levels in ground 20 water, improved all-purpose liquids containing reduced concentrations of inorganic phosphate builder salts or non-phosphate builder salts have appeared. A particularly useful self-opacified liquid of the latter type is described in U.S. Patent No. 4,244,840.
However, these prior art all-purpose liquid detergents containing detergent builder salts or other equivalent tend to leave films, spots or streaks on cleaned 25 unrinsed surfaces, particularly shiny surfaces. Thus, such liquids require thorough rinsing of the cleaned surfaces which is a time-consuming chore for the user.
In order to overcome the foregoing disadvantage of the prior art all-purpose liquid, U.S. Patent No. 4,017,409 teaches that a mixture of paraffin sulfonate and a reduced concentration of inorganic phosphate builder salt should ~e employed.

W O 97/32968 PCT~US97/04065 However, such compositions are not completely acceptable from an environmental point of view based upon the phosphate content. On the other hand, another alternative to achieving phosphate-free all-purpose liquids has been to use a major proportion of a mixture of anionic and nonionic detergents with minor amounts of glycol ether solvent and organic amine as shown in U.S. Patent NO. 3,935,130. Again, this approach has not been completely satisfactory and the high levels of organic detergents necessary to achieve cleaning cause foaming which, in turn, leads to the need for thorough rinsing which has ~een found to be undesirable to today's consumers.
Another approach to formulating hard surfaced or all-purpose liquid detergent composition where product homogeneity and clarity are important considerations involves the formation of oil-in-water (o/w) microemulsions which contain one or more surface-active detergent compounds, a water-immiscible solvent (typically a hydrocarbon solvent), water and a "cosurfactant" compound which provides product15 stability. By definition, an o/w microemulsion is a spontaneously forming colloidal dispersion of "oil" phase particles having a particle size in the range of 25 to 800 A in a continuous aqueous phase.
In view of the extremely fine particle size of the dispersed oil phase particles, microemulsions are transparent to light and are clear and usually highly stable against 20 phase separation.
Patent disclosures relating to use of grease-removal solvents in o/w microemulsions include, for example, European Patent Applications EP 0137615 andEP 0137616 - Herbots et al; European Patent Application EP 0160762 - Johnston et al;
and U.S. Patent No. 4,561,991 - Herbots et al. Each of these patent disclosures also 25 teaches using at least 5% by weight of grease-removal solvent.
It also is known from British Patent Application GB 2144763A to Herbots et al, published March 13, 1985, that magnesium salts enhance grease-removal performance of organic grease-removal solvents, such as the terpenes, in o/w microemulsion liquid detergent compositions. The compositions of this invention W 097/32968 PCT~US97/04065 described by Herbots et al. require at least 5% of the mixture of grease-removal solvent and magnesium salt and preferably at least 5% of solvent (which may be a mixture of water-immiscible non-polar solvent with a sparingly soluble slightiy polar solvent) and at ieast 0.1% magnesium salt.
The following representative prior art patents also relate to liquid detergent cleaning compQsitions in the form of o/w microemulsions: U.S. Patents Nos.. 4,472,291 - Rosario; 4,540,448 - Gauteer et al; 3,723,330 - Sheflin; et al.
Liquid detergent compositions which include terpenes, such as d-iimonene, or other grease-removal solvent, although not disclosed to be in the form of o/w 10 microemulsions, are the subject matter of the following representative patentdocuments: European Patent Application 0080749; British Patent Specification 1,603,047; and U.S. Patent Nos. 4,414,128 and 4,540,505. For example, U.S. Patent No. 4,414,128 broadly discloses an aqueous liquid detergent composition characterized by, by weight:
(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 mixture thereof, at a weight ratio of (a):(b) being in the range of 5:1 to 1:3; and (c ) from 0.5% to 20% of a polar solvent having a solubility in water at 1 5~C in 20 the range of from 0.2% to 10%. Other ingredients present in the formulations disclosed in this patent include from 0.05% to 10% by weight of an alkali metal, ammonium or alkanoiammonium soap of a C1 3-C24 fatty acid; a calcium sequestrant from 0.5% to 13% by weight; non-aqueous solvent, e.g., alcohols and glycol ethers, up to 10% by weight; and hydrotropes, e.g., urea, ethanolamines, salts of lower alkylaryl sulfonates, 25 up to 10% by weight. All of the formulations shown in the Examples of this patent include relatively large amounts of detergent builder salts which are detrimental to surface shine.
U.S. Patent 5,03~,826 teaches liquid crystal compositions but these compositions exhibit thermal stability in the limited temperature range of 1 9~C to 3~~C.

W097/32968 PCTrUS97/04065 Hard surface cleaners, such as bathroom cleaners and scouring cleansers, have been known for many years. Scouring cleansers normally include a soap or synthetic organic detergent or surface active agent and an abrasive. Such products can scratch relatively soft surfaces and can eventually cause them to appear dull. These products 5 are often ineffective to remove lime scale (usually encrusted calcium and magnesium carbonates) in normal use. Because lime scale can be removed by chemical reactions with acidic media various acidic cleaners have been produced and have met with various degrees of success. In some instances such cleaners have been failures because the acid employed was too strong and damaged the surfaces being cleaned.10 At other times, the acidic component of the cleaner reacted ob3ectionably with other components of the product which adversely affected the detergent or perfume. Some cleaners required rinsing afterward to avoid leaving objectionable deposits on the cleaned surfaces. As a result of research performed in efforts to overcome the mentioned disadvantages there has recently been made an improved liquid cleaning15 composition in stable microemulsion form which is an effective cleaner to remove soap scum, lime scale and greasy soils from hard surfaces, such as bathroom surfaces and which does not require rinsing after use. Such a product is described in U.S. Patent 5,076,954 which patent is hereby incorporated by reference. In particular, Example 3 of that application discloses an acidic, clear, oil-in-water microemulsion which is therein 20 described as being successfully employed to clean shower wall tiles of lime scale and soap scum that had adhered to them. Such cleaning was effected by applying the cleaner to the walls followed by wiping or minimal rinsing after which the walls were allowed to dry to a god shine.
The described thickened microemulsion cleaner of U.S. Patent 5,076,954 is 25 effective in removing lime scale and soap scum from hard surfaces and is easy to use, but it has been found that its mixture of acidic agents (succinic, glutaric and adipic acids) could damage the surfaces of some hard fixtures, such as those of materials which are not acid resistant. One of such materials is an enamel that has been extensively employed in Europe as a coating for bathtubs, herein referred to as W O 97/32968 PCT~US97/04065 European enamel. It has been described as zirconium white enamel or zirconium white powder enamel and has the advantage of being resistant to detergents, which makes it suitable for use on tubs, sinks, shower tiles and bathroom enamelware. However, such enamel is sensitive to acids and is severely damaged by use of the microemulsionacidic cleaner based on the three organic carboxylic acids previously mentioned. This problem was been solved by EPO Patent Application No. 0336878A2, wherein additional acidic materials were incorporated in the cleaner with the organic acids and rather than exacerbating the problem, they prevent harm to such European enamel surfaces by such organic acids. Also, a mixture of such addltional acids, phosphonic 10 and phosphoric acids surprisingly further improves the safety of the aqueous cleaner for use on such European enamel surfaces and decreases the cost of the cleaner.
The instant compositions of the present invention allow the cleaning of Europeanenamel surfaces, as weli as any other acid resistant surfaces of bathtubs and other bathroom surfaces. The product can be used on various other materials that are 15 especially susceptible to attack by acidic media, such as marbie. Additionally, the instant compositions are stabie at 25~C for at least 3 months and are shear thinning.
The present invention relates to a thickened acidic aqueous liquid crystal cleaner for bathtubs and other hard surfaced items, which are acid resistant or are of zirconium white enamel, wherein the cleaner has a pH in the range of 1 to 4 and the cleaner 20 removes lime scale, soap scum and greasy soil from surfaces of such iterns without damaging such surfaces.
U.S. Patent 5,~3~,826 teaches liquid crystal compositions but these compositions exhibit thermal stability in the limited temperature range of 1 9~C to 36~C.
Summary of the Invention The present invention provides an improved acidic liquid crystal detergent composition having improved interfacial tension which improves cleaning hard surface in the form of a ~iquid crystal which is suitable for cleaning hard surfaces such as plastic, vitreous and metal surfaces having a shiny finish, oil stained floors, automotive engines and other engines. More particularly, the improved cleaning compositions ~ ~ ~ , c v. ~ J. . _, J 1 ~ . ~ . r...~ " ~
' - CA 0224790i i998-08-28 exhibit g~od grease sail removal ~.rope~ s due to the improved interfaclal t~nsions and leave the cleaned susfaces shiny withol~t the need of or requiring oniy minimal a~ nal rinsin~ or wlping. The lat~er characteristic is e~/idenced by little or no visible r~sldues on the unrinscd cleaned surfac~s and, accordin~ly, overcomes one of thedisadvantages of prior art produ~.
Surpris;ngly, these desirable results ar~ accomplished cYen in the absence of polyphosphate or other inor~anic or cr~anic d~l~r~nt builder salts and also in th~
complete absQnce or s~lbst~rlti~lly complete absence of ~reas~removal solvent.
In ons asFe~t. the Inv~ntion ~enerally provides a stable, liquid crystal, hard surface oleaning comrosition especially effective ;n tho removal of oily and greasy oil.
The liquid crystal composition includes, on a weight basis:
~ a) 1% to 2û~/., o~ an ethoxylated ~kyl ether sult~te surtactant or sod~umlauryl sulfate;
(b) 1% to 30% of a water-mixable cosurfaotant having ~ither limited ability or suhs~ntially no ability to dissolve oi~y or ~roasy soil;
(c) t % to 30% of an ethoxyiated nonionic surfactant;
(d) 1% tC 10% of a ma~nesium salt Such a~ ",a~nesium sul~ate heptahydrate and~or ma~nesiLlm ~hloride;
(e) 0.6% to 1 OCK of a perFume, essential oil, or water insoluble hydroc~rbon havin~ 6 to 18 rarbon atoms;
(~ 1~~ to 5~fO of ar. aliphatic carboxylic acid havin~ abo~n 2 to about 10 c~rbon atorns;
(9) 0.1% to 3% of we~k baso; and (h) the balancs bnin~ water, whercin th~ acidic liquid crystal ~etergent composition does not cont~in any sultonate surfactsnt, and the liquld detergent eompositic~n has a storage modv~ equal to or higher than one Pascal ~1 Newton/sq.
m.), more pr~l~r~!y hi~her than t 0 Pascal at a t~"~ re of 20~C to 40~C at a strain of 0.1% to 5% and a freguency of 10 radians/second as measurQd on a Carr-Med~A

AMENDED Sl IEEr IPEAJEP

'- CA 02247902 1998-08-28 ~B
-CS Rheometer and is thermally stablQ and exist ~s ~ liquid cryst~l in the temperature ran3e f~om 8~C to 43~C~ mot~ prefera~ly 4cC tc 43~C.

A~E~-D S~ T
~P~ E~

. .. ~ ... ..

: c u. J. ~ ., J . u . J . . ~
'- CA 02247902 1998-08-28 _ 9A

ne~ 3f~ nescrir~tion of the Invention The present invention r~lates t~ a st~ble acidic liquid cryst~l detergent composition co"~,risil)~ approxiinately by weiQht 1% to 15% of an ethoxylat6d alkyl eth~r sulf~t~ surtactant, 1% to 30% of a cosurfactant, 1% to 30% of an ethoxylated nonionic surfactant, 0.6% to 10% of a wat6r insolubla hydrocarbon, essential oil or a perfume. 1% to 5% of an aliphatic ~;UiJoxylic add, 0.1% to 3% of weak base, and the balance being ~at~r, wherein the acidic liquid crystal composibon does n~t contain any sulf~nate surfactant, and the liquid d~L~ge~l composition has a storage modulus aqual to or high~r than one Pascal (1 Nev~on/sq.m.), more p.~t~raL)Iy high~r than 10 Pascal at a temperature of 20CC to 40~C at a strain of 0.1% to ~~fO at a trequency of 10 radianslsecond as m~asured on a Carr-Med~M CS Rheometer and is therrnally stableand exist as a clear liq~lid crystal in the t~mperatur~ range from 8~C to 43~C, more preferably 4~C to 43CC.
According to the pr~sent in~ention, th~ role of the water insoluble ~ydrocarbon can be provid~d by a non-wate~-soluble perfume. Typically, in a~ o-ls based compositions the presence of a solubili~ers, such as alkali metaJ lower alkyl aryl sulfonate hy i~ul~pe~ triethanolamine, urea, etc., Is required tor perfurne diss31utionJ
espBcially at perfume leYeJs of 1% and hi3her, since perfum2s are g~nera~ly a mixture of fragrant essential olls and aromatic co~npounds which are ~enerally no~ water-s~Juble.
As used herein and in the appended claims the tPrm "parfume" is used in its ordinary ssnse to refer to and includ~ any non-water soluble frasrant s~hst~Qce or mixture of su~ ces including natural (i.e., obtained by extra~tion of tJower, herbt blossom or plant)? arlifi~al (i.e., mixtur~ of natural oils or oil constituents) and syntheti~ally produ~ subcPrlce) oLl~,rifefous substances. Typical~y, p~rfumes are complex mixtur~s of bl~nds of various or~anic compounds such as alcohols, aldehydes, ethers, aru~ c compounds and vary;n~ amounts of essentiai oils (e.~.,terp~nes) such as from ~% to ~0%, usually from 10% to 70% by weight, the essenUal AMI~NDED SH~ET
IPEaJEP

. .

gB
-0il5 themselves bsing volatile o~oriferous compounds and also servin~ to dissolve the other com,u~ f the perfume.

AMENDtD SHEET
- IPE,'.~EP

.. . . , ~,--. . .... . .. .. .. . .

W 097/32968 PCT~US97104065 Quite surprisingly a~though the perfume is not, per se, a solvent for greasy or oily soil, --even though some perfumes may, in fact, contain as much as 80% of terpenes which are known as good grease solvents -- the inventive compositions in dilute form have the capacity to solubilize up to 10 times or more of the weight of the perfume of 5 oily and greasy soii, which is removed or loosened from the hard surface by virtue of the action of the anionic and nonionic surfactants, said soil being taken up into the oil phase of the o/w microemulsion.
In the present invention the precise composition of the perfume is of no particular consequence to cleaning performance so long as it meets the criteria of water lû immiscibility and having a pleasing odor. Naturally, of course, especially for cleaning compositions intended for use in the home, the perfume, as well as all other ingredients, should be cosmetically accepta~le, i.e., non-toxic, hypoailergenic, etc.
The hydrocarbon such as a perfume is present in the liquid crystal composition in an amount of from 0.6% to 10% by weight, preferably from 0.8% to 8% by weight, 15 especially preferably from 1% to 6% by weight. If the amount of hydrocarbon (perfume) is less than ~.6% by weight it becomes difficult to form the liquid crystal. If the hydrocarbon (perfume) is added in amounts more than 10% by weight, the cost is increased without any additional cleaning benefit and, in fact, with some diminishing of cleaning performance insofar as the total amount of greasy or oily soil which can be 20 taken up in the oil phase of the microemulsion will decrease proportionately.
Furthermore, although superior grease removal performance will be achieved for perfume compositions not containing any terpene solvents, it is apparently difficult for perfumers to formulate sufficiently inexpensive perfume compositions for products of this type ~i.e., very cost sensitive consumer-type products) which includes less than 25 20%, usually less than 30%, of such terpene solvents.
Thus, merely as a practical matter, based on economic consideration, the liquid crystal cleaning compositions of the present invention may often include as much as 0.2% to 7% by weight, based on the total composition, of terpene solvents introduced thereunto via the perfume component. However, even when the amount of terpene W 097/32968 PCT~US97/04065 solvent in the cleaning formulation is less than 1.5% by weight, such as up to 0.6% by weight or 0.4% by weight or less, satisfactory grease removal and oil removal capacity is provided by the inventive compositions.
In place of the perfume in either the microemulsion composition or the all 5 purpose hard surface cleaning composition at the same previously defined concentrations that the perfume was used in either the microemulsion or the all purpose hard surface cleaning composition one can employ an essential oil or a water insoluble organic compound such as a water insolubie hydrocarbon having 6 to 18 carbon such as a paraffin or isoparaffin such as isoparH, isodecane, alpha-pinene, 10 beta-pinene, decanol and terpineol.
Suitable essential oils are selected from the group consisting of: Anethole 20/21 natural, Aniseed oil china star, Aniseed oil globe brand, Balsam (Peru), Basil oil (India), Black pepper oil, Black pepper oleoresin 40/20, Bois de Rose (Brazil) FOB, Borneol Flakes (China), Camphor oil, White, Camphor powder synthetic technical, Cananga oil 15 (Java), Cardamom oil, Cassia oil (China), Cedarwood oil (China) BP, Cinnamon bark oil, Cinnamon leaf oil, Citronella oil, Clove bud oil, Clove leaf, Coriander (Russia), Coumarin 69~C (China), Cyclamen Aldehyde, Diphenyl oxide, Ethyl vanilin, Eucalyptol, Eucalyptus oil, Eucalyptus citriodora, Fennel oil, Geranium oil, Ginger oil, Ginger oleoresin (India), White grapefruit oil, Guaiacwood oil, Gurjun balsam, Heliotropin, 20 Isobornyl acetate, Isolongifolene, Juniper berry oil, L-methyl acetate, Lavender oil, Lemon oil, Lemongrass oil, Lime oil distilled, Litsea Cubeba oil, Longifolene, Menthol crystais, Methyl cedryl ketone, Methyl chavicol, Methyl salicylate, Musk ambrette, Musk ketone, Musk xylol, Nutmeg oil, Orange oil, Patchouli oil, Peppermint oil, Phenyl ethyl alcohol, Pimento berry oil, Pimento leaf oil, Rosalin, Sandalwood oil, Sandenol, Sage 25 oil, Clary sage, Sassafras oil, Spearmint oii, Spike lavender, Tagetes, Tea tree oil, Vanilin, Vetyver oil (Java), Wintergreen The nonionic surfactant is present in amounts of 1% to 30%, preferably 3% to 18% by weight of the liquid crystal composition and provides superior performance in the removal of oily soil and mildness to human skin.

",, ; . ~

lZA

The water soluble ethoxylated nonionic surfactants utili~ed in this invention are comrnercially w~lt known and inolucle the prlrnary allphatic alcohol ethoxylates ~nd secondary aliphatic alcohol ethoxylates. The len~h of the polyeth~noxy chain c~n be adjusted to achi~v~ the d~sired balance betw6en the hydropinobic and ny~r~philicel~ments.
The nonionic surfactant class includ~s the condensation products of a higher alcoh~l (e.g., an alkanol containing about 8 to 16 carbon atorns in a straight or branched chain configuration) condensed with abcut 4 to 20 mol~s ot ethylene cxidE~, for example, lauryl or myristyl alcohol condensed ~ith about 16 moles of ethylene oxide (EO~, tridecanol condsnsed wit~ about 6 to rnoles of EO, myristyl a~cohol cond~nsed with about 10 moles of EO per mole of myristyl alcohol, the conderlsation product of EO with a cut o1 coconut fatty alcohol contalnin~ a mixture of fany alcohols with alkyl chair~ls varying from 10 to about 14 carbon ~toms in length and wherein the cond~nsate conta~ns either about 6 moles o~ EO pQr mole ot total alooi~l or about 9 moles of EO
per mole of 21cohol ~nd tallow alcoilol ethoxylates contalning 6 E0 to 11 E0 pBr mole of alc~hol A preferred group ot the foregoing nonionic surfactants are the NeodolTM
ethoxylates ~Shsll Co.). which ar~ hi~her aliphatic, primary alcohol containing a~o~t 9-15 c~rbon atoms, such as Cg-C1 1 ali-canol condensed with 4 to 10 moles of ~tl~ylene oxide (Neodol~M 91-8), C12 13 alkanot cw~ nsed Yvith 6.~ rnoles ~thylene oxlde (Neodol~M 23-6.5~, C12 1~; alkanol condensed with 12 moles ethyiens oxid~ (N~odol~
25-i ~), C1 4-1~ alkanol condensed with 13 moles ethylene oxide (Neodol~ 45-13), and the like. Such etl-oxal"Qrs have an HLB (hydrophobic lipophilic balance) value of about 8 to 15 and ~ive good O/W emulsifi~tion, whereas eti~ox~ners with HLB ~lues below 7 contain 16ss than 4 ethyleneoxide ~roups and tend to bo poor amulsifiers and poor detergents.
A~ditional ~lisfa~tory w~ter soluble alcohol et~.ylene oxide cond~nsates are thecon~ensation produ~ts of a secondary aliphatic alcohol containing 8 to 18 carbon IP~i~ . .. ..

' CA 02247902 l998-08-28 atoms in a ~Ir~ hl or branched ch~in configuration condensed w;th 5 to 30 moles of sthylene oxide. Examples of commercially av~ilable nonioni~ de~ergents o~ the A~/IEN~ED SH~ET
.. IPE~i/E~--~ . .. . _ .. , . .. .. . . . " . .

' CA 02247902 1998-08-28 foregolng type ar~ Cl 1-C1~ s~condary aikanol conden~ed with either 9 E0 ~ergitol~M
15-S-9) or 1~ EO tTerg~ 7~ t5-S-12) n~srke~a~ by Union Garbide.
The anionic surFactants which may be used in the detergent of this invention are water soluble salts and include the sodium, potassium, ammonium. triethanolamineand ethanolammaniu~ saltq of an Cg 1 8 ethoxylated a~kyl ether sultate surfactar1ts which have the structur~-+
R-(OCHCH~)nOSC~3M
whersin n is about 0 (it n ~ O then it is sodium lauryl sulfate ~SLSI) to about ~ and R i-Q
an alkyl ~roup having ~bout 8 to a~Qut 1B carbon ~toms, more prafer2bly 12 to 15 and natural cuts, for example, C~2 14; C~12-16 and M is an ammonium cation ~r a m~tal cation, most prefera~ly sodium. The ethoxylated alkyl ether sulfata is prd~enl i~ the composition ~t a conoentration of about 1~~ tc about 20% ~y wei~ht, m~re prefarabl~
ab~ 2~h to 15% by weigt~t.
Th~ ethoxylat~d alkyl ether sulfate may be made by sulfatin3 thQ condensation product of ethylene oxide an~ ~8-10 alkanol, and neutralizing the resultant prcduct.
The ~thoxylated alkyl ether sultates ditte~ from one another in the nurnber of carbon ~torrls in the alcohols and in th~ number of rnoies of ethylene oxlde !e~cted wKih one mole of such al~oh~l Pref~r,e~ ethoxylat~d alkyl ether polyethenoxy sulfates contain 12 to 1~ on atoms in tlle alc~hols and irl the a~kyl 3ro~ps tnereof, e.g., sodium rnyristyl (3 EO) sulfate.
Ethoxylated Cg~18 alkylphenyl ether sulfates ~ontainin~ ~ro~ 2 to 6 moles ot ethylene oxide in the molecule are also suitable for use in the fnvsntion cornposhions.
These d~ter~ents can be prepared by rea~tin~ an alkyl pheno~ with ~ to 6 mo~es of ethylene oxide and sulfating ~nd n~ul(dli~ing the rssult~nt ethoxylated alkyJphenol. The Concenl~liOn of the ethoxylated alkyl ethar sulfate s~ nt is about 1 to about B ~Ht.
%.
The major c~ass of compounds found to prwidP hi~hly suitable cosur~actanls for ~he rnicroemulsion over temperature ran~es extendin~ from 5~C to 43~C for inst~nce AI~ENDED Sf IEEJ
IPEA/Ep . ...
.

~r~ ;C~ L~.-.LL '~ L_'L~ L~I _'L~
' CA 02247902 1998-08-28 13~

are g~ycerol, ethylene ~lycol, water-soluble polyet~lylene ~Iycols having a molecular wei~ht ot 3W to 1 ooa, polypropylene glycol of th~ formula I IO(CH3C~lCH20)nll Al~"~N~-L, SH'-ET
l p--,~_p ~ - CA 02247902 1998-08-28 whQrein n is a number from 2 to 18, mixtur~s of polyethylene glycol and polypropyl ~Iycol (SynaloxTM) and mono C1-C6 alkyl ethe~s and aslers of ethylene glyooi andpropylene ~Iycol having the structural formulas R(X)r,011 and R1 (XjnOH wherein R iS
C1-C6 alkyl group, R1 is ~2-C4 ~cyl group, X is (OCH2CH2) or (OCH2(CH3~CH) and n is a number from 1 to 4, diethyl0na glycoi, triethylene ~Iycol, an alkyl lactate, wherein the alkyl 3~oup has 1 to 6 carbon atoms, lmethoxy-2-propanol, lmethoxy-3-propanol, and 1 methoxy 2-, 3- or 4-butanol.
R~3prssQntative members of the polypropylene glycol include dipropyienQ gJycol and polypropylene glycol havin~ a molecular weight cf 200 to 1000, e g., polypropylene glycol 400. Oth~r sali~t~,1e,y glycol ethers ar~ ethylBlle glycol monobutyl ether (butyl cellosolve), diethylene glycol monoblltyl eth9r (butyl carbitol), tri~thylene ~Iycol monobutyl ether, mono, di, tn propylene glyr,~l monobutyl ether; tetraethylene glyool monobutyl ether, mono, di, tripropylene ~Iycol monomethyl sther, propylene 31ycol monomethyl ethsr, ~thylene ~Iycol monohexyl Qthor, die~hylene ~Iycol monohaxyl Qther, propylen~ glycol tertiary butyl ether! ethylen~ ~Iycol rnono~thyl ~ther, ~thylene glycol monomethyl other, ethylene gly~ol monopropyl ether, ethylene glycol rnonopontyt ether, r~iothylene ~Iycol monomethyl sther, diethylene 31ycol mcnoethyl ether, diethylene glycol rnonoprGpyl ether, diethylene glycol monopr ntyl ethar,triethylene glycol monomethyl ether, friethyl~ne ~Iycol monoethyl eth~r, tri~thylene glycol ,,,onG~Jlupyl ~ther, triethylene glycol ",o"o~entyl ether, tn~thylen~ glycol monohexyl sther, mono, di, tripropy~ene glycol mono~thyl other, mono, di tripropylene ~Iycol Illo~)op~pyl eth~r, mono, di, tripropylene glycol monopentyl ether, mono, di, tripropylens ~Iyeol monohexyl ether, mono, di, tributylene ~Iycol mono methyl ether, mono, di, tributylene glycol monoothyl ether, mono, di, tributylen~ glycol monopropyl ether, mono, di, tri~utylene ~Iycol monobutyl eth~r, mono, di, tributylene glycol monopentyl ether and mono, d~, tributylene glycol monohexy~ ~ther, ethylene glyool monoac~tat~ and dipropylene ~Iycol propion~te Tripropylene glycol n-butyl ether is the pr~[~r-~ cosurtactant ~ecn~se ot i-ts h~dl~phobic ~haraoter.

A~ E~

. ....

Th~ amount of cosurfactant required to stabilize the iiql~id crysta~ compositions will, of course, d~pend on such factors as th~ surface tenslQn charact~ristics of the cosurfactant. th~ type ~nd amounts o~ th~ primal~r surfactants and pPrtumes, and th~
type and arnounts of any ~ther additionat ingredients which may be present in ~he ccmposition and urhich have an infiuQnc~ on t~le thermodynamic factor~ enumcrat~d above. Amounts of cosurfactant used In the iiquid crysta~ composition is ;n the ran~e ~f from 1% to 30%, preferably from 2% to 20%, espe~lly p,~f~r~bly from 3% to 16%, ~y weight prov;de stable liquid crystal composition for the above-d~sc, iL ed l~vels of primary sur~arXants and psrfume and a~ly ~ther additional ~n~redients as described below.
Th8 aliphatic carboxylic acid having about 2 to about 10 ~arbon atoms is presr~nt in the ~o",posilio~ a. a ~ncantration of ~bout ~ w~. % to about ~ wt %, more prefer~bly about 1.2~ wt. % to about 4 wt. %.
R~pressntative mem~ers of the aliphatic carboxylic acids include C3-C6 a~kyl and aikenyl monobasic acids su~h as acryl~c acid and propionic ac~d and dibasic acids havinQ 2 to 10 ~arbon atoms s~ch as glutaric acid and m;xtures of ~lutarir acid ~v~th ~dipic aaid and ~u~cinic aùd, as we11 as mixtures of th~ foreg~in~ adds. GeneralJy, wei~ht ratios of adipic zcid: ~lutaric acid:succinic aad is 1-3:1~ , praf~rably 1-2:1-6:1-3, such as t ~ 2:1, 2:2~ 2;1.5, 1:~:2, 2:3:2, etc. can be used with equally good results.
Of the dicar~oxylic ~cids group, which inoludes those o~ 2 to 10 carbon atoms, ~rom oxalic acid through sebacic acid s~Jbcric, ~la;o and s~b~ic a~cids Rre of lower solubiiW~s and theretor~ are not as ~Ise~l in t~e prssent emu~sions as the other dibasic ali~l ,a~ic ~atty aci~s, all of which ~re p~eferably saturated and ~lr~ight chain~.. Oxalic and malonic acids. althou~h useful as reducln~ agents too, may t)B too strong for delica~e hard surtace cleaning. Pr~erre~ such dibasic acids are those of the middi~
portion ot the 2 tc t O carbon atom acid range, succinlc. glutaric, adipic and pimalic AMEND0 SHEE~.
IPEA/EP ~

~~T\ : k~A ~J cr~ J~ ~ ~Lt~ ~t'. ' JJJ IU~ U ' ~ 'J r. L L 1 1'~ _ Il. J L . ~ ~ . 1 i 1 _ L~ I ~ L I
' CA 02247902 1998-08-28 acids, espe~ially the first three ther~of. which fortllnately are avall~ble ~ommercially, in ~ixturs. Citric acld can also b~ employed as th~ acid.

AMENDEC~ S~JEET
IPE~/EP

CA 02247902 l998-08-28 W O 97/32968 PCT~US97/~4065 The preferred aiiphatic carboxylic acid is an alpha hydroxy aliphatic acid which is strong enough to lower the pH of the microemulsion to one in the range of one to four.
Various such carboxylic acids can perfornn this function but those which have been found effectively to remove soap scum and lime scale from bathroom surfaces best, 5 while still not destabilizing the emulsion, are alpha hydroxy aliphatic acids having the structure:
X

Y ~ OH

10 wherein Y is seiected from the group consisting of hydroxy or a COOH group and X is (CH2)nW, wherein W is selected from the group consisting of CH3 or COC~H and n is 0, 1, or 2. Preferred alpha hydroxy aliphatic acids are citric acid, lactic acid and malic acid, wherein a mixture of lactic acid and malic acid is preferred, wherein the weight ratio of lactic acid to malic acid is preferred to be ~:1 to 1:1, more preferably 4:1 to 1:1.
15 The at least one alpha hydroxy aliphatic acid is incorporated in the composition in an amount of 1 to 9 wt. %, more preferably 2 to 7 wt. %.
The alpha hydroxy aliphatic acid, after being incorporated in the acidic emulsion, may be partially neutralized to produce effectiveness, with safety.
Phosphoric acid can be used at a concentration of 0 to 1 wt. % and is one of the20 additional acids that helps to protect acid-sensitive surfaces being cleaned with the present emulsion cleaner. Being a tribasic acid, it too may be partially neutralized to obtain an emulsion pH in the desired range. For example. It may be partially neutralized to the biphosphate, e.g., NaH2PO4, or NH4H2PO4.
Phosphonic acid used at a concentration of 0 to 1 wt. % can also be used for 25 protecting acid-sensitive surfaces from the dissolving action of the dicarboxyiic acids of the present thickened emulsions, apparently exists only theoretically. but its derivatives are stable and are useful in the practice of the present invention. Such are considered to be phosphonic acids as that term is used in this specification. The phosphonic acids are of the structure.

, . .. . . ~ . .. .
,, OH
Y- ' -O
OH
wherein Y is any suitable substituent, but preferably Y is alkylamino or N-substituted 5 alkylamino. For example, a preferred phosphonic acid component of the present thickened acidic emulsions is aminotris (methylenephosphonic~ acid which is of the formula N (CH2PHXO3) Among other useful phosphonic aclds are ethylene diamine tetra-(methylenephosphonic) acid, hexamethylenediamine tetra-(methylenephosphonic) acid, ad diethylenetriamine penta-(methylenephosphonic) acid. Such class of 10 compounds may be described as aminoalkylenephosphonic acids containing in theranges of 1 to 3 amino nitrogen, 3 or 4 lower alkylenephosphonic acid groups in which the lower alkylene is of 1 or 2 carbon atoms, and 0 to 2 alkylene groups of 2 to 6 carbon atoms each, which alkylene(s) is/are present and join amino nitrogen when a plurality of such amino nitrogen is present in the aminoalkylenephosphonic acid. It has ~ 15 been found that such aminoalkylenephosphonic acids, which also may be partially neutralized at the desired pH of the microemulsion cleaner, are of desired stabilizing and protecting effect in the invented cleaner, especially when present with phosphate acid, preventing harmfui attacks on European enamel surfaces by the diacid(s) components of the cleaner. Usually the phosphorus acid salts, if present, will be mono-20 salts of each of the phosphoric and/or phosphonic acid groups present.
The liquid crystal composition contains a weak base such as diethanolamine ortriethanol amine at a concentration of 0.1 wt. % to 2 wt. %. The weak base is employed in the composition to adjust the pH of the composition.
The instant composition contains 0.5 to 8 wt. %, more preferably 1 to 6 wt. % of25 a magnesium salt such as magnesium chloride and/or magnesium sulfate heptahydrate and mixtures thereof.
The ability to formulate neutral and acidic products without builders which havegrease removal capacities is a feature of the present invention because the prior art o/w microemulsion formulations most usually are highly alkaline or highly built or both.

~ ~ . J JrUII jU ~ u ~
rCu~ v CA 02247902 1998-08-28 In addition to their exc~l'Qnt capacity for cleaninQ gr~asy and oily soils, the low pH liquid crystal formulations also exhibit e~ llent cleaning perfornlance e~nd rernoval ot soap scum and lime sca~e in neat (undiluted) as ~~fell as in diluted usage.
The flnal ssselltial in~redient in th~ inventiv~ acidic liquid c~stal compositions havin~ irnprov2d interfacial tenslon prop~i ~ies is water. The proportion of wat~r in thB
liquid crystal ~le~ent cor",vosilion generally is in the range ot Z0% to 97%, p.t,~er~ly 70% to 97% by weight.
A co,..~Jo~:t:~n of this In~ention is in ~ liquid crystal state when it is of Iypotropic structure, is transpar~nt or sHghtly turbid (oF~i~s~enl) but no O,M~I ~9, and has st~,~ge modulus squaf to or higll~r than one Pascal (1 N~w~ton/sq. m.), more preferably higher than 10 Pascal and n~ost pl~fef2bly higher than 20 ~ascal and when measured at a te-l,p~rdt-lr~ ot 20 to 40~C, at a frequency of ten~radians per second and at a str~in of 0.1 to 5%. ~he rheolo~ ehavlor of the compos;liol-s of ~h~s invention were measured at 25~C by means of a Carri-M~dTM (~S Rlleometsr. In making the measvrement, a cone and plats are used at a cone angle of 2 degrees: 0 minut~s: 0 s~conds with a cone diameter of 6.0 &m, rneasurement system gap ot 5Z.0 micro m and a measurement system inertia of 17.02 micro Nm sec-2.
To make the liquld crystal ccn,posit;ens ot the invontion is relatively simpl~
be~ se they tQnd to form spontaneously ~~vith little n~Qd for th~ addition o~ energy to promote ~,ar.~t~l~r,.~;ion to the liquici crystal state. However~ to ~,un,ol~ uniformity of the c~"~ clt;on mixin~ will normally be l,-,J6,~1.an ~nd it has baen ~ound r~SirP~IB
~irst to mix the surfactants and cosu- f~_~a"l wlth the water, followed by admixin~ of ~he lipophilic componont, usually a hydrocar~on ~but estQrs or mixtures of hydrocarbons and esters may also be employed). It is not na~s~r~ to employ he~ and mo~t mixin~s are preferably carried out at abo~t room t~mpera~urs ~2~-25CC).
rhe invonted compositions ~nay bo applied to such surfaces by pounng onto thom, by ~'ic-'ien with a cloth or spon~, or by various otl e- contacting means but it AMENDED SHE~
IPEA/EP

- CA 02247902 l998-08-28 ' 18B
is pr~fel r~d to apply them in the form Of a spray by spraying them onto the substrate from a hand or ~inger pressure operatad sprayer or sq~ee~e bottle. Such application AMENDE~) SHEET
IPEA/EP ~

, . , .. , . , ... . . . ,, . . , . . , . , ... . . . ... .. . ~.. =

WO 97/32968 PCTfUS97104065 may be onto hard surfaces, such as dishes, walls or floors, from which lipophilic (usually greasy or oily) soil is to be removed, or may be onto fabrics, such as laundry, which has previously been stained with lipophilic soiis, such as motor oii. The invented compositions may be used as detergents and as such may be employed in the same 5 manner in which liquid detergents are normally utilized in dishwashing, floor and wall cleaning and laundering, but it is preferred that they be employed as pre-spotting agents too, in which applications they are found to be extremely useful in loosening the adhesions of lipophilic soils to substrates, thereby promoting much easier cleaning with application of more of the same invented detergent compositions or by applications of 10 different commercial detergent compositions, in liquid, bar or particulate forms.
The various advantages of the invention have already been set forth in some detail and will not be repeated here. However, it will be reiterated that the invention relates to the important discovery that effective liquid detergent compositions can be made in the liquid crystal state and that because they are in such state they are 15 especially effective in removing lipophilic soils from substrates and also are effective in removing from substrates non-iipophilic materials. Such desirable properties of the liquid crystal detergent compositions of this invention make them ideai for use as pre-spotting agents and detergents for them ideal for use as pre-spotting agents anddetergents for removing hard-to-remove soils from substrates in various hard and soft 20 surface cleaning operations.
The following examples illustrate but do not limit the invention. Unless otherwise indicated, all parts in these examples, in the specification and in the appended claims are by weight and all temperature are in ~C.

"~ f ~ ; '.'5 ?. ' J

' CA 02247902 1998-08-28 -FY~-nPI~ I
The following formulas (wt. ~/O) were nlade at 25CC by simp~e rnlxin~.
A ~er~nc~ B C D
NaAEOS ¢2EO) ~2 t2 6 12 olTM 3 3 6 3 'r;~ J~c.. e g~ butyl ether 1 . 12 1 12 ,ono~ ~ 4 ~ 4 hl~SO4~7H~O 0. 8 0.98 0.~8 0.98 Cilr~ acid 3 3 Di~ 8nolam~ t 1 0.33 W~-r Bal. Bal. Bal. 3al.
G!~ asln~ss index on soap ~cum proto A YS. AME 1:1 0.22 -prot~ B v~. AME 1:1 o 39 pr~to A vs. GQI bath -0.06 proto B v~. ~I bath 0.14 prot~ A YS. B 0.26 p~to B vS A 0.;!1 proto A YS Mr. Pr~perTM u~tra bath -0.7t proto B ~s Mr. P~perTM ultra balh 0-~6 Pl~ 6.35 3 The cleaning easiness index is exp,~ssed as:
~1-(strokes numb~r A.PRO~O)~ o~ number expstt bathroom products~]
If strokes number pro~D - stroke-Q numbsr r~., then the indax is ~ ~cleaning equivalenc~ between prototype and ~ rttnce) If str~l.G3 numb~r proto :~ s~s nurnber ref. then the index is characterised by a neQative value (the more negatiYe the index, the less e~ficient the prototype~.
If strok~s nurnber proto c strokes number ref. then the ind~x is ch~racterised by a positive value (th~ mors positive ths ind~x, the more efficient the protot~rpe).
Th~ soap scum is generated by direct spray~n~ of Oleate Na and and stoechi~n,stl~c quanti~r of catcium chloride on csr~mic tllc.
The cleanin~ e~sinsss indsx of A vs dlfferent r~.f~r~nc~s was c~ J~d by indirec~ comparison l~et,s~an th~ neutral proto (A) and the refsrences. In other wotds, A and ref~rence~ ~4ere not directly ev~lu~ in the same tile.

AMENDED SHEET
IPEA/EP

'~ , CA 02247902 1998-08-28 . 21 The formula of the gei bath is:
~%
Xanthan gum 5.0 r~ ;n sulfonate 4 0 LF400 Pluraf~c nonionic 3.0 H3PO4 (35%) 0.26 ~rnino trim~thyJ phosphonic add 0.05 Perfurne Q.75 Wat~r Baian~e The formula of AiaxTU~ AME 1:1 is th~ same tormula as the gal bath sxcept there is no xanthan ~um and in there is an a~dition 1.5 wt. ~,~0 of MQS04~7H20.

IPEA/Ep

Claims (7)

22a What is Claimed is;

1. An acidic liquid crystal detergent composition which comprises by weight;
(a) 1% to 30% of an ethoxylated nonionic surfactant containing ethylene oxide groups;
(b) 1% to 5% of an aliphatic carboxylic acid having 2 to 10;
(c) 1% to 15% of a water soluble salt of an ethoxylated C8-18 alkyl or alkyl phenyl ether sulfate having 2 to 6 moles of EO surfactant or sodium lauryl sulfate;
(d) 0.1 to 3% of a weak base;
(e) 0.6% to 10% of a water insoluble organic compound selected from the group consisting of perfumes, essential oils and water insoluble hydrocarbons;
(f) 1% to 30% of a water-mixable glycol ether cosurfactant which is a mono C1-6 alkyl mono-, di-, tri- or tetra-ethylene or propylene glycol or of mono-, di-, or tri-butylene glycol;
(9) 0.48% to 8% of a magnesium salt; and (h) the balance being water, said liquid crystal detergent composition does not contain sulfonate surfactant and has a storage modulus measured at a temperature between 20°C to 40°C, at a strain of 0.1% to 5% and a frequency of 10 radians/second of equal to or higher than one Pascal and is thermally stable and exists as a liquid crystal in the temperature of 8°C to 43°C.

2. The composition of Claim 1, wherein said nonionic surfactant is a condensation product of one mole of a higher fatty alcohol having about 9 to about 11 carbon atoms with 2 to 5 moles of said ethylene oxide groups.

3. The composition of Claim 2 wherein said water soluble salt of said ethoxylated C8-18 alkyl ether sulfate surfactant has a cation selected from the group consisting of sodium, potassium and ammonium.

4. The composition of Claim 3 wherein said aliphatic carboxylic acid is citric acid.

22b

5. The composition of Claim 3, wherein said water insoluble hydrocarbon is selected from the group consisting of d-limonene, alpha-terpineol, alpha-pinene, and beta pinene and mixtures thereof.

6. The composition of Claim 1, wherein said carboxylic acid is citric acid.

7. A process for removing any one or more of lime scale, soap scum, and greasy soil from bathtubs or other hard surfaced items, which are acid resistant or are of zirconium white enamel, which comprises applying to such a surface a composition in accordance with Claim 1 and removing such composition and the lime scale and/or soap scum and/or greasy soil from such surface.