Note: Descriptions are shown in the official language in which they were submitted.
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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)
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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
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- IP~A/EP
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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
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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.
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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
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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.
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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
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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...~ " ~
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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
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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.
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~P~ E~
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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
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0il5 themselves bsing volatile o~oriferous compounds and also servin~ to dissolve the
other com,u~ f the perfume.
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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
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11
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.
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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
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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
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' CA 02247902 1998-08-28
13A
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~
. ....
CA 02247902 1998-08-28
- 15A
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
- 15B
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
16
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
C02H
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.
, . .. . . ~ . .. .
,,
CA 02247902 1998-08-28
W O 97132968 PCTAUS97/04065
17
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
18A
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 ~
, . , .. , . , ... . . . ,, . . , . . , . , ... . . . ... .. . ~.. =
CA 02247902 1998-08-28
WO 97/32968 PCTfUS97104065
19
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.
AMEND0 SHEET
IPEA/Ep
