Note: Descriptions are shown in the official language in which they were submitted.
IR f1321 '
LIQUID CRYSTAL COMi~OSll lONS
Fietd of the Inv~ntion
This invention relates to a liquid crystal d~t~rgent composition containing woodparticles and an ab~asive. ~lore specifically, it is of a liquid detergent composition in a
liquid crystal state which whon ~rought into contact with oily soil is superior to other
liquid deter~ent compositions in detergency and in other physical ptoperties.
Rs~ck~rol~nd of the in~/ention
Uquid a~,u~o~s synthetic organic detergent ~ompositions have lon~ been
employed for human hair shampoos and as dis~washing detergents ~or hand washing
of dishes ~as distinguished fr~m autom~tic dishwashing rnachine washin~ ot dishes~
Liquid detergent co"~cositi~ns have also ~een employed as hard surface clearlers, as
in pine oil liquids, tor cleaning tloors and walls. More recently they have prov~n
succsssful as laundry detargonts too, apparantly ~callse they are convenient to u~e,
are instanUy soluble in ~ash w~tar, ~nd may be employed in "pre-spoffing" applic~ions
to ~acilitate rernovals of soils r~nd stains from laundry upon subsequent washin~. Li~uid
detergent com,oositions ha~ e compri~e~ anionic, cationjc and noniGnic surta~e ~ctive
agents, builders and adju~fants, inci~ding, as adjuvants, lipophilic materi~ls which o~n
act as solvents ~or iipophllic soils and stains. The vario~ls liquid aqueous synth~tic
organic deter~ent compo~i~ions men~ionad serv~ to emulsity lipophilic materials,inciuding oiiy soils, in ~ q~tlS media, such as wash water, by formin~ mice~lar
disperaions and emulsions.
Although emulsification is a rnechanism of s~il remo\ al, it has be~n o~lly
comparativeiy recently that it was discovered how to make m~croemulsi~ns which are
much more offectiYe than ordinary em~isions in removing lipophilic mat~rials trom
substrat~s. SWtl microemulsions are described in British Patent Specific~tion No.
2,1~0,681 and in U.S. Patonts 5.075,026; 5,Q78,~54 and 5,082.584 and 5,108,643,
most ot which ra~ate to acidic microemulsions US8fU11'0r c~eanin~ hard surFaced items.
CA 92247816 1-98-68-28 ~p ~ ,p
,, . t .-- 2
such as bathtubs and sinks wh.ch mi~:roemulsions ar~ especia!ly eff3ctive in removin~
soap scum and lime scale from them.
The vari~us microernulsions referred to include a lipophil~, which may be a
hydrocarbon. a surfactant, which may ~e an anionic andfor a nonionic det~rgent(s), a
co-surfactant, which may ba a poly-lower alkylene r~lycol lower alkyl ether, e.g.,
tripropylene glycol monomethyl ether, and water.
Although the m~nufacture and USB of detergent compositions n microemulsion
form signiticantly improv~d cleaning powet and ~re~sy soil removal, compared te the
usual emulsions, th~ present inven~ion ~mproves th~ n still ~urther ~nd also increases
the capacity o~ the deter~ent compositions t~ adhero to s~rtaces to ~Hhioh th~y haYe
been appli~d. Thus, tney drop or run s~lbstantially less than cleanin~ compss~t~ons of
"similar" cleaning powor which are in micrcemulsion or normal liquid d~lsrgent fcrm.
Also, b6cause thsy form micro~mulsions with iipophilic soii or stain matsrial
spontaneo-lsly with essentially no requitement for addition of any snergy, either
thetmal or mech2nical, they are rnore effectivr cleaners at room tempe,ature and at
higher and l~wer temper&tures that are norma~ly employed in cleaning ~perations t~an
are ordinary liquid det~r~ents, and ars also more effective than detersent comp~sitions
in microemulsion form.
The presr nt liquld crystal detergent compositions may b~ e.;ther clear or
somewhat cloudy or milky ~ra~escent) in a;opearance but both torms thereof are stablo
on ,~ e and c~rnponants thereof do not settl~ out or become inet~ective. even onstorage at somewhat elevat~d temperatures for pr rinds as long a~ six months and up
to a year. Th~ ptesence of thr~ cosurfactant in the li~uid crystal det~rg~nt compositions
helps to make such compositions r~sist freezinc at low temperatures.
~ he present ;nvention relates to ~ liquid detergent composition ccntainin~ wood
particles which act as an abrasive as well as a su-f~ anl ~arrier. The compositions are
suitable at room tempri-at~re or co!der, for pre-troating and ~leaning materials soiled
with lipoph~iic soil, is in liquid crystal form and comprises synthetic orç1~nic sur~ace
CA 02247816 1998-08-28 AMEN~ED ~ ET
ac.tive a~ents, a cesurtactant, a solvent for th~ soil, and wa~er. The ir;vention also
re!ates to processes for treating items and rnaterials soiled with lipophilic soil with
compositions of th~s Invention to loosen or remove such so;l, by applying to the IQCUS of
such soil on;such material a soil loosening or remQving amount of an invented
composition. In another aspect of the invention lipophilic ~oil is a~sorbed trom the
soiled sur~ace into the liquid crystal.
In recent years all-purpose liquid detergents ~ave become widely accepted tOr
cleanin~ hard surfaces, e.~., paint~d ~.400dw4rk and panels, tiled walls, wash bowls,
bathtubs, linoleum or tile floors, washable ~rall paper, etc.. Such all-purpose liquids
comprise clear and op~q~e aqueous mixtures of water-soluble synthetic organic
ciet~rQents and water-soluble ~etergent builder salts. In ord~r to achieve comparable
cleaning efficienoy with ~ranular or powdere~ all-purpose cleaning compositions, use of
water-soluble inorganic phosphate ~uilder salts was favored in the prior art all-purpose
liquids. For exa",ple, such early phosphate-containing composiliu"s are ~escribed in
U.S. Patent Nos. 2,560,833; 3,234,138; 3,~50,319; and British Patent No. 1,223,73g.
In view of the environmentali~t's efforts to redu~ phosphate levels in ~round
water, improved all-purpose liquids containing r9~l ~ce~ conc~rttra~ions of inor~anic
phosphate ~uilder sa~ts or non-phosphate builder salts have appeared A particularly
useh~ seH-opacified liquid af the latter type is described in U.S. Patent No. 4,244,84G.
However. these prior art all-p~rpose li~quid ~ ler~snts containing dQtergent
bullder salts or other equivalent tend to lea~e fiims, spots or streaks on cleaned
unrins~d surfaces, particularly shiny surfaces. Th~s, such liquids req~lire thorough
rinsing of th~ cleaned surfaces which is a time-consuming ohore for the u~er.
In crder to overcome the toregoin~ disadvanta~e of the prior ar~ all purpose
liquid, U.S. Patent No. 4,017,409 teaches that a mixturs of pal~ffin sulfonate and a
re~uce~ conoentration of inorganic phosphate builder sal~ should be employed.
Ilowever, such co-"positions ate not completely acceptable from an environrnentai
point of view based upon the phosphat~ content, On the othsr hand, another
CA 02247816 1998-08-28 ~;;-_ ;-,--,.;~,-~-.-
,.. _ ~
altematiYe to achi6ving phosphat~-fre~ all-purpose liquids has been to use a major
proportion of a mixture of anionic and nonionic deter~ents with mtnor ~mounts ot glycol
ether solYent and or~anic amine as shown in U.S. Patent N~. 3,935,130. Again. this
approach has not been compl~tely satis~actory and ~he high levels of organio
detergents neces~ary to achi~v~ cleanin~ cause foamin~ w~ich, in turn, leads to the
need for thorol~gh rinsing which has been found to be undesirable to today's
consumers.
Anethor appro~ch ~ hrmulating hard sur~acsd cr all-p~rpose liquid det~r~ent
composition wh~re product homogenelty and clarity are importan~ considsrations
involves the forrnatlon of oi~in wa~r (oJw) microemulsions which contain or~e or mcre
sur~ac~active deter9ent compounds, a water~ mis~ible s31vent ttypiG~l~y a
hydrocarbon so~ant~. water and a "cosurfactant" cornpound which provides productstability. By definhtion, an o/w mic~oernlJlsion is a spontaneously forrF ing CQI'3~ ~al
dispersion of "oil" phase particles havin~ a pa~ticlo size in the ran~e o~ 25 to 800 A in a
continuous aqueous ph~se.
In Yiaw of the extremQly fine particle size of the dispQrs~d oil phase part~cles,
microQmulsions are transpar6nt t~ ht and are clear and us~ally hi~hly sta~le ag~inst
phase separation.
Patant di~clo~ures rela~ing to use of grease-removal sr Ivsnts in olw
m~croemulsions include, for exampl~, European Pat~nt Appllcations EP 013761~ and~P 01~761~ rl~ts et al; ~urop~an Patent Application EP ~160762 - Johnston et al;
~nd V.S. Patent No. 4,561,3~1 - Herbots et a~. Each ot th~se pa~ent di~closures aise
teaches using at least 5% by weight of ~reas~remoYal solvent.
It also is known from Bntish ~atent App~ica~ion aa 21 44763A to Herbots ~t al,
published March 1~ 85, that ma~nesiurn sal~s enhance grease-re~no~
perfcrman~e of organic ~rease-removal solY~nts, such as the terpenes, in olw
microemulsion liquid deter~ent Gornposfflons. Ths c~m~,~osilions of thls ;nventidn
~escribed by Her~ots et ~I. r6quire at least 5% of the mixture of grease-removal solvent
CA 02247816 1998-08-28 AMENDED SHEET
IP A/EP
and magnesium salt and preferably at least ~% of solvent (which may be a mixture ef
water-immiscible non-polar solvent with a sparin31y soluble sllghtly potar solvent) and
at least 0.1% magnes~um salt.
The following representative prior art palerlls also relate to liquid detergent
claanlng compos~tions in the forrn o~ o/w microernulsions: U.S. Patents ~los.. 4,472,~91
- R~sario; 4,~40,448 - Gauteer et al; 3,72~,3~0 - Sheflin; at al.
Liquid deterg~nt compositions which include terpenes! such as d-lin~onen~. or
other grease-removat solv~nt, although n~t ~iscl~sed to be in the form of o~w
microemulsions, are the S! ~iect matter ot the followin~ representative p~tent
docum~nts: European Patent Application 00~0749; E~ritish Patent Specification
1,603,047; and U S. F'atent ~os. 4,414,1 2a and 4,540,505. For example, U.S. Patent
Nc. 4,414,128 broadiy discloses an aqL~o~ls liquid deter~ent composition
characteri~er~ by, by Y~ L;
(a) from 1% to 20% of a synth~tic anionic, nonionic, amphoteric or
zwlnerionic surfactant or mixture thereot;
(b) from 0.~% to 10% of a mono- or sesquiterpene or mixture thereof, at 2
weight ratio of (a):(b~ being in the ran~e ot 5:1 to 1:3; and
~ c ) ~rom 0.5% to 20% of ~ polar so~Yent having a solubility in water at 1 ~~C in
th~ ran~e of from 0.2% to 10%. Other ingredienls pr~sent in the tormulations disciosed
in this patent include from 0.05% to 2% by weight of an alkali metal, ammonium or
alkanolammonium soap of a C1 3-C24 fatty ~cid; a calcium sequsstta~t trom 0.~% to
13% by wei~ht; non~ eo~s soiYent~ e.~., alcohols and glycol ethers. up to 10% byweight; and hydrotropes, e.g., urea, ethanolaminQs, salts of lower alkylaryl sulfonates,
up to 10% by wei9ht. All of ths formulations shown in the Examples ot this patent
include ralatively largQ amounts of dQtergsnt builder salts which are .l~tri,r~ental to
surface shine.
U.S. Patent 5,035,826 teaches liquid crystal compositions but these
compositions exhi~it ther-nal stability in the limited temperature range of 1 g~C to 36~C.
CA 02247816 1998-08-28 AMENDED SHEET
~PE.~!EP --
, ,~r~ ~r ~ ,L. ~ tJ,7~
WC)~4/057~7 teach6s a hard surface cleaner h~ving an abrasive with a particle
size in the micron range.
EP ~pplication 033547~ A2 teaches a h~rd surface cle~ner having an abrasive in
the micron range.
EP Application ~125711A1 teaches a genera! purpos~ cleaner req~iring the
presence of a partially esterifled resin.
~mm~ry of the In~Jention
~ he present invsnti~n provide~ an improved, liquid c~ystal det~rg~nt composi~ian
havin~ improve~ scouring abilrty. The cornpositions have improved inter~acla~ tension
which impro~/es ~leaning hard sur~ace in the form of a liquid crystai which is sLJitable for
cleaning hard surfaces such as plastic, vitreous and metal sur~aces having E~ shiny
finish, oil stainad floors, autornotive en~Ines and other ~ngines. More particularty the
impreved cleanin~ c~mposHions exhibit ~oot~ ~rease soil removaZ properties d~le to the
improved interfacial tensions and leave the cleaned surfaces shiny without the need of
or r~uinng only minimal additicnal rinsin~ or wipin~. The latter ch~racterlstic is
~videnced by littl0 or no visible r~sidues on the unrinsed cleaned s~lrfacPs and,
acc~rdingly. overcomes one of the disadv~nt~es of prior art produ~ts.
Surprisingly, thcso dqslrabis resu~ts are accomplished even in the absence of
polyphosphate or other fnor~anic or ot~anlc det~rgent builder salts and also in the
complote absence or s~hstPntially c~-n,,~I~t~ ~bsence of grease-removal so~vent.In one ~ec~, the invention ~enerally provid~s a stable, liquid crystal, hard
surFacs cl~anin~ composition especiaOy effective in ths rsmoval o~ oily and ~r~asy oil
The liquid crystal ~ pcsition includesr cn a wei~ht basis:
1% to 1 5~f~ of an etho~cyiated C~-C1 8 ~Ikyi ~her sulfate suri~r.~ant;
1% to 30% of a water-n~ ~le cosurfac~ant havin~ oither limited ability or
S! ~b~t~ntially no abilit;y to dissohfe oily or sreasy s~
1~~0 to 30% of an ethoxylated nonionic slJlf~.;tant~
1 % 'lO 10% of maanesium sulf~te heptahydrate or ma~neslurn chloride;
CA 02247816 1998-08-28 AMENDED SHEET
I~EA/EP
-
J ~ J . ~ L - ~- L _ L '~ L
o.~a~O to 10% of a perfume. essential oil, or water insolu~le hydrocarbon ha~lng 6
t~ 18 carbon atoms;
0.1% to 10% of wood particles; and
the bal~nce belng water, wherein the liquid crystal detergent compositian dQes
not oontain any sultonate surfactant, and the iiquid deterQent ccrnpositiQn has a
s~orag~ modulus equal to or hi3herth~n on~ Pascal (1 Newtonlsq. m.), more
preferably hi~her than 10 ~asoal at a temp~ratur~ of 20~ to 40~C at a stra~n of 0.1 ~/O
to 5~/c second as measured on a Carri-Med CS~ Rheom~ter and is thermally stable
and exist as a clear liquid crystal In ths tEmperature range from 8~C to 43~C, more
preferably 4~C to 4~DC.
In another aspect, the in~ention ~enorally provides a stable, liquid crystal, hard
surface cleanin~ composition especially effec~ive in th~ rem~Yal of oily and greasy o~l.
The liquid crystal comp~sition includes; on a wei~ht basis:
1% to 20% of an eth~xylated Cg-C1 8 alkyl ether suifate surfactant or sodium
lauryl sulfate (SLS~;
1 ~/c tc 30% o~ a water-mixai~le cosur~actant having elther limited ability or
substantially no ability to dissolve o;ly or sroasy soil,
1% to 30% of an ethoxylated nonionic surfact~nt;
1% to 10% of a ma~nesium salt suoh ~s magnesium sulfat~ heptatlydrate c~r
magnesiurn chlond~;
0.6% to 10% o~ a perfume. ~ssential oil, or wat~r insolubie hydrocarbon havir,g 5
to 18 ~ari~on at~rns;
0.1% to 10% ol an abrasive; and
the balan~ being water, wherein the liquid crystal det~rgent composition does
rot contain any sulfonate surfactant. and the liquid detergent composition has astorage modulus equal to or higher than one Pascal ~1 Newtonlsq. m.), more
pr~ra~ly higher thar 10 PascaJ at a temperature of 20~C to 40~C at a strain of 0.1%
to 5% second as measured on a Carri-Med CSTM Rheom~er and Is thermaily stable
CA 02247816 1998-08-28 AMENDt-~ ~HEET
and exist as a clear liquid crystal in th~ ternperature range from 8CC to 43~C, more
preferably 4~C to 43~C.
De~ d Descrirt~on of the Inv~ntion
The present invention relat~s to a stable opticalty clear liquid crystal detergent
composition r,~rnprising by wei~ht: 1% to t5% of an ethoxylated alkyl ether sulfate
surfactant, 1% to ~0% of a cosurfactant. 1% to 30% of an ethoxylated nonionic
surfactar~, 0.6% to 1 0~Jo of a water ins~luble hydroc~rbon, essential oii or a perfurne,
~.1% to 10% of wood p~rticles, and the balance being watar, ~.lvherein the llquid
deter~ent composition does not contain any s~lfonate surfactant, and the liquid
detergent cornposition has a storage madulus equal to or hi~her than one Pascal (1
Newton/sq. m.), more preferably hl~her than 10 Pascal at a temperatl ~re of ~0~C to
4~C at a strain of û.1% to ~% second as measur~d on a Carri-Med CSTM Rheometar
and is thermatly stablc and exist as a l;quid crystal in the temp8ratur~ ran~e from 8~C
to 43~C, more preferabty 4~C~ to 43~C.
Th0 present invention also rolates to a stable liquid crystal detergent
composition comprising by wei~ht: 1% to 20% of an ethoxylated alkyl ether suifate or
sodium lauryl sulfate ~SLS) surfactant, 1% to 30~/O of a cc~surfacta~t, 1% to 3~% of an
ethoxylated nonionic surfactant, 0.~% to 10% of a water insoiuble hydrocarbon,
essential oil or a perfum~. Q.1% to 10% of an abrasive, and the ~alanoe being wat~r,
wherein the Uquid deter~ent ~ .iliOn does not contain any sullon~l~ surtact~nt, and
the liquid detergent composttion has a stora~e modulus squaJ to or hi~her than one
Pascal (1 Newton~sq. m.), morQ prcfQrably hi~her than 10 Pascal at a temperature of
20~C to 4Q~C at a strain of 0.1% to 6% second as measured on a Carri-Med CSTM
Rha~meter and is thermally stable and exist as a ~iquid crystal in the temp~rature ran~e
trom 1 O~C to 4~~C, mor~ preferably 8aC to 43~C
Accordin~ to the present invcntion, the role of the water insolu~le hydrocarbon
can be provided by a non-water-soluble perfume. Typically, in aqueous based
composHions the pr~sence cf a solubiiizers, such as alkali metal lower alkyl aryl
CA 02247816 1998-08-28 ~ ~ ~, r~_~~
T~ A/tl'<)~<>t~ K I, 5iw I J ~
J U .., ' J. . ~ U..1 ~ _ _ '. ,~. L . ~ L . ~ ' J ' . .. .
sulfonate hydrotrop~, trie~hanolamlne, u~ea, ~tc., is required lo~ perfurne dissolution.
espa&ially at perfurne levels of 1% and higher, since parfumes are gen~rally a mixture
of fra~rant essantial oils and aromatic compounds which are generally not water-soluble.
As used her~in and in the app~nded claims the term "perfume" is used in ~s
ordinary sense to reter to and include any non-~ater soluble fra~rant s~bstance or
mixture of s~bst~nces including natural (i.e. obtained by extraction of flower, he~b,
biossom or plant), artificial (i.e., mixture of natural oils or oil constituents) and
synth6tlcally produced substance~ odoriferous s~Jbst~nces. Typically, perfumes are
complex mixtu~es of blends of various orQanic cornpounds such as alcohols,
aldehyd~s, ethers, aromatic compounds and Yaryino amounts of assential oils (e.g.,
terpenes) such as from 0% to 8û%, usually from 1 0~o to 70~/O by weight, the ~ssential
oils the~nselves bèin~ volatile odoriferous compounds and ~Iso serving to dissolve the
other components of the psr~ume.
~ uite surprisingly a thou~h the perF~Ime is not7 per se, a solvent for greasy or
oily soil, -~eYen though som~ perfumes may, in fact, ~ontain as much as 80~~ of
terpenes which are known as good gr~ase solvents -- the inventive composltions in
dilute form have the capacity to sol~b~ e up to 1 O times or more of the w~ight o~ the
perfume o~ oily and greasy soil, whlch is removed or loosened from the hard surface by
virtus of the action of the anionic and nonionic surfactants, said soii beTng taken up into
ths oil phas8 of the o/w microemuls~on.
~ n tho present invention the precise compositian ot the p~rfume is of no
particular cons3quCnCQ to cleaning performance so long as it me~ts the c~teria of
water irn~niscibility and having a ~leasi~g odor. Naturally, of course, esp~c~ally for
oloanlng compositions ;nt~nded for USQ in the home, the perfume, as wel~ as all othsr
ingr~di~nt~, should b~ cosmetically ac~epL~I~, i.e., non-toxic. hypoallergenic, etc.
Tho hydrocarbon such as a porfume is present in the liquid crystal composition
In an amount of from 0.6% to 10% by weipht, preferably from 0.8% to 8% by weight,
CA 02247816 1998-08-28 ~ lp E ~ E p
t~ J', n I J ~ ~ _c ~ , ; J~, , ~, ,
~sp~cially preferabiy from 1% to 6~/~, by weight. If the amoun~ of hydrocar~or.
(p~lfume) is less than 0.6% by weight it becomes diff~cult to form the liquld crystal. ~f
the hydr~carbon (p~fume) is added in amounts more than 10% by weighl~ the cost is
increased without any addi~ional cleaning benefit and, in fact. with some dlminishlng of
cleaning performance insotar as the total amount o~ sreasy or oily soil which can be
taken up in the oil phase ot the microemuisi~n ~ill decrease proportionately,
Furthermore, althou~h superior ~rsase removal p~rform~nce will be achieved
for perfume compositions not contalning any terpene solvents, it is ~pparently difficult
for perfumers to ~ormulale sufficiently inexpensiYe perfume compositions ~or produc~s
of this type (i.~., very cost sensitive consumer-type products) which inciudes less than
20%. usually less thar~ 30%, ~f such tzrpene solvents.
Thus. m~raly as a practical matter, bassd cn ~conomic consideration, ~he liquid
crystaJ cleaning compositions o~ the present invention may oftsn include as mucn as
0.2% to 7% by weight, based on the total composition, of terpene solvent~ introduced
thareunto via the perfurne component. However, even when the amount of terpene
solvent in the cleanin~ formulation is less than 1 .~~~o by wei~ht, such as up tG Q.6% ~y
weight or 0.4% by weisht or less, s~t~ rr grease removal and oil remo~al capacity
is provided by tho inventive compositions.
In place of the perfume in either the microemul5jon comp~sition or thP all
purpose hard surface cieaning composition at the sarne previously defined
conc~. .Lr~ions that the perfume was used in either the microemulsion or the allpurpos0 hard surface cleanlng composition ons can employ an essentiaJ oil or a water
insoluble organic compound such as a water insoluble bydrocarbon having 6 tc 18
carbon such as a ~af~in or isopa~a~ffn such as isoparl 1, isodecane, alpha-plnene,
beta-pinene, decanol and terpineol.
Suitable essen~ial oils are selected from the group cGI~sisling of: ~nethole 20J~ -
natural, Anisaed oil china st~r. Aniseed oll globe brand, Balsam (Peru~, Basil oil (india),
Black pepper oil, Black pepper oleoresin 40/2û, Bois de RQse (Brazil) ~OB, Borneol
CA 02247816 1998-08-28 A~EN~ H~T
! r- ~
. r ~ cr ~ , _ _ _ ! ~ 5 ~---
11
Flakes (China)r Camphor oil, White, Camphor powd~r synthetic lechnlcal, Cananga oil
(Java), Cardamom o;l, Cassia oil (China~, Cedarwood oil (China) BP, Cinnamon ~ark
oil, Cinnamon leaf oil, C,itron~lla oil, Clove bud oil Clove 'eaf, Corian~er (Russia)
Coumarin 6g~C (China), CycJamen Aldehyde, DiphenyJ ox;de, Ethyl Yanilin, EucaJyptol,
Eucalyptus oil, Eucalyptus citrlodora, Fennei oil, Geranium oii, G~nger oi~, Ginger
oleoresin (India), White grapefruit oil, Guaiacwood oil, Gurjun balsam, Heliotr~pln,
IsQbornyl acetate. Isolongifolene, Juniper berry oil, L-methyl acetat~, Lavender oil,
Lemon oil, Lsmon~rass oil, Lime oil distilled, Litsea Cubeb~ oil, Longifolene, Menthol
crystals, Methyl cedryl ketone, Methyl ch~vi~ol, ~ethyl salicylate, Musk ambrette, Musk
ketone, Musk xylol, Nu~me~ oil, Orange oil, r~tcllouli oll, Peppermint oil, Phenyl ethyl
aicohol, Pimento berry oil, Pimento leaf oil, Rosalin, Sandalwood oil, Sandenol, Sage
oil, Clary sage. Sass~ s oil, Spearmint oil, Spike lavender, Tagetes, T~a tree oil,
Vanilin, V~ty~rer oJI (Java~, Wintergreen
The nonioni~ SUI fa~tant is pres~nt in amounts of 1% to 30%, pref~ra~ly 3% to
18% by wei~ht of the liquid crystal composition and provides superior perforrnance in
the removal ot oi~ soil and mildness to human skin.
The wator soluble ethoxytated nonionic surfactants utili7e~ fn this invent~on are
commercially well known and inc~ud~ the primary aliphatic alcohol ethoxylates ~nd
secondary aliphatic afcohol ethoxylates. Th~ nonionic synth~tic or~anic surfactants
generally are the condensation products of an organic aliphatic hydrophobic compound
and hydrcph;lic ethy~ne oxidc groups. The length of the polysthenoxy chain can be
adjustcd to achleve the desired ba~ance ~et~ Lcn the hydrophob;c and hydroph~liceiements.
The nonionic surfactant claes includes the condensation products of a hi~her
alcohol (e.~, an alkanol containin~ 8 to 16 carbon aton!~s in a straight or ~ranched
chain configuration) condonsed with ~ to 30 mol~s of ethylcne oxide. for example,
lauryl Ot myri~yl alcohol condensed with 16 males ot ethylQne oxide (EO), tridecanol
condensed ~nth 6 to rnoles of EO. myristyl al~ohol condensed ~th 10 mo!~s of EO per
CA 02247816 1998-08-28 lP E ~ ~ P
12
mole ef myristyl alcohol, the condensation product of E0 with a cut of coconut fatty
alco~ol containing a mixture of fatty alc~hols with alkyl chains varying from 10 to 14
carbon atoms in tensth and wl~erein the condensate contains either 6 moles o, E0 p~r
mole of tot~l alcohol or ~ moles of E0 per mole of alcohol and t~llow a~cohol
ethoxylat~s containing 6 E0 to 11 E0 per rnole of alcohoi.
A preferred group of the foregoin~ nonionic surtactants are the Neodo!TM
ethoxylates (Shell ::o.~, which are higher aliphatic, primary alc~hol contalning g-~5
carbon atoms. such as Cg-Cl 1 alkanoJ condens~d with 4 to 10 moles of ethylene oxide
(NecdolTM 9t-8 or NeodolTM ~1-5J, Ct2 13 alkanol condensed with 6.5 moles ethylene
oxide (NeodolTM 23-6.~). C12 15 all;anol condensed with 12 rnoles ~thyiene oxid~(NeodolT~ 25-12), C14 15 alkanol condensed with 13 mol~s ~thylene oxide (Neodol745-13), and the like. Such ethcxamers have an HLB (hydrophohic lipophilic ballancB)
value of B to 15 an~T give 300d O~V emulsification, wh~reas ~thoxamers wlth HLB
values ~elow 7 ~o~ ) less than 4 Qthyleneoxide groups and tend to ~e p~or
emulsifi~rs and poor detergents.
A~ditional sallsfd~lery water soluble alcohol ~thylene oxide condensates are thecondensation products of a secondary aliphahc alcohol containin~ 8 to 18 carbon
atoms in a straight or branche~ chain confi~uration condense~ with 5 to 30 moles of
~thylen~ oxide. Examples ot commercially available nonionic detergents of the
fore~oing typQ are C~ s secondary aikanol condensed with either 3 EO ~Te~3itoi
15-S-~ or 12 E0 (Tergitol~ 15-S-12) marketQ~ by IJnion G~rbide.
The ~hoxylated alkyl eth~r su~fate or SLS surfactants which may be used in th~
detergent of this invention are water soluble such as the trieth:~no~arnine sodiurn,
potassium, arnmonium and ethanolammonium salts of an Cg 18 ethoxylat~?d alkyl ~ther
sulfate surfactants have thQ structure:
+
R-~OCHCH2~nOS03M
wherein n is t to 5 and R is an alkyl group ha-~ing 8 to 18 carbon atoms, mora
preferably 12 to t5 and natural clns, for example, C12 14; C1z 1~ and M is an
CA 022478l6 l998-08-28 ~r ~
r ~ . t: t .~ / ~ r ~ " ~
13
.
ammonium cation or ~ metal cation, most preferably sodium. ~he ethoxylated alkylether suifate is prBsent in the composition at a concentration of 1% to 1 ~~fi by weigh~
more pr~fe,~l; ly 2~~,. to 1 3~~o by weight.
~ he ethoxylated alkyl ether sulfa~e may bQ mad~ by sulfa~ing the condensation
product of ethylene oxide and Cg-10 alkanol, and neutralizing tne resul~ant product.
Th~ ethoxylated alkyl ether sulfa~es differ from one another in the number o~ carbon
atoms in the alcohols and in the number of moles ~1 ethylene oxid~ reacted with on~
mol~ ot such aîcohoî Pr~ferred cthoxyl~ted alkyl ether polyethenoxy sulfates cantain
12 to 15 carbon atoms in the alcohols and in the alkyl groups thereof, e.g., sodium
myristyl ~3 EO) sulfate.
Fthoxylated Cg.18 ~Ikylphonyl e~h~r sulfatQs containing from 2 to 6 moles of
ethylene oxide in thr~ molocule are also suitable for use in the invention compositions.
These deter~ents can be pr~pared by rearting an alkyl phenol ~~nth 2 to 6 mo~es of
ethylene oxide and sulfating and neutrallzing the r~sul~ant ethoxylated alkylph~nol.
The concsntration o~ th~ ethoxylated ~Ikyl e~her su!fate surfactant is ~ to 8 wt %.
The major class of cornpounds found to provide highly suita~ls cosurtactants f~rth~ microemulsion ov~r temperature ranges extendin~ trom 5~C to 43 C for instanc~
are glycarol, ethylane gfycol, water-soluble polyethylene glycols having a molecu!ar
weigh.t of 3~0 to 1000, polypropyl~ne glycol of the formula HO~CH3CHCH20)nH
wherein n is ~ number from 2 to 18, mixtures of polyethyl~ne 31yco1 and p~lypropyl
~Iycol ~SynaloxTM) and m~no C1 C6 alkgl ethers ~nd esters of ethylene olycol andglycol havin~ the structural tormulas R(X)nO~ and Fl 1 (X)nOH wherein ~ is
C1-C6 alicyl 9roup, Pl1 is C2-C4 acyl group, X is (OCH~C~12) or (OCH2(GH3)CH) and n
is a nurnber from t to 4, di~thylene ~Iycol, tnethylene ~Iyc~l, an alkyl ~actat~. wherein
~he alkyl ~roup has t to 6 carb~n atoms, 1 methoxy-2-propanol, 1 m~hoxy-3 propanol.
and 1 methoxy 2-, 3- or 4-butanol.
Represantativ~ mQmbers of th~ polypropylene glycol include dipro,oylene glycol
and polyprQpylene ~Iycol havin~ a molecular weight of 2Q0 to 1000, e.g., polypropylene
CA 02247816 1998-08-28
. . . ~
~ I \ U~ cr ~ J ~
14
glycol 400. Othe~ satisfactory glycol eth~rs ar~ ethylene glycol mono~utyl ether (butyl
celtosolve), diethylene giyool monoblltyl ethar ~butyl carbitol), triRthy4n~ glycol
morlobu~yl ether, mono, di, tri propylen~ ~Iycol monobutyl ether tetraethylene ~Iycol
monobutyl ether, mono, di, tnpropylen~ glycol monomethyl ether, propylene ~Iycolm~nomethyl sth~r, ethylene glycol monohexyl ethar, di6thylene ~yc~l monohexyl
e~her, propyiene glycol tertiary butyl ether, e~hylene ~ l monoethyl ether, ~thyl~ne
glycol monomethyi ether, ethyl3ne glycol monopropyl eth~r, ethylene ~Iycol
rncnepentyl ether, diethylene glycol monomethyl ether, di~thylene ~lycol monoethyl
e~har, diethylene gly~ol monopropyl ether, dlethylenc ~Iycol mon~pen~yl ether.
triethylene glycol monomethyl eth~r~ triethylene gtycol ,~olioethyl ether, triethylene
~Iycol nlanopropyl ~ther, triethylen~ glycol monopen.yl ether. triethylene ~Iycol
monohr xyl ether. mono, di, tripro~ylene ~Iycol monoethy~ 6ther~ mono, di tripropyl~ne
glycol monopropyl sther. mono, di, tripropylene ~Iycol monopentyl ether, mono, di,
tripropylene glycol monohexyl ether, mono, di, tributy~ene glycol mono methy~ sthet,
mono, dl, tributyiene gly~ol monoethyl ether, rnono, di, tributylr ne g~yool rnono,~ropyl
ether, mono. di. tributylene slycol mono~utyl ether, mono, di, tributylen~ glycol
moncpentyl ether and monc, di, tributylene glycol rn~nohexyl ether, ethylene glyc~l
mono~tate and dipropylene ~lycol propionate. Tripropytene glycol n-buty~ ether is
the prefcrred ccs~l la~ant becau~a of its hydroph~bic charac~er.
Th~ amount of cosurfactant reqlJir~d t~ st~ 7e the liquid crystal compesi~ions
~ill, of oours~. del e~-J on such factors as the surfac~ tsnsion character;stics of the
cosurfactant, the typ~ and amounts of the primar~r sult~ ls and perfumes, and the
~ype and amounts of any other ad~lilional in~redi~nts which may ~e present in the
composition and ~4hich have an influenc~ on the thermodynam~c fact~rs enumeratedabove. Amounts of cosurfactant used in the liquid crystal composition is in the ran~ of
from 1% to ~0%, pr~ferably ~rom 2% tO 2~o, ~Sr9~ y preferabty from 3% to 16%, ~ywei~ht provide stable dilute liquid crystal c~n~pesition for the ~bove-described ievels of
C.~ n22478 16 1 99B- 98-28 A~AE~4DEEA~ES~E
.
prim~ry sun'actants and pe~ume ~nd any other ~dditional ingredients as aescrib~d
bel~w.
In addition to their excellent ~apacity for ct~anlng gr~asy and oily soils. the low
pH liquid crystal form~lations a~ exhibit excellent cl~anin~ perform~nce and removal
of soap scum and lime sG~le in neat (unrlilu~ed) ~s well as in ~iluted usage.
The instant llquid ~rystal d~tergent compositions can contain wood partlcles
which are a~rasive particles designed to improve ths scourin~ power of the instan;~
liqui~ crystal detergen~ composition. Th~ surfact~nt in ths composition is also
abso~ed on the surface of the wood p~rtlcles. This ,~la,~ s the wood particlos to act
~s a sur~act~nt carri~r ~here~y ~mprovin~ the deposiUn~ of the surfactant on the s~iie~
surfsctant. The wood particlos have a particle diamet~r o~ 200 miilimicrons to 60~
millimicrons, more pr~ferably 400 milimicrons to 500 millimicrons. Preferred wood
particles are Picea abies having a particie diametsr size o~ 425 mil~imicrons. The
concentration of the woo~ partictes in the liquid crystal datergent co~nposition is fr~m
0.~ ~o 10 wt. %, more prefe~bly 0.2 to 6 wt. %.
The wood partic~es can be formed trom any ti ne of semi hard or hard wood
such as m~pte, birch, o~c, pins and apple ~s well as from apricot shell, walnut shell
and corn cob. The apparent densny of wood particles is O.t lo 0.5 ~I, mors prefatably
0.3 to 0.6 and h~ve a pa-t~cle ~iz~ of 400 millimicrons.
The instan~ liquid crystai c~n~po~i~ons contain 0.1 to 2.5 w~ %l more prefera~ly0.25 ~o 2.0 wt. ~ o~ an abrasi~/e selected trom the group conslstin~ of amorphous
hydratcd silica and polyethylene ~owder p~ri cl~s and mixtu~es ther~of.
Th~ amo~ ous silica (oral ~rade) used to enhanc~a the sc~urin~ ability ot the
liqwd cryst~ et was providad ~y Zeoffln. Th~ mean particles size of ZeofflnT~ sillca is
8 up to 10 mm. Its apparent d~nsity is ~.32 to 0.37 ~Iml.
An a,..or~.hous hydrated sillca h~m Crostie~d ~ dmersn~ particles sizes (9, 15
and 30~ mm). and same apparr~nt density can also ~e usod.
- CA 02247816 1998-08-28 AMEND--D SH'~
E~ ( )t~ J!~i W, ~ " _ ~,
~6 . _ .
i
-
The polyethylene powder uses:i in the instant inventlon has a particle size of 200
to 500 micron~ ~nd a density of 0.91 to C.99 g/Iiter, more ~ f~r~bly 0.94 to 0.96.
In additlon to their sxceil~nt scouring ability and c~ra~-ity for cleaning ~easy and
oily soils, th~ low pH liquid crystal formulations aiso axhi~i~ excallent cleaning
performance and rernoval of soap scum and lime scale in nea~ (undiIIJted) as well as in
diluted usa~e.
The instar~ compositlon contains 0.5 to 10 wt. %. more preferably ~ to 8 wt % ota magnesium salt such as magnesium chlorlde and~or magnesium sulfate and mixt~res
thereof.
The final ess~"lial ingr~disnt in the inventl~re tiquid ctystal compositions having
improYed intsr~adat tension ptopenies is water. Tha proportion of water in the liquid
crys~al deter~snt composition ~enerally is ~n the range of 20% to 97%, preferably 70%
to 97% by weight.
A compos tion of this invention i~ in a Ilquid crystal ~tn:te when it is of IypotroPic
stn~cture, is t~anspar~nt or sli~htly turbid ~p~escent) bu~ no cr~q~e, and has astorage modulus equa~ to or hlgher than one Pasral (1 Newton~s~. m.), more
prs~erably hi~her than 10 Pascal and most pre~rably high~r than 20 Pascal and when
measured at a te--,pel~llurs ot 20 to 40~C, at a frequ~ncy of ten radians per second and
~t a stra~n ot O.t to 5%. The rheolo~ical behavior of the oon.~Josilions ot thls invention
were measurad at 25~C by means of a Carn-Med CSTM Rheome~r. In making the
m~asurement, a cone and plat~ are usc a cone an~ls of 2 dsgrees: 0 mlnutes: 0
sec~nds with a cone diameter ~t 6.0 cm, measurement system gap of 52.0 micro m
and a mcasurernent system inertia of 17.02 micro ~rn se~2.
To make the li~uid crystal cG~..posilions o~ the invenffcn is relative~y simplr~~ec~ Is~ thsy tand to form spontaneously w3~h little need ~or the addition of energy to
promot~ tr~ns~r",~ion ~o the liquid crys~ ~at~. However, to ~rumo~e uniforrrity ot
the cGn-position m;x3n~ will normally be und~ Laken and it has been found desirable
flrst to mix the sur~actants and cosu~ ~a.tant with the watQr, ~IIow~d by admixin~ o~ the
CA 02247816 1998-08-28
.. .. . ..
17 - .
lipcph,lic compon~nt~ usual~y a hydrocarbon (b~Jt estcrs or ~nixtures o~ hydroca~ons
and esters may also be employ~d). It is not necessar~ to emp~oy heat and most
mixings are preterably carried olJt at room t~mperature ~20-2~C).
The invented oomposi~ions may be ~ to such surfaces by pourlng onto
them, by apl,tica~iun with a cloth or s,c~nge, or by various other contacting means but it
is pret~rred to apply them in th~ f~rm of a 6pray ~y spray~ng them onto tne substrate
from a t~.and or fing~r pressure operated sprayer ar squeeze ~ottle. Such apptioation
may be onto hafd surfacas, such as dishss, walls or floors, ~rom which lipophi~ic
(usually ~reasy or oily) soil is to be removad, or may be onto fabrics, such as laundry,
which has previously been stained with Itpophiiic soils, such as mot~r oil. The in~ent2d
compositions may be us~d as deter3~nts and as su~h m~y be employad In the ~rne
mannar in which liquid detefgents are normally utilized in dishwashlng, fleor and wall
c~eanin~ and launderins, but i~ is pre~err~d that they be emp~oye~ as p~e-spettin~
a~ents too, ln which applicatians they are ~ound to bs extremely usef~ll in loosening the
adhesions of lipophilic s~il8 to sul~t-~Les, theteby promoting much sasier ~leaning with
~rpl o~tion of more o~ ttls s~m~ in\~nted deter~ent compositi3ns or by app~i~atlon~ of
d~ftercnt c~mmercial de~ergent cornpositions, in liquid, bar or particulate forms.
The ~JariOUS advs~ntages of the invention haYQ alroady bsen set ~orth in som~
deta~l ~nd w~ll not be repeated here. Howev~r, It will be reiterated that the in~ention
rslates ~o th~ important ~iscoYery that effectlve liquid d~ter~eni composiUans can be
ma~e in the li~uit crystal state and that bsoause they ~r~ in such ~tat~ they are
esp~cially etf~c~h~e in removlng lipoph~ic 50iiS ~om s~ al~s and also ar~ eff~ctive in
r~moving ~rom s~ tas non-lipophilic matoria~s. Such dasirabl~ propertl~s of the
iiquid cryst~l deter~ent compositions o~ this inventi~n make them ide~ for use as pre-
spo~ti,~ c~ts and deter~ents for them ideal for us6 as pre-spottin~ a~en~s and
deter~ents t~r removin~ hard-to-remo~.re 80ils from subsl.~es in various hard an~ so~
surface ct~anin~ operations.
- CA 02247816 1998-08-28 AM NDED SHE~
IPEA/EP
18
The follo~nng examples illustrate but do net limit the inYention. Unless other~ise
indicated, all parts in thess examples. in the specification and in the appended claims
are h y we~ght an~ all temper~ture are in ~C.
FY~ le I
The ~ollowing formulas (wt. %) were made at 25~C ~y simple mixing.
l~ ~ C D E F G
91-5 DobandT~ 12 12 12 12 12 12 12
~1 AEOS (2EO) 3 3 3 3 ~ 3 3
npropylen~ alYcol n-b~nyl ether 1 1 .2S1 .~51 .25 1 1 .25 - 1 .~5 1 1 .25 1 .2
"~ 3.75 .75 .75 3.75 .76 3.75 .75
MgSO4~7~20 0.98 0.9~ ~.9B 0.~8 .g8
Picea abi~ls woo~ pa~es d~nsny 0 0.2 o.s ~.3 1 2 4
~I.~g/liter
~later Bal. ~al. 3al. 8al. 3~. Baf. Bal.
--h~al stabi~ ~C 1~36 18-96 18-36 18-36 18~ 8-~6 18~6C~ n~S jndeX
10% hard t8~ .52 0.34 -0.25 0 0 O.Og6 0.34
10S~. hard t~lOW ~ 5YD W1t ~eef -1.a3 0 0 0 0 0 0.43t~nOw
The cleaning performance of tho dlfter~nt prototyp~s was evaluated vQrsus a
C~SSi~ cream cleaner (Cifl as re~erence.
The Ci~ formula composition ~as:
anionic ~.9~~a
nonion~c 1.4%
C;~ Q 35%
soap 0.5~~
Th~ resuits ~re ~iv~n in terms of cbanin~ easiness index:
11-(strokes nL~mber protoistrokes number r~)l
If ~t~okss numb~r prcto - strol~s numbar re~ hen the index is 0 (d~anin~
squi~/alenc~ between prototyp~ and ~ef~rence).
If st.~ es numb~r pro~o ~ strokes number ref. th~n the index is char~ctQrized ~ya ne~ative ~ B (th~ more ne~ative the index, ~he less efficient the prototype~.
CA 02247816 1998-08-28
AM~NI~ SHE~
, C ~ P
r~ : Ef~-~ / t () / ~ ~ K I J :t ~ I J r. ~ _c- ~ I - .~ . . , ~= = ~ =
_ ._ _
~he following tonnulas (ut. %) w~re nlade ~t 25C~, by sitrlpl~ mixing.
A B ''- ~ E
NaAEOS (2~) 12 12 - ~ 12
gl -5 ~)obano~T~
Tr~prapylene $1~01 n-butyl ether - 1.251 .25 ~ 1.25 t .25 1 .2S
D~ onen~ 75 75 7~; 75 75
Mç~S04 7H20 ~ , 9~ r ~ g~
~E p~ s density 0.95~1iter particl~ siz~ 300-400 microns - - -
pt~us hY~trated silica zQo~ 0._ ~ 5 o.
~ater Bal. Ba. B~. ea. Bal.
at stabiUty ~C 18-36 1~'6 18~6 18 ' 6 18 30
C eaning ~ ;..es~ inctax
10~. hard tallo~4 ~.41 0 0.12 0.26 0.455% hatctt~ltow & 5% sot~ b~ttattow 1.5 -1.2 0 0 ~.8
Drie~ foocl
F G i
NaAEOS ~2E0~ 12 12 2 i2
1 5Do~ M 3 3 3 3
'r~ropyl~ne ~tycoi r~styl ether I t .25 ~1.25 1.25 1.25
~ e 3.~S 3.75 .75 .7
MgS0~ 7H2~ o.g8 0.98 r 9~ 8
PE paricbs der si't~r 0 .95~ ter pilrticlQ see 30~-40û ml~ons 1 G.5 0. 0.
~mon: lousl. d h~~ilica~f~nn 05 0 o
~at~r i3al.Bal. Ba ~33.
~hemal s~abTlity ~C 1~36 1B-36 18-~6 18-3
Cl~anin~ s irul~x
10-h hard talhw - ~O d,7 -0.19 C.5 o.la
5% h~ taibw 8. 5Y. sott beet s~llow - - . .
~r ed tood
J K L
2 12
SL~S-2E0 12
91-5 Dobanol~M ~ 8 8
TPr1e 11.25 1 t .25 11.25
d-LI~ e 3.75 3.75 ' 75
M~SC)4.71~20 ~ .5 .S .5
Ç~ 7 6~0 .5 .S ~.5
Amorphou~ hydrated silica Zeofinn J.8 .B _ a~
wa~ '~al ~la~
therm~ ~abirdyQ~ ~3 d~ 4~3
~ ~ss index
10%h~r~tallow 3.2 0.~6 0.52
bako~on foo~ 0 0.2 0.064
soaP scum 0.46 Q.a8 0.60
._. _ . , .
- CA 02247816 1998-08-28
