CA2247816A1 - Liquid crystal detergent compositions - Google Patents

Liquid crystal detergent compositions Download PDF

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Publication number
CA2247816A1
CA2247816A1 CA 2247816 CA2247816A CA2247816A1 CA 2247816 A1 CA2247816 A1 CA 2247816A1 CA 2247816 CA2247816 CA 2247816 CA 2247816 A CA2247816 A CA 2247816A CA 2247816 A1 CA2247816 A1 CA 2247816A1
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Prior art keywords
composition
water
ether
soil
alkyl
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CA 2247816
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French (fr)
Inventor
Myriam Mondin
Georges Yianakopoulos
Genevieve Blandiaux
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Colgate Palmolive Co
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Individual
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00Liquid crystal materials
    • C09K19/52Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54Additives having no specific mesophase characterised by their chemical composition
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00Liquid crystal materials
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/83Mixtures of non-ionic with anionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0026Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/14Fillers; Abrasives ; Abrasive compositions; Suspending or absorbing agents not provided for in one single group of C11D3/12; Specific features concerning abrasives, e.g. granulometry or mixtures
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/18Hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2068Ethers
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/382Vegetable products, e.g. soya meal, wood flour, sawdust
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00Liquid crystal materials
    • C09K19/52Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K2019/528Surfactants
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29Sulfates of polyoxyalkylene ethers
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)

Abstract

This invention relates to a liquid crystal composition comprising an ethoxylated nonionic surfactant, wood particles or an abrasive, an ethoxylated alkyl ether sulfate surfactant or alkyl sulfate surfactant, a cosurfactant, a water-insoluble organic compound selected from perfumes, essential oils and hydrocarbons, and water.

Description

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 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.

~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;

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 ~---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

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 ~ " ~

.

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 . . . ~

~ I \ U~ cr ~ J ~

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 .. .. . ..

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

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~.

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

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 ._. _ . , .

Claims (13)

What is Claimed is:
1. A liquid crystal detergent composition which comprises by weight:
(a) 1% to 30% of a nonionic surfactant containing ethylene oxide groups;
(b) 0.1% to 10% of wood particies wherein said wood particles having a particle diameter size of 200 millimicrons to 600 millimicrons;
(c) 1% to 15% of a water soluble salt of an alkyl sulfate or ethoxylated C8-18 alkyl ether sulfate surfactant or a C8-18 alkyl phenyl ether sultate having 2-6 moles of ethylens oxide;
(d) 1% to 30% of a water mixable glycol ether cosurfactant which is a C1-C6 alkyl ether of mono-, di-, tri- or tetra-ethylene or propylene glycol or of mono-, di-, or tri-butylene glycol;
(e) 0.6% to 10% of a watar insoluble organic compound selected from the group consisting of perfumes, essential oils and water inslouble hydrocarbons having 6 to 18 carbon atoms;
(f) 48% to 10% of magnesium sultate heptahydrate or magnesium chloride;
and (g) the balance being water, said liquid crystal detargent composition 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/sscond of at least one Pascal and is one phase at a temperature of 18°C to 36°C, said composition does not contain any sulfonate surfectant.
2. The composition of Claim 1, wherein said nonionic surfactant is a condensation product of one mole of a higher fatty alcohol having 9 to 11 carbon atoms with 2 to 6 moles of said ethylene oxide groups.
3. The composition of Claim 2 wherein said water soluble salt of said ethoxylated C8-18 alkyl etner sultate surfactant has a cation selected from the group consisting of sodium, potassium and ammonium.
4. The composition of Claim 3, wherein said water insoluble hydrocarbon is d-limonene, selected from the group consisting of alpha-terpineol, alpha-pinene, and beta pinene and mixtures thereof.
5. The composition of Claim 3, wherein said cosurfactant is tripropylene glycol n-butyl ether.
6. A process for treating materials soiled with lipophilic soil to loosen or remove it which comprises applying to the locus of such soil on such material a soil loosening or removing amount of a composition according to Claim 1.
7. A process according to Claim 6 wherein the composition is applied as a pre-treatment to material soiled with hard-to-remove lipophilic soil at the locus thereof on the material, after which application the soil is removed by application of the same or a different detergent composition and water.
8. A liquid crystal detergent composition which comprises by weight:
(a) 1% to 30% of a nonionic surfactant containing ethylene oxide groups;
(b) 1% to 20% of a water soluble salt of an ethoxylated C8-18 alkyl ether sulfate surfactant or alkyl sulfate surfactant or a C8-18 alkyl phenyl ether sulfate having 2-6 moles of ethylene oxide;
(c) 0.1% to 5% of an amorphous hydrated silica abrasive having a particle size of 8 to 300 millimicrons;
(d) 1% to 30% of a water mixable glycol ether consurfactant which is a C1-C6 alkyl ether of mono-, di-, tri- or tetra-ethtlene or propylene glycol or of mono-, di-, or tri-butylene glycol;
(e) 0.5% to 10% of a water insoluble organic compound selected from the group consisting of perfumes, essential oils and water insoluble hydrocarbons having 8 to 18 carbon atoms;
(f) 1% to 10% of magnesium sulfate heptahydrate or magnesium chloride;
and (g) the balance being water, said liquid crystal detergent composition 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 at least one Pascal and is one phase at a temperature of 18°C to 38°C, said composition does not contain any sulfonate surfactant.
9. The composition of Claim 8, wherein said nonionic surfactant is a condensation product of one mole of a higher fatty alcohol having 9 to 11 carbon atoms with 2 to 6 moles of said ethylene oxide groups.
10. The composition of Claim 8 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.
11. The composition of Claim 10, wherein said water insoluble hydrocarbon is d-limonene, selected from the group consisting of alpha-terpineol, alpha-pinene, and beta pinene and mixtures thereof.
12. The composition of Claim 10, wherein said cosurfactant is tripropylene glycol n-butyl ether.
13. A process for treating materials soiled with lipophilic soil to loosen or remove it which comprises applying to the locus of such soil on such material a soil loosening or removing amount of a composition according to Claim 8.
CA 2247816 1996-03-06 1997-03-06 Liquid crystal detergent compositions Abandoned CA2247816A1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US61192496A 1996-03-06 1996-03-06
US61263396A 1996-03-06 1996-03-06
US08/611,924 1996-03-06
US08/612,633 1996-03-06

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AU (1) AU711075B2 (en)
CA (1) CA2247816A1 (en)
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EP0834548A3 (en) * 1996-10-02 1998-12-30 Richard Reichmann Cleaning agent and method for its production
US5922666A (en) * 1998-10-28 1999-07-13 Colgate-Palmolive Co. Liquid crystal compositions
DE19935083A1 (en) * 1999-07-29 2001-02-08 Benckiser Nv Detergent for glass ceramic surfaces

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GB8310529D0 (en) * 1983-04-19 1983-05-25 Unilever Plc General-purpose cleaning composition
US4869842A (en) * 1988-03-31 1989-09-26 Colgate-Palmolive Co. Liquid abrasive cleansing composition containing grease-removal solvent
IN180345B (en) * 1990-04-10 1998-01-24 Albright & Wilson U K Ltd
IN185580B (en) * 1991-08-30 2001-03-03 Albright & Wilson Uk Ltd
EP0829530B1 (en) * 1992-09-09 2000-12-20 Unilever Plc Improvements to hard surface cleaners
SK53294A3 (en) * 1993-05-07 1995-04-12 Albright & Wilson Concentrated aqueous mixture containing surface active matter and its use

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PL187385B1 (en) 2004-06-30
CO4770890A1 (en) 1999-04-30
PL328708A1 (en) 1999-02-15
NZ331724A (en) 1999-08-30
EP0888447A1 (en) 1999-01-07
AR006130A1 (en) 1999-08-11
AU2321897A (en) 1997-09-22
AU711075B2 (en) 1999-10-07

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