CA2253477A1 - Hard surface cleaning compositions - Google Patents
Hard surface cleaning compositions Download PDFInfo
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- CA2253477A1 CA2253477A1 CA002253477A CA2253477A CA2253477A1 CA 2253477 A1 CA2253477 A1 CA 2253477A1 CA 002253477 A CA002253477 A CA 002253477A CA 2253477 A CA2253477 A CA 2253477A CA 2253477 A1 CA2253477 A1 CA 2253477A1
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- composition
- alcohol
- nonionic surfactant
- weight
- hard surface
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2006—Monohydric alcohols
- C11D3/201—Monohydric alcohols linear
- C11D3/2013—Monohydric alcohols linear fatty or with at least 8 carbon atoms in the alkyl chain
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
Abstract
The cleaning of hard surfaces is addressed, where no visible streaks or residues are left on the surfaces which have been cleaned. The invention encompasses several embodiments which combine a hydrophilic nonionic surfactant with a selected alcohol, in specific ratios, or a hydrophobic nonionic surfactant with a selected alcohol and a sulfated anionic surfactant, in specific ratios, or all these components together.
Description
W O 97/42276 PCTrUS97/07228 Hard Surface Cleaning Compositions Techr~ical Field The invention relates to the eie~nin~ of hard surfaces, particularly but not exclusively floors.
Bacl~ ,ul~d Compositions for the cleQning of hard surfaces have been extensively ~ c~ ed in the art. It is desirable that such compositions should have, in addition to the ability to clean eI~ ly~ the ability to provide a good shine to the surfaces they have cle~ned However, surface shine is often COIIIIJlUllUSed by residues of the compositions which are lefc on the surfaces, and which appear as streaks as water evaporation is co~--plete~l This problem becon~es more acute when the compositiûns are used without rinsing after ~ A~ g, and when the co~ )oslliolls are fol~ ed as conce..LI~Led compositiQn~ which co".l,.;se more actives and less water.
It is thus an obiect of the present invention to provide compositions for the ~le~nin~
of hard s~r~-cr~, which clean effectively in conc~ ed or diluted form, and whichleave no or little streaks after the clo~ning Sullllll&ly ofthe invention In a first embo~limPnt~ the invention enco.~ a~ses the use, in a hard surface cle~
compositiOn of -(a)-a L~l-uplulic nonio-uc surfactant; and ~ -(b)-a C8-C18 ~Icohoi in a weight ratio of (a):(b) of from 1:1 to 10:1, for improved shine of hard surfaces which have been cleaned thc.t;wilh.
W O 97142276 PCTrUS97107228 In a second embodiment, the invention encol"?asses the use, in a hard surface c~e~ning composition, of:
-(c)-a hydrophobic nonionic surfactant; and -(d)-a sl~lf~Dted anionic surfactant; and -(b)-a C8-C18 alcohol;
in weight ratios of (c):(b) of from 5:1 to 2S: 1, and of (d):(c) of ~om 1:1 to 1:10, for improved shine of hard surfaces which have been cleaned the.~
In a third embodiment, the invention corlll~;llcs the first two emborlim~ntc and thus e.lco...i.ACc~5 the use, in a hard surface cJe~ning composition, of -(a)-a hydrophilic nor~ionic surfactant; and -(b)-a C8-C18 alcohol; and -(c)-a hydrophobic nnniQnic surfactant; and -~d)-a sll~f~ted anionic surfactant;
in weight ratios of (a):(b) of from 1:1 to 10:1, of (c):(b) of from 5:1 to 25:1, and of (d):(c) of from 1:1 to 1:10, for improved shine of hard surfaces which have beencleaned therewith.
In a fourth embodiment, the invention ~col~ asses a hard surface Gle~nin~
composition co~ .;s...g -(c)-a l.~.l.ophobic noniol-ic surfactant; and -(d)-a s..lfD-ted anionic surfactant; and -(b)-a C8-C18 ~Icohol;
in weight ratios of(c~:(b) offrom 5:1 to 25:1, and of(d):(c) offrom 1:1 to 1:10.
~cfe.-~,d in that fourth embodiment is a composition which further coll-},-ises a l~rdluphiIic non;oltiC surfactant (a), and wL~;e.n additionally the weight ratios of (a):(b) offrom ~:1 to 10:1.
The invention further e~-~G~ Dcces processes of cle~nin~ hard surfaces with the co--.po~i;l;ons, either dilute or neat.
W O 97/42276 PCTrUS97/07228 Detailed Description of the Invention The Hard Surfaces:
In some embodiments of the invention, various components are combined and used in a hard surface cleaning col"~osilion with a view to provide shine to the hard surfaces which are cleaned with the compositions. As used herein, "hard surfaces", typically refers to floors, wails, windows, kitchen and bathroom furniture, appliances anddishes.
Shine:
Olll~nillg a good shine end result is essçnti~lly the sum of two factors, namely: a good spreading of the cl~aning product on the surface, and no cryst~ cAtiQn while drying. If both are achieved, a streak-free end result is ob~ ed. The streaking phe.lc,lllenon can thus be dcs_libed as the apparition of visible residues from the cle~ni~ composition, as the water from the composition or the rinse water evaporates. Mole~ r crystallinity and aggl~g~Lion during evaporation cause ,aLill~, thus give a bad shine end result. Thus, as used herein, the abili.ty of a composition to provide "shine" to sulr~ces refers to the colll~osilion's ability to leave little or no eye-visible residues on the surfaces, after evaporation of the water. In most cases, the ability of various co-"l)osilions to provide shine can be evaluated by the human eye, but it is also possible to evaluate the difference by means of a gloss-meter, such as a Sheen ~) 155 gloss meter. A suitable method to evaluate a col~l)osilion's ability to leave no or little residues is to first measure the gloss of a given surface, then apply the cl~A~ g composition on the surface, then leave theCC--.pGS l;on to dry, and finally measure again the gloss of the surface on which the composition has been applied. The smaller the dilI~. encc, the better the shine.
The Co,.")on~.lls;
As a first conlpol.~..L, ccsmponenl (a), the compositions herein co-,-,Ulise a hydrophilic nnnin~iC surfactant, or Illi~Urti thereof. Suitable hydrophilic noninnic surf~nt~nts for use herein include alko~lal~,d alcohols, preferably ethoxylated alcohols. Such ~u~r~ nj can be ~e~ s~,n~ed by the formula CxEOyH, where C symbolises the hydrocarbon chain of the alcohol starting material, x rt;prese.~li the length of its CA 022~3477 1998-10-30 W O 97/42276 PCT~US97/07228 hydrocarbon chain. EO replcse.~Ls ethoxy groups and y r~ es_.,Ls the average degree of ethoxylation, i.e. the average number of moles of ethoxy groups per mole of alcohol. Suitable hydrophilic nonionic surf~r,tArlt~ for use herein include those where x is of from 9 to 18, preferably 9 to 14, and average y is of from 8 to 30, preferably 10 to 20 Also suitable hydrophilic nonionic surf~ct~nt~ are ethoxyl~ted and propoxylated ~tcQholc which can be I~Jlese.lled ~y the formula CxPOyEOy', where x is as above, and (y+y') is as y above. The compositions herein can co,.,l"ise mixtures of such hydrophilic nonionics, and the compositions colnplisc from 0.5% to 8.0%,~r~f~,.ably from 1% to 4% by weight of the total composition of such hydrophilicnonionic surf~ctAnt~ or mixtures thereof.
As a second component, component (b), the compositions herein comprise an alcohol having a hydrocarbon chain comprising 8 to 18 car~on atoms, p,~.ably 12 to 16.
The hydrocarbon chain can be b- ~cl-ed or linear, and can be mono, di or polyAIcohol~ The compos;lions herein should colllplise from 0.1% to 3% by weightof the total composition of such alcohol, or mixtures thereof, plef~ bly from 0.1% to 1%.
As a third component, the compositions herein comprise a hydrophobic nonionic surfactant (c~, or mixtures thereof. Suitable hydr ,pl obic nonionic s~,l rhc~ for use herein include allcoxylated ~ICQhnlc ~refe~,lbly etho~ylaLed alcohols. Such surfPctAnte can be rep,ese.dc;l by the formula CxEOyH, where C symbolises the h~d~uc&ll~oll chain of the alcohol starting material, x fe~ s-~Ls the length of its hydrocarbon chain. EO lepres_.lls ethoxy groups and y Icpre3c.lls the average degree of ethoxylation, i.e. the average number of moles of ethoxy groups per mole of ~Icohol !~uittlb'e hydrophobic nnr~i~nic surfActAn1s for use herein include those where x is of from 9 to 18, preferably 9 to 16, and y is of from 2 to 7, ~ bly 4 to 7. S-it~'e hydrophobic no-~c surfil~Ant~ also include ethoxylated and ~lopo,~lalc~ AICQhnl~ which can be repr~,sen~cd by the formula CxPOyEOy', where x is as ~ove x and where (y+y') is as y above. The compositions herein can comprise mixtures of such l"/dlol)h~ ~ic nOlLO~CS, and the compositions coln~ise from 1% to 20%, pl~f~ bly from 3C~ to 15% by weight ûf the total composition of such hydrophobic nonionic surfAct~nts, or mixtures thereof.
As a fourth COIllyt)l~ , (d), the cû,,-yo;~ olls herein should C~ l;3C an anionic s~-r~c~ which is sl~lf~ted anionic su,r..cL~ , as oyposed to a s~llfor~t~d anionic surfactant. Suitable slllf~ted anionic ~r~c/~ for use herein include alkyl sulfates W O 97/42276 PCT~US97~7Z28 and alkoxylated alkyl sulfates which can be made by s ~tf~ting an alcohol, or analcohol alkoxylate" Gs~e~ilively. Typical alkoxylating groups for such surf~ct~nts are ethox,v and propoxy groups, and suitable alkyl ethoxy sulfates for use herein can be ~eprese.lled by the formula CxEOyS where C symbolises the hydrocarbon chain of the alcohol starting materisl, x le,c-esG.lLs the length of its hydrocarbon chain. E0 replesG.Il~ ethoxy groups snd y r eprese.ll~ the average degree of ethoxylation, i.e. the average number of moles of ethoxy groups per mole of alcohol. And S stands for asulfate group. Suitable slkyl ethoxy sulfates anionic surf~ nts for use herein include those where x is from 10 to 14 and y is from 1 to 5. Tdçntie~lly, suitsble slkylpoAy sulfates can be IGplese-lled as CxPOyS, with idçntic~l ranges for x and y.
A particulsr sl-lf~ted anionic surfactant for use herein is a mixture of an ethoxylated allyl sulfate and a propoxylated alkyl sulfate acco..ling to the formulas above. The con~po~ herein colll~..;3e from 0.5% to 10%, pl~.f~,.ably from 0.5% to 4% of said s -lf~t~d anionic surfactant, or n. ALulcs thereo~
An optionsl but highly p,ere"-,d co.l.poae,ll herein is a particular builder system which further improves tke rle~ning p~.~-ll.ance without negatively affecting the shine. This fifth component, CO1ll~1i3eS a carbonate or polyphosphate salt, and a poly~a.b~Aylate salt, and pr~fe.~bly the weight ratio of polycarboxylate to carbonate or polyph~sph~te is at least 1:0.05. As used herein, "salt" refers to both the acidic form of all the builders s~it~ble for use herein, or any of their salts.
Suitable c~l,ona~e builders for use herein are according to the formula X2C03 orXHC03 whcre X is a suitable cuu.lL~,.ioll, typically K+, Na+ NH4+. Suitable polyphosphates for use herein include compounds of formula XaHbP04, where a and b are ~ gG~ such that a+b=3, and a or b can be 0, or XaHbP301o where a and b are such that a 1~5, and a or b can be û, and where X is a suitable counterion, particularly K+, Na+ or NH4+.
Suitable poly~ln~ylates for use herein include organic polycarboxylates where the highest LogKa, measured at 25~C/O.lM ionic :j~lG~glll is between 3 and 8, wherein the sum of the LogKCa ~ LogKMg, measured at 25~C/0. lM ionic SLI ell~,LII is higher than 4, and Wh~ JI LogKCa = LogKMg + 2 units, prGfef~bly 1.5 units, measured at25~C/O.lM ionic ~L~G1I~lh.
W O 97/42276 PCTrUS97/07228 Such suitable and pref~,.,ed polycarboxylates include citrate and compounds of the formuia CH(A)(COOX)-CH(COOX)-O-CH(COOX)-CH(COOX)(B) wherein A is H or OH; B is H or -O-CH(COOX)-CH2(COOX); and X is H or a salt-forming cation. For example, if in the above general fo~nula A and ~3 are both H, then the compound is oxy li~ ccinic acid and its water-soluble salts. If A is OH and B is H, then the compound is tartrate monos~cc;nic acid (TMS) and its water-soluble salts. If A is H and B is -O-CH(COOX)-C~2(COOX), then the compound is tartrate di~ucrinic acid (TDS) and its water-soluble salts. Mixtures of these builders are especi~lly ~ ,d fior use herein. Particularly TMS to TDS, these builders are disclosed in U.S. Patent 4,663,071, issued to Bush et al., on May 5, 1987.
Still other ether polycarboxylates suitable for use herein include copolyrners of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulfonic acid, and carboxymethyloxysuccinic acid.
Other useful polycarboxylate builders include the ether hydroxypolycarboxylates ,.,~rescnled by the structure:
H~-[C(R)(COOM)-C(R)(COOM)-O~n-H
wh~,re.n M is hydrogen or a cation wherein the r~lh~nt salt is water-soluble, ~er~.al,ly an alkali metal, ammonium or snbstit~1ted ~ Ol~ , cation, n is from sbout 2 to about 15 (p.er~.ably n is ~om about 2 to about 10, more preferably n averages from about 2 to about 4) and each R is the same or di~.en~ and s~lectedfrom hydrogen, Cl 4 alkyl or Cl 4 s~lbstituted alkyl (pl~,Çe~ably R is hydrogen).
Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those desc~ ed in U.S. Patents 3,923,679; 3,835,163;
4,158,635; 4,120,874 and 4,102,903, all of which are incorporated herein by re~ ce.
Plefe.led ~mongst those cyclic compounds are dipicolinic acid and chelidanic acid.
Also suitable pol~carl,oAyiates for use herein are mellitic acid, succinic acid,polymaleic acid, ~enze.1e 1,3,5-tricarboxylic acid, benzene pentacarboxylic acid, and - C~bOA~ IYIOXYSUC~;n;C acid, and soluble salts thereo~
W 097/42276 PCTrUS97/07228 Still suitable carboxylate builders herein include the carboxylated carbohydrates disclosed in U.S. Patent 3,723,322, Diehl, issued March 28, 1973, incorporated herein by reference.
.
Other suitable carboxylates for use herein, which do not meet the above criteria are alkali metal, ammonium and substituted ammonium salts of polyacetic acids.
FY;~ of polyacetic acid builder salts are so~h-m~ pot~i--m, lithium, a-,u,lol~ium and s lbstitl~ted ammonium salts of ethylç~e~ p7 tetraacetic acid and nitrilotriacetic acid.
Other suitable polycarboxylates are those also known as alLyl;.~ oacetic builders such as methyl imino diacetic acid, alanine diacetic acid, methyl glycine diacetic acid, hydroxy propylene imino diacetic acid and other alkyl imino acetic acid builders.
Most pl ~r~ ,d of a~i polycarboxylate builders for use herein is citrate.
The compositions herein coln~,.ise from 0.5% to 5% by weight of the total composition of the builder system, prl fe.~bly from 0.5% to 3%.
Another feature of the compositions herein is that CG~ )OIIC.~l~S (a) to (d) should be present in certain specified ratios. Acco,Ji"~ly, components (a) and (b~ should be present in a weight ratio of (a) to (b) of from 1:1 to 10:1, preferably 2:1 to 7:1.
Co",pol~ s (c) and (b) should be present in a weight ratio of (c) to (b) of from S: 1 to 25:1, p~ 10:1 to 20:1. And components (d) and (c) should be present in aweight ratio of (d) to (c~ of from 1:1 to 1:10, preferably 1:2 to 1:6. Where a compo~ is c~-"~,osed of a ..u~lu,e of ingredients, as opposed to a single ingredient, the weight ratios herein are e~lcul~ted on the basis of the weight arnount of the cGm~oncnl, i.e. the added a~ ul~ls of the individuai ingredients forming the c~ n~
It is ~,pe~ ed that the compositions herein are comb;luing three technology blocks which function on their own, but which find their preferred application when they are used together.
4 The first technology bloc~ is the col,lbinaLion of the seiected h~dlophilic nonionic surfactant with the sele.,led alcohol, in the sPle~led ratios. Indeed, these nonionic surf~ct~nt~ are particularly effective on particulate soils and on greasy soils, but they will cause streaking if they are used on their own.
W O 97142276 PCT~US97/07228 The second technology block is the combination of the selected hydrophobic nonionic surfactant with the selected alcohol in the selected ratios, together with the selected sulfate anion-c surf~ct~ntc Similarly to the first building block, these nonionic surfAct~ntc and anionic surf~ct~nte are particularly effective on particulate soils and on greasy soils, but they will cause streaking if they are used on their own. Addition of alcohol, in the selected ratios, results in a clear shine benefit.
The third technology block is the mixed builder system. Polyca.l,oxylates with surf~ct~nts would cause streaking, and cd~lJondte or polyphos~h~tes with surf~r,t~nts would cause a crystalline film to be deposited on the surface. But the co~ a~ion of these builders, together with surf~ct~ntc, leaves no visible streaks and no film. This y~f;ullllallce improvement is particularly visible in presence of anionic surf~nts, as these surf~ct~nts tend to form streaks already when pure.
The compositions herein can further comprise a variety of further, optional, ingle.li~n~s. Such optionals include bleaches, e.~llles, dyes, perfumes and other nesthP,ti~s The compositions herein are preferably formnl~ted as aqueous liquids. They can co,nylise from 1% to 30~/~ by weight of the total col.,pos;~ion of actives, i.e. from 99% to 70% water. As used herein, "neat" refers to a composition colllplish,g that amount of actives.
In a first mode, the composition herein is applied neat onto a surface so as to clean the surface, and is optionally but preferably subsequently removed by rinsing with water. In a second mode, the compositions is first diluted in water, typically from 40 to 320 times, and it is then applied to the surface to be rle~ne~l Th~,~call~ in this second mode, the composition can but does not neces~ have to be rinsed offof the surface. The first mode is generally more convenient for heavily soiled surfaces while the second mode is generally more convenient for large and lightly soiled surfaces such as floors.
The invention is further illustrated by the following examples W O 97/42276 PCTrUS97/07228 E7~ ,1cs C12-14 EO20 - - 1 1.7 C10-12 EOI0 - 1.5 C9-1 lEOS 2.8 - 2.4 - 2.4 2.4 CllEOS - 5 C12-14 EO5 4.2 3.0 3.6 - 3.6 3.6 C9-11 EO4 - 3.0 C12-OEI - o 3 2-Hesyl - 0 4 decsnol 2-Butyloctanol 0.3 - 0.3 - 0.3 0.3 C12-14 S - - 1.0 - 1.0 1.0 C12-14 EO3S 1.0 1.3 - 1.5 Citrate 0.7 1.0 0.7 1.0 0.7 0.7 Na2CO3 0.6 0.7 0.6 0.3 0.6 0.6 C12-14 EO20 - 1.4 - 2.5 1.8 C1~12 EO10 2.0 - 1.0 C9-1 lEOS - 2.0 - 6 4.3 Cl lEOS 4.0 C12-14 l:OS - 3.6 4.5 9 6.4 C9-11 EO4 - - 3.0 2-Elesyl - 0.3 decanol 2-Butyl octanol 0.3 - 0.2 0.5 0.5 W 097/42276 PCT~US97/07228 C12-14S 1.2 1.5 - - 1.8 C12-14 E03S - - 1.5 2.5 Citrate 0.5 1.0 0.5 0.7 0.7 Na2C03 0.3 0.4 0.4 1 1.0
Bacl~ ,ul~d Compositions for the cleQning of hard surfaces have been extensively ~ c~ ed in the art. It is desirable that such compositions should have, in addition to the ability to clean eI~ ly~ the ability to provide a good shine to the surfaces they have cle~ned However, surface shine is often COIIIIJlUllUSed by residues of the compositions which are lefc on the surfaces, and which appear as streaks as water evaporation is co~--plete~l This problem becon~es more acute when the compositiûns are used without rinsing after ~ A~ g, and when the co~ )oslliolls are fol~ ed as conce..LI~Led compositiQn~ which co".l,.;se more actives and less water.
It is thus an obiect of the present invention to provide compositions for the ~le~nin~
of hard s~r~-cr~, which clean effectively in conc~ ed or diluted form, and whichleave no or little streaks after the clo~ning Sullllll&ly ofthe invention In a first embo~limPnt~ the invention enco.~ a~ses the use, in a hard surface cle~
compositiOn of -(a)-a L~l-uplulic nonio-uc surfactant; and ~ -(b)-a C8-C18 ~Icohoi in a weight ratio of (a):(b) of from 1:1 to 10:1, for improved shine of hard surfaces which have been cleaned thc.t;wilh.
W O 97142276 PCTrUS97107228 In a second embodiment, the invention encol"?asses the use, in a hard surface c~e~ning composition, of:
-(c)-a hydrophobic nonionic surfactant; and -(d)-a sl~lf~Dted anionic surfactant; and -(b)-a C8-C18 alcohol;
in weight ratios of (c):(b) of from 5:1 to 2S: 1, and of (d):(c) of ~om 1:1 to 1:10, for improved shine of hard surfaces which have been cleaned the.~
In a third embodiment, the invention corlll~;llcs the first two emborlim~ntc and thus e.lco...i.ACc~5 the use, in a hard surface cJe~ning composition, of -(a)-a hydrophilic nor~ionic surfactant; and -(b)-a C8-C18 alcohol; and -(c)-a hydrophobic nnniQnic surfactant; and -~d)-a sll~f~ted anionic surfactant;
in weight ratios of (a):(b) of from 1:1 to 10:1, of (c):(b) of from 5:1 to 25:1, and of (d):(c) of from 1:1 to 1:10, for improved shine of hard surfaces which have beencleaned therewith.
In a fourth embodiment, the invention ~col~ asses a hard surface Gle~nin~
composition co~ .;s...g -(c)-a l.~.l.ophobic noniol-ic surfactant; and -(d)-a s..lfD-ted anionic surfactant; and -(b)-a C8-C18 ~Icohol;
in weight ratios of(c~:(b) offrom 5:1 to 25:1, and of(d):(c) offrom 1:1 to 1:10.
~cfe.-~,d in that fourth embodiment is a composition which further coll-},-ises a l~rdluphiIic non;oltiC surfactant (a), and wL~;e.n additionally the weight ratios of (a):(b) offrom ~:1 to 10:1.
The invention further e~-~G~ Dcces processes of cle~nin~ hard surfaces with the co--.po~i;l;ons, either dilute or neat.
W O 97/42276 PCTrUS97/07228 Detailed Description of the Invention The Hard Surfaces:
In some embodiments of the invention, various components are combined and used in a hard surface cleaning col"~osilion with a view to provide shine to the hard surfaces which are cleaned with the compositions. As used herein, "hard surfaces", typically refers to floors, wails, windows, kitchen and bathroom furniture, appliances anddishes.
Shine:
Olll~nillg a good shine end result is essçnti~lly the sum of two factors, namely: a good spreading of the cl~aning product on the surface, and no cryst~ cAtiQn while drying. If both are achieved, a streak-free end result is ob~ ed. The streaking phe.lc,lllenon can thus be dcs_libed as the apparition of visible residues from the cle~ni~ composition, as the water from the composition or the rinse water evaporates. Mole~ r crystallinity and aggl~g~Lion during evaporation cause ,aLill~, thus give a bad shine end result. Thus, as used herein, the abili.ty of a composition to provide "shine" to sulr~ces refers to the colll~osilion's ability to leave little or no eye-visible residues on the surfaces, after evaporation of the water. In most cases, the ability of various co-"l)osilions to provide shine can be evaluated by the human eye, but it is also possible to evaluate the difference by means of a gloss-meter, such as a Sheen ~) 155 gloss meter. A suitable method to evaluate a col~l)osilion's ability to leave no or little residues is to first measure the gloss of a given surface, then apply the cl~A~ g composition on the surface, then leave theCC--.pGS l;on to dry, and finally measure again the gloss of the surface on which the composition has been applied. The smaller the dilI~. encc, the better the shine.
The Co,.")on~.lls;
As a first conlpol.~..L, ccsmponenl (a), the compositions herein co-,-,Ulise a hydrophilic nnnin~iC surfactant, or Illi~Urti thereof. Suitable hydrophilic noninnic surf~nt~nts for use herein include alko~lal~,d alcohols, preferably ethoxylated alcohols. Such ~u~r~ nj can be ~e~ s~,n~ed by the formula CxEOyH, where C symbolises the hydrocarbon chain of the alcohol starting material, x rt;prese.~li the length of its CA 022~3477 1998-10-30 W O 97/42276 PCT~US97/07228 hydrocarbon chain. EO replcse.~Ls ethoxy groups and y r~ es_.,Ls the average degree of ethoxylation, i.e. the average number of moles of ethoxy groups per mole of alcohol. Suitable hydrophilic nonionic surf~r,tArlt~ for use herein include those where x is of from 9 to 18, preferably 9 to 14, and average y is of from 8 to 30, preferably 10 to 20 Also suitable hydrophilic nonionic surf~ct~nt~ are ethoxyl~ted and propoxylated ~tcQholc which can be I~Jlese.lled ~y the formula CxPOyEOy', where x is as above, and (y+y') is as y above. The compositions herein can co,.,l"ise mixtures of such hydrophilic nonionics, and the compositions colnplisc from 0.5% to 8.0%,~r~f~,.ably from 1% to 4% by weight of the total composition of such hydrophilicnonionic surf~ctAnt~ or mixtures thereof.
As a second component, component (b), the compositions herein comprise an alcohol having a hydrocarbon chain comprising 8 to 18 car~on atoms, p,~.ably 12 to 16.
The hydrocarbon chain can be b- ~cl-ed or linear, and can be mono, di or polyAIcohol~ The compos;lions herein should colllplise from 0.1% to 3% by weightof the total composition of such alcohol, or mixtures thereof, plef~ bly from 0.1% to 1%.
As a third component, the compositions herein comprise a hydrophobic nonionic surfactant (c~, or mixtures thereof. Suitable hydr ,pl obic nonionic s~,l rhc~ for use herein include allcoxylated ~ICQhnlc ~refe~,lbly etho~ylaLed alcohols. Such surfPctAnte can be rep,ese.dc;l by the formula CxEOyH, where C symbolises the h~d~uc&ll~oll chain of the alcohol starting material, x fe~ s-~Ls the length of its hydrocarbon chain. EO lepres_.lls ethoxy groups and y Icpre3c.lls the average degree of ethoxylation, i.e. the average number of moles of ethoxy groups per mole of ~Icohol !~uittlb'e hydrophobic nnr~i~nic surfActAn1s for use herein include those where x is of from 9 to 18, preferably 9 to 16, and y is of from 2 to 7, ~ bly 4 to 7. S-it~'e hydrophobic no-~c surfil~Ant~ also include ethoxylated and ~lopo,~lalc~ AICQhnl~ which can be repr~,sen~cd by the formula CxPOyEOy', where x is as ~ove x and where (y+y') is as y above. The compositions herein can comprise mixtures of such l"/dlol)h~ ~ic nOlLO~CS, and the compositions coln~ise from 1% to 20%, pl~f~ bly from 3C~ to 15% by weight ûf the total composition of such hydrophobic nonionic surfAct~nts, or mixtures thereof.
As a fourth COIllyt)l~ , (d), the cû,,-yo;~ olls herein should C~ l;3C an anionic s~-r~c~ which is sl~lf~ted anionic su,r..cL~ , as oyposed to a s~llfor~t~d anionic surfactant. Suitable slllf~ted anionic ~r~c/~ for use herein include alkyl sulfates W O 97/42276 PCT~US97~7Z28 and alkoxylated alkyl sulfates which can be made by s ~tf~ting an alcohol, or analcohol alkoxylate" Gs~e~ilively. Typical alkoxylating groups for such surf~ct~nts are ethox,v and propoxy groups, and suitable alkyl ethoxy sulfates for use herein can be ~eprese.lled by the formula CxEOyS where C symbolises the hydrocarbon chain of the alcohol starting materisl, x le,c-esG.lLs the length of its hydrocarbon chain. E0 replesG.Il~ ethoxy groups snd y r eprese.ll~ the average degree of ethoxylation, i.e. the average number of moles of ethoxy groups per mole of alcohol. And S stands for asulfate group. Suitable slkyl ethoxy sulfates anionic surf~ nts for use herein include those where x is from 10 to 14 and y is from 1 to 5. Tdçntie~lly, suitsble slkylpoAy sulfates can be IGplese-lled as CxPOyS, with idçntic~l ranges for x and y.
A particulsr sl-lf~ted anionic surfactant for use herein is a mixture of an ethoxylated allyl sulfate and a propoxylated alkyl sulfate acco..ling to the formulas above. The con~po~ herein colll~..;3e from 0.5% to 10%, pl~.f~,.ably from 0.5% to 4% of said s -lf~t~d anionic surfactant, or n. ALulcs thereo~
An optionsl but highly p,ere"-,d co.l.poae,ll herein is a particular builder system which further improves tke rle~ning p~.~-ll.ance without negatively affecting the shine. This fifth component, CO1ll~1i3eS a carbonate or polyphosphate salt, and a poly~a.b~Aylate salt, and pr~fe.~bly the weight ratio of polycarboxylate to carbonate or polyph~sph~te is at least 1:0.05. As used herein, "salt" refers to both the acidic form of all the builders s~it~ble for use herein, or any of their salts.
Suitable c~l,ona~e builders for use herein are according to the formula X2C03 orXHC03 whcre X is a suitable cuu.lL~,.ioll, typically K+, Na+ NH4+. Suitable polyphosphates for use herein include compounds of formula XaHbP04, where a and b are ~ gG~ such that a+b=3, and a or b can be 0, or XaHbP301o where a and b are such that a 1~5, and a or b can be û, and where X is a suitable counterion, particularly K+, Na+ or NH4+.
Suitable poly~ln~ylates for use herein include organic polycarboxylates where the highest LogKa, measured at 25~C/O.lM ionic :j~lG~glll is between 3 and 8, wherein the sum of the LogKCa ~ LogKMg, measured at 25~C/0. lM ionic SLI ell~,LII is higher than 4, and Wh~ JI LogKCa = LogKMg + 2 units, prGfef~bly 1.5 units, measured at25~C/O.lM ionic ~L~G1I~lh.
W O 97/42276 PCTrUS97/07228 Such suitable and pref~,.,ed polycarboxylates include citrate and compounds of the formuia CH(A)(COOX)-CH(COOX)-O-CH(COOX)-CH(COOX)(B) wherein A is H or OH; B is H or -O-CH(COOX)-CH2(COOX); and X is H or a salt-forming cation. For example, if in the above general fo~nula A and ~3 are both H, then the compound is oxy li~ ccinic acid and its water-soluble salts. If A is OH and B is H, then the compound is tartrate monos~cc;nic acid (TMS) and its water-soluble salts. If A is H and B is -O-CH(COOX)-C~2(COOX), then the compound is tartrate di~ucrinic acid (TDS) and its water-soluble salts. Mixtures of these builders are especi~lly ~ ,d fior use herein. Particularly TMS to TDS, these builders are disclosed in U.S. Patent 4,663,071, issued to Bush et al., on May 5, 1987.
Still other ether polycarboxylates suitable for use herein include copolyrners of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulfonic acid, and carboxymethyloxysuccinic acid.
Other useful polycarboxylate builders include the ether hydroxypolycarboxylates ,.,~rescnled by the structure:
H~-[C(R)(COOM)-C(R)(COOM)-O~n-H
wh~,re.n M is hydrogen or a cation wherein the r~lh~nt salt is water-soluble, ~er~.al,ly an alkali metal, ammonium or snbstit~1ted ~ Ol~ , cation, n is from sbout 2 to about 15 (p.er~.ably n is ~om about 2 to about 10, more preferably n averages from about 2 to about 4) and each R is the same or di~.en~ and s~lectedfrom hydrogen, Cl 4 alkyl or Cl 4 s~lbstituted alkyl (pl~,Çe~ably R is hydrogen).
Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those desc~ ed in U.S. Patents 3,923,679; 3,835,163;
4,158,635; 4,120,874 and 4,102,903, all of which are incorporated herein by re~ ce.
Plefe.led ~mongst those cyclic compounds are dipicolinic acid and chelidanic acid.
Also suitable pol~carl,oAyiates for use herein are mellitic acid, succinic acid,polymaleic acid, ~enze.1e 1,3,5-tricarboxylic acid, benzene pentacarboxylic acid, and - C~bOA~ IYIOXYSUC~;n;C acid, and soluble salts thereo~
W 097/42276 PCTrUS97/07228 Still suitable carboxylate builders herein include the carboxylated carbohydrates disclosed in U.S. Patent 3,723,322, Diehl, issued March 28, 1973, incorporated herein by reference.
.
Other suitable carboxylates for use herein, which do not meet the above criteria are alkali metal, ammonium and substituted ammonium salts of polyacetic acids.
FY;~ of polyacetic acid builder salts are so~h-m~ pot~i--m, lithium, a-,u,lol~ium and s lbstitl~ted ammonium salts of ethylç~e~ p7 tetraacetic acid and nitrilotriacetic acid.
Other suitable polycarboxylates are those also known as alLyl;.~ oacetic builders such as methyl imino diacetic acid, alanine diacetic acid, methyl glycine diacetic acid, hydroxy propylene imino diacetic acid and other alkyl imino acetic acid builders.
Most pl ~r~ ,d of a~i polycarboxylate builders for use herein is citrate.
The compositions herein coln~,.ise from 0.5% to 5% by weight of the total composition of the builder system, prl fe.~bly from 0.5% to 3%.
Another feature of the compositions herein is that CG~ )OIIC.~l~S (a) to (d) should be present in certain specified ratios. Acco,Ji"~ly, components (a) and (b~ should be present in a weight ratio of (a) to (b) of from 1:1 to 10:1, preferably 2:1 to 7:1.
Co",pol~ s (c) and (b) should be present in a weight ratio of (c) to (b) of from S: 1 to 25:1, p~ 10:1 to 20:1. And components (d) and (c) should be present in aweight ratio of (d) to (c~ of from 1:1 to 1:10, preferably 1:2 to 1:6. Where a compo~ is c~-"~,osed of a ..u~lu,e of ingredients, as opposed to a single ingredient, the weight ratios herein are e~lcul~ted on the basis of the weight arnount of the cGm~oncnl, i.e. the added a~ ul~ls of the individuai ingredients forming the c~ n~
It is ~,pe~ ed that the compositions herein are comb;luing three technology blocks which function on their own, but which find their preferred application when they are used together.
4 The first technology bloc~ is the col,lbinaLion of the seiected h~dlophilic nonionic surfactant with the sele.,led alcohol, in the sPle~led ratios. Indeed, these nonionic surf~ct~nt~ are particularly effective on particulate soils and on greasy soils, but they will cause streaking if they are used on their own.
W O 97142276 PCT~US97/07228 The second technology block is the combination of the selected hydrophobic nonionic surfactant with the selected alcohol in the selected ratios, together with the selected sulfate anion-c surf~ct~ntc Similarly to the first building block, these nonionic surfAct~ntc and anionic surf~ct~nte are particularly effective on particulate soils and on greasy soils, but they will cause streaking if they are used on their own. Addition of alcohol, in the selected ratios, results in a clear shine benefit.
The third technology block is the mixed builder system. Polyca.l,oxylates with surf~ct~nts would cause streaking, and cd~lJondte or polyphos~h~tes with surf~r,t~nts would cause a crystalline film to be deposited on the surface. But the co~ a~ion of these builders, together with surf~ct~ntc, leaves no visible streaks and no film. This y~f;ullllallce improvement is particularly visible in presence of anionic surf~nts, as these surf~ct~nts tend to form streaks already when pure.
The compositions herein can further comprise a variety of further, optional, ingle.li~n~s. Such optionals include bleaches, e.~llles, dyes, perfumes and other nesthP,ti~s The compositions herein are preferably formnl~ted as aqueous liquids. They can co,nylise from 1% to 30~/~ by weight of the total col.,pos;~ion of actives, i.e. from 99% to 70% water. As used herein, "neat" refers to a composition colllplish,g that amount of actives.
In a first mode, the composition herein is applied neat onto a surface so as to clean the surface, and is optionally but preferably subsequently removed by rinsing with water. In a second mode, the compositions is first diluted in water, typically from 40 to 320 times, and it is then applied to the surface to be rle~ne~l Th~,~call~ in this second mode, the composition can but does not neces~ have to be rinsed offof the surface. The first mode is generally more convenient for heavily soiled surfaces while the second mode is generally more convenient for large and lightly soiled surfaces such as floors.
The invention is further illustrated by the following examples W O 97/42276 PCTrUS97/07228 E7~ ,1cs C12-14 EO20 - - 1 1.7 C10-12 EOI0 - 1.5 C9-1 lEOS 2.8 - 2.4 - 2.4 2.4 CllEOS - 5 C12-14 EO5 4.2 3.0 3.6 - 3.6 3.6 C9-11 EO4 - 3.0 C12-OEI - o 3 2-Hesyl - 0 4 decsnol 2-Butyloctanol 0.3 - 0.3 - 0.3 0.3 C12-14 S - - 1.0 - 1.0 1.0 C12-14 EO3S 1.0 1.3 - 1.5 Citrate 0.7 1.0 0.7 1.0 0.7 0.7 Na2CO3 0.6 0.7 0.6 0.3 0.6 0.6 C12-14 EO20 - 1.4 - 2.5 1.8 C1~12 EO10 2.0 - 1.0 C9-1 lEOS - 2.0 - 6 4.3 Cl lEOS 4.0 C12-14 l:OS - 3.6 4.5 9 6.4 C9-11 EO4 - - 3.0 2-Elesyl - 0.3 decanol 2-Butyl octanol 0.3 - 0.2 0.5 0.5 W 097/42276 PCT~US97/07228 C12-14S 1.2 1.5 - - 1.8 C12-14 E03S - - 1.5 2.5 Citrate 0.5 1.0 0.5 0.7 0.7 Na2C03 0.3 0.4 0.4 1 1.0
Claims (13)
1. The use, in a hard surface cleaning composition, of:
(a)-a hydrophilic nonionic surfactant; and (b)-a C8-C18 alcohol;
in a weight ratio of (a):(b) of from 1:1 to 10:1, for improved shine of hard surfaces which have been cleaned therewith.
(a)-a hydrophilic nonionic surfactant; and (b)-a C8-C18 alcohol;
in a weight ratio of (a):(b) of from 1:1 to 10:1, for improved shine of hard surfaces which have been cleaned therewith.
2. The use, in a hard surface cleaning composition, of (c)-a hydrophobic nonionic surfactant; and (d)-a sulfated anionic surfactant; and (b)-a C8-C18 alcohol;
in weight ratios of(c):(b) of from 5:1 to 25:1, and of(d):(c) of from 1:1 to 1:10, for improved shine of hard surfaces which have been cleaned therewith.
in weight ratios of(c):(b) of from 5:1 to 25:1, and of(d):(c) of from 1:1 to 1:10, for improved shine of hard surfaces which have been cleaned therewith.
3. The use, in a hard surface cleaning composition, of (a)-a hydrophilic nonionic surfactant; and (b)-a C8-C18 alcohol; and (c)-a hydrophobic nonionic surfactant; and (d)-a sulfated anionic surfactant;
in weight ratios of (a):(b) of from 1:1 to 10:1, of (c):(b) of from 5:1 to 25:1, and of (d):(c) of from 1:1 to 1:10, for improved shine of hard surfaces which have been cleaned therewith.
in weight ratios of (a):(b) of from 1:1 to 10:1, of (c):(b) of from 5:1 to 25:1, and of (d):(c) of from 1:1 to 1:10, for improved shine of hard surfaces which have been cleaned therewith.
4. A hard surface cleaning composition comprising (c)-a hydrophobic nonionic surfactant; and (d)-a sulfated anionic surfactant; and (b)-a C8-C18 alcohol;
in weight ratios of(c):(b) of from 5:1 to 25:1, and of(d):(c) of from 1:1 to 1:10.
in weight ratios of(c):(b) of from 5:1 to 25:1, and of(d):(c) of from 1:1 to 1:10.
5. A hard surface cleaning composition according to claim 4, which additionally comprises a hydrophilic nonionic surfactant (a), and wherein the weight ratio of(a):(b) is of from 1:1 to 10:1.
6. A composition or use according to any of the preceding claims, wherein said composition additionally comprises from 0 5% to 5% by weight of the total composition, preferably from 0.5% to 3%, of a builder system comprising a carbonate or a polyphosphate salt, and a polycarboxylate salt, preferably a citrate salt
7. A composition or use according to claim 6, wherein the weight ratio of said carbonate or polyphosphate to said polycarboxylate is at least 1:0.05.
8. A composition or use according to any of the preceding claims, wherein said composition comprises from 0.5% to 80% by weight of said hydrophilic nonionic surfactant (a), or mixtures thereof, and wherein said hydrophilic nonionic surfactant is an ethoxylated alcohol of formula C x EO y H, or an ethoxylated and propoxylated alcohol of formula C x PO y EO y', wherein x is an integer of from 9 to 15, and y and (y+y') are an integer of from 8 to 30, preferably from 10 to 20.
9. A composition or use according to any of the preceding claims, wherein said composition comprises from 1% to 20% by weight of said hydrophobic nonionic surfactant (c), or mixtures thereof, and wherein said hydrophobic nonionic surfactant is an ethoxylated alcohol of formula C x EO y H or an ethoxylated andpropoxylated alcohol of formula C x PO y EO y', wherein x is an integer of from 9 to 14 and y and (y+y) is an integer of from 2 to 7, preferably 4 to 6.
10. A composition or use according to any of the preceding claim, wherein said composition comprises from 0.1% to 3% by weight of said alcohol (b), and said alcohol is a C12-C16 alcohol.
11. A composition or use according to any of the preceding claims wherein said sulfated anionic surfactant (d) is a mixture of an ethoxylated alkyl sulfate of formula C x EO y S and a propoxylated alkyl sulfate of formula C x PO y S wherein x is an integer of from 10 to 14 and y is an integer of from 1 to 5.
12. A process of cleaning a hard surface wherein a composition according to any of the claims 4 to 11 is applied neat onto the surface, and optionally subsequentlyrinsed off of the surface
13. A process of cleaning a hard surface wherein a composition according to of the claims 4 to 11 is diluted in water, then applied onto the surface, and subsequently optionally rinsed off of the surface.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP96870058A EP0805200B1 (en) | 1996-05-03 | 1996-05-03 | Hard surface cleaning compositions |
| EP96870058.3 | 1996-05-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2253477A1 true CA2253477A1 (en) | 1997-11-13 |
Family
ID=8226140
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002253477A Abandoned CA2253477A1 (en) | 1996-05-03 | 1997-05-01 | Hard surface cleaning compositions |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0805200B1 (en) |
| JP (1) | JPH11508321A (en) |
| AT (1) | ATE245187T1 (en) |
| AU (1) | AU3056597A (en) |
| CA (1) | CA2253477A1 (en) |
| CZ (1) | CZ351398A3 (en) |
| DE (1) | DE69629104T2 (en) |
| ES (1) | ES2201165T3 (en) |
| TR (1) | TR199802219T2 (en) |
| WO (1) | WO1997042276A1 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0948892A1 (en) * | 1998-04-08 | 1999-10-13 | The Procter & Gamble Company | Disinfecting compositions and processes for disinfecting surfaces |
| CA2632934A1 (en) * | 2005-12-20 | 2007-07-05 | Novozymes Biologicals, Inc. | Surfactants systems for surface cleaning |
| JP5235102B2 (en) * | 2008-06-16 | 2013-07-10 | 花王株式会社 | Aqueous hair cleanser |
| US8071520B2 (en) | 2009-11-06 | 2011-12-06 | Ecolab Usa Inc. | Sulfonated alkyl polyglucoside use for enhanced food soil removal |
| US8172953B2 (en) | 2009-11-06 | 2012-05-08 | Ecolab Usa Inc. | Alkyl polyglucosides and a propoxylated-ethoxylated extended chain surfactant |
| US8216994B2 (en) | 2009-11-09 | 2012-07-10 | Ecolab Usa Inc. | Phosphate functionalized alkyl polyglucosides used for enhanced food soil removal |
| US8389463B2 (en) | 2009-11-09 | 2013-03-05 | Ecolab Usa Inc. | Enhanced dispensing of solid compositions |
| JP6423789B2 (en) | 2012-09-04 | 2018-11-14 | ルブリゾル アドバンスド マテリアルズ， インコーポレイテッド | Polyurethane-acrylic / styrene hybrid dispersions for glossing applications in home care |
| US20150252310A1 (en) | 2014-03-07 | 2015-09-10 | Ecolab Usa Inc. | Alkyl amides for enhanced food soil removal and asphalt dissolution |
| JP2019507232A (en) * | 2016-03-04 | 2019-03-14 | エス．シー． ジョンソン アンド サン、インコーポレイテッド | Neutral floor cleaner composition |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2536107A1 (en) * | 1975-08-13 | 1977-02-24 | Hoechst Ag | DISHWASHING LIQUID |
| US4692277A (en) * | 1985-12-20 | 1987-09-08 | The Procter & Gamble Company | Higher molecular weight diols for improved liquid cleaners |
| US5075026A (en) * | 1986-05-21 | 1991-12-24 | Colgate-Palmolive Company | Microemulsion all purpose liquid cleaning composition |
| GB9027416D0 (en) * | 1990-12-18 | 1991-02-06 | Unilever Plc | Detergent composition |
| MA22617A1 (en) * | 1991-08-14 | 1993-04-01 | Procter & Gamble | DETERGENT COMPOSITIONS FOR HARD SURFACES. |
| US5382376A (en) * | 1992-10-02 | 1995-01-17 | The Procter & Gamble Company | Hard surface detergent compositions |
| US5393468A (en) * | 1993-07-14 | 1995-02-28 | Colgate Palmolive Company | Hard surface cleaner |
| US5376298A (en) * | 1993-07-29 | 1994-12-27 | The Procter & Gamble Company | Hard surface detergent compositions |
| EP0666308B1 (en) * | 1994-02-03 | 2000-08-09 | The Procter & Gamble Company | Multi-purpose liquid cleaning compositions |
| US5476614A (en) * | 1995-01-17 | 1995-12-19 | Colgate Palmolive Co. | High foaming nonionic surfactant based liquid detergent |
-
1996
- 1996-05-03 ES ES96870058T patent/ES2201165T3/en not_active Expired - Lifetime
- 1996-05-03 DE DE69629104T patent/DE69629104T2/en not_active Expired - Fee Related
- 1996-05-03 AT AT96870058T patent/ATE245187T1/en not_active IP Right Cessation
- 1996-05-03 EP EP96870058A patent/EP0805200B1/en not_active Expired - Lifetime
-
1997
- 1997-05-01 AU AU30565/97A patent/AU3056597A/en not_active Abandoned
- 1997-05-01 CA CA002253477A patent/CA2253477A1/en not_active Abandoned
- 1997-05-01 WO PCT/US1997/007228 patent/WO1997042276A1/en not_active Application Discontinuation
- 1997-05-01 TR TR1998/02219T patent/TR199802219T2/en unknown
- 1997-05-01 CZ CZ983513A patent/CZ351398A3/en unknown
- 1997-05-01 JP JP9540003A patent/JPH11508321A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| TR199802219T2 (en) | 1999-02-22 |
| WO1997042276A1 (en) | 1997-11-13 |
| CZ351398A3 (en) | 1999-04-14 |
| JPH11508321A (en) | 1999-07-21 |
| AU3056597A (en) | 1997-11-26 |
| DE69629104T2 (en) | 2004-04-22 |
| EP0805200A1 (en) | 1997-11-05 |
| DE69629104D1 (en) | 2003-08-21 |
| ES2201165T3 (en) | 2004-03-16 |
| ATE245187T1 (en) | 2003-08-15 |
| EP0805200B1 (en) | 2003-07-16 |
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