CA2220131C - Glass cleaner compositions having linear alkyl sulfate surfactants - Google Patents

Abstract

The present invention relates to an aqueous, liquid hard surface detergent composition having excellent surface lubricity and filming/streaking characteristics. Said composition comprises less than about 1 %, by weight of the composition, of a C8-C18 linear alkyl sulfate detergent surfactant wherein more than about 30 %, by weight of said surfactant, has a C14 chainlength, is essentially free of unreacted fatty alcohol and alkanolamine compounds and is suitable for cleaning glass.

Description

WO 96134933 PCT/US!36/OJ~,Gl . - ., -- 1 --Glass cleaner compos~t~ons hav~ng l~near alkyl sulfate surfactants.

FIELD OF INVENTION
This invention pertains to glass rle~ning compositions, preferably clear liquid detergent compositions, for use in cle~ning glass and, preferably, other hard surfaces.
BACKGROUND OF THE INVENTION
It has recently been discovered that there is a strong consumer p,~r~lel-ce for liquid cleaning compositions, especially compositions prepared for cle~ning glass, that impart a smooth "gliding" feel, based on good surface lubricity, as the ~ ning implement wipes and dries.
At first glance, the task of making a ~le~ning composition that feels slipl)e~y, 20 or imparts a smooth "gliding" feel while it is being used seems fairly straightforward.
One would think it possible to use a wax or a silicone, as is known in the art, to provide good lubricity. However, it is also well known that liquid cleaning compositions, and especially compositions prepared for cleaning glass, need exceptionally good filming/streaking pl opel Lies. Because good filming/streaking 25 properties are required especially for glass cleaners, the levels of surf~t~nt~ and other actives must be kept low in order to achieve this benefit. Therefore, the level of s -rf~r~nt is too low to solubilize and/or stabilize waxes or silicones in the product, especially when a hydrophobic perfume is also present.
Also, it is known in the art that water-sheeting and anti-spotting benefits are 30 preferred in glass cleaning compositions. These water-sheeting and anti-spotting benefits are typically achieved by providing a composition which leaves behind a hydrophilic residue. Waxes and silicones are extremely hydrophobic and therefore are entirely incompatible with this requirement.
It has been discovered that long chain, i.e., C14 or longer, alkyl sulfate 35 detergent surf~-,t~nt~ provide the desired amount of surface lubricity as the composition is wiped dry on glass as well as contributing detergency and providing acceptable filming/streaking results and product clarity. Furthermore, the long-chain alkyl sulfate surf~ct~ntc are soluble in water and help to l~hlrol~ie the surface hydrophilicity that is required in order to obtain water-sheeting and anti-spotting benefits.
SUMMARY OF THE INVENTION
The present invention relates to de~el~,ell~ compositions, plerel~bly glass cleaning compositions, that impart good surface lubricity and cle~nin,~ without leaving objectionable levels of filming and/or streaking. Preferably said compositions contain an effective amount of substantive material which provides the glass with long lasting higher hydrophilicity and are in the forrn of an aqueous, liquid, hard surface detergent composition having illlploved r~le~ning and good spotting characteristics after l~w~L;ng, COlll~lisillg:
(A) less than about 1%, by weight of the composition, of a linear alkyl sulfate detergent surfactant having the general formula:

whelt:~l M is a suitable counter ion; R is an alkyl group having a chain length of from about C8 to about C1g or ~ Ul~;S thereof; wht;lt:ill more than about 30%, by weight of said surfactant, of said surfactant has a C14 chainlength;
(B) from about 0.5% to about 30%, by weight of the composition, of a hydrophobic solvent having a hydrogen bonding parameter of from about 2 to 7.7;
(C) the balance being an aqueous solvent system selected from the group consisting of water and non-aqueous polar solvents having a hydrogen bonding p~lllt;Lel of greater than 7.7; and wherein said composition is ess~nti~lly free of unreacted fatty alcohol and alkanolamine compounds and wherein said composition is suitable for cleaning glass.
DETAILED DESCRIPTION OF THE ~ENTION
The present invention relates to dt:~el~ell~ compositions, preferably aqueous, liquid hard surface de~el~en~ compositions having excellent surface lubricity and filming/streaking characteristics, comprising:
(A) less than about 1%, by weight of the composition, of a linear alkyl sulfate d~Lergell~ surfactant having the general formula:

wherein M is a suitable counter ion; R is an alkyl group having a chain length of from about C8 to about Clg or mixtures thereof; wherein more than about 30%, by weight of said surfactant, of said surfactant has a Cl4 - chainlength;

WO 96/34933 PCT/US96/0'~

(B) from about 0.5% to about 30%, by weight of the composition, of a hydrophobic solvent having a hydrogen bonding parameter of from about 2 to 7.7;
(C) the balance being an aqueous solvent system selected from the group consi~l,ng of water and non-aqueous polar solvents having a hydrogen bonding parameter of greater than 7.7; and wherein said composition is ess~onti~lly free of unreacted fatty alcohol and alkanolamine compounds and wherein said composition is suitable for cleaning glass.
(A) THE LONG CHAIN ALKYL SULFATE PRIMARY SI~RFACTANT
The aqueous, liquid hard surface detergent compositions herein contain less than about 1%, by weight of the composition, preferably from about 0.01% to about 1%, more preferably from about 0.02% to about 0.3%, by weight ofthe composition,of one or more chainlengths of a linear alcohol sulfate dc;lel~enL surfactant having the general formula:

wherein M is any suitable counterion, preferably sodium, pot~c~ m etc.; and wherein R is an alkyl group with a chainlength of from about Cg to about Clg andmixtures thereof, preferably from about C12 to about Clg and mixtures thereof, more preferably from about C14 to about Clg and mixtures thereof, and wherein R is C14 in more than about 30%, pr~rel~.bly more than about 35%, more preferably more than about 40.~/O, by weight of the alkyl sulfate. The entire alkyl sulfate surfactant can contain R of C14 and longer ~h~ F~ (S)~ but more than 30%, by weight of the alkyl surfactant must be a C14 r.h~inlFn~h Compositions co..~ g only alkyl sulfate surf~ct~nt~ with higher chainlengths, i.e., C16 18 provide good surface lubricity benefits. However, these chain lengths, without the required amount of C 14 chainlengths, exhibit poor filming/streaking properties. On the other hand, compositions which are solely made up of lower-chain alkyl sulfate surf~ct~nt~, i.e., Cg 12 alkyl sulfate surf~c.t~nts, provide acceptable filming/streaking plOpellies but show poor surface lubricity properties. The presence ofthe C14 ~h~inlPn~h at levels of more than about 30%, by weight of the alkyl sulfate surfactant, in col~lbind~ion with other chainlengths, or alone, provide a product with both excellent surface~ Iubricity properties and excellent filming/streaking properties. Particularly pl~Ç~lled compositions contain from about 0.05% to about 0.25%, by weight of the composition, of a C12/14 blend in which the C12 to C14 weight ratio is from about 1:10 to about 2:1, preferably from about 1:5 to about 1.5:1, and more preferablyfrom about 1:3 to about 1:1. This col"bh~alion has been found to provide sufficient surface lubricity while avoiding objectionable filming/streaking. The alcohol sulfate WO 96/34933 PCT/US9C~'u~5~1 detergent raw materials selected are ~ss~nti,.lly free from unreacted fatty alcohol wherein the term "ess~nti,.lly free" is defined as having less than about 2%, by weight of the composition, preferably less than about 1.8%, and more preferably less than about 1.5%, by weight of the composition of unreacted fatty alcohol in a nominally 30% active raw material.
A more pl~rell~;d alkyl sulfate sllrf~7ct~nt is a mixture of Stepanol WA-Extra~), available from the Stepan Company, with extra C14 alkyl sulfate added such that the C12/14 ratio is nearly 1:1.
Concentrated compositions can also be used in order to provide a less expensive product. When a higher concellLldLion is used, i.e., when the level of alkyl sulfate surfactant used is from about 0.10% to about 2.5%, by weight of the composition, it is preferable to dilute the composition before using it to clean a hard surface, especially glass. Dilution ratios of the alkyl sulfate concenLldLe(s) to water can range, preferably, from about 1:1 to 1:10, more plerc~l~bly from about 1:1.5 to 1:5, and most preferably from about 1:2 to 1:5.
(B) THE OPTIONAL CO-SUR~ACTANTS
The aqueous, liquid hard surface detergent compositions of the present invention can contain optional co-surf~r.t~nte Suitable co-sllrf~ct7nte which can be used are as follows:
(1) The Amphocarboxylate DeLel~:ellL Surfactant The aqueous, liquid hard surface deLel~c:llL compositions (cleaners) herein can contain from 0% to about 0.5%, by weight of the composition, p,t rt ldbly from about 0.01% to about 0.5%, more pl~;r~bly from about 0.02% to about 0.2%, and even more preferably from about 0.03% to about 0.08%, by weight of the composition, of C6 10 short chain amphocarboxylate de:LelgellL sllrf~rt~nf It has been found that these amphocarboxylate, and, especially glycinate, deLelgenL sllrf~(.t~nt.e provide good rle~ninp with superior filming/streaking for d~;LelgenL compositions that are used to clean both glass and/or lelaLiv~ly hard-to-remove soils. Despite the short chain, the detergency is good and the short chains provide improved filming/streaking, even as co,ll~,al~d to most ofthe zwitterionic dc:Lel~ellL surfactants described hereinafter. Depending upon the level of cleaning desired and/or the amount of hydrophobic material in the composition that needs to be solubilized, one can either use only the amphocarboxylate detergent surfactant, or can combine itwith cosurfactant, preferably said zwitterionic surf~ct~nte.
The "amphocarboxylate" detergent surfactants herein pl~reldbly have the generic formula:
R~(Rl )(CH2)nN(R2)(CH2)pC(O)OM

wo 96/34933 PcTrusg6/0556 wherein R' is a C6 10 hydrophobic moiety, typically a fatty acyl moiety co.~
from about 6 to about 10 carbon atoms which, in combination with the nitrogen atom forms an amido group, R1 is hydrogen (preferably) or a Cl 2 alkyl group, R2 is aC1 3 alkyl or, substituted Cl 3 alkyl, e.g., hydroxy substituted or carboxy methoxy 5 substituted, preferably, hydroxy ethyl, each n is an integer from 1 to 3, each p is an integer from 1 to 2, preferably 1, and each M is a water-soluble cation, typically an alkali metal, ammonium, and/or alkanolammonium cation. Such deLelge,~L
surf~c.t~ntc are available, for example: from Witco under the trade name Rewoteric AM-V~, having the formula C7H15C(O)NH(CH2)2N(CH2CH2OH)CH2C(O)O(-) Na(+);
Mona Industries, under the trade name Monateric 1000~, having the formula C7H15C(O)NH(CH2)2N(CH2CH2OH)CH2CH2C(O)O(-) Na(+);
and Lonza under the trade name Amphoterge KJ-2 g), having the formula C7,9H 15,1 9c(o)NH(cH2)2N(cH2cH2ocH2c(o)o(-)Na(+))cH2c(o)o(-) Na(+)-

(2) Zwitterionic Dt:telgellL Surfactant The aqueous, liquid hard surface detergent compositions (cleaners) herein can contain from about 0% to about 1%, by weight of the composition, of suitable zwitterionic detergent surfactant co-~ P a cationic group, preferably a quate~,a,y ammonium group, and an anionic group, preferably carboxylate, sulfate and/or sulfonate group, more preferably sulfonate. A more plerelled range of zwitterionic detergent surfactant in~ ion is from about 0.005% to about 0.3% of surfactant, amost p,t;fe"ed range is from about 0.01% to about 0.2%, by weight of the composition.
Zwitterionic d~;lel~,e"L sl~rf~ct~nt~ as mentioned hereinh~fore, contain both a cationic group and an anionic group and are in substantial electrical neutrality where the number of anionic charges and cationic charges on the d~Le,ge"L surfactant molecule are subst~nti~lly the same. Zwitterionic detergents, which typically contain both a quaternary ammonium group and an anionic group selected from sulfonate and carboxylate groups are desirable since they m~int~in their amphoteric character over most of the pH range of interest for cle~ning hard surfaces. The sulfonate group is the pl~rt:lled anionic group.
P,~felled zwitterionic detergent surf~ct~ntc have the generic formula:
R3 -[C(O)-N(R4)-(CR52)nl ]mN(R6)2(+)-(CR52)p 1 -Y(~) wherein each Y is preferably a carboxylate (COO~) or sulfonate (SO3-) group, more preferably sulfonate; wherein each R3 is a hydrocarbon, e.g., an alkyl, or alkylene, group cont~ining from about 8 to about 20, preferably from about 10 to about 18, more preferably from about 12 to about 16 carbon atoms; wherein each (R4) is either hydrogen, or a short chain alkyl, or substituted alkyl, cont~ining from one to about four carbon atoms, preferably groups selected from the group consisting of methyl, ethyl, propyl, hydroxy substituted ethyl or propyl and mixtures thereof, preferably methyl; wherein each (RS) is selected from the group consisting of hydrogen and hydroxy groups with no more than one hydroxy group in any (CR52)pl group;
wherein (R6) is like R4 except preferably not hydrogen; wherein m is 0 or 1; andwherein each nl and pl are an integer from 1 to about 4, plerel~bly from 2 to about

3, more preferably about 3. The R3 groups can be branched, uns~-Lu~ ed, or bot and such structures can provide filming/streaking benefits, even when used as part of a mixture with straight chain alkyl R3 groups. The R4 groups can also be connected to form ring structures such as imidazoline, pyridine, etc. Preferred hydrocarbyl ~mido~1kylene sulfobetaine (HASB) d~:Le,ge--L surfactants wherein m = 1 and Y is a sulfonate group provide superior grease soil removal and/or filming/streaking and/or "anti-fogging" and/or perfume solubili7~tiQn properties. Such hydrocarbyl~mi-lo~lkylene sulfobeL~ es, and, to a lesser extent hydrocarbyl~mido~1kylene belaines are ~Y~el1~nt for use in hard surface cleaningdeLe~gellL compositions, especially those form~ t~od for use on both glass and hard-to-remove soils. They are even better when used with monoethanolamine and/or specific beta-amino alkanol as disclosed herein.
A more plerelled specific delel~,ell~ surfactant is a C10 14 fatt,v acylamidopropylene(l.ydlu~y~ /lene)sulfobetaine, e.g., the deLel~;enL surfactantavailable from the Witco Co--lpall~ as a 40% active product under the trade name"REWOTERIC AM CAS Sulfobetaine~)."
The level in the composition is dependent on the eventual level of dilution to make the wash solution. For glass rle~ning, the composition, when used full :~LlèngLll, or wash solution co,-l~;,-;.~g the composition, should contain from about 0.0% to about 1%, p-ere-~bly from about 0.005% to about 0.5%, more preferably from about 0.01% to about 0.25%, by weight of the composition, of deLe.~,e..L
30 surfactant. For removal of difficult to remove soils like grease, the level can, and should be, higher, t,vpically from about 0% to about 10%, p-ere ~bly from about 0.005% to about 2%, by weight of the composition. Concentrated products will typically contain from about 0% to about 10%, preferably from about 0.005% to about 5%, by weight of the composition. It is an advantage of the zwitterionic 35 detergent, e.g., HASB, that compositions coll~ it can be more readily diluted by consumers since it does not interact with hardness cations as readily as conventional CA 02220l3l l997-ll-04 WO 96/34933 PCT/US9G~ 3561 anionic detergent surf~ct~nts. Zwitterionic detergents are also extremely effective at very low levels, e.g., below about 1%.
Other zwitterionic detergent surf~çt~ntc are set forth at Col. 4 of U.S. Pat. No.

4,287,080, Siklosi, incorporated herein by reference. Another detailed listing of ,, S suitable zwitterionic detergent surf~ct~ntc for the detergent compositions herein can be found in U.S. Pat. No. 4,557,853, Collins, issued Dec. 10, 1985, inco~lJo~ ed by reference herein. Commercial sources of such surf~ct~nts can be found in McCutcheon's EMULSIFIERS AND DETERGENTS, North American Edition, 1984, McCutcheon Division, MC Publishing Company, also incorporated herein by 1 0 reference.
(3) The Optional Anionic Deter~ent Surf~çt~ntc The deLelgenl compositions, plerc;l~bly aqueous, liquid hard surface detergent compositions, herein can contain as the cosurfactant, pr~r~,~bly, fromabout 0.0% to about 2.0%, more preferably from about 0.005% to about 0.99% of suitable anionic de~el~,e"l surfactant other than the esCPnti~l alkyl sulfate detergent surfactant. While it is understood that the longer chain alkyl sulfate surf~çt~ntc disclosed herein are considered the primary surfactant system, additional co-surf~r,t~ntc can be added inr.ll-~ing alkyl sulfate surf~ct~ntc of even lower chain lengths. The optional anionic surf~r.t~ntc are suitably water-soluble alkyl or alkylaryl compounds, the alkyl having from about 6 to about 20 carbons, and inr.lll~ling asulfate or sulfonate substituent group, but ex~ lin~ the ecs~nti~l alkyl sulfated~lelge"l surfactant. Dependi,.g upon the level of cleaning desired one can use only the ~cs.onti~l anionic dele~ge"l surfactant, or, more p,erel~bly, the anionic detergent surfactant can be co",l,ined with a cosurfactant, preferably an amphoteric cosurfactant. Nonionic surf~çt~ntc, e.g., ethoxylated alcohols and/or alkyl phenols, can also be used as cos--rf~r,t~ntc but are not plc:rt;llt:d.
The anionic detergent surf~çt~nt.c herein ~,~re,ably have the generic formula:
R9-(R10)o 1 -SO3(-)M(+) wherein R9 is a C6-C20 alkyl chain, plt;rel~bly a Cg-C16 alkyl chain; R10, when present, is a C6-C20 al'Kylene chain, preferably a Cg-C16 alkylene chain, a C6H4phenylene group, or O; and M is the same as before.
The patents and references disclosed hereinbefore and incorporated by reference also disclose other detergent surf~ct~ntc, e.g., anionic, and, less preferably, nonionic detergent surfactants, that can be used in small amounts, preferably ascosurfactants for the ~ss~nti~l alkyl sulfate delelge,-l surfactant and plert;lled amphoteric/zwitterionic d~:lel~e"l cosurfactant. The cosurfactant level can be small WO 96/34933 PCT/U~

in relation to the primary surfactant. Typical of these are the alkyl- and alkylethoxylate- (polyethoxylate) sl-lf~tec, paraffin sulfonates, olefin sulfonates, alkoxylated (especially ethoxylated) alcohols and alkyl phenols, alkyl phenol sulfonates, alpha-sulfonates of fatty acids and of fatty acid esters, and the like, which are well-known from the detergency art. When the pH is above about 9.5, detergent t surf~ct~nt.c that are amphoteric at a lower pH are desirable anionic detergent cosurf~ct~ntc For example, detergent surfactants which are C12-Clg acylamido alkylene amino alkylene sulfonates, e.g., compounds having the formula R-C(O)-NH-(C2H4)-N(C2H4OH)-CH2CH(OH)CH2SO3M wherein R is an alkyl group co~ g from about 9 to about 18 carbon atoms and M is a com~aLible cation are desirable cos--rf~ct~ntc. These detergent s -rf~t~ntc are available as Miranol~) CS, OS, JS, etc. The CTFA adopted name for such s ~rf~ct~ntc is cocoamphol,y.ilo~y~ yl sulfonate. It is pl~r~ ed that the compositions be substantially free of alkyl naphth~lçn~ sulfonates.
In general, d~lel~,elll surf~ct~nt.c useful herein contain a hydrophobic group, typically COI~ an alkyl group in the Cg-C1g range, and, optionally, one or more linking groups such as ether or amido, preferably amido, groups. The anionic d~lelgenl s~rf~t~nte can be used in the form of their sodium~ pot~e.ci~-m, or alkanolammonium, e.g., tri~th~nol~mmonium salts; the nonionics, not pl ~:rt~ d, generally contain from about 5 to about 17 ethylene oxide groups.
Some suitable surf~ nt.c for use herein in small amounts are one or more of the following: sodium linear Cg-C1g alkyl benzene sulfonate (LAS), particularly Cl l-C12 LAS; the sodium salt of a coconut alkyl ether sulfate co"l~;";llg 3 moles of ethylene oxide; the adduct of a random secondary alcohol having a range of alkylchain lengths of from 11 to 15 carbon atoms and an average of 2 to 10 ethylene oxide moieties, several commercially available ~Y~mples of which are Tergitol~ 15-S-3,Tergitolg) 15-S-5, Tergitol~) 15-S-7, and Tergitol~ 15-S-9, all available from Union Carbide Corporation; the sodium and potassium salts of coconut fatty acids (coconut soaps); the con~i~n.c~tion product of a straight-chain plilllaly alcohol colll~ ;"g from about 8 carbons to about 16 carbon atoms and having an average carbon chain length of from about 10 to about 12 carbon atoms with from about 4 to about 8 moles of ethylene oxide per mole of alcohol; an amide having one ofthe pl~r~;lled formulas:
o Il R7 C N(R8)2 wherein R7 is a straight-chain alkyl group cc,ll~ g from about 7 to about 15 35 carbon atoms and having an average carbon chain length offrom about 9 to about 13 WO 96/34933 PCI~/US~J6/O'SGl _ 9 _ carbon atoms and wherein each R8 is a hydroxy alkyl group CO.~ g from 1 to about 3 carbon atoms; a zwitterionic surfactant having one ofthe pr~r~.led formulas set forth heleillaner; or a phosphine oxide surfactant. Another suitable class of surfactants is the fluorocarbon surf~ct~nts, examples of which are FC-129g), a

5 potassium fluorinated alkylcarboxylate and FC-170-C~, a mixture of fluorinatedalkyl polyoxyethylene ethanols, both available from 3M Corporation, as well as the Zonylg) fluorosurf~ct~nte, available from DuPont Corporation. It is understood that mixtures of various surf~ct~nte can be used.
(4) Mixtures Mixtures of amphocarboxylate, zwitterionic dt;Lt;l~ellL surf~ct~nte, and/or anionic detergent surf~ct~nte as rlieclle.ee~ he,eillberu,c~, can be present in the present invention.
When a co-surfactant is added to the composition of the present invention, the total surfactant level can be from about 0.01% to about 5%, by weight of the total 15 composition however, the alkyl surfactant should be present at a level less than 1%, by weight of the composition. The ratio of zwitterionic deLe~ s-lrf~ct~nt to amphocarboxylate de~el~ell~ surfactant is typically from about 3:1 to about 1:3,pl~rt;l~bly from about 2:1 to about 1:2, more plerelably about 1:1. The ratio of the primary C14 alkyl sulfate dt;L~lgellL surfactant to cosurfactant, or cosurf~ct~nte, is 20 typically from about 3:1 to about 1:1.
(C) HYDROPHOBIC SOLVENT
In order to improve r~le~ning in liquid compositions, one can use a hydrophobic solvent that has cl~nin~ activity. The solvents employed in the hard surface cle~ning compositions herein can be any of the well-known "degreasing" solvents commonly 25 used in, for c,.~lll}~le, the dry ~le~ning industry, in the hard surface cleaner industry and the metalworking industry.
A useful definition of such solvents can be derived from the solubility parameters as set forth in "The Hoy," a publication of Union Carbide, incorporated herein by reference. The most useful parameter appears to be the hydrogen bonding 30 parameter which is calculated by the formula:
-- 1l2 a - 1 yH -yT a wherein yH is the hydrogen bonding parameter, a is the aggregation number, (Log a = 3.39066 Tb/TC - 0.15848 - Log ~), and yT is the solubility parameter which is obtained from the formula:

rT = (~H25 - RT)d M

where ~H2s is the heat of vaporization at 25~C, R is the gas consl~-L (1.987 caVmole/deg), T is the absolute temperature in ~K, Tb is the boiling point in ~K, Tc is the critical temperature in ~K, d is the density in g/ml, and M is the molecular 1 0 weight.
For the compositions herein, hydrogen bonding p~ lle~ 7 are preferably less than about 7.7, more preferably from about 2 to about 7, and even more preferably from about 3 to about 6. Solvents with lower r,uml~el~, become increasingly difficult to solubilize in the compositions and have a greater tendency to cause a haze on15 glass Higher numbers require more solvent to provide good greasy/oily soil cleanlng.
Hydrophobic solvents are typically used at a level of from about 0.5% to about 30%, preferably from about 2% to about 15%, more preferably from about 3% to about 8%. Dilute compositions typically have solvents at a level of from about 1% to 20 about 10%, ~ r~l~bly from about 3% to about 6%. ConcellLI~ed compositions contain from about 10% to about 30%, preferably from about 10% to about 20% of solvent.
Many of such solvents comprise hydrocarbon or halog~n~ted hydrocarbon moieties of the alkyl or cycloalkyl type, and have a boiling point well above room 25 temperature, i.e., above about 20~C.
The formulator of compositions of the present type will be guided in the selection of cosolvent partly by the need to provide good grease-cutting plopelLies, and partly by ~estheti~ considerations. For example, kerosene hydrocarbons function quite well for grease cutting in the present compositions, but can be malodorous.
30 Kerosene must be exceptionally clean before it can be used, even in cornmercial situations. For home use, where malodors would not be tolerated, the formulator would be more likely to select solvents which have a relatively pleasant odor, or odors which can be reasonably modified by perfuming.
The C6-Cg alkyl aromatic solvents, especially the C6-Cg alkyl benzenes, 35 preferably octyl benzene, exhibit excellent grease removal properties and have a low, CA 02220l3l l997-ll-04 WO 96/34933 PCT/US9~ i5~1 pleasant odor. Likewise, the olefin solvents having a boiling point of at least about 100~C, especially alpha-olefins, preferably 1-decene or 1-dodecene, are excellent grease removal solvents.
Generically, the glycol ethers useful herein have the formula R11 ~, S O-(R120-)mlH wherein each R11 is an alkyl group which contains from about 3 to about 8 carbon atoms, each R12 is either ethylene or propylene, and m1 is a number from 1 to about 3. The most plerelled glycol ethers are selected from the group consisting of monopropyleneglycolmonopropyl ether, dipropyleneglycolmonobutyl ether, monopropyleneglycolmonobutyl ether, ethyleneglycolmonohexyl ether, ethyleneglycolmonobutyl ether, diethyleneglycolmonohexyl ether, monoethyleneglycolmonohexyl ether, monoethyleneglycolmonobutyl ether, and mixtures thereo~
A particularly pl~r~lled type of solvent for these hard surface cleaner compositions comprises diols having from 6 to about 16 carbon atoms in their molecular structure. Plerellt;d diol solvents have a solubility in water of from about 0.1 to about 20 g/100 g of water at 20~C.
Solvents such as pine oil, orange terpene, benzyl alcohol, n-hexanol, phthalic acid esters of Cl 4 alcohols, butoxy propanol, Butyl Carbitol~ and 1(2-n-butoxy-1-methylethoxy)propane-2-ol (also called butoxy plol)u~y propanol or dipropylene glycol monobutyl ether), hexyl diglycol (Hexyl Carbitol~)), butyl triglycol, diols such as 2,2,4-trimethyl-1,3-pPnt~nP~iol, and mixtures thereof, can be used. The butoxy-propanol solvent should have no more than about 20%, preferably no more than about 10%, more preferably no more than about 7%, of the secondary isomer in which the butoxy group is att~hP,cl to the secondary atom of the propanol for improved odor.
(D) OPTIONAL ALKALrNITY SOURCE
The compositions of this invention can contain an optional ~lk~linity source.
Suitable compounds which can be used include but are not limited to alkali metalhydroxides, i.e., sodium, pot~cci~m etc., and carbonates or sodium bicarbonates.The ~Ik~linity source can be present at a level of 0% to about 0.2%, by weight of the composition. Typically said ~Ik~linity source is present at a level of from about 0.001% to about 0.1%, preferably from about 0.005% to about 0.05%, by weight of the composition. It is undesirable to use alkanolamine compounds as an ~lk~linity source in the present invention. Said alkanolamine compounds interfere with the surface lubricity benefit achieved by the long-chain alkyl sulfate surf~ct~ntc Said composition is therefore eccPnti~lly free of alkanolamine compounds. "Fcc~nti~lly free" as defined herein means less than about 0.5%, preferably less than about 0.1%, more preferably less than about 0.01%.
(E) OPTIONAL SOLUBLE CARBONATE AND/OR BICARBONATE SALTS
Water-soluble alkali metal carbonate and/or bicarbonate salts, such as sodium 5 bicarbonate, potassium bicarbonate, potassium carbonate, cesium carbonate, sodium carbonate, and mixtures thereof, are added to the composition of the present invention in order to improve the filming/streaking when the product is wiped dry on the surface, as is typically done in glass cleaning. Preferred salts are sodium carbonate, pot~ m carbonate, sodium bicarbonate, potassium bicarbonate, their 10 respective l~ydl~es, and ~.fi~Lules thereo~ Solubilized, water-soluble alkali metal carbonate and bicarbonate salts are typically present at a level of from about 0% to about 0.5%, preferably from about 0.001% to about 0.1%, more preferably from about 0.005% to about 0.05%, by weight of the composition. The pH in the composition, at least initially, in use is from about 7 to about 11, preferably from about 7.5 to about 10.5, more preferably from about 8 to about 10. pH is typically measured on the product.
(F) OPTIONAL SUBSTANTIVE MATERL~L THAT INCREASES
HYDROPHILICITY OF GLASS
An optional but pr~rt;--c~d ingredient of this invention is the substantive 20 material that improves the hydrophilicity of the surface being treated, especially glass.
This increase in hydrophilicity provides improved appearance when the surface isrewetted and then dried. The water "sheets" offthe surface and thereby ...;..i,.,;~
the formation of, e.g., "rainspots" that form upon drying. Many materials can provide this benefit, but the prert;.led m~tf~ri~lc are polymers that contain hydrophilic 25 groups, especia11y carboxylate or :julronaLe groups. Other m~teri~l~ that can provide S~sl~Livily and hydrophilicity include cationic materials that also contain hydrophilic groups and polymers that contain multiple ether linkages. Cationic materials include cationic sugar and/or starch derivatives and the typical blockcopolymer d~e.ge..L surf~ct~nt~ based on mixtures of polypropylene oxide and 30 ethylene oxide are representative of the polyether materials. The polyether materials are less substantive, however.
The pl~rc~ d polycarboxylate polymers are those formed by polymerization of monomers, at least some of which contain carboxylic functionality. Common monomers include acrylic acid, maleic acid, ethylene, vinyl pyrrollidone, methacrylic 35 acid, methacryloylethylbetaine, etc. The pl~rc:"ed polysulfonate polymers are those based upon a polystyrene backbone. Preferred polymers for substantivity are those - having higher molecular weights. For example, polyacrylic acid having molecular -weights below about 10,000 are not particularly substantive and therefore do notnormally provide hydrophilicity for three lc~w~;LLings with all compositions, although with higher levels and/or certain surf~ct~nts like amphoteric and/or zwitterionic detergent surfactants, molecular weights down to about 1000 can provide some results. In general, the polymers should have molecular weights of more than 10,000, preferably more than about 20,000, more preferably more than about 300,000, and even more preferably more than about 400,000. It has also been found that higher molecular weight polymers, e.g., those having molecular weights of more than about 3,000,000, are extremely difficult to formulate and are less effective in providing anti-spotting benefits than lower molecular weight polymers. Accordingly, the molecular weight should normally be, especially for polyacrylates, from about 20,000 to about 3,000,000; preferably from about 20,000 to about 2,500,000; morepreferably from about 300,000 to about 2,000,000; and even more l,r~re;lably from about 400,000 to about 1,500,000.
An advantage for some polycarboxylate polymers is the d~:Lel~enL builder effectiveness of such polymers. Surprisingly, such polymers do not hurt filming/streaking and like other detergent builders, they provide increased ~le~nin~
effectiveness on typical, common "hard-to-remove" soils that contain particulatematter.
Some polymers, especially polycarboxylate polymers, thicken the compositions that are aqueous liquids. This can be desirable. However, when the compositions are placed in cont~in~rs with trigger spray devices, the compositions are desirably not so thick as to require ~"~ces~ e trigger pressure. Typically, the viscosity under shear should be less than about 200 cp, preferably less than about 100 cp, more preferably less than about 50 cp. It can be desirable, however, to have thick compositions to inhibit the flow of the composition offthe surface, especially vertical surfaces.
Ex~l,plcs of su*able materials for use herein include poly(vinyl pyrrolidone/acrylic acid) sold under the name "Acrylidone"g) by ISP, polystyrenesulfonic acid and polystyrene sulfonate salts sold under the name "Versafiex"~) by National Starch, and poly(acrylic acid) sold under the name "~cllm~r"~ by Rohm &Haas.
The level of substantive material should normally be from about 0% to about 1.0%, preferably from about 0.01% to about 0.5%, more preferably from about 0.02% to about 0.2%, by weight of the composition. In general, lower molecular weight materials such as lower molecular weight poly(acrylic acid), e.g., those having molecular weights below about 10,000, and especially about 2,000, do not provide- good anti-spotting benefits upon l~w~lLi,Ig, especially at the lower levels, e.g., about CA 02220l3l l997-ll-04 WO 96/34933 PCT/US9~'05~,61 0.02%. One should use only the more effective materials at the lower levels. In order to use lower molecular weight materials, substantivity should be increased, e.g., by adding groups that provide improved ?~tt~c.hmrnt to the surface, such as cationic groups, or the materials should be used at higher levels, e.g., more than S about 0.05%. ,~
(G) AQUEOUS SOLVENT SYSTEM
The balance of the formula is typically water and non-aqueous polar solvents with only minim~l cleaning action like meth~nol, ethanol, isopropanol, ethylene glycol, glycol ethers having a hydrogen bonding parameter of greater than 7.7, 10 propylene glycol, and mixtures thereof, preferably ethanol. The level of non-aqueous polar solvent is usually greater when more concentrated formulas are prepared.
Typically, the level of non-aqueous polar solvent is from about 0.5% to about 40%, preferably from about 1% to about 10%, more p-~r~l~bly from about 2% to about 8% (especially for "dilute" compositions) and the level of water is from about 50% to about 99%, preferably from about 75% to about 95%.
(H) OPTIONAL INGREDIENTS
The compositions herein can also contain other various adjuncts which are known to the art for detergent compositions. Pl~r~l~Lbly they are not used at levels that cause Im~cceptable filming/streaking. Non-limiting examples of such adjuncts are:
Enzymes such as proteases;
Hy-lluLlopes such as sodium toluene sulfonate, sodium cumene sulfonate and potassium xylene sulfonate; and Aesthetic-enhancin~ ingredients such as colorants and perfumes. providing they do not adversely impact on filming/streaking in the cleaning of glass. Most hard surface cleaner products contain some perfume to provide an olfactory ~esthr.ticbenefit and to cover any ~rh~mic~ odor that the product may have. The main filnr.tinn of a small fraction of the highly volatile, low boiling (having low boiling points), perfume components in these perfumes is to improve the fragrance odor of the product itself, rather than imp~cting on the subsequent odor of the surface being cleaned. However, some of the less volatile, high boiling perfume ingredients can provide a fresh and clean impression to the surfaces, and it is sometimes desirable ?
that these ingredients be deposited and present on the dry surface. The perfumes are preferably those that are more water-soluble and/or volatile to ~ e streaking and filming. The perfumes useful herein are described in more detail in U.S. Patent 5,108,660, Michael, issued April 28, 1992, at col. 8 lines 48 to 68, and col. 9 lines 1 WO 96/34933 PCT/US9G/C~

to 68, and col. 10 lines l to 24, said patent, and especially said specific portion, being incorporated by reference.
Antibacterial agents can be present, but preferably only at low levels to avoid filming/streaking problems. More hydluphobic ~ntih~ct~riaVgermicidal agents, like 5 orthobenzyl-para-chlorophenol, are avoided. If present, such materials should be kept at levels below about 0.1%.
Stabilizin~ in~redients can be present typically to stabilize more of the hydrophobic ingredients, e.g., perfume. The stabilizing ingredients include acetic acid and propionic acids, and their salts, e.g., NH4, MEA, Na, K, etc., preferably acetic acid and the C2-C6 alkane diols, more preferably butane diol. The stabilizing ingredients do not function in acco,dallce with any known principle. NonPth.ole~s, the co--ll,-~ ion of amido zwitterionic detergent surfactant with linear acyl amphocarboxylate detergent surfactant, anionic deLel~ ellL surfactant, nonionic detergent surfactant, or mixtures thereof, and stabilizing ingredient can create a microemulsion. The amount of stabilizing ingredient is typically from about 0.01%
to about 0.5%, preferably from about 0.02% to about 0.2%. The ratio of hydrophobic material, e.g., perfume that can be stabilized in the product is related to the total s-lrf~r,t~nt and typically is in an amount that provides a ratio of surfactant to hydrophobic material of from about 1:2 to about 2:1.
Other de~e.~e"L builders that are lo.ffici~nt for hard surface cleaners and havereduced filming/streaking characteristics at the critical levels can also be present in the compositions of the invention. Addition of specific detergent builders at critical levels to the present composition further improves cleaning without the problem of filming/streaking that usually occurs when deLelgellL builders are added to hard25 surface cleaners. There is no need to make a co".~rose between improved r.l~ninp and acceptable filming/streaking results, which is especially important for hard surface cleaners which are also directed at çle~nin~ glass. These compositions co~ g these specific additional detergent builders have exceptionally good cleaning properties. They also have exceptionally good "shine properties, i.e., when used to clean glossy surfaces, without rinsing, they have much less tendency than, e.g., carbonate built products to leave a dull finish on the surface and filming/streaking .
Suitable additional optional deLelgellL builders include salts of ethylPne~ minetetraacetic acid (hereinafter EDTA), citric acid, nitrilotriacetic acid (hereinafter NTA), sodium carboxymethyl~lcçinic acid, sodium N-(2-hydroxypropyl)-iminodiacetic acid, and N-diethyleneglycol-N,N-diacetic acid (hereinafter DIDA). The salts are preferably compatible and include ammonium, sodium, potassium and/or alkanolammonium salts. The alkanolammonium salt is p,~ d as described hel~:indnel. A ple~r~ d detergent builder is NTA (e.g., sodium), a more p~re"ed builder is citrate (e.g., sodium or monoethanolamine), and a most pl ~:r~ d builder is EDTA (e.g., sodium).
S These additional optional detergent builders, when present, are typically at levels of from about 0.01% to about 0.5%. more preferably from about 0.02% to about 0.3%, most preferably from about 0.02% to about 0.15%. The levels ofthese additional builders present in the wash solution used for glass should be less than about 0.2%. Therefore, typically, dilution is highly plc;r~;lled for r.lç~ning glass, while 10 full strength is plert:lled for general purpose cleaning, depending on the concentration of the product.
Typically the best filming/streaking results occurs most when the builder is combined with amphoteric and/or zwitterionic detergent surfactant compositions although an improvement is also seen with anionic or anionic/nonionic de~elgenl 15 surfactant compositions.
The invention is illustrated by the following nonlimitin~ F.Y~mpl~r Static Friction Hei~ht Test A 12" x 12" pane of glass is sprayed with product (one spray from a standard spray device) and wiped to near dryness with one paper towel. A 550 gram 20 plexiglass block is wrapped with a paper towel by taking one sheet and folding it twice into a square. The towel is taped to the bottom of the block so it is stretched taut with no wrinkles or creases and no tape is on the bottom surface that will be in contact with the glass. The block is placed on the glass toward one end. The end of the glass is raised slowly until the block begins to move. The ~ e that the glass 25 was raised is measured. The higher the height, the higher the friction and the static friction height. A normal dry clean glass has a high coefficient of friction (0.9-1.0), and therefore a high static friction height (greater than 5 inches with this method).
End Result Wipe Test Procedure:
Five sprays of the product to be tested are applied to a 2ft. x 3ft. glass window (which can be soiled with body oils from a handprint) and wiped with two paper towels to near dryness, cim~ ting actual consumer usage of the product.
Grading:
Expert judges are employed to evaluate the specific areas of product 35 application for amount of filming/streaking, with the aid of a floodlight to .cimlll~te a sunbeam. A numerical value describing the quality of the end result is ~c.ci~nçd to =

each product. For the test results reported here a 0-6 scale is used, in which 0 =
good end result with no film/streak, and 6 = very poor end result.

EXAMPLE I

Wt.% Wt.% Wt.% Wt.% Wt.%
Butoxypropanol 2.8 2.8 2.8 2.8 2.8 Ethanol 2.8 2.8 2.8 2.8 2.8 Polystyrene Sulfonate (Versaflex~ 7000) 1 0.10 0.10 0.10 0.10 0.10 Sodium Octyl Sulfate 0.05 0.05 0.05 0.05 0.05 SodiumDodecyl Sulfate 0.06 --- --- 0.06 ---Sodium Tetradecyl Sulfate 0.06 0.06 0.06 --- ---Sodium ~clecyVoctadecyl Sulfate --- --- 0.04 --- ---Available from National Starch The above formulas were tested according to the above methods for static 20 ~iction height and end result wipe, with the results as follows (average of 3 replic~t~s with standard deviation):
Static Friction ~eight End Result Wipe Grade Formula (inches) (0 = best~ 6= worst) 1 1.82 + 0.06 0.75 + 0.00 2 1.82+0.06 0.83 +0.11 3 1.52 + 0.06 0.83 + 0.11 4 2.44 + 0.06 0.75 + 0.17 2.46+0.05 0.92+0.11 30 Relative Humidity = 30%

As can be seen by the above example, formulas 1-3 of the present invention provide lower static friction height than formulas 4-5 which are outside the scope of the present invention while .,.~ g good end results. For relatively low and 35 constant surfactant levels (about 0.1 to 0.2%) which are consistent with good end result, the C14 and longer ~h~inl~ngth.~ provide the most smoothness (lowest static , friction height). Qualitative evaluation shows that Formulas 1-3 provide noticeably improved surface lubricity while wiping to dryness than do Formulas 4-5.

W096/34933 PCTrUS96/05561 E~ PLE II

Wt.% Wt.% Wt.% Wt.%
Buto,Yypropanol 2.8 2.8 2.8 2.8 Ethanol 2.8 2.8 2.8 2.8 Poly(vinylpyrrolidone/acrylate) 0.025 0.025 --- ---Sodium Hydroxide 0.04 0.04 --- ---Sodium Dodecyl Sulfate 0.20 --- --- ---Sodium Tetradecyl Sulfate 0.08 0.05 0.05 0.02 Stepanol WA-extra (70/30 blend C12/14 aL~yl sulfate)2 --- --- 0.10 0.10 Sodium Bicall,onate --- 0.015 --- 0.015 Sodium Carbonate --- 0.005 --- 0.005 Fragrance 0.03 0.03 0.07 0.07 End Result Wipe Grade (Relative ~llmi~ity= 35%) 1.8 0.56 0.80 0.55 End Result Wipe Grade (Relative Humidity= 54%) NA NA 1.65 1.00 20 2Available from the Stepan Co.

The above ~Y~mple shows that the ~ 1ition of a small amount of carbonate provides for a modest improvement in the end result wipe grade, both for formulas which contain a polymer for hydrophilic surface moriific~tinn and for those which do 25 not. The improvement is even more pronounced at higher hllmitliti~?e

Claims (18)

WHAT IS CLAIMED IS:

1. An aqueous, liquid hard surface detergent composition having excellent surface lubricity and filming/streaking characteristics, comprising:
(A) less than about 1%, by weight of the composition, of a linear alkyl sulfate detergent surfactant having the general formula:

wherein M is a suitable counter ion; R is an alkyl group having a chain length of from about Cg to about C18 or mixtures thereof; wherein more than about 30% of said alkyl sulfate surfactant, by weight of said alkyl sulfate surfactant, has a C14 chain length;
(B) from about 0.5% to about 30%, by weight of the composition, of a hydrophobic solvent having a hydrogen bonding parameter of from about 2 to 7.7;
(C) the balance being an aqueous solvent system selected from the group consisting of water and non-aqueous polar solvents having a hydrogen bonding parameter of greater than 7.7; and wherein said composition is essentially free of unreacted fatty alcohol and alkanolamine compounds and wherein said composition is suitable for cleaning glass.

2. The composition of Claim 1 wherein said alkyl sulfate surfactant is present at a level of from about 0.01% to about 0.9%, by weight of the composition.

3. The composition of Claim 2 wherein said alkyl sulfate surfactant is present at a level of from about 0.02 to about 0.3%, by weight of the composition.

4. The composition of Claim 1, 2 or 3 wherein R is an alkyl group having a chain length of from about C12 to about C18 and wherein more than about 35% of said alkyl sulfate surfactant, by weight of said alkyl sulfate surfactant, contains a C14 chain length.

5. The composition of Claim 4 wherein R is an alkyl group having a chain length of from about C14 to about C18 and wherein more than about 40% of said alkyl sulfate surfactant, by weight of said alkyl sulfate surfactant, has a C14 chain length.

6. The composition of any one of Claims 1 to 4 wherein R is an alkyl group having a chain length of a C12/14 blend having a C12 to C14 weight ratio of from about 1:10 to about 2:1.

7. The composition of any one of Claims 1 to 6 further comprising up to about 4.9%, by weight of the composition, of a co-surfactant selected from the group consisting of:
(A) amphocarboxylate detergent surfactants;
(B) zwitterionic detergent surfactants;
(C) anionic detergent surfactants; and (D) mixtures thereof.

8. The composition of any one of Claims 1 to 7 further comprising from about 0% to about 0.5%, by weight of the composition, of solubilized, water-soluble alkali metal carbonate salt, bicarbonate salt, or mixtures thereof.

9. The composition of Claim 8 wherein said salt is selected from the group consisting of sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, their respective hydrates, and mixtures thereof.

10. The composition of Claim 9 wherein said salt is present at a level of from about 0.001% to about 0.1%, by weight of the composition.

11. The composition of Claim 9 wherein said salt is present at a level of from about 0.005% to about 0.5%, by weight of the composition.

12. The composition of any one of Claims 1 to 11 further comprising from about 0% to about 1.0% of a substantive material that increases hydrophilicity of glass.

13. The composition of Claim 12 wherein said substantive material is polycarboxylate polymer.

14. The composition of Claim 13 wherein said polycarboxylate polymer has a molecular weight of from about 1,000 to about 3,000,000.

15. The composition of Claim 14 wherein said polycarboxylate polymer has a molecular weight of from about 20,000 to about 2,500,000.

16. The composition of Claim 15 wherein said polycarboxylate polymer has a molecular weight of from about 400,000 to about 1,500,000.

17. A liquid, aqueous hard surface detergent composition having both excellent surface lubricity characteristics and excellent filming/streaking characteristics, comprising:
(A) from about 0.01% to about 0.9%, by weight of the composition, of a linear alkyl sulfate detergent surfactant having the formula:

wherein M is a sodium counterion; R is an alkyl group having a chain length consisting of a C12/14 blend having a C12 to C14 weight ratio of from about 1:10 to about 2:1 and wherein more than about 30% of said alkyl sulfate surfactant, by weight of said alkyl sulfate surfactant, is comprised of a C14 chain length;
(B) from about 0.005% to about 0.9%, by weight of the composition, of a C14 alkyl sulfate co-surfactant;
(C) from about 0.001% to about 0.1%, by weight of the composition, of sodium carbonate;
(D) from about 0.5% to about 30%, by weight of the composition, of butoxypropanol;

(E) the balance being a mixture of ethanol and water; and wherein said composition is essentially free of unreacted fatty alcohol and alkanolamine compounds and wherein said composition is suitable for cleaning glass.

18. A process of cleaning glass, the process comprising:
(A) spraying the composition of any one of Claims 1 to 17 onto a glass surface using a spraying device; and (B) wiping said surface to near dryness.