CA2074823C - Liquid hard surface detergent compositions containing zwitterionic detergent surfactant and monoethanolamine and/or beta-aminoalkanol - Google Patents

Abstract

Aqueous, liquid hard surface detergent compositions contain zwitterionic detergent surfactant and monoethanolamine and/or other specific beta-aminoalkanols as solvents and/or buffers for improved spotting/filming and good cleaning. Some formulas do not contain large amounts of builders and are suitable for general purpose cleaning including cleaning of glass.

Description

W O 91/11505 2 0 7 ~ 8 2 3 PCTtUS9t/00337 LIQUID HARD SURFACE-DETERGENT COMPOSITIONS
CONTAINING ZWITTERIONIC DETERGENT SURFACTANT
AND MONOETHANOLAMINE AND/OR BETA-AMINOALKANOL

FIELD OF THE INVENTION
This invention pertains to liquid detergent compositions for use in cleaning hard surfaces. Such compositions typicatly 1~ con~in detergent surfactants, solvents, builders, etc.
~ACKGROUNQ OF T~E INVENTIO~
Ine use of solvents and organic water~soluble synthetic detergents at low ~evels for cleantng glass are known.
General purpose household cleaning compositions for hard iu,fàc2s such as metal, glass, ceramic, plastic and linoleum surfaces, are commercially available in both powdered and liquid form. Liquid detergent compositions are disclosed in Australian Pat. Application 82/88168, filed Sept~ 9, 1982, by The Procter &
Gamble Company; U.K. Pat. Application GB 2,166,153A, filed Oct. 24, 1985, by The Procter & Gamble Company; and U.K. Pat.
Application G~ 2,160,887A, filed June 19, 1985, by Bristol-Myers Company, all of said published applications being incorporated herein by reference. These liquid detergent compositions comprise certain organic solvents, surfactant, and optional builder and/or abrasive. The prior art, however, fails to teach, or recognize, the advantage of the specific organic solvents/'buffers disclosed hereinafter, in liquid hard surface cleaner formulations.
Ltquid claaning compositions have the great advantage that they can be applied to hard surfaces in neat or concentrated form so that a relattvely high level of surfactant material and organic solvent is delivered directly to the soil. Moreover, it is a rather more straightforward task to incorporate high concentra-tions of anionic or nonion c surfactant in a liquid rather than a granular composition. For both these reasons, therefore, liquid 3~ cleaning compositions have the potential to provide superior soap scum, grease, and oily soil removal over powdered cleaning com-positions.

W 0 91/ltS05 2 0 7 ~ 82 3 - 2 - PCT/US91/00337 Nevertheless, liquid cleaning compositions, and especially compositions prepared for cleaning glass, still suffer a number of drawbacks which can limit their consumer acceptabil i Ly. Tney have to have good spotting/filming properties. In addition, they can suffer problems of product form, in particular, inhcm~ga,.a ~
lack of clarity, or inadequate viscosity characteristics, or excessiYe "solvent" odor for consumer uso.
An object of the present invention is to provide deLerg~n~
compositions which provide good glass cleaning without e~cas;l~;~
f;lming and~or streaking.
SUMMARY OF THE INV'NTTON
The present inYention relates to an aqueous, liquid. h~r~
surface detergent composition comprising: (a) ~wittor ~n c ~ ar-g~ont surfactant, containi~a a ationic group, ~r~erabl~ d qua~-ernary ammonium group, and an anionic group, preferably a car-boxylate, sulfonate, or sulfate group, more preferably a sulfonate group; (b) solvent/buffer system that comprises either mono-ethanolamine, beta-aminoalkanol which contains from about three to about six carbon atoms, or mixtures thereof, preferably mono-ethanolamine; (c) optional detergent builder; and the balancebeing (d) aqueous solvent system and, optionally, minor ingre-dients. The composition preferably does not contain amounts of materials, like conventional detergent builders, etc., that deposit on the surface being cleaned and cause unacceptable spotting/filming. The compositions can be formulated at usage concentrations, or as concentrates, and can be packaged in a container having means for creating a spray to make application to hard surfaces more convenient.
All percentages, parts, and ratios herein are "by weight"
unless otherwise stated.
DETAI~ED DESCRIPTTON OF THE INVENTION
In accordance with the present invention, it has been found that superior aqueous liquid detergent compositions for cleaning shiny surfaces such as glass contain zwitterionic detergent 3~ surfactant (containing both cationic and anionic groups in sub-stantially equivalent proportions so as to be electrically neutral at the pH of use, typically a least about 9.5, preferably at least about 10) and monoethanolamine and/or certain beta-amino-w O 91/lt505 2 ~ 7 ~ ~ ~ 3 PCT/US91/00337 alkanol compounds.
The Oeterqent Surfactant The aqueous, liquid hard surface detergent compositions (cleaners) herein contain from about 0.001% to about l5Y. of suit-able zYitterionic detergent surfactant containing a cationic grou~, o,~~f~rably a quaternary ammonium group, and an anionic arouo~ oreforably carboxylate, sulfate and/or sulfonate group, nure pr~r~rably sulronate. Successively more preferred ranges of 4~Ji~rionic detergent surfactant inclusion are from about 0.02%
o~ ' o,- iur,~actant, and from about 0.1~ to about 5% of n~.
~ arionic de~rgPn~ surfactants, as mentionPd herein-be;or~, contain both a cationic group and an anionic group and are in c~s~.~n ial electrical neutrality where the number of anionic oha-~-s rd c tionic charges on the detergent surfactant molecule are substantially the same. Zwitterionic detergents, which typic311y contain both a quaternary ammonium group and an anionic group selected from sulfonate and carboxylate groups are desirable since they maintain their amphoteric character over most of the pH
range of interest for cleaning hard surfaces. The sulfonate group is the preferred anionic group.
Preferred zwitterionic detergent surfactants ha~e the generic formula:
R3-~C(o)-N(R4)-~cR52)n]mN(R6)2(+)-(cR52)p-y(-) wherein each y is preferably a carboxylate (C00~) or sulfonate (S03-) group, preferably sulfonate; wherein each R3 is a hydro-CarDOIl, 2.9., an alkyl, or alkylene, group containing from about 8 to a~out 20, preferab7y from about lO to about 18, more preferably from about 12 to about 16 carbon atoms; wherein each (R4) is 3Q either hydlogen, or a short chain alkyl, or substituted alkyl, containing 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, prefer-ably methyl; wherein each (R5) is selected from the group con-sisting of hydrogen and hydroxy groups; wherein (R6) is like R4except Dreferably not hydroaen: wherein m is 0 or li and wherein e~ch n and p are a number from l to about 4, preferably from 2 to w o slttl505 ~ O ~ ~ 3 2 ~ PCT/US9l/00337 about 3, more preferably about 3; there being no more than about one hydroxy group in any (CR52) moiety. ~he R3 groups can be branched and/or unsaturated, and such structures can provide spotting/filming benefits, even when used as part of a mixture with straight chain alkyl R3 groups. The R4 groups can also ~e connected to form ring structures. Preferred hydrocarbyl amico-alkylene sulfobetaine (HASB) detergent surfactants wherein m - 1 and y is a sulfonate group provide superior grease ioi7 nemova, and/or filming/streaking and/or "anti-fogging" and!or perfume solubillzation properties. Such hydrocarbylamidoal~lene ~qtai;e~
and, aspec,ally, hydrocarbylamidoal'.iyleil2 iu7~obeLain~s an2 exceilent for use in hard surrac~ cleaning detargen~ composi~,oils, especially those formulated for use on both glass and hard-;o-remove soils. They are even better when used with monoethanol-amine and/or specific beta-amino alkanol as disclosed herein.
A more preferred specific detergent surfactant is a C10 14 fatty acylamidopropylene(hydroxypropylene)sulfobetaine, e~g., the detergent surfactant available from the Sherex Company as a 407.
active product under the trade name "Varion CAS Sulfobetaine."
~he level of zwitterionic detergent surfactant, e.g., HASB, in the composition is typically from about 0.001% to about 15%, preferably from about 0.05X to about 10%, more preferably from about 0.2% to about 57O. The level in the composition is dependent on the eventual level of dilution to make the wash solution. For glass cleaning, the composition, when used full strength, or wash solution containing the composition, should contain from about 0.02% to about 1%, preferably from about 0~05% to about 0~5%, more preferably from about 0.1X to about 0~25X, of detergent surfac-tant. For removal of difficult to remove soils like grease, the level can, and should be, higher, typically from about 0.1% to about 10%, preferably from about 0.25% to about 2%~ Concentrated products will typically contain from about 0~2% to about 10%, preferably from about 0.3~O to about 5X~ It is an advantage of the zwitterionic detergent, e.g~, HAS8, that compositions containing it can be more readily diluted by consumers since it does not interact with hardness cations as readily as conventional anionic detergent surfactants. Zwitterionic detergents are also extremely effective at very low levels, e.c., below about 1%.

w 0 9t/ll505 2 0 7 ~ ~ 2 3 PCT/US9l/00337 Other zwitterionic detergent surfactants are set forth at Col. 4 of U.S. Pat. No. 4,287,080, Siklosi, incorporated herein by r~.orence. Another detailed listing of suitable zwitterionic letergent surfactants for the detergent compositions herein can be ,~ur,d in U.S. Pat. No. 4,557,853, Collins, issued Cec. 10, 1985, ~n i ~or-;_d ~y re-,~erence herein. Commercial sources of such su,factants can be found in McCutcheon's EMULSIFIERS AND
n_ -~ ~E~!TS, Ncrth ~morican Edition, 1984, McCutcheon Di~ision, MC
Publishing Company, also incorporated herein by reference.
1l) ',he lb~ e p~tents ~nd referenc~ also disclose other detergent~:r'~ s, e.3., nl~n~,c, and ncnicnic detsrgPnt surfactants, ~ U1 ~,e ~Sa~J ill Slltal ~ dmOUilCS in the composition o; this i~n~:~nrion as coiur;ac~an~j.. TYPjCA1 of these are the alkyl~ and al;<~io~noxviate- (polyelhoxylate) sulfates, parafrin sul;onates, olerin sul;onates! alkoxylated (especially ethoxylated) alcohols ~nd alkyl phenols, alpha-sulfonates of fatty acids and of fatty acid esters, and the like, which are well-known from the deter-gency art. When the pH is above about 9.5, detergent surfactants that are amphoteric at a lower pH are desirable anionic detergent cosurfactants. For example, detergent surfactants which are CI2-cl8 acylamido alkylene amino alkylene sulfonates, e.g., compounds having the formula R-C~O)-NH-(C2H4)-N(C2H40H)-CH2CH(OH)CH2S03M wherein R is an alkyl group containing from about 9 to about 18 carbon atoms and M is a compatible cation are desirable cosurfactants. These detergent surfactants are avail-able as Miranol CS, OS, JS, etc. The CTFA adopted name for such surfactants is cocoamphohydroxypropyl sulfonate. It is preferred that the compositions be substantially free of alkyl naphthalene sulfonttes.
In general, detergent surfactants useful herein contain a - hydrophobic group, typically containing 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 detergent surfactants can be used in the form of their sodium, potassium or alkanolammonium, e.g., triethanolammonium salts; the nonionics generally contain from about 5 to about 17 ethylene oxide groups.

wo 9~ SoS 2 0 7 ~ 8 2 ~ PCT/US91/00337 C12-C1g paraffin-sulfonates and alkyl sulfates, and the ethoxy-lated alcohols and alkyl phenols are especially preferred in the compositions of the present type.
Some suitable surfactants for use in such cleaners are one or more of the following: sodium linear Cg-Clg al~yl benzene sulfo-nate (LAS), par~icularly Cll-C12 LAS; the sodium salt or a coconut alkyl ether sulfate containing 3 moles of ethylene oxide; the adduct of a random secondary alcohol having a range of alkyl chain lengths of from 11 to 15 carbon atoms and an average of 2 to 10 ethylene oxide moieties, several commercially availabl~ ~xampl3s of ;.hi;h arP Te;~gitol 15-S-3, Tergitol 15-S-~, Tergitol ;;-S-,, anà lergitol l~-S-9, a71 availa31e from Union Carbide Corporation:
the sodium and potassium salts Ot coconut fatty acids (coconu~
soaps); the condensation procuct of a straight-chain primary 1~ alcohol containing from about 8 carbons to about 1~ 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 of the preferred formulas:

~.
Rl - C - N(R2)2 wherein Rl is a straight-chain alkyl ~,roup containing from about 7 to about 15 carbon atoms and having an average carbon chain length of from about 9 to about 13 carbon atoms and wherein each R2 is a hydroxy alkyl group containing from 1 to about 3 carbon atomsi a ~witterionic surfactant having one of the preferred formulas set forth hereinafter; or a phosDhine oxide surfactant. Another suitable class of surfactants is the fluorocarbon surfactants, examples of which are FC-129, a potassium fluorinated alkylcar-boxylate and FC-170-C, a mixture of fluorinated alkyl polyoxy-ethylene ethanols, both available from 3M Corporation, as well as the Zonyl fluorosurfactants, available from DuPont Corporation.
It is understood that mixtures of various surfactants can be used.
'35 MONOETHANOLAMINE dND/OR 8ETA-AMINOALKANOL
Monoethanolamine and/or Deta-aminoalkanol compounds serve primarily as solvents when the -pH is above about 10.0, and w o 9t/1lSOS 2 ~ 7 4 ~ 2. 3 PCT/US91/00337 especially above about 10.7. They also provide alkaline buffering capaci Ly during use. However, the most unique contribution they ma~o is to improve the spotting/filming properties of hard surface cl~nlng compositions containing zwitterionic detergent surfac-a tanL~ here~s they do not provide any substantial improvement in spù~"~gjiilming wnen used with conventional anionic or ethoxy-la~od nonionic detergent surfactants. The reascn for the improve-me~ noi !~no~Yn. ;t is not simply a pH effect, since the ~m~r~emen~ ls not seen ~ h conventional a~kalinity sources.
~; , j""~" ;~ dl~ ~"~ Ire iolvents do not provide the same oeile, ~ anc ~,~,e e,-;ec~ can ae cir''erent depenaing upon the other e~ ; S i~ je~, '.Jnen pe?'.~'~ lei ~n L have a high percentage of 'Lerpenei are incorporated~ ~he benefit is greater for the beta-~ n,~i ?.minos~ ~nd thoV ~ro orten ~referrod~ ~heroas the mono-~ ~ h ~ j n - i s ~ ~ s ~ ? ~ d ~onoethanolamine and/or beta-alkanolamine are used at a level of from about 0.05% to about lO~, preferably from about 0.2% to about 5%. For dilute compositions they are typically present at a level of from about 0.05% to about 2X, preferably from about O.lX
to about 1.0%, more preferably from about 0.2% to about 0.7~/0. For concentrated compositions they are typically present at a level of from about 0.5Y0 to about 10%, preferably from about l~/o to about P~eferred bet~-aminoal~nols have a primary hydroxy group.
Suitable beta-aminoalkanols nave the formula:
R R

p~ ~ - C - 0~

wherein each R is selected from the group consisting of hydrogen and alkyl groups containing ~~rom one to four carbon atoms and the tot l o,~ carbon atoms in ~he compound is from three to six, preferably four. The amine group is preferably not attached to a primary carbon atom. More prer~erably the amine group is attached to a tertiary carbon atom to minimize the reactivity of the amine sroup. Specific preferred beta-aminoalkanols are 2-amino,l-W O 91/11505 ~ g ~'~ PCT/US91/00337 butanol; 2-amino,2~methylpropanol; and mixtures thereof. The most preferred beta-aminoalkanol is 2-amino,2-methylpropanol since it has the lowest molecular weight of any beta-aminoalkanol which has the amine group attached to a tertiary carbon atom. The beta-aminoal~anols preferably have boiling points below about 175-C.
~ne,'erauly, the boiling point is within about 5-C of 165-C.
Such beta-aminoalkanols are e~cellent materials for hard surr~ace cleaning in general and, in the present application, have c~rtain desirabla characteristics.
d,a ~a~a-aminoalkanols are surprisingly better than, e.g., monoeiilanoiamine for hard surrace detergent compositions that con~aia r~r,~ume ingredients li~e terpenes and similar mat~rials.
~owever~ normally the monoethanolamine is preferred for its efrect in im~rQving the spotting~filming oerformance of compositions conta~ning 7witterionic detergent surfactant~ The improvement in spotting/filming of hard surfaces that is achieved by combining the monoethanolamine and/or beta aminoalkanol was totally unexpected.
Cood spotting/f;lming, i.e., minimal, or no, spotting/film-ing, is especially important for cleaning of, e.g, window glass ormirrors where vision is affected and for dishes and ceramic surfaces where spots are aesthetically undesirable. Beta-amino-alkanols provide superior cleaning of hard-to-remove greasy soils and superior product stability, especially under high temperature conditions, when used in hard surface cleaning compositions, especially those containing the zwitterionic detergent surfactants.
Beta-aminoalkanols, and especially the preferred 2-amino-2-methylpropanol, are surprisingly volatile from cleaned surfaces considering their relatively high molecular weights.
The COSQ1 vent In order to obtain good cleaning without any appreciable amount of detergent builder, ~ne can use a cosolvent that has cleaning activity in addition to the monoethanolamine and/or beta-3j aminoalkanol. The cosolvents employed in the solvent/buffersystem in the hard surface cleaning compositions herein can be any of the well-kno~n "degreasing;' solvents commonly used in, for W O 91/t1505 2 ~ 7 4 ~ % 3 PCT/US91/00337 example, the dry cleaning industry, in the hard surface cleaner industry and the metalworking industry.
A us~ful definiticn of such solvents can be derived from the solubility parameters s set forth in "The Hoy," a publication of Union C~rbide~ incorporated herein by reference. The most useful - parameeer appears to be the hydrogen bonding parameter which is c~l C'll ~t~~ h~ th~ formula . l 1 0 ,~

Whei~~iil '~.J is ~n~ llyOrO9ei~ ao~ la parame~er~ ~ is the aggregation number.
~ C~ !c~ ~) , and d ~T is the solubility parame~er which is obtained from the formula ~T - (~H2s - RT)d M
where ~H2s is the heat of vaporization at 25-C, R is the gas constant (1.987 cal/mole/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 weight.
For the compositions herein, hydrogen bonding parameters are preferably less than about 7~J, more preferably from about 2 to about 7, and even more preferably from about 3 to about 6.
Solvents with lower numbers become increasingly difficult to solubilize in the compositions and hava a greater tendency to cause a haze on glass. Higher numbers require more solvent to provide good greasy/oily soil cleaning.
Cosolvents are typically used at a level of from about lY. to about 30%, preferably from about 2% to about 15%, more preferably from about 4X to about 8%. Dilute compositions typically have cosolvents at a level of from about 1% to about 10%, preferably from about 3% to about 6%. Ooncentrated compositions contain from - about 10% to about 30%, preferaDly from about 10% to about 20% of cosolvent.

WO 91/11505 PCl'/US91/00337 2~ ~ ~8%3 - lo -Many of such solvents comprise hydrocarbon or halogenated hydrocarbon moieties of the alkyl or cycloalkyl type, and have a boiling ~oint well above room temperature, i.e., above about 20-C.
The rormulator of compositions of the present type will be 5guided in the selection of cosolvent partly by the need to provide '~OG~ grea,e-cu~ g properties. and partly by aesthetic consid-erations. For example, kerosene hydrocarbons function quite well i~on yrPase cu~ting in the present compositions, but can be mal-~dor~us~ ~erosene must be axcPptionally clean before it can be 0uied~ a'i'~il in cvr,im~rcial situations. For home use, where malodors ~ul noc oe ~olera~Pà. the formulator would be more likely to ~ s sol~ian;s ~.~h',c'l have a rela~ively pleasant odor, or odors .~hic'l can be reasonably modified by perfuming.
The C,-~-09 al~vl aromatic solvents. esoPcially the C~-~g al'~<yl ~on ~nos pr~farably cctyl ben2ene, exhibit excellent grease removal properties and have a low, pleasant odor. Likewise, the olefin solvents having a boiling point of at least about lOO-C, especially alpha-olefins, preferably l-decene or l-dodecene, are excellent grease removal solvents.
20Generically, the glycol ethers useful herein have the formula R6 o~R70~mH wherein each R6 is an alkyl group which contains from about 3 to about 8 carbon atoms, each R7 is either ethylene or propylene, and m is a number from 1 to about 3. The most pre-ferred 97ycol ethers are selected from the group consisting of monopropyleneglycolmonopropyl ether, dipropyleneglycolmonobutyl ether, monopropyleneglycolmonobutyl ether, diethyleneglycolmono-hexyl ether, monoethyleneglycolmonohexyl ether, monoethylenegly-colmonobutyl e~her, and mixtures thereof.
A particularly preferred type of solvent for these hard surface cleaner compositions comprises diols having from 6 to about 16 carbon atoms in their molecular structure. Preferred diol solvents have a solubility in water of from about 0.1 to about 20 9/'OO 9 of water at 20-~
Some examples of suitable diol solvents and their solubil-ities in water are shown in Table 1.

W o 91/11505 2 ~ 7 ~ PCT/USsl/00337 Solubilitv of Selected Diols in 20'C ~ater Solubility Diol(q/100~ H20 1,4-Cyclohe~anedimethanol 20.0*
2,5-DimeLhyl-2,5-hexanediol 1~.3 2-Phenyl-1,2-oropan~diol 12.0*
Phenyl-1,2-ethanedioi 12.0*
2-Ethyl-1,3-hexan2dlol 4.2 2~ T,i~ e~ ; i.9 i~2-~ctanediol 1.0*
~Oeterminea ~iia ' i~O!'_'~O ~ ~ m.~as ~r:~me(l ~S .
All other values are ;rom oublished literature.
i5 The diol solvents are ~speciall; pre,~er,ed be;ause, in addi-tion to good grease cutting ability, they impart to the compo-sitions an enhanced ability to remove calcium soap soil$ from surfaces such as bathtub and shower stall walls. These soils are particularly difficult to remove,' especially for compositions which do not contain an abrasive. The diols containing 8~12 carbon atoms are preferred. The most preferred diol solvent is 2,2,~-trimethyl-1,3-pentanediol.
Solvents such as pine oil, orange terpene, benzyl alcohol, n-hexanol, phthalic acid esters of Cl ,l alcohols, butoxy propanol, Butyl Carbitol~ and 1(2-n-butoxy-1-methylethoxy)propane-2-ol (also called butoxy propoxy proDanol or dipropylene glycol monobutyl ether), hexyl diglycol ~Hexyl Carbitol~), butyl triglycol, diols such as 2,2,4-trimethyl-1,3-pentanediol, and mixtures thereof, can be used. The butoxy-propanol solvent should have no more than about 20%, pre~erably no more than about 10%, more preferably no more than about 7%~ of the secondary isomer in which the butoxy group is attached to the secondary atom of the propanol for improved odor.
The Cobuffer~AlkalinitY-Source The solvent/buffer system is formulated to give a pH in the product and, at least initiallv, in use of from about 9.5 to about 13, preferably from about ~.7 ~o about 12, more preferably from about 9.7 to about 11.5. ~H is usually measured on the product.-w O 91/11505 ~ 0 7 ~3,~J~ PCT/US91/00337 The buffering system comprises monoethanolamine and/or beta-aminoa,'<anol and, optionally, but preferably, cobuffer and/or al!~aline m~terial selPcted from the group consisting of: ammonia;
o':ler v~ al'xanoiamines; alkaîi metal hydroxides; silicates;
~;-aC25: c,rbona;es; andior bicaroonates; and mixtures thereof.
~ U ,_''O''''n!.'5/ a ~ a~erials are alkali metal hydroxides. The level of ~he cobuffer/alkal;nity-source is from ~ Ji .'nemi ~ 0 a~out 5~0. Monoethanolamine and,/or ~ata-~minoal'can~l bur,ering material, in the system is iC ~e ~n~~ ;Im~3~ is surpristng that mono-~r~ "~ ov~d spotting/~
,''; '' ~;' -, ~i: 1 'ni' ~ '~''llC de~ergent surfac-ant~
nt S~:st~m ~he ~a,a,lc~ ;ne ,ormuia is ;ypically water and non~aqueous lS ooiar c~lven~s with onlv minimal cleaning action like methanol, ethanol~ isopropanol, ethylene glycol, propylene glycol, and mixturos thereor. The levol of non-aqueous polar solvent is greater when more concentrated formulas are prepared~ Typically, the level of non-aqueous polar solvent is from about 0.5% to about 20 40y., preferably from about 1% to about 10% and the level of water is from about 50% to about 99%, preferably from about 75~ to about 95X.
O~tional Tnqredients The comoositions herein can also contain other various 2; adjuncts which are known to tne art for àetergent compositions.
Preferably they are not used at levels that cause unacceptable spotting,~filming. Nonlimitin.g examples of such adjuncts are:
Enzy~.es such as prcsaasas:
Hydrotropes such as sodium toluene sulfonate, sodium cumene sulfonate and potassium xylene sulfonate; and Aesthetic-enhancing ingredients such as colorants and per-fumes, providing they do not adversely impact on spotting/-filminq in the cleaninG of alass. The perfumes are prefer-ably those that are more water-soluble and/or volatile to 3S minimi~e spotting and filming.
~n;i3acterial agents can ue Dresent, but preferably only at low 1eveis tO avoid spotting!filming problems. More hydrophobic WO 91/1 1505 . PCT/US91/00337 . ' 2 ~ 7 L~

antibacterial/germicidal agents, like orthobenzyl-para-chloro-phenol, are avoided. If present, such materials should be kept at levels below about 0.1%.
Deteraent ~uilder An optional ingredient for general cleaning purposes, is from 0% to about 30%, prereraDly ,~rom abou~ to a~ou; I5~o~ ~ore preferably from about 1% to about 12%, of detergent builder. For use on glass and/or other shiny sul~iâceâ~ a l~vel o, ~uilder of from about 0.1% to about O.5YO, preferably from about 0.1~, to ~bout 0.2%, is useful. While any of t,~e ~uil~ers e~ '.n~'ng2,7i_ sal~; Cln ~e used herein, scme exa~ s o;~ ~ui,d~nà ~O~~ u je har~irl arP
sodium nitrilotri~cetate~ ~o~ass~ ;'J',''~nOS'?aa'~, yO~SSlU~
tripolyphosphate, sodium ~r po~assium e;~a~e~ ydroxyl-1,1-di-phosphonate. the nonphosDhorouâ chelat~,na agents describQd in the copending U.S. Pat. Application of Culshaw and Yos, Ser. No.
285,337, filed Dec. 14, 1988, said application being incorporated herein by reference (e.g., carboxymethyltartronic acid, oxydi-malonic acid, tartrate monosuccinic acid, oxydisuccinic acid, tartrate disuccinic acid, and mixtures thereof), sodium citrate, sodium carbonate, sodium sulfite, sodium bicarbonate, and so forth.
Other suitable builders are disclosed in U.S. Pat. No.
4,769,172, Siklosi, issued Sept. 6, 1g88, and ;ncorporated herein by reference, and chelating agents having the formula:

R - N

wherein R is selected from the sroup consisting of:
-CH2CH2CH20H; -CH2CH(OH)CH3; -CH2CH(OH)CH20H;
-CH(CH20H)2; -CH3; -CH2CH20CH3; -C-CH3; -CH2-C-NH2;
O O
-CH2CH2CH20CH3; -C(CH20H)3; and mixtures thereof;
and each M is hydrogen or an al~ali metal ion.
Chemical names of the acid form of some chelating agents useful herein include:
N(3-hydroxypropyl)imino-N~N-diacetic acid (3-HPIDA);
N(-2-hydroxypropyl)imino-N.N-diacetic acid (2-HPIDA);

w O 91/11505 ~ ~) 7 ~ J ~' PCT/US91/00337 N-glycerylimino-N,N-diacettc acid (GLIDA);
dihydroxyisopropylimino-(rl~1)-diacotic acid (DHPIDA);
methylimino-(N,N)-diacetic acid (MIDA);
2-methov~ thylimi;,o~ diacetic acid (,lEIDA);
a""doim,nodlace~ic ;ld (also ~no;in as sodiu~ amidonitrilo~

acetamidoiminodiacetic acid (AIDA);
,-"met.ho~yrjrooyl-";tiao-'',!l-;, ace' c ~cid M~~P~DA); and tris(hydroxyme~hyl)methylimino-N~-diacetic acid (TRIDA).
~2~.10dS 0~' Or?ltr'.''iOi~ '.' e;le imiia~ldiace-~,c derivatives ~C~ùS~~S ~ S~ r~ .W.r' a!i~ ;L'.~1;
~"ei". ''I~Sl~; .-(') a. ~ ,iayer, ~iecanska el al., publica~ion o; ~lar. 2O~ 1379~ ror GLIDA;
C.A. 104(6)450O2 d ;or ~'lIDA: and Biochemistry ;, p. 467 (196O) for AIDA.
The levels of builder present in the wash solution used for glass should be less than about 0.5Y., preferably less than about 20 0.2YTherefore, dilution is highly preferred for cleaning glass, while full strength use is preferred for general purpose cleaning.
Other effe~tive detergent builders, e.g~, sodium citrate, ~ sodium ethylenediamine'tetraacetate~ etc., can also be used, preferably at lcwer levals, e.3., frcm about O.l~o to about 1%, preferably from àbout 0.1~fi ;o a~out O.5'~.
Inclusion of a detergent builde-r improves cleaning, but harms spotting and filming and has to ~e considered as a compromise in favor of cleaning. Inclusion of a detergent builder is optional and low levels are usually more preferred than high levels.
Perrumes Most hard surface cleaner products contain some perfume to provide an olfactory aesthetic benefit and to cover any "chemical"
odor that the product may have. The main function of a small fraction of the highly volatil . low boiling (having low boiling points), perfume components ir, ~hese perfumes is to improve the fragrance odor of the product i self, rather than impacting on the subsequent odor of the surfac~ 3eing cleaned. However, some of WO 91/11505 2 0 7 4 ~ 2 ~ PCI'/US91/00337 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. It is a special advantage of this invention th~t perfume ingredients are readily solubilized in the composi~ions by the acylamidoalkylene detergent surfactant. Oth~r s,mil~r ~a~
gent surfactants will not solubilize as much perfume, especially substantive perfume, or maintain uniformity to the same low temperature.
10The perfume ingredients and compositions Oc 'his ,nven~io~
are the conventional ones known in the art. Selec~ on of ~y p~rfume component, or amcunt of per,u~ ~ a~ s,'~
aesthetic considerations. Suitable ~erfume ccmpounds ar.~ c3mpo-sitior,s can be found in 'ho ar~ includir,s ~ ~ ?a~. ,loi.:
154,145,184, Brain and Cummins, issued Mar. 20. 1~379; 4,209.417, Whyte, issued ~une 24, 1980i ~515.705. Moeddel, issued May 7, 1985; and ~,152,272, Young, issued May 1, 1979, all of said patents being incorporated herein by reference. Normally, the art recognized perfume compositions are not very substantive as described hereinafter to minimize their effect on hard surfaces.
In general, the degree of substantivity of a perfume is roughly proportional to the percentages of substantive perfume material used. Relatively substantive perfumes contain at least about 1~., preferably at least about lO~o~ substantive pertume materials.
Substantive perfume materials are those odorous compounds that deposit on surfaces via the cleaning process and are detect-able by people with normal olfactory acuity. Such materials typically have vapor pressures lower than that of the average perfume material. Also, they typically have molecular weights of about 200 or above, and are detectable at levels below those of the average perfume material~
Perfumes can also be classified according to their volatil-ity, as mentioned hereinbefore. The highly volatile, low boiling, perfume ingredients typically have boiling points of about 250-C
or lower. Many of the more m,oderately volatile perfume ingre-dients are also lost substantially in the cleaning process. The W O 91/11505 ~ ~ 7 ~ ~ ~ 3 PCT/US91/0033~

moderately volatile perfume insredients are those having boi1ing points of from about 250~C to about 300-C. The less volatile, high boiling, perfume ingredisnts referred to hereinbefore are those having boil ing pOi"~.S 0,' ~o; ' ~~U'0~C 0,~ highqr. ~ signifi~
S cant portion of '?~/~.?~ '.h?~? '~;''h 'O' 1 innJ ~er~Umm'? ingredients,considerc?-. ~o o ? i'~ '~': :.': ' ' ' ' '. ''''~ O ' ' .'? ''; ?S'~
and it is desirabie ;o have me_lls ~o retain more Ot ~hese ingre-dients on the d,~y c:~r~ an\~ o~ ';? oqrfum~.q insrqdiqnts, along with th.qir oào, cnal aC~C-ï ~ and ~qi,~ physicàl and chemical 10 pro~q, ti~s, s~c~ ? ~ /eil ln "Perrul~e a,l~i ri~~ r ~ ?~n~ t.qff?n ~rct~?~q~ h ~ . r~ J, referenc~.

lS oients are: anec~oi , ~ , a.ven~ve~ o_n.J'i aC~alte~ b~nzyl alcohol, benzyl forma~e, ~,so-vcrnyl 3C~lt', cl~phene, cis-citral (neral), citronellal, ci~ronellol, ;iLronellyl aceta~e, para-cymene, decanal, dihydrolinalool, dihydromyrcenol, dimethyl phenyl carbinol, eucalyptol, geranial, geraniol, geranyl acetate, geranyl nitrile, cis-3-hexenyl acetate, hydroxycitronellal, d-limonene, linalool, linalool oxide, linalyl acetate, linalyl propionate, methyl anthranilate, alpha-methyl ionone, methyl nonyl acetalde-hyde, methyl phenyl carbinyl acetate, laevo-menthyl acetate, menthone, iso-menthone~ mvrcene~ myrcenyl acetate, myrcenol, nerol, neryl acetate, nonyl ace ~tee, pnenyl ethyl 21 cohol, alpha-pinene, beta-pinene, gamma-;erpinene, alpha-terpineol, beta-ter-pineol, terpinyl acetate, and verteneY (para-tertiary-butyl cyclohexyl acetate)~ Some nat~. 21 oils also contain large per-centages of highly volatile perfume ingredients. For example, lavandin contàins as major components: linalool; linalyl acetate;
geraniol; and citronellol~ Lemon oil and orange terpenes both contain about 957O of d-limonene.
Examples of moderately vola~ile perfume ingredients are: amyl cinnamic aldehyde, iso-amyl salicylate, beta-caryophyllene, cedrene, cinnamic alcohol, coumarin~ dimethyl benzyl carbinyl acetate, ethyl vanillin, -u -ol, iso- eugeno1, '~1 or acetate, heliotropine, 3-cis-nexenyl -~a~. cyla~e~ ne~yl salicylate, lilial W o 91/11505 2 ~ 7 s g ~ ;i PCT/US91/00337 (para-tertiarybutyl-alpha-methyl hydrocinnamic aldehyde), gamma-methyl ionone, nerolidol, patchouli alcohol, phenyl hexanol, beta-selinene, trichloromethyl phenyl carbinyl acetate, triethyl citrate, vanillin, and veratraldehydP. Cedarwood terpen4s ar4 composed mainly of alpha-cedrene, beta-cedrene, and other C
sesquiterpenes.
Examples of the less volatile, high boiling, perfume ingre-dients are: benzophenone, benzyl salicylate, ethylene brassyl~t4, galaxolide (1,3,4,6,7,8 hexahydro-4,6,6,7,8,8-hexamethyl-cyclo-penta-gama-2-benzopyran), hexyl cinnamic aldehyde, l~~~al (~
hydroxy-4-methyl pentyl)-3-cyclohexene-10-carboxaldehv~e!. ~et,~yl c~d,ylone, methyl dihydro ~asmonate, mothyl-b~tA-nap~,thyl '~~t~
musk indanone, musk ketone~ musk tibetene, and phenylath~l ph n,~i acetate.
lS Selection of any particular perfume ingredient is primari1y dictated by aesthetic considerations, but more water-soluble materials are preferred, as stated hereinbefore, since such materials are less likely to adversely affect the good spotting/-filming properties of the compositions. If the terpene types of perfume ingredients are used, the beta-aminoalkanols are preferred for product stability.
These compositions have exceptionally good cleaning prop-erties. They can also be formulated to have good "shine" prop-erties, i.e., when used to clean glossy surfaces, without rinsins.
The compositions can be formulated to be used at full strength, where the product is sprayed onto the surface to be cleaned and then wiped off with a suitable material like cloth, a paper towel, etc. They can be packaged in a package that com-prises a means for creating a spray, e.g., a pump, aerosol pro-pellant and spray valve, etc.
The invention is illustrated by the following Examples.

wo 91/1 1505 2 0 7 ~ ~ 2 ~ Pcr/us9l/0033?z EXAMPLE I
Formula No.* ('.~t.~.~
Inqred;ent 1 2 3 4 Propylene Glycol Mono-butylether ~.C .0 2.0 2.0 Isopropanol Cocoamidopropyl (Hydroxy-propyl)sulfobetaine 0 1~ 0 1 ~ .15 Monoethanolamine l~C ~ - -1-amino-2-propanol 2-amino-1-butanol - - ~; n 2-~mino-2-~etbyl-1-~u~n~
Perfume ~ C.'C
DPioni-eà '.~ater q~ a~
li *pH adjusteà tO aavU; .1~3 .XA~lPIE li Formula No~ (Wt.oi.) Inqredient 1 2 3 Lauryl-dimethYl~3-sulfopropylbetaine 0.20 Cocoyl-dimethyl-2-hydroxy-3-sulfopropylbetaine - 0.20 Lauryl-dimethyl-betaine - - 0.20 Cocoamidipropyl-dimethyl~
betaine Cocoamidopropyl-dimethyl-~-hydroxy-3-sulfopropylbetaine Sod,um Alkyl (-C13) Sulfa~e 2-Amino-2-methyl-1-propanol Monoethanolamine 0.5 0.5 0.5 Propylene Glycol Mono-butylether 3.0 3.0 3.0 Isopropanol 3.0 3.0 3.0 35' Deionized Water and Minors (e.g., Perfume) q~s. q.s. q.s.
*All pH's adjusted 'o -bout 10~9 W 0 91/11505 2 0 7 ~ 8 ~ ~ PCT/US9t/00337 . -~ .

- 19 - .
EXAMPLE II (Continued) tormula No.* (Wt.~o) Inqredient 4 5 6 Lauryl-dimethyl-3-sulfopropylbetaine Cocoyl-dimethyl-2-hydroxy-3-sulfopropylbetaine Lauryl-dimethyl-betaine - -Cocoamidipropyl-dimethyl-betaine 0.20 Cocoamidopropyl-dimethyl-2-hydroxy-3-sulfopropylbe-aine - 0.20 O.i~
Sodium Alkyl (-Cl3) Sulfate - - 0.02 2-Amino-2-methyl-1-propanol Monoethanolamine 0.5 0.5 0,5 Propylene Glycol Mono-butylether 3.0 3,0 3.0 Isopropanol 3.0 3.0 3.0 Deionized Water and Minors (e.g., Perfume) 4.s. g.s. g.s.
*All pH's adjusted to about lO.9 W O 91/llS05 PCT/~IS91/00337 2 ~

EXAMPLE Tl (Continued) For~ul a ~n. '~ ('J, .~'~
Inaredient 1 8 9 Lauryl-dimethyl-3-sulfopropylbetaine Cocoyl-dimethyl-2-hyaro~y-3-sulfopropylbetaine Lauryl-dimethyl-betaire -Cocoamidipropyl-dimethyl-betaine Cocoamidcpropyl~d~methyl~~-hydroxy-~-iull~opropy,~a Sodium Alkyl (-C13) Sul,~a~ - -2-amino-2-methyl-i-proodnoi ,~
Monoethanolamine - o.
Propylene Glycol Mono-butylether 3.0 4.0 Ethylene Glycol Monobutylether - 3.0 Isopropanol 3.0 2.0 3.0 Deionized Water and Minors (e.g., Perfume) q.s. q.s. q.s.
~AIl pH's adjusted to about 10.9 W O 91/11505 2 ~ 7 ~ 8 2 ~ PC~/US91/00337 EXAMPEE Il (Continued) Formula No.* (Wt.%) Inqredient 10 11 12 Lauryl-dimethyl-3-sulfopropylbetaine Cocoyl-dimethyl-2-hydroxy-3-sulfopropylbetaine Lauryl-dimethyl-betaine Cocoamidipropyl-dimethyl-betaine Cocoamidopropyl-dimethyl-2-~vdroxy-3-sulfopropylbetaine 0.19 0.15 0.18 Sodium Alkyl ~-C13) Sulfate - - -2-~mino-2-methyl-1-propanol 0.5 - 1.0 ~onoethanolamine - 0.5 Propylene Glycol Mono-butylether 4.0 - 3,0 Ethylene Glycol Monobutylether - 3.0 Isopropanol 2.0 3.0 3.0 Deionized Water and Minors (e.g., Perfume) q.s. q.s. q.s.
*All pH's adjusted to about 10.9 The following example shows the Filming/Streaking performance for ~arious formulations including the preferred zwitterionic/-alkanolamine combinations.

EXAMPLE III
Formula No,* (Wt.%) Inqredient 1 2 3 Ralufon~ DL 0.20 0.20 0.20 Monoethanolamine - 0,5 0.5 Isopropanol - - 3,0 Propylene Glycol Mono-butylether Sodium Hydroxide Deionized Water q.s. q.s. q.s.

w o 91/11505 ~ 3 2 :3 PCT/US91/00337 Ralufon~ DL (Raschig ~orp.) is Lauryl-dimethyl-ammonium-3-sulfopropyl 3-(lauryl,dimethyl,ammonium)-propylsulfonate) *pH adjusted to 10.8 with NaO~, this matcles ~e~ ~l or the products wi~h monoetilanollline in EXAMP~E Ili (Continued) Formul~ l'lo.t Inqredient Ralufon~ DL ~.~a ~ ,u.
~ Monoethanolamine Isopropanol ~.3 Propylene Glvcol ~lono-~utylether Sodium Hydroxide - ~ - ~
Deionized Water q.s. q.s. q.s. g.s Ralufon~ DL (Raschig Corp.) is Lauryl-dimethyl-ammonium-3-sulfopropyl 3~(1auryl,dimethyl,ammonium)-propyl-sulfonate) *pH adjusted to 10.8 with NaOH, this matches the pH of the products with monoethanolamine in them.
In Example III, the following test was used to evaluate the products' performance.
Filminq/Streakinq Stress Test Procedure:
A paper towel is folded into eighths. Two milliliters of test product are applied to the upper half of the folded paper - towel. The wetted towel is applied in one motion with even pressure from top to bottom of a previously cleaned window or mirror. The window or mirror with the applied product(s) is allowed to dry for ten minutes before grading by expert judges.

WO 91/11505 2 0 ~ 4 8 2 3 PCI'/US91/00337 . ~ , . ~

Grading:
Expert iudges are employed to evaluate the specific areas of product application for amount of filming/streaking. A numerical - value describing the amount of filming/streaking is assigned to each product. For the test results reported here a 0-10 scale was used.
0 ~ No Filming/Streaking 10 ~ Poor Filming/Streaking Room temperature and humidity have been shown to influence filmingtstreaking. Therefore these variables are always recorded.
Filminq/Streakinq Stress Test on Glass Windows tFour Replications at 73-F and 537~ Relattve Humidity) Formula Mean No. Ratinq 1 3.8 2 0.3 3 0.4 4 1.0 5.4 6 7.3 7 8.2 The least significant difference between mean ratings is 0.8 at - 957. confidence level.

Claims (13)

1. An aqueous liquid hard surface detergent composition comprising: (a) zwitterionic detergent surfactant; (b) solvent/buffer system that comprises monoethanolamine and/or beta-aminoalkanol containing from three to about six carbon atoms; and (c) the balance being an aqueous solvent system and minor ingredients.

2. The composition of Claim 1 wherein (b) is monoethanolamine.

3. The composition of Claim 2 wherein the anionic group in said zwitterionic detergent surfactant (a) is a sulfonate group and (b) is present at a level of from about 0.001% to about 15%.

4. The composition of Claim 3 wherein said detergent surfactant (a) comprises from about 0.02% to about 10%
hydrocarbyl-amido-alkylenesulfobetaine which has the formula:
R3-C(O)-N(R4)-(CR52)n-N(R6)2(+)-(CR52)p-SO3(-) wherein each R3 is an alkyl, or alkylene, group containing from about 10 to about 18 carbon atoms, each (R4) and R6) is selected from the group consisting of hydrogen, methyl, ethyl, propyl, hydroxy substituted ethyl or propyl and mixtures thereof, each (R5) is selected from the group consisting of hydrogen and hydroxy groups, and each n and p is a number from 1 to about 4; with no more than about one hydroxy group in any (CR52) moiety.

5. The composition of Claim 2 wherein said detergent surfactant (a) comprises from about 0.001% to about 15%
hydrocarbyl-amido-alkylenebetaine which has the formula:
R3-C(O)-N(R4)-(CR52)n-N(R6)2(+)-(CR52)n-COO(-) wherein each R3 is an alkyl, or alkylene, group containing from about 10 to about 18 carbon atoms, each (R4) and (R6) is selected from the group consisting of hydrogen, methyl, ethyl, propyl, hydroxy substituted ethyl or propyl and mixtures thereof, each (R5) is selected from the group consisting of hydrogen and hydroxy groups, and each n and p is a number from 1 to about 4; with no more than about one hydroxy group in any (CR52) moiety.

6. The composition of Claim 1 wherein the level of detergent surfactant is from about 0.001% to about 15%.

7. The composition of Claim 1 wherein said detergent surfactant comprises from about 0.001% to about 15% zwitterionic detergent surfactant which has the formula:
R3-[C(O)-N(R4)-(CR52)n-]mN (R6)2(+)-(CR52)p-Y(-) wherein each R3 is an alkyl, or alkylene, group containing from about 10 to about 18 carbon atoms, each (R4) and (R6) is selected from the group consisting of hydrogen, methyl, ethyl, propyl, hydroxy substituted ethyl or propyl and mixtures thereof, each (R5) is selected from the group consisting of hydrogen and hydroxy groups, with no more than about one hydroxy group in any (CR52) moiety; m is 0 or 1: and each n and p is a number from 1 to about 4.

8. The composition of Claim 7 wherein y is a sulfonate group, said R3 group contains from about 9 to about 15 carbon atoms, R4 is hydrogen, each R6 is methyl, one of the R5 groups between the (+) and the (-) charge centers is a hydroxy group and the remaining R5 groups are hydrogen, and each n and p is 3.

9. The composition of Claim 7 containing at least one cosurfactant.

10. The composition of Claim 1 wherein said detergent surfactant (a) comprises from about 0.02% to about 10%
hydrocarbyl-amido-alkylenebetaine which has the formula:
R3-C(O)-N(R4)-(CR52)n-N(R6)2(+)-(CR52)p-COO(-) wherein each R3 is an alkyl, or alkylene, group containing from aboùt 10 to about 18 carbon atoms, each (R4) and (R6) is selected from the group consisting of hydrogen, methyl, ethyl, propyl, hydroxy substituted ethyl or propyl and mixtures thereof, each (R5) is selected from the group consisting of hydrogen and hydroxy groups, and each n and p is a number from 1 to about 4; with no more than about one hydroxy group in any (CR52) moiety.

11. The composition of Claim 1 containing sufficient buffer/-alkalinity-source to give a pH of from about 9.5 to about 13.

12. The composition of Claim 11 wherein said pH is from about 9.7 to about 12.

13. The composition of Claim 1 wherein said cobuffer/alkalinity-source is alkali metal hydroxide to give a pH of from about 9.7 to about 11.3.