CA2176695A1

CA2176695A1 - Liquid hard surface detergent compositions containing specific builders

Info

Publication number: CA2176695A1
Application number: CA002176695A
Authority: CA
Inventors: Ronald Anthony Masters; Michael Stephen Maile; David Charles Underwood; Michael Joseph Kupneski; Timothy Clair Roetker
Original assignee: Individual
Current assignee: Procter and Gamble Co
Priority date: 1993-12-30
Filing date: 1994-12-15
Publication date: 1995-07-06
Also published as: WO1995018210A1; EP0737243A1; US5531933A; AU1306495A

Abstract

Aqueous, liquid hard surface detergent compositions having improved cleaning and good filming/streaking characteristics contain specific polycarboxylate detergent builders at critical levels. Preferred formulas contain a zwitterionic/anionic detergent surfactant mixture at levels (e.g., from about 0.02 to about 15 %); hydrophobic solvent; alkaline material, especially volatile alkaline materials comprising monoethanolamine or certain beta-amino-alkanol compounds and salt of ethylenediaminetetraacetic acid as the detergent builder in levels (e.g., from about 0.05 % to about 0.5 %, by weight of the composition).

Description

~ WO 95/18210 2 1 7 6 G q 5 Pcr/uss4/l4295 LIQUID HARD SURFACE DETER~ENT COMPOSITIONS
CONTAINING BUILDERS

This is a co.~ ;on-in-part of application Serial No. 08/175832, filed on Dece"~e, 30, 1993.
~LD OF THE INVENTION
This invention pe.k--ns to li~uid d~L~.~. .Il compositions for use in rle~l-;..g hard ~ .ces. Such compositions typically contain dctel~e"l surf~rt~ntc, solvents, builders, etc.
BACKGROIJND OF THE INVENTION
The use of solvents and organic water-soluble syl~ c deler~e~ll SUl r,~ ,., C atlow levels for cle~nin~ glass are known.
Known liquid dete.~.,." compositions co,.".,ise certain organic solvents, deh.~ L surf~ct~nt~ and optional builders and/or abrasives. The prior art, however, fails to teach, or l ~cG~ , the advantage of specific builders at critical levels disclosed h~ ,.n~l~,r, in liquid hard surface cleaner formul~tionc Liquid rle~nin8 co..-po~ ns have the great advantage that they can be applied 25 to hard ~.l.r~ces in neat or CQl)cç~ led form so that a relatively high level of, e.g., surfactant material and/or organic solvent is delivered directly to the soil. Thererul e, liquid ~ 9 co,,,l~o~;l;orlC have the pole"L;al to provide superior soap scum, grease, and oily soil removal over dilute wash solutions p,~,l)a~d from powdered cle~ning . c~",~os;~ .c.
The inclu~;on of d~el~,.,l builders in li~uid hard surface rle~nin~ compositionsincrea3es the pot~,.,Lial to provide superior cle~nirl~ However, in the past, the inclusiQ~ of such dele.35~ builders has usually produced unacceptable results for WO 9S/18210 PCTJUS94/14295 ~

filminglstreaking. The inclusion of detergent builders has therefore been considered a compromise in favor of cle~ning Liquid r,lç~ning compositions, and especially compositions prepared for r lf ~ning glass, need eY. çptinnally good filming/streaking properties. In addition, they 5 can suffer problems of product form, in particular, inhomogeneity, lack of clarity, or excessive "solvent" odor for concl.mer use.

Sll~fMARY OF THE INVENTION
The present invention relates to an aqueous, liquid, hard surface delt;lge., 10 composition having improved clç~ning and good filming/streaking Ch&l~-;L~ ic co~ lising. (A) det~ enl surfactant selected from the group concicting of anionic surf~ct~nts, al~lphol-lic delergenl surf~ct~nts inf;lufling zwitterionic surf~ct~ntc; and mixtures thereof; (B) hydrophobic solvent; (C) ~lk~line material; (D) delelge., builder selected from the group consisLing of ethyle.~ç.li~...;nelel.~acetic acid, citric acid, N-(2-h~d~(,~eLIlyl)-imino~ cetic acid, N-(2-hydroxypropyl)-iminodiacetic acid, N-diethyleneglycol-N,N-diacetic acid, carboxymethylsuccinic acid, nitrilotriactetic acid, and mixtures thereof; and (E) the balance being an aqueous solvent system Cf~ illg water and, optionally, non-aqueous polar solvent with only minim~l rlrA~ g action s~le~,led from the group co~ of m.oth~nol, ethanol, isoplupanol, ethylene glycol, polypropylene glycol, glycol ethers having a hydrogen bonding pa~lwh. of greater than 7.7, and Il~Lul~s thereof and any minor ingredients. Thecompositions can be form~ ted at usage conce~L~Iions, or as concenl,dles, and can be pa~l ~ged in a co~ er having means for creating a spray to make application to hard surfaces more convenient.
All pe.cenlages, parts, and ratios herein are "by weight" unless otherwise stated.

~ WO95/18210 2 1 766q5 PCTtUS94/14295 DETAILED DESCRIPTION OF THE INVENTION
In accordance with the present inventio4 it has been found that superior aqueous liquid d~lelgc.ll compositions for rle~ning shiny surfaces such as glass contain (A) dele gelll surfactant selected from the group con~isting of anionic surf~ct~nt~, amphoteric delelge,ll surf~ct~nts inc1urlin~ zwitterionic surf~ct~nt~; and mixtures lhc.eur, p~efel~bly, C6-Clo "amphocarboxylate" detergent surfactant, zwitterionic dele~elll surfactant (co.~ .;,.g both cationic and anionic groups in subst~nti~lly equivalent prol)olLions so as to be electrically neutral at the pH of use), or mixtures thereof; (B) hydlophobic, volatile, cle~ning solvent; (C) alkaline buffer, preferably monoeth~nol~mine or certain beta-amino-alkanol compounds as defined heleinan~l, (D) critical level of specific polycarboxylate detergent builders such as ethylene ;n9 tetraacetic acid (EDTA), citric acid, or nitrilotriacetic acid (NTA) at a pH of at least about 9.5, preferably at least about 10; and (E) the balance being an ~queous solvent system cGlllplisin~ water and, optionally, non-aqueous polar solvent with only minim~l cle~ P action sfle~led from the group consislil.g of l.~e~ -ol, ethanol,isopropal-ol, ethylene glycol, polypropylene glycol, glycol ethers having a hydrogen bonding pa,~ Ler of greater than 7.7, and mixtures thereof.
(A) THE DETERGENT SURFACTANT
(1) The Amphocarboxylate Detergent Surfactant The ~queou~ liquid hard surface detergent compositions (cleaners) herein can contain from about 0.001% to about 1%, pl~r~l~bly from about 0.01% to about 0.5%, more preferably from about 0.02% to about 0.2%, and even more preferably from about 0.03% to about 0.08%, of C6 l0 short chain amphocarboxylate detergent ~u~r~ L. It has been found that these ~mphoc~rboxylate, and, espe~i~lly gly~,;llale, d~terge.ll surf~ct~nts provide good cle~ninE with superior filming/streaking for- detergent compositions that are used to clean both glass and/or relatively hard-to-remove soils. Despite the short chain, the detergency is good and the short chains WO 95/18210 PCTIUS94/14295 ~--provide improved filming/streaking, even as con,pared to most of the zwitterionic deler~,e,.~ surf~ct~ntc described hereinafter. Depending upon the level of cle~ning desired and/or the amount of hydrophobic material in the composition that needs to be solubilized, one can either use only the amphocarboxylate d~lergelll surfactant, or can 5 cûlllbine it with cosurfactant, preferably said zwitterionic surf~ct~nt~
The "amphocarboxylate" delelg~ surf~ct~ntc herein plt;f~bly have the generic formula:

RN(Rl)(CH2)nN(R2)(CH23pC(O)OM

wherein R is a C6 10 hydrophobic moiety, typically a fatty acyl moiety co.~ g from about 6 to about 10 carbon atoms which, in co~binalion with the n.l.ugen atom forms an amido group, R1 is hydrogen (preferably) or a C1 2 alkyl group, R2 is a Cl 3 alkyl or, substituted C1 3 alkyl, e.g., hydroxy substituted or carboxy methoxy s~lbstitllte~
15 ple~el~bly, hydroxy ethyl, each n is an integer from 1 to 3, each p is an integer from 1 to 2, plefel~bly 1, and each M is a water-soluble cation, typically an alkali metal, an....ol~ium, and/or alkanolammonium cation. Such delergenl surf~ct~ntc are available, for e.Aa..lple from Witco under the trade name Rewoteric AM-V, having the formula C7H15C(O)NH(CH2)2N(CH2CH2OH)CH2C(O)O(-) Na(+);
20 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, having the formula C7 gHl 5 1 gC(O)NH(CH2)2N(CH2CH20CH2C(O)O(~)Na(+))CH2C(O)O(~) Na(+) (2) Zwitterionic Detcr~,e..l Surfactant The aqueous, liquid hard surface dct~ l conlposilions (cleancls) herein can contain from about 0.02% to about 15% of suitable zwitterionic detergent surfactant CO~ g a ç~tio~ic group, pre~el~bly a qualelllaly ammonium group, and an anionic 30 group, pléfel~bly ca.l,oAylate, sulfate and/or sulfonate group, more preferably 5--lfon~te A more p~ elled range of zwitterionic delel~selll surfactant inclusion is from about 0.1% to about 5% of surfactant, a most plerel~d range is from about 0.02% to about 0.2%.
Zv~ ,ionic detergent surf~ct~nts as mentioned hereh~berore, contain both a c~tionic group and an anionic group and are in subsL~ ial electrical neutrality where 5 the number of anionic charges and cationic charges on the detergent surfactantmslecl~le are s~lbs~ y the same. Zwitterionic detergents, which typically contain both a qualelllaly ~mmoni~m group and an anionic group s~?lected from sulfonate and carboxylate groups are desirable since they ~ in their amphoteric character overmost of the pEI range of interest for cleaning hard surfaces. The sulfonate group is the 10 pre~lled anionic group.
P~èr~;lled zwitterionic detergent surf~ct~nts have the generic formula:

R3 -[C(o)-N(R4)-(CR52)n 1 ]mN(R6)2(+)-(CR52)p 1 -Y(~) 15 v~Lc.~in each Y is pr~rel~bly a carboxylate (COO~) or sulfonate (SO3-) group, more preferably sulfonate; wherein each R3 is a hydrocarbon, e.g., an alkyl, or alkylene, group con~ ;ng from about 8 to about 20, preferably from about 10 to about 18, more plt;reldbly from about 12 to about 16 carbon atoms; wherein each (R4) is either hy~llogen, or a short chain alkyl, or substituted alkyl, co..l~;n;.~g from one to about 20 four carbon atoms, I"erel~bly groups sçlected from the group concicting of methyl, ethyl, propyl, hydroxy substihlted ethyl or propyl and mixtures thereof, preferably methyl; wherein each (R5) is selected from the group col.si~Lillg of hydrogen and hydroxy groups with no more than one hydroxy group in any (CR52)p 1 group; wherein (R6) is like R4 except pl~r~rably not hydrogen; wherein m is 0 or 1; and wherein each 25 nl and pl are an integer from 1 to about 4, preferably from 2 to about 3, more p~f~,,ably about 3. The R3 groups can be branched, unsaturated, or both and suchstructures 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 c~ s such as imitl~7Oline pyridine, etc. Plerellcd hydrocarbyl ~mi~lo~lkylene 30 sulrobctaillc (HASB) d~lergenl surf~çPnt~ wLeleill m = 1 and Y is a sulfonate group provide superior grease soil removal and/or filming/streaking and/or "anti-fogging"
and/or perfume sol~bili7~tion properties. Such hydrocarbyl~mi~lo~lkylene sulfobet~in~s and, to a lesser extent hydrocarbyl~mitloalkylene betaines are excellent for use in hard surface cle~ning detergent compositions, especially those forn~ ted 35 for use on both glass and hard-to-remove soils. They are even better when used with monoeth~nol~mine and/or specific beta-amino alkanol as rlicclosed herein.

WO 95/18210 PCT/US94114295 ~

A more plefelled specific detergent surfactant is a C10 14 fatty acylarnidopropylene(hydroxypropylene)sulfobetaine, e.g., the de~ surfactant available from the Witco Company as a 40% active product under the trade name "REWOTERIC AM CAS Sulfobetaine."
S The level of zwitterionic d~L~r~e.lL surfactant, e.g., HASB, in the composition is typically from about 0.02% to about 15%, preferably from about 0.05% to about 10%.
The level in the composition is dependent on the eventual level of dilution to make the wash solutiQn For glass r.le~nin~ the composition, when used full s~.engLh, or wash solution cG.~ n;ng the composition, should contain from about 0.02% to about 1%,pl~,fel~bly from about 0.05% to about 0.5%, more prefel~bly from about 0.1% to about 0.25%, of deLe~c.lL surfactant. For removal of .liffic.llt 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%. Conce..~r~led products will typically contain from about 0.2% to about 10%, preferably from about 0.3% to about 5%. It15 is an advantage of the zwitterionic det~.~,enl, e.g., HASB, that compositionsco~ g it can be more readily diluted by con~un.e.~ since it does not interact with h~dl-ess cations as readily as conventional anionic d~tel~,t;nL surf~ct~nte Zwitterionic d~iLe.ge.lLs are also c,~ .nely effective at very low levels, e.g., below about 1%.
Other ~,~vilLe.iol ic d~le-g~..l surf~ct~nts are set forth at Col. 4 of U.S. Pat. No.
4,287,080, Siklosi, inco.l.o-~led herein by rerer~nce. Another detailed listing of suitable zwitterionic detergenL sUl r~el~ for the detergent conl,uosilions herein can be found in U.S. Pat. No. 4,557,853, Collins, issued Dec. 10, 1985, incorporated byreference herein. Conl-llelcial sources of such surf~ct~nte can be found in McCutc.heQn's EMULSIFIERS AND DETERGENTS, North American Edition, 1984, McCutcheon Division, MC Publishing Company, also incol~uol~led herein by refe. ,nce.
The above patents and references also ~lieclose other detergent surf~ct~ntc, e.g., ~nioni~, and, less p~fel~bly, nonionic d~Lel~wll surf~c.t~nte, that can be used in small ~mo..nte in the composition of this invention, either as primary surf~r,t~nte as30 diecu~eed he.e;llaner, or as cosurf~ct~nte for the prer~l,ed amphoteric/zwitterionic deler~ nl sulçacla~ the cosurfactant level being small in relation to the primary slllr~cL~ll. Typical of these are the alkyl- and allylethoxylate- (polyethoxylate) sulf~tes, p~Lrln sUIrol~es olefin sulfonates, alkoxylated (especially ethoxylated) alcohols and alkyl phenol.e alkyl phenol S~lrotl~e~e~ alpha-sulrondLes of fatty acids and 35 offatty acid esters, and the like, which are well-known from the d~ elley art. When the pH is above about 9.5, detel~en~ surf~ct~nt~ that are amphoteric at a lower pH are desirable anionic dete~elll cosurf~ct~nts For example, detergent surf~ct~nts which ~, WO 95/18210 2 1 7 6 6 9 5 PCI~/US94/14295 are C12-Clg acylamido alkylene amino alkylene sulfonates, e.g., compounds havingthe formula R-C(O)-NH-(C2H4)-N(C2H40H)-CH2CH(OH)CH2S03M wherein R is an alkyl group co..lA;..;l-g from about 9 to about 18 carbon atoms and M is a co...~ ble cation are desirable cosurf~ct~nts. These detergent surf~l~t~ntc are available as Miranol CS, OS, JS, etc. The CTFA adopted name for such surf~ct~ntc is coco~mphol.ydluxy~.opyl sulfonate. It is plerellèd that the compositions be sub~ ly free of allyl naphth~lP~le sulfonates.
In general, dele.~ t surf~ct~nts useful herein contain a hydrophobic group, typically co.~ ing an alkyl group in the Cg-Clg range, and, optionally, one or more linking groups such as ether or amido, preferably amido groups. The anionic detergent surf~ct~ntc can be used in the form of their sodium, potassium or alkanolammonium, e.g., I,;eLhanolammonium salts; the nonionics, not prerelled, generally contain from about S to about 17 ethylene oxide groups. C12-Clg p_-aLrln-sulfonates and alkylsulfates are especially prèrellèd in the compositions ofthe present type.
Some suitable surf~ct~ntc for use herein in small amounts are one or more ofthe following: sodium linear Cg-Clg alkyl benzene sulfonate (LAS), particularly Cll-C12 LAS; the sodium salt of a coconut alkyl ether sulfate con'~;.-;.~g 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 cGlllJllel.,;ally available ~ les of which are Tergitol 15-S-3, Tergitol 15-S-5, Tergitol 15-S-7, and Tergitol 15-S-9, all available from Union Carbide Co.l,o.alion;
the sodium and pot~ceium salts of coconut fatty acids (coconut soaps); the con~i~nc~tio~ product of a straight-chain primary alcohol col~lAi~;ng 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 ethyleneoxide per mole of alcohol; an amide having one of the pr erelled formulas:
o Il R7--C N(R8)2 v~heleill R7 is a straight-chain alkyl group co..~;nil~g from about 7 to about 15 carbon atoms and having an average carbon chain length of from about 9 to about 13 carbon 30 atoms and wh~,.e;ll each R8 is a hydroxy alkyl group co~ from 1 to about 3 carbon atoms; a zwitterionic surfactant having one of the p.éÇe. ed formulas set forth herèinanel, or a phosphine oxide surfactant. Another suitable class of surf~ct~ntc is the fluorocarbon surf~ct~nte c Aa...ples of which are FC-129, a potassium fluo.i.1ated alkylcarboxylate and FC-170-C, a mixture of fluorinated alkyl polyoAyèlllylene WO 95/18210 ` PCT/US94/14295 I:~

21 76~95 -8-ethanols, both available from 3M Corporation, as well as the Zonyl fluorosurf~ct~nts, available from DuPont Corporation. It is understood that mixtures of various surf~ct~nte can be used.

(3) Anionic Dele,~G,ll Surf~ct~nts The aqueous, liquid hard surface detergent compositions herein can contain, as the primary detergent surfactant, less plGfGllGd, or as the cosurfactant, preferably, from about 0.01% to about 2.0%, more p,efel~bly from about 0.1% to about 1.0% of suitable anionic detergent surfactant of the types described hereinbefore. The anionic surf~ct~nte are suitably water-soluble alkyl or alkylaryl compounds, the alkyl having from about 6 to about 20 carbons, inc~ ling a sulfate or sulfonate s~lbstihlent group. Depending upon the level of cle~ning desired one can use only the anionic deLe,gGl,l surfactant, or more preferably the anionic detergentsurfactant can be co",bined with a cosurfactant, prefGlably a amphoteric cosurfactant.
Nonionic surf~ct~nte, e.g., ethoxylated alcohols and/or alkyl phenols, can also be used as cosurf~ct~nts The anionic detergent surf~ct~nte herein prGrel~bly have the generic formula:

R9-(R10)o 1-S03(-)M(+) v~hGrein R9 is a C6-C20 alkyl chain, preferably a Cg-C16 alkyl chain; R10, when present, is a C6-C20 alkylene chain, preferably a Cg-C16 alkylene chain, a C6H4 phenylene group, or O; and M is the same as before.

(4) Mixtures Mixtures of amphocarboxylate, zwitterionic dGle.gGlll surf~ct~nte, and/or anionic delGl~,GllL surf~ct~nts as diqc~-~sed he.eilll)erore, can be present in the present invention. The zwitterionic detergent surf~ct~ntc can be present at levels from about 0.02% to about 15%. The amphocarboxylate d~Lel~ surf~ct~nte can be present at levels from about 0.001% to about 15%. The ratio of zwitterionic detergent surfactant to amphocarboxylate d~L~l~enL surfactant is from about 3:1 to about 1:3, pre~,ably from about 2:1 to about 1:2, more pl~r~-~bly the ratio is about 1:1. The ratio of plilllaly det~ l surfactant to cosurfactant or cosurf~ct~nte is ~om about 3:1 toabout 1:1.
B. HYDROPHOBIC SOLVENT

~ Wo95/18210 21 76695 Pcrluss4ll4295 g In order to obtain good çle~ning one can use a hydrophobic solvent that has rle~ning activity. The solvents employed in the hard surface çle~ning co",posilions herein can be any of the well-known "degreasing" solvents commonly used in, for eY~mplP-, the dry cle~ning industry, in the hard surface cleaner industry and the S metalwolking industry.
A useful de-finition of such solvents can be derived from the solubility elel~ as set forth in "The Hoy," a publication of Union Carbide, incol~uldled herein by reference. The most useful parameter ap~ to be the hydrogen bonding p~.~..,el~.r which is calc~ ted by the formula:

a - 1 yH =yT a~

wl,c.~.n ~H is the hydrogen bonding p~r~met~r~ a is the aggl~alion number, (Log a = 3.39066 Tb/T - 0.15848 - Log ~) , and c d yT is the solubility p~r~meter which is oblailled from the formula:

~T = (~H2s - RT~d M
where ~H2s is the heat of v~rori7~tiQn at 25C, R is the gas constant (1.987 caVmole/deg), T is the absolute te",peldture in K, Tb is the boiling point in K, Tc is the critical te.,.~ldture in K, d is the density in g/ml, and M is the molecular weight.
For the compo~itions herein, hydlo~en bonding p~r~meterS are preferably less than about 7.7, more ~ler~ldbly from about 2 to about 7 or 7.7, and even more ~.ef~bly from about 3 to about 6. Solvents with lower mlmbers become increasingly difficult to solubilize in the colllpos;lio~ and have a greater tendency to cause a haze on glass. Higher numbers require more solvent to provide good greasy/oily soil rle~ning.
Hydrophobic solvents are typically used at a level of from about O.5~o to about 30%, preferably from about 2% to about 15%, more preferably from about WO 95/18210 PCT/US94/14295 '--21766q5 lo-4% to about 8%. Dilute compositions typically have solvents at a level of from about 1% to about 10%, preferably from about 3% to about 6%. Cs)nce~-t~
col..positions contain from about 10% to about 30%, preferably from about 10% to about 20% of solvent.
More hydrophobic solvents such as, hydrocarbons and mono and/or dise~uil~.~ncs should not be present at a level of more than about 0.4%, by weight of the co.,.~;,ilion, and preferably, the composition is e~cçnti~lly free of said solvents, çspe~i~lly when they have limited volatility. Many of such solvents comprise l~yd,~l,ol or halogenated hydrocarbon moietiPs of the alkyl or 10 cycloalkyl type, and have a boiling point well above room l~-pe,~Lu~, i.e., above about 20C.
The formulator of compositions of the present type will be guided in the sPle~tion of co-solvent partly by the need to provide good grease-cutting ~,r~pellies, and partly by ~sthPtic consider~tions. For example, kerosel e hydrocarbons 15 function quite well for grease cutting in the present colo~;liQns, but can bem~lndorous. Kerosene must be exceptionally clean before it can be used, even in commercial ~itu~tioll~. For home use, where malodoM would not be tolerated, the formulator would be more likely to select solvents which have a relatively ple~nt odor, or odors which can be reasonably morlified by ~.rullling.
The C6-Cg alkyl aromatic solvents, es~i~lly the C6-Cg alkyl l!e.~7~-es, pl~Ç~dl)ly octyl ben7Pne, exhibit eYcPll~nt grease removal pn)pelLies and have alow, ple~nt odor. Likewise, the olefin solvents having a boiling point of at least about 100C, ç~ lly alpha-olefins, preferably l-decene or l-dodecene, are eYcPllent grease removal solvents. However, the co...l)os;tions are preferably 25 e~".l;~lly free of these very hydrophobic solvents.
np~ ny~ the glycol ethers useful herein have the formula Rl 1 o (R12O)mlH wl.cr~;n each Rll is an alkyl group which cont~in~ from about 3 to about 8 carbon atoms, each R12 is either ethylene or propylene, and ml is a r.u..lbcr from 1 to about 3. The most ~iere~ed glycol ethers are selected from the group cor ~i~ting of ,lono~n,~yleneglycolmonopropyl ether, di~n~leneglycolmonobutyl ether, monopropyleneglycolmonobutyl ether, ethyleneglycolmonohexyl ether, ethyleneglycolmonobutyl ether, diethyleneglycolmQnohexyl ether, monoethyleneglycolmonohexyl ether, .... .ono~ yleneglycolmonobutyl ether, and mixtures thereof.
A particularly pl~:feiled type of solvent for these hard surface cleaner co...ros;l;on~ comprises diols having from 6 to about 16 carbon atoms in their ~I Wo 95/18210 2 1 7 6 ~ q 5 PCT/US94/14295 molecular structure. Preferred diol solvents have a solubility in water of from about 0.1 to about 20 g/100 g of water at 20C.
Solvents such as pine oil, orange terpene, benzyl alcohol, n-hexanol, phthalic acid esters of Cl 4 alcohols, butoxy propanol, Butyl Carbitol R and 1(2-n-butoxy-1-methylethoxy)l~r~ane-2-ol (also called butoxy pl~OXy propanol or dipropylene glycol monobutyl ether), hexyl diglycol (Hexyl Carbitol R), butyl triglycol, diols such as 2,2,4-trimethyl-1,3-pent~n~diol, and mixtures thereof, can be used although the levels of hydr~hobic material such as pine oil and orange terpene should be kept very low, if present. The butoxy-propanol solvent should have no more than about 20%, ~ fel~bly no more than about 10%, more preferably no more than about 7%, of the secondary isomer in which the butoxy group is ~tt~hed to the secon~ y atom of the propanol for improved odor.

C. ALKALINITY SOURCE
The aqueous liquid hard surface co-.lpo~itions can contain herein from about 0.05% to about 10%, by weight of the composition, of ~lk~line m~t~ri~l, preferably comprising or con~i~ting çs~e~ lly of, monoeth~nol~mine and/or beta-~minoplk~nol co---~ounds.
Monocll.~nol~-~ine and/or beta-~mino~lk~nol co...l~ui--ls serve prim~rily as solvents when the pH is above about 10.0, and especially above about 10.7. They also provide ~lk~line buffering capacity during use. However, the most unique contribution they make is to improve the filming/streaking prupel~ies of hard surface çle~nin~ co~ osil;on~ cont~ining zwitt~rionic detelg~llt sllrf~ct~nt amphoc~l.uAylale d~ sel t surfactant, or nli~lu~cs thereof, whereas they do not provide any ~.lb~ l improvement in filming/streaking when used with convention~l ariionic or ethoxylated nonionic dcl~lE,ent surf~çt~nt~. The reason for the improvement is not known. It is not simply a pH effect, since the improvement is not seen with conventio~ lk~linity sources. Other similar m~t~rial~ tha~ are solvents do not provide the same benefit and the effect can be different depen~ing upon the other materials present. When perfumes that have a high percentage of terpenes are incol~o~dled, the benefit is greater for the beta-alkanol~mines, and they are often plef~ lled, whereas the monoeth~nol~mine is usually l.lcfe~led.
Monocll~A,lolAmine and/or beta-alkanolamine are used at a level of from about 0.05% to about lO~o, preferably from about 0.2~o to about 5%. Por dilute co,.~ ;on~ they are typically present at a level of from about 0.05% to about 2%, preferably from about 0.1% to about 1.0%, more preferably from about 0.2% to 2 1 7~6 95 about 0.7%. For concç~ti~ted compositions they are typically present at a level of from about 0.5% to about 10%, preferably from about 1% to about S%.
Pref~ .lcd beta-~mino~lk~nol~ have a primary hydroxy group. Suitable beta-~mino~lk~nols have the formula:

Rl 3 R13 R1~ Ç C--OH

wherein each R13 is sP-lpctp~d from the group con~i~ting of hydrogen and alkyl groups cont~ining from one to four carbon atoms and the total of carbon atoms in10 the co~ vw~d is from three to six, preferably four. The amine group is ~lcrcldbly not ~tt~r,hed to a primary carbon atom. More preferably the amine group is ~tt~rhed to a tertiary carbon atom to .~;n~ ;7e the reactivity of the amine group.
Specific l,r~f~.,cd beta-~mino~lk~nols are 2-amino, l-butanol; 2-amino,2-methylprv~ ol; and ~ ul~s thereof. The most ~cfellcd beta-~mino~lk~nol is 2-15 amino,2-methyl~,vl~ol since it has the lowest molecul~r weight of any beta-~mino~lk~nQl which has the amine group ~ttarhçd to a tertiary carbon atom. The beta-~mino~lk~nol~ preferably have boiling points below about 175C. Preferably,the boiling point is within about 5C of 165C.
Such beta-~mino~lk~nols are excPllent m~tçri~l~ for hard surface clç~ning in 20 general and, in the present application, have certain desirable ch~ teri~tiesThe beta-~mino~lk~nol~ are surprisingly better than, e.g., monoeth~nolamine for hard surface de~e.~ent cvlllposi~ions that contain perfume ingredients like lc~nes and similar m~tPri~l~. However, norrnally the monoeth~nol~mine is y~ re.r~d for its effect in improving the filming/streaking ~.Çol",ance of 25 coll~os;t;on~ cor.~ zwitt~P~ionic deLel~ent surfactant. The improvement in filming/streaking of hard surfaces that is achieved by combining the monoe~ ol~minP and/or beta-~mino~lk~nnl was tot.ally unr~
Good filminglstreaking~ i.e., minim~l, or no, filminglstreaking7 is espe~i~lly illl~l~t for clP~nin~ of, e.g., window glass or mirrors where vision is affected30 and for dishes and cç~mic surfaces where spots are ~esthetir~lly ~md~Psir~hle. Beta-~mino~lk~nol~ provide superior clç~ning of hard-to-remove greasy soils and superior product stability, es~-i~lly under high telllpel~ture con~iition~, when used ~I WO95/18210 21 76695 PCr/USs4/14295 in hard surface çle~ning compositions, espe~i~lly those cont~ining the zwitterionic detergent surf~t~t~nt~.
Beta-~mino~lk~nols, and espe~i~lly the p~re.led 2-amino-2-methyl~ ,pallol, are surprisingly volatile from cleaned s-lrf~ces con~iderin~ their relatively high S molecul~r weights.
The compositions can contain, either alone or in addition to the ~ r~lled ~lk~nol~ s more conventional ~lk~lin~ buffers such as ammonia; other C2 4 alk~no~ 7 alkali metal hydroxides; silic~tes; borates; carbonates; and/or bicarbonates. Thus, the buffers that are present usually comprise the pler~lled 10 monoethanolamine and/or beta-~mino~lk~nol and ~d-iitior ~l conventional alkaline material. The total amount of ~lk~linity source is typically from 0% to about 5%, pref~l~bly from 0% to about 0.5%, to give a pH in the product, at least initially, in use - of from about 9.5 to about 12, preferably from about 9.7 to about 11.5, more preferably from about 9.7 to about 11.3. pH is usually measured on the product.
(D) DETERGENT BUILDER
DeL~r~ent builders that are efficient for hard surface cleaners and have reduced filming/streaking ch~-~cteri~tics at the critical levels are an ç~enti~lclf- ,.~t of the present invention. ~d~lition of specific det~E;ent builders at critical levels to the present comrositi~n improves cle~ning without the problem of filming/streaking that usually occurs when dele~enl builders are added to hard surface cleaners. Through the present invention there is no longer the need to make a co,lll.rol,lise between improved cle~ning and acceptable filming/streaking results which is espe~i~lly Ll~llant for hard surface cleaners which are also directed at cl~nin~ glass. These colllpos;lions co~ ing the del~.~ent builders herein at thelevels herein, have exceptionally good cle~ning pr~ Lies. They also have exceptionally good "shine ~ropellies, i.e., when used to clean glossy surfaces, willloul Ansing, they have much less tendency than, e.g., carbonate built products to leave a dull finish on the surface and filminglstreaking.
Suitable d~le~el t builders include salts of ethylenY~i~minetetraacetic acid (helt;inafler EDTA), citAc acid, nitrilotriacetic acid (hereinafter NTA), sodiumcarboxymethyl~ucc-inic acid, sodium N-(2-hydroxypropyl)-imino~ cetic acid, t~lrt~riC acid. and N-diethyleneglycol-N,N~ retic acid (hereinafter DIDA). The salts are preferably collll,atible and include ammonium, so~ m, potassium and/or3s ~lk~nol~mmoni~lm salts. The ~lk~nol~m~on~ salt is ~lefc.led as descAbed hele;n~ler. A pler~red delel~ellt builder is NTA (e.g., sodium), a more prer. .1~ d =

WO 95/18210 . PCT/US94/14295 '-- 2 ~ 766 95 builder is citrate (e.g., sodium or monoeth~nol~mine), an even more ~.lefell~d builder is tartaric acid. and a most p~fell~d builder is EDTA (e.g., sodium).
The dct.~e~,t builders are present at levels of from about 0.05% to about 0.5%. more preferably from about 0.05% to about 0.3%, most preferably from about 0.05% to about 0.15%. The levels of builders present in the wash solution used for glass should be less than about 0.2%. Thel~Çolc, typically, dilution ishighly ~ f._.led for cl~nin~ glass, while full strength is ~.re~erled for general ul~se cle~nin~, ~epen~ling on the concçntT~tiQn of the product.
Typically the improvement with regard to acceptable filming/streaking results occurs most when the builder is combined with amphoteric and/or zwitterionic dele.~,c,l~ surfactant compositions although an improvement is also seen with the less pr.,fc..ed anionic or anionic/nonionic d~le~gc,~l surfactant compositions.

(E) AOUEOUS C~SOLVENT SYSTEM
The balance of the formula is typically water and non-aqueous polar solvents with only rninim~l cle~ning action, having hydrogen bonding pal~ clers greater than about 7.7, pr~fw~bly greater than about 7.8, like .~e~ ol~ eth~nol~ isop,upallol~
ethylene glycol, glycol ethers having a hydrogen bonding par~",.~-~er of greater than 7.7, propylene glycol, and mixtures thereof, plercl~bly isop,opanol, more preferably ethanol. The level of non-aqueous polar solvent is usually greater when more conc~..l,aled formulas are p~cpaled. Typically, the level of non-aqueous polar solvent is from about 0.5% to about 40%, preferably from about 1% to about 10%, more preferably 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 25 95%.

~f WO 95/18210 2 1 7 6 h 9 5 PCT/US94/14295 _ 15 _ (F) OPTIONAL INGREDIENTS
The compositions herein can also contain other various adjuncts which are known to the art for deLe~enL compositions. Preferably they are not used at levels that cause l~nAcce~ ble filming/streaking. Non-limitin~ examples of such adjuncts are:
Enzymes such as p~oteases, IIydlol.o,oes such as sodium toluene sulfonate, sodium cun~ne sulfonate and potassium xylene sulfonate; and Aesthetic-çnh~n~ing ingredients such as colorants and perfumes. providing they do not adversely impact on filming/streaking in the cleaning of glass. Most hardsurface cleaner products contain some perfume to provide an olfactory ~esthetic benefit and to cover any "shemiC~l" odor that the product may have. The main fi~nction 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 rle~ned However, some of the less volatile, high boiling perfume illglcdi~ s can provide a fresh and clean implesSion to the surfaces, and it is so... ~;...es desirable that these ingredients be deposited and present on the dry surface. The perfumes are preferably those that are more water-soluble ancVor volatile to ...;.~;...;~e spotting and filming. The perfumes useful herein are described in more detail in U.S. Patent 5,108,660, ~i~h~l issued April 28, 1992, at col. 8 lines 48 to 68, and col. 9 lines 1 to 68, and col. 10 lines 1 to 24, said patent, and especi~lly said specific portion, being incorporated by reference.
~ntibacterial agents can be present, but preferably only at low levels to avoid filming/streaking probl~rn~ More hydrophobic ~ntib~ct~riaVgermicidal agents, like orthobenzyl-para-chlorophenol, are avoided. If present, such materials should be kept at levels below about 0.1%.
Sl~bil;~ g ingredients can be present typically to stabilize more of the hydlophobic ing,edie,lLs, e.g., perfume. The stabilizing ingredients include acetic acid and pl ~p.~l ic acids, and their salts, e.g., N~, MEA, Na, lK, etc.,prere.~bly acetic acid and the C2-C6 alkane diols, more preferably butane diol.
The stabilizing ingredients do not function in accordance with any known principle. Nonetheless, the col..binaLion of amido zwitterionic dt:Le.ge.,L
surfactant with linear acyl amphocarboxylate detergent surfactant, anionic dt;~ ,nt surfactant, nonionic detergent surfactant, or mixtures thereof, and st~bili7ir~ in~ledi~,.lL can create a microemulsion. The amount of stabilizing ingledi~.,L 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 WO 9S/18210 PCT/US94/14295 '~\
2~ 76~5 16-be stabilized in the product is related to the total surfactant and typically is in an amount that provides a ratio of surfactant to hydrophobic material of from about1:2 to about 2:1.
Conc~i.",~led compositio~c of the present invention can also be used in order to provide a less c~l,ensi~e and more ecologically sound product.
Conce~lllalions of up to lOX the original concentration, preferably up to 5X
more prere,~bly up to 2X the original concentration can be used and can be diluted using tap water, dictilled water, and/or deionized water, down to a lX
concenl~alion.
The invention is illustrated by the following nonl;...;~ p Ex~mrles Filming/Streaking Stress Test Procedure:
A paper towel is folded into eighths. Two mil~ ters 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 min~ltes before grading by expert judges. Mer initial grading, the residues are then buffed with a dry 20 paper towel with a un~r~llll, conc Cl~ .l motion. The buffed residues are then graded by expert judges.

Ciradin~:
Expert judges are employed to evaluate the specific areas of product 25 application for amount of filming/streaking. A numerical value describing the amount of filming/streaking is ~si~ned to each product. For the test results reported here a 0-6 scale is used.
0 = No Filming/Streaking 6 = Poor Filming/Streaking 30 Room te-l-pe-a~-lre and humidity have been shown to influense filming/streaking.
The,erore, these variables are always recorded.

~ wo 95/18210 2 1 7 6 6 q 5 Pcr/uss4ll4295 EXAMPLE I
Forrnula No. (Wt. %) In~redient 1 2 3 4 5 6 IPA1 6.0 6.0 6.0 6.0 6.0 6.0 gp2 3.0 3.0 3.0 3.0 3.0 3.0 MEA3 0.50 0.50 050 050 050 050 ct!co~midQpropyl-hydroxy-sultaine 0.16 0.16 0.16 0.16 0.16 0.16 So~ m Lauryl Sulfate 0.02 0.02 0.02 0.02 0.02 0.02 EDTA4 0.05 0.10 0.25 0.50 1.0 Perfume 0.13 0.13 0.13 0.13 0.13 0.13 Soft Water to Balance ~ BALANCE

5 1Isop.upanol 2gUlO~y~l~upa 3Monoeth~n~l~minf~
4Ethylene ~i~mine tetraacetic acid Filming/Streaking Stress Test on Glass Windows (Four Replications at 73 F and 32% Relative ~llmidity) Formula No.Before/Aflcer Bufflng Rating 2.3/2.6 2 2.5/0.3 3 1.8/0.5 4 2.0/0.5 2.8/1.4 - 6 3.4/2.8 The least significant di~.ence between before buffing mean ratings is 0.9 at 95%confidPnce level. The least si~nific~nt difference between after buffing mean ratings is 0.4 at 95% confidence level.

WO 95/18210 PCT/US94/14295 ~

The above shows that the addition of detergent builders at critical levels does -not cause unacceptable filming/streaking results, and in some cases actually improves -filming/streaking results, especially after bufflng if the level of detergent builder is 0.5% or less S E~AMPLE II
Formula No. (Wt.%) T~ ,d;enl 1 2 3 4 5 6 ~A 5.4 5.4 2.0 2.0 2.0 2.0 MEA 0.4 04 05 05 05 05 BP ~~~ ~~~ 3 0 3.0 3.0 3.0 Ethylene Glycol Monohexyl Ether 0.9 0.9 --- --- --- ---Ethylene Glycol Monobutyl Ether 1.0 1.0 --- --- --- -LAS5 0.07 0.07 SodiumLauryl Sulfate --- --- --- --- 0.1 0.1 Cg 0.03 0.03 Alkylphenolethoxylate C8 o. 1 o. 1 Alkylphenolethoxylate EDTA --- 0.1 --- 0.1 --- 0.1 ~mmoni~ 0.1 0.1 --- --- --- ---Dei^rli~ed (I)I) Water to R~l~nce ~ 3ALANCE
5Linear alkyl ~cr.zene sulfonate ~ Wo 95/18210 2 1 7 6 6 9 5 PCr/Uss4/14295 Filming/Streaking Stress Test on Glass (Four Replications at 79 F and 36% Relative Humidity) Formula No.Before/A~er Bufflng Rating 2.8/0.12 2 3.3/0.38 3 4.7/4.5 4 5.2/4.4 2.9/1.4 6 3.25/2.3 The least ~ ific~nt di~,t;nce, in the above example, between before buffing mean5 ratings is 0.3 at 95% confidçnce level. The least ~i~nific~nt di~lence between after buffing mean ratings is 0.4 at 95% confidence level.
EXAMPLE III
Formula No. (Wt.%) Ing.~.i,e.lt 1 2 3 IPA 6.0 6.0 6.0 BP 3.0 3.0 3.0 MEA 0.50 0.50 0.50 Coco~mi-lopropylhy-droxy Slllt~ine 0.16 0.16 0.16 So~illm Lauryl Sulfate 0.02 0.02 0.02 Sodium Carbonate --- --- 0.06 EDTA --- 0.1 ---Perfume 0.13 0.13 0.13 So~ Water to R~l~nce ~ BALANCE

21 766q5 Filming/Streakin~ Stress Test on Glass (Four Replications at 73 F and 29% Relative Humidity) Formula No. Before/~Pcer Buffing Rating 2.0/2.9 2 2.4/1.0 3 4.5/0.6 The least ~i~,.,.r.c~ di~lence, in the above example, between before bufffing mean 5 ratings is 1.04 at 95% confidence level. The least significant di~lence b~een after buffing mean ratings is 0.49 at 95% confidence level.
The above example shows that initially call,ondLe leaves an unacceptable filming/streaking ap~oe&lailce and that more work, i.e., buffing must be done in order to obtain an accept~ble result with carbonate whereas the EDTA leaves an acceptable10 appe~nce both before and after buffing.
The following test is used to evaluate the compositions' cle~nin~ pelrollllance. ~l epal aLion of Soiled Panels Enamel splash panels are selected and cleaned with a mild, light duty liquid rJ~n~er~ then cleaned with isopropanol, and rinsed with rlictille~ or deionized water.
15 Greasy-particulate soil is weighed (2.0 grams) and placed on a sheet of alllmin--m foil.
The greasy-particulate soil is a mixture of about 77.8% collllllelcial vegetable oils and about 22.2% particulate soil composed of humus, fine cement, clay, ferrous oxide, and carbon black. The soil is spread out with a spatula and rolled to Ulli~olllu~y with a small roller. The u~ir~llll soil is then rolled onto the clean enamel plates until an even 20 coating is aclf.e~cd. The panels are then equilibrated in air and then placed in a preheated oven and baked at 140 C for 45-60 mimltçs Panels are allowed to cool to room telll~,c~aL~lre and can either be used immedi~tely, or aged for one or more days.
The aging produces a tougher soil- that typically requires more clç~ning effort to remove.
Soil Removal A Gardner Straight Line Washability Machine is used to pt;lrolll~ the soil removal. The m~.hine is fitted with a carriage which holds the weighted cleaningi~llplemçnt The rl~nin~ implemlont~ used for this test were clean cut sponges. Excess 30 water is wrung out from the sponge and 5.0 grams of product are uniformIy applied to one surface of the sponge. The sponge is fitted into the carriage on the Gardnerm~hine and the cle~nin~ test is run.
The average number of Gardner m~hine strokes nece~ry to achieve 95-99%
removal of soil are obtained.
., 5 EXAMPLE IV
Formula No. (Wt.%) Ingredient 1 2 3 4 5 6 IPA 6.0 6.0 5.4 2.0 2.0 2.0 BP 3.0 3.0 --- 3.0 3.0 3.0 MEA 0.50 0.50 0.40 0.50 0.50 0.50 Cocoamidopropyl-hydroxy sultaine 0.16 0.16 --- 0.075 0.075 0.075 Sodium Lauryl Sulfate 0.02 0.02 --- --- ---Ethyleneglycol-monohexyl ether --- --- 0.90 ---Ethyleneglycol-monobutyl ether --- --- 1.0 --- ---LAS --- --- 0.07 --- --- ---Cg Alkylphenol-ethoxylate --- --- 0.03 --- --- ---C8 lo-carboxymeth-oxyglycinate --- --- --- 0.075 0 075 ---C8, lo-hydroxy-methyl~ .,inale --- --- --- --- -- 0.075 Sodium Acetate - --- --- 0.05 0.05 0 05 O. 1 0 -J EDTA --- 0.1 ---Perfume 0.13 0.13 unkno 0.11 0.13 0.11 n Soft Water to Ral~nce ~ I3ALANCE

Formula No.Average Number of Strokes 7.5 3 7.5 4 6.5 6.0 6 6.5 *Two rçplic~tes, greasy-particulate soil.
The above shows the cleaning improvement when a dele~ell~ builder is added to the composition. There is a ele~nin~ benefit from adding as little as 0.1% EDTA
5 detergent builder to a composition co..~ either a zwitterionic or cosurfactant-~u~ra~;Lanl mixture.
There is a pluslrninus one stroke difference between strokes at the 95%
corlfi~ ce level.

EXAMPLE V
Forrnula No. (Wt.%) Ingredients 1 2 E~anol 1.5 17.00 Butox~.o~lol 3.2 16.00 Monoeth~nolall~ine 0.5 2.50 Coco~midohydroxypropyl 0.16 0.80 Sulfobetaine Tartaric acid 0.06 0.30 P~,.rullle 0.02 0. 10 Dyes 0.0005 0.003 Water Balance R~l~nce

Claims

WHAT IS CLAIMED IS:

1. An aqueous liquid hard surface detergent composition having excellent filming/streaking characteristics, comprising:

(A) detergent surfactant selected from the group consisting of:
(1) from 0.001% to 15%, by weight ofthe composition, of detergent surfactant having the generic formula:

RN(R1)(CH2)nN(R2)(CH2)pC(O)OM

wherein each R is a C6-C10 hydrophobic moiety;
each R1 is hydrogen or a C1-2 allyl group;
each R2 is a C1-2 alkyl, carboxymethoxy ethyl, or hydroxy ethyl;
each n is an integer from 1 to 3, preferably 2;
each p is an integer from 1 to 2, preferably 1; and M is a water soluble cation selected from alkali metal, ammonium, alkanolammonium, and mixtures thereof, cations;
(2) from 0.02% to 15%, preferably from 0.02% to 0.2%, by weight of the composition, of detergent surfactant having the generic formula:

R3-[C(O)-N(R4)-(CR52)nI-]mN(R6)2(+)-(CR52)pI-Y(-) wherein each R3 is an alkyl, or alkylene, group containing from 10 to 18 carbon atoms, preferably from 9 to 15 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, preferably R6 is a methyl group;
each (R5) is selected from the group consisting of hydrogen and hydroxy groups, with no more than one hydroxy group in any (CR52)p1 moiety, preferably one of the R5 groups between the (+) and the (-) charge centers is a hydroxy group and the remaining R5 groups are hydrogen;
each m is 0 or 1;
each n1;and p1 is a number from 1 to 4, preferably p1 is 3; and Y is a carboxylate or sulfonate group, preferably a sulfonate group;
(3) from 0.01% to 2.0%, by weight of the composition, of detergent surfactant having the generic formula:

R9-(R10)0-1-SO3(-)M(+) wherein each R9 is a C6-C20 alkyl chain;
each R10 is a C6-C20 alkylene chain, a C6H4 phenylene group, or O; and M is the same as before; and (4) mixtures thereof; and (B) from 0.5% to 30%, preferably from 2% to 15%, by weight of the composition, of hydrophobic solvent, having a hydrogen bonding parameter of from 2 to 7.7, preferably selected from the group consisting of monopropyleneglycolmonopropyl ether, dipropyleneglycolmonobutyl ether, monopropyleneglycolmonobutyl ether, ethyleneglycolmonohexyl ether, ethyleneglycolmonobutyl ether, diethyleneglycolmonohexyl ether, monoethyleneglycolmonobutyl ether, and mixturesthereof, more preferably monopropyleneglycolmonobutyl ether, and wherein said solvent preferably comprises no more than 0.4%, by weight of the composition, ofmono or sesquiterpenes;

(C) from 0.05% to 10%, by weight of the composition, of alkaline material preferably comprising alkanolamine selected from the group consisting of: monoethanolamine;beta-amino-alkanol, containing from three to six carbons; and mixtures thereof, preferably comprising monoethanolamine, and more preferably also comprising alkali metal hydroxide, to give the composition a pH of from 9.5 to 12, preferably from 9.7 to 12, more preferably from 9.7 to 11.3.

(D) from 0.05% to 0.5%, preferably from 0.05% to 0.3%, more preferably from 0.05%
to 0.15%, by weight of the composition, of detergent builder.

(E) the balance being an aqueous co-solvent system comprising water and any organic co-solvent having a hydrogen bonding parameter of greater than 7.8, preferably ethanol, and more preferably isopropanol.

2. The composition of Claim 1 comprising a mixture of (A)(1) and (A)(3), wherein (A)(3) is selected from the group consisting of C12-C18 alkyl sulfates, C12-C18 paraffin sulfonates, C12-C18 acylamidoalkylene sulfonates at a pH of more than 9.5, and mixtures thereof.

3. The composition of Claim 1 comprising or a mixture of (A)(2) and (A)(3), wherein (A)(3) is selected from the group consisting of C12-C19 alkyl sulfates, C12-C18 paraffin sulfonates, C12-C18 acylamidoalkylene sulfonates at a pH of more than 9.5, and mixtures thereof.

4. The composition of Claim 1 wherein the mixture (A)(4) comprises (A)(1) and (A)(2) in a weight ratio of from 3:1 to 1:3, preferably from 2:1 to 1:2, and more preferably 1:1.

5. The composition of Claims 1 or 4 comprising a mixture of (A)(1) or (A)(2) and a nonionic detergent surfactant, prererably selected from the group consisting of alkoxylated alcohols and alkyl phenol ethoxylates.

6. The composition of Claims 1,2,3,4, or 5 wherein said detergent builder is selected from the group consisting of water soluble salts of ethylenediaminetetraacetic acid, citric acid, N-(2-hydroxyethyl)-iminodiacetic acid, N-(2-hydroxypropyl)-iminodiacetic acid, N-diethyleneglycol-N,N-diacetic acid, carboxymethylsuccinic acid, tartaric acid, nitrilotriacetic acid, and mixtures thereof, preferably tartaric acid, or citric acid, or ethylenediaminetatraacetic acid

7. The composition of Claim 6 wherein said builder is ethylenediaminetetraacetic acid.

8. The composition of Claim 6 wherein said builder is citric acid.

9. The composition of Claim 6 wherein said builder is tartaric acid.

10. The composition of Claim 9 wherein said co-solvent is ethanol.