CA2238194A1 - Liquid hard surface detergent compositions containing specific concentration of tartaric acid detergent builder - Google Patents

Abstract

Aqueous, liquid hard surface detergent compositions having improved cleaning and good filming/streaking characteristics contain tartaric acid as a detergent builder at critical levels. Preferred formulas contain anionic detergent surfactant at levels (e.g., from about 0.01 to about 1 %);
hydrophobic solvent; alkaline material, especially volatile alkaline materials comprising monoethanolamine or certain beta-amino-alkanol compounds; and salt of tartaric acid as detergent builder in levels (e.g., from about 0.001 % to about 0.05 %, by weight of the composition).

Description

LIQUID HARD SURFACE DETERGENT COMPOS~TIONS
CONTAIN~NG SPECIFIC CONCENTRATION OF TARTARIC ACID
DETERGENT BUILDER

This invention pertains to liquid detergent compositions for use in cleaning hard surfaces. Such compositions typically contain detergent surfactants, solvents, builders, etc.
BACKGROUND OF THE I~V~NTION
The use of solvents and organic water-soluble synthetic d~ ellt surf~t~n at low levels for cleaning glass are known.
Known liquid d~l.,L~,enL compositions comprise certain organic solvents, detergent surf~-t~nt~, and optional builders and/or abrasives. The prior art, however, fails to teach, or recognize, the advantage of specific builders at critical levels 20 disclosed hereinafter, in liquid hard surface cleaner forrnulations.
Liquid cleaning compositions have the great advantage that they can be applied to hard surfaces in neat or concentrated form so that a relatively high level of, e.g., surfactant material and/or organic solvent is delivered directly to the soil.
Therefore, liquid cleaning compositions have the potential to provide superior soap 25 scum, grease, and oily soil removal over dilute wash solutions prepared from powdered cleaning compositions.
The inclusion of dt;:le,gellt builders in liquid hard surface cleaning compositions increases the potential to providie superior cleaning. However, in the past~ the inclusion of such d~elg~..L builders has usually produced unacceptable CA 02238194 1998-0~-20 ~ _ results for filming/streaking. The inclusion of detergent builders has therefore been considered a compromise in favor of cleaning.
Liquid cleaning compositions. and especially compositions prepared for cleaning glass~ need exceptionally good filming/streaking properties. ln addition, 5 they can suffer problems of product form. in particular, inhomogeneity, lack of clarity, or excessive "solvent" odor for consurner use.

SUMMARY OF T~IE INVENTION
The present invention relates to an aqueous, liquid, hard surface detelge 10 composition having improved cleaning and good filming/streaking characteristics comprising: (A) detergent surfactant selected from the group consisting of anionic surf~t~nt~ amphoteric detergent surf~rt~nt~ including zwitterionic surfactants; and mixtures thereof; (B) hydrophobic solvent; (C) ~Ik~line material; (D) tartaric acid detergent builder; and (E) the balance being an aqueous solvent system comprising 15 water and, optionally, non-aqueous polar solvent with only minim~l cleaning action selected from the group con~icting of methanol, ethanol, isoplu~.allol, ethylene glycol, polypropylene glycol, glycol ethers having a hydrogen bonding parameter of greater than 7.7, and mixtures thereof and any minor ingredients. The compositions can be form~ ted at usage conc~ dlions, or as conc~llLlates, and can be packaged in a 20 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.

W O 97/19158 PCT~US96/17429 _, DETAILED DESCRIPTION OF THE INVENTION
In accordance with the present invention, it has been found that superior aqueous liquid detergent compositions ~or cleaning shiny surfaces such as glass contain (A) detergent surfactant selected from the group consisting of anionic surfactants, amphoteric detergent surfactants including zwitterionic surfactants; and mixtures thereof; preferably, C6-C l o "amphocarboxylate" detergent surfactant, zwitterionic detergent s~factant (cont~inir~ both c~tiomc and anionic groups in substantially equivalent proportions so as to be electrically neutral at the pH of use), or mixtures thereof; (B) hydrophobic, volatiile, cleaning solvent; (C) AlkS~Iine buffer, preferably monoethanolamine or certain beta-arnino-alkanol compounds as defined hereinafter; (D) critical level of tartaric acid deteLge.ll builder at a pH of at least about 9.5, preferably at least about 10; and (E) the balance being an aqueous solvent system comprising water and, optionally, non-aqueous polar solvent with only mintm~l cleaning action selected from the group con~ tin~ of methanol, ethanol, iso~.~,p~lol, ethylene glycol, polypropylene glycol, glycol ethers having a hydrogen bonding pararneter of greater than 7.7, and mixtures thereof.
(A) THE DETERGENT SURFACTANT
(1) Anionic Dt:lel~ellt Surfactants The aqueous, li~uid hard sul~ace dc;lelgc;-,t compositions herein can contain from about 0.01% to about 2.0%, more preferably from about 0.1% to about1.0% of suitable anionic d~Lelgel~t s~ t~nl of the types described hereinbefore and heL~illarltr. The anionic surfactants are suitably water-soluble alkyl or alkylaryl compounds, the alkyl having from about ~ to about 20 carbons, including a sulfate or ~ sulfonate substituent group. Depending upon the level of cleaning desired one can use only the anionic detergent surfactant, or, less preferably, the anionic detergent ~ sl--fact~nt can be combined with a cosurfactant, preferably an amphoteric WO 97/19158 PCTnUS96/17429 cosurfactant. Nonionic surfactants, e.g., ethoxylated alcohols and/or alkyl phenols.
can also be used as cosurfactants.
The anionic d~lclg~nt surf~t~ntc herein are selected from the group consisting of C6-C,0 alkyl sulfates, alkyl ethoxy ether sulfates, alkyl benzene sulfonates, olefin 5 sulfonates, and mixtures thereof. Preferably, the anionic detergent surfactant is C6-C20 alkyl sulfate, more preferably C8-CI6 alkyl sulfate.
( 3 Zwitterionic Deter~ent Surfactant The aqueous, liquid hard surface d~ g~l" compositions (cleaners) herein can contain, as the primary d~telg~ surfactant, less pl~.led, or as the cosurfactant, preferably, from about 0.02% to about 15% of suitable zwitterionic detergent s-l-f~rt~nt cont~ining a cationic group, preferably a qu~ y ammonium group, and an anionic group, preferably carboxylate, sulfate and/or sulfonate group, more preferably sulfonate. A more pr~f~l,ed range of zwitterionic detergent surfactant inclusion is from about 0.01% to about 1.0% of surfactant, a most preferred range is from about 0.02% to about 0.2%.
Zwitterionic detergent sllrf~t~nt~, as mentioned hereinbefore, contain both a cationic group and an anionic group and are in substantial electrical neutrality where the number of anionic charges and cationic charges on the detergent surfactant molecule are substantially the same. Zwitterionic d~l~ .g~llt~, which typically contain 20 both a qll~t~m~ry ammoniurn group and an anionic group selected from sulfonate and carboxylate groups are desirable since they m~int~in their arnphoteric ch~r~cter over most of the pH range of interest for cleaning hard surfaces. The sulfonate group is the preferred anionic group.
Preferred zwitterionic d~Lc.~e~ll surf~ t~ntc have the generic formula:
R 1 -[C(o~-N(R2)-(CR32)n 1 ]mN(R4)2(+)-(CR32)p 1 -Y(-) wherein each Y is preferably a carboxylate ~COO~) or sulfonate (SO3-) group, more preferably sulfonate; wherein each R1 is a hydrocarbon? e.g., an alkyL or alkylene, group cont~ining from about 8 to about 20, preferably from about 10 to about 18,more preferably from about 12 to about 16 carbon atoms; wherein each (R2) is either S hydrogen, or a short chain alkyl, or substituted alkyl, cont~ining from one to about four carbon atoms, preferably groups selected from the group consisting of methyl, ethyl, proryl~ hydroxy substituted ethyl or propyl and mix~ures thereof, preferably methyl; wherein each (R3) is selected from the group consisting of hydrogen and hydroxy groups with no more than one hydroxy group in any (CR32)p1 group;
10 wherein (R4) is like R2 except preferably not hydrogen; wherein m is 0 or 1; and wherein each nl or pl is an integer from 1 to about 4, preferably from 2 to about 3, more preferably about 3. The ~I groups can be branched, unsaturated, or both andsuch structures can provide filming/streaking benefits, even when used as part of a mixture with straight chain alkyl Rl groups. The R2 groups can also be connected to 15 fo~m ring structures such as imidazolinle, pyridine, etc. Preferred hydrocarbyl ~micio~lkylene sulfobetaine (HASB) detergent surfactants wherein m = I and Y is a sulfonate group provide superior grease soil removal and/or filming/streaking and/or "anti-fogging" and/or perfume solubilization properties. Such hydrocarbyl~rni~lo~lkylene sulfobet~int~s, and, to a lesser extent 20 hydrocarbylamidoalkylene betaines are excellent for use in hard surface cleaning detergent compositions, especially those formulated for use on both glass and hard-to-remove soils. They are even better when used with monoethanolamine and/or specific beta-amino alkanol as disclosed herein.
More l,ie~l.~d detergent sllrf~t~nt~ have the generic formula:

R5-[~(o)-N(R6)-(CH2~I,]- N((: H3)2(+)-(cR7)3-so3(-) -wherein each R~ is an alkyl, or alkylene, group cont~ining from about 10 to about 1~
carbon atoms: each (R6) is selected from the group consisting of hydrogen, methyl, ethyl, propyl. hydroxy substituted ethyl or propyl and mixtures thereof: each {R7) is selected from the group consisting of hydrogen and hydroxy groups wherein one ofS the R7 groups between the (+) and the (-) charge centers is a hydroxy group and the rem~ining R7 groups are hydrogen with no more than one hydroxy group in the (C
R72~3 moiety and n is a number from 1 to about 4.
A more ~ler~"~d specific d~ genL surfactant is a C10 14 fatty acylarnidopropylene(hydroxypropylene)sulfobetaine, e.g., the detergent surfactane available from the Witco Company as a 40% active product under the trade narne "REWOTERiC AM CAS Sulfobetaine."
The level of zwitterionic detergent surfactant, e.g., HASB, iIl the composition is typically from about 0.02% to about 15%, preferably from about 0.05% to about10%. 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 cont~ining tne composition, should contain from about 0.02% to about 1%, preferably from about 0.05% to about 0.5%, more preferab}y from about 0.1% to about 0.25%, of detergent s~ ct~nt For removal of difficult to remove soils like grease, the level can, and should be, higher, typically from about ~.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% to about 5%. It is an advantage of the z~,vitterionic deL~.g~ , e.g., HASB, that compositions Cont~ining it can be more readily diluted by consurners since it does not interact with hardness cations as readily as conventional anionic d~ ,en~ surfactants. Zwitterionic detergents are also extremely effective at very low levels, e.g., below about 1%.
Other zwitterionic detergent surf~rtzint~ are set forth at Col. 4 of U.S. Pat. No.
4,287,080, Siklosi, incorporated herein by reference. Another detailed listing of W O 97/191~8 PCTAUS96/17429 suitable zwitterionic detergent surf~t~nt~ for the detergent compositions herein can be found in U.S. Pat. No. 4,557,853, Collins, issued Dec. 10, 1985, incorporated by reference herein. Commercial sources of such surfactants can be found in McCutcheon's EMULSIFIERS AND DETERGENTS, North American Edition~ 1984, McCutcheon Division. MC Publishing C'ompany, also incorporated herein by reference.
The abQve patent~ and references also disclose other detergent surfact~ts, e.g., anionic. and~ less preferably, nonionic detergent surf~t~nt~, that can be used in small amounts in the composition of this invention, either as primary sllrf~f~t~ntc as discussed hereinbefore, or as cosurf~ct~nt~ for the preferred amphoteric/zwitterionic detergent surfactant, the cosurfactant level being small in relation to the primary surfactant. Typical of these are the alkyl- and alkylethoxylate- (polyethoxylate) sulfates, paraffin sulfonates, olefin sulfonates, alkoxylated (especially ethoxylated) alcohols and alkyl phenols, alkyl phenol sulfonates, alpha-sulfonates of fatty acids and of fatty acid esters, and the like, which are well-known from the detergency art.
When the pH is above about 9.5, detergent j", rn~ t~ that are amphoteric at a lower pH are desirable anionic deh~gt;llt cosurf~ nt~ For example, detergent surfactants which are C12-Clg acylamido alkylene amino alkylene sulfonates, e.g., compounds having the forrnula R-C(O)-NH-(C2H4)-N(C2H4OH)-CH2CH(OH)CH2SO3M
wherein R is an alkyl group COnt~ining from about 9 to about 18 carbon atoms and M
is a compatible cation are desirable cl s~ st~ntc These dete~gellL surfactants are available as Miranol CS, OS, JS, etc. The CTFA adopted name for such surfactants is cocoarnphohydroxypropyl sulfonate. It is preferred that the compositions be substantially free of alkyl n~phth~l~n~ sulfonates.
In general, detergent surf~5t~nt~ useful herein contain a hydrophobic group, typically cont~inin~ an alkyl group in the C~-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 sodiurn? potassium or alkanolarnmonium, e.g., triethanolammonium salts. the nonionics, not p.eft~ d~
generally contain from about S to about 17 ethylene oxide groups. C 1 ~-C 18 paraffin-sulfonates and alkyl sulfates are especially l~.ef~ d in the compositions of the5 present type.
Some suitable surfactants for use herein in small amounts are one or more of the ~olLowing: sodium linear Cg-Clg alkyl ben7Qne sulfonatQ (L~S3, p~ticularly C1 l-C12 LAS; the sodium salt of a coconut alkyl ether sulfate cont~ining 3 moles of ethylene oxide; the adduct of a random secondary alcohol having a range of alkylchain lengths of from 1 1 to 15 carbon atoms and an average of 2 to 10 ethylene oxide moieties, several commercially available examples of which are Tergitol 15-S-3, Tergitol 1 5-S-5, Tergitol 1 5-S-7, and Tergitol 1 5-S-9, all available from Union Carbide Corporation; the sodium and potassium salts of coconut fatty acids (coconut soaps); the con-len~tion product of a straight-chain primary alcohol cont~ining from lS about 8 carbons to about 16 carbon atoms and having an average carbon chain length of from about 10 to about 12 carbon atoms with from about 4 to about 8 moles of ethylene oxide per mole of alcohol; an amide having one of the preferred formulas:
o R8 C N(R9)2 wherein R8 is a straight-chain alkyl group cont~inin~ from about 7 to about 15 carbon 20 atoms and having an average carbon chain length of from about 9 to about 13 carbon atoms and wherein each R9 is a hydroxy alkyl group cont~inin~ from 1 to about 3 carbon atoms; a zwitterionic surfactant having one of the preferred formulas set forth hereinafter; or a phosphine oxide snrf~rt~nt Another suitable class of surfactants is the fluorocarbon surf~rt~nt~ examples of which are FC-129, a potassiurn fluorinated 25 alkylcarboxylate and FC-170-C, a mixture of fluorinated alkyl polyoxyethyleneethanols, both available firom 3M Corporation, as well as the Zonyl fluorosurf~rt~nt.s, available from DuPont Corporation. It is understood that mixtures of v arious surfactants can be used.

(3) Mixtures Mixtures of zwitterionic detergent surfactants, and/or anionic detergent surfactants as discussed hereinbefore, can be present in the present invention. The zwitterionic d~L~ L surfactants can be present at levels from about 0.02% to about 15%.
B. HYDRQPHOBIC SOLVENT
In order to obtain good cleaning one can use a hydrophobic solvent that has cleaning activity. The solvents employed in the hard surface cleaning compositions herein can be any of the well-known "degreasing" solvents cornmonly used in, for15 example, the dry cleaning industry, in the hard surface cleaner industry and the metalworking industry.
A useful definition of such solvents can be derived from the solubility pararneters as set forth in "The Hoy," a publication of Union Carbide, incorporated herein by reference. The most useful pararneter appears to be the hydrogen bonding 20 pararneter which is calculated by the formula:

a - 1 ~H=yT a wherein yH is the hydrogen bonding pararneter, a is the aggregation number, (Log a = 3.39066 Tb/T - 0.15848 - LogM), and yT is the solubility parameter which is obtained from the forrnula:

CA 02238194 1998-0~-20 W O g7/19158 PCT~US96/17429 yT= (~H7s - RT)d M

where ~H~s 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 5 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 7.7~ more preferably from about 2 to about 7 or 7.7, and even more preferably from about 3 to about 6. Solvents with lower numbers become increasingly difficult to solubilize in the compositions and have a greater tendency to 10 cause a haze on glass. Higher numbers require more solvent to provide good greasy/oily soil cle~ning Hydrophobic solvents are typically used at a level of from about 0.5% to about 30%, preferably from about 2% to about 15%, more preferably from about 4% to about 8%. Dilute compositions typically have solvents at a level of from about 1% to 15 about 10%, preferably from about 2% to about 6%. Concentrated compositions 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 disesquiterpenes should not be present at a level of more than about 0.4%, by weight 20 of the composition. and preferably, the composition is Pss.-nti~lly free of said solvents, especially when they have limited volatility. Many of such solvents comprise hydrocarbon or halogenated hydrocarbon moieties of the alkyl or cycloalkyl type, and have a boiling point well above room tenll.e~ re, i.e., above about 20~C.
The formulator of compositions of the present type will be guided in the 25 selection of co-solvent partly by the need to provide good grease-cutting properties, and partly by aesthetic considerations. For example, kerosene hydrocarbons function ~uite well for grease cutting in the present compositions, but can be malodorous.

CA 02238194 1998-0~-20 W O 97/19158 ~ PCT~US96/17429 Kerosene must be exceptionally clean before It can be used. even in commercial situations. For home use, where malodors would not be tolerated, the formulator would be more likely to select solvents which have a relatively pleasant odor. or odors ~ which can be reasonably modified by perfuming.
The C6-Cg alkyl aromatic solvents. especially the C6-Cg alkyl ben7P~
preferably octyl benzene, exhibit excellent grease removal properties and have a low, pleasant odor. Likewise the olefin solvents having a boiling point of at least about 1 00~C, especially alpha-olefins, preferably 1 -decene or 1 -dodecene, are excellent grease removal solvents However, the compositions are preferably essentially free of these very hydrophobic solvents.
Generically, the glycol ethers usel ul herein have the formula R 12 o_ (R13O)mlH wherein each R12 is an alkyl group which contains from about 3 to about 8 carbon atoms, each R13 is either ethylene or propylene, and ml is a number from I to about 3. The most plefell~;d glycol ethers are selected from the groupconsisting of monopropyleneglycolmonopropyl ether, dipropyleneglycolMonobutyl ether, monopropyleneglycolmonobutyl ether, ethyleneglycolmonohexyl ether, ethyleneglycolmonobutyl ether, diethyleneglycolmonohexyl ether, monoethyleneglycolmonohexyl ether, monoethyleneglycolmonobutyl ether, and mixtures thereof.
A particularly ~l~felled 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 g/100 g of water at 20~C.
Solvents such as pine oil, orange teryene, benzyl alcohol, n-hexanol, phthalic acid esters of Cl 4 alcohols, butoxy propanol, Butyl Carbitol R and 1(2-n-butoxy-1-methylethoxy)propane-2-ol (also called buloxy propoxy propanol or dipropylene glycol monobutyl ether), hexyl diglycol (Hexyl Carbitol R), butyl triglycol, diols such W O 97/19158 PCT~US96tl7429 -12-as 2,2.~-trimethyl-1~3-pentanediol, and mixtures thereof, can be used although the levels of hydrophobic material such as pine oil and orange terpene should be kept very low. if present. The butoxy-propanol solvent should have no more than about20%, preferably no more than about 10%, more preferably no more than about 7%, of 5 the secondary isomer in which the butoxy group is attached to the secondary atom of the propanol for improved odor.

C. ALKALINITY SOURCE
The aqueous liquid hard surface compositions can contain herein from about 0.05% to about 10%, by weight of the composition, of ~Ik~line material, preferably comprising or consisting essentially of, monoethanolarnine and/or beta-~mino~lk~nQl compounds.
Monoethanolamine and/or beta-aminoalkanol compounds serve primarily as solvents when the pEI is above about 10.0, and Pspeci~lly above about 10.7. They15 also provide ~lk~line b~ ;.,g capacity dunng use. However, the most unique contribution they make is to improve the filming/streaking properties of hard surface cleaning compositions c~ ";"g zwitterionic del~ s~ t~nt, arnphocarboxylate d~t~l~sellL surfactant, or mixtures thereof, whereas they do not provide any substantial improvement in filming/streaking when used with conventional anionic or 20 ethoxylated nonionic d~ ,lgelll surfactants. The reason for the improvement is not known. It is not simply a pE~ effect, since the improvement is not seen with conventional alkalinity sources. Other similar materials that are solvents do not provide the same benefit and the effect can be different depending upon the other mz~t~?ri~l~ present. When perfumes that have a high percentage of ~ oenCS are 25 incorporated, the benefit is greater for the beta-alkanol~minP~, and they are often , w~ ,as the monoethanolarnine is usually p-eI; .led.
Monoethanolamine and/or beta-alkanolamine are used at a level of from about 0.05% to about 10%, preferably from about 0.2% to about 5%. For dilute W O 97/19158 -13- PCT~US96/17429 compositions they are typically present at a level of from about 0.05% to about 2%~
preferably from about 0.075% to about 1.0%. more preferably from about 0.075% toabout 0.7%. For concentrated compositions they are typically present at a level of from about 0.5% to about 10%, preferably fro3m about 1% to about 5%.
5Preferred beta-aminoalkanols have a primary hydroxy group. Suitable beta-~mino~lk~nnls have the formula:
R14R,14 NH2R.l 4 wherein each R14 is selected from the group consisting of hydrogen and alkyl groups cont~ining from one to four carbon atoms and the total of carbon atoms in the 10compound is from three to six, preferably four. The amine group is preferably not he~l to a primary carbon atom. More preferably the amine group is attached to a tertiary carbon atom to minimi7- the reactivity of the amine group. Specific preferred beta-aminoalkanols are 2-amino,l-butanol; 2-amino,2-methylpropanol; and mixturesthereof. The most preferred beta-aminoalkanol is 2-~mino,?-methylpropanol since it 15has the lowest molecular weight of any beta-~lmino~lk~nnl which has the arnine group ht?cl to a tertiary carbon atom. The beta-~mino~lk~nols ~IcÇ~ably have boiling points below about 175~C. Preferably, the boiling point is within about 5~C of 1 65~C.
Such beta-aminoalkanols are excellent materials for hard surface cleaning in 20general and, in the present application, have certain desirable characteristics.
The beta-~minn~lk~n~ls are surprising;ly better than, e.g., monoethanolamine for hard surface detergent compositions that contain perfume ingredients like terpenes and similar materials. However, normally the monoethanolarnine is preferred for its effect in improving the filming/streaking p~lro~l.lance of compositions cont~ining 25 zwitterionic detergent surfactant. The improvement in filming/streaking of hard W O 97/19158 PCT~US96/17429 surfaces that is achieved by combining the monoethanolamine and/or beta-arninoalkanol was totally unexpected. r Good filming/streaking, i.e.~ minim~l, or no~ filming/streaking~ is especially important for cleaning of. e.g., window glass or mirrors where vision is affected and for dishes and ceramic surfaces where spots are aesthetically undesirable. Beta-arninoalkanols provide superior cleaning of hard-to-remove greasy soils and superior product stability, ecpecially under high temperat~-re ~onditiorls. whPn used in hard surface cleaning compositions, especially those cont~inin~ the zwitterionic detergent Cllrf~ t.~lntc Beta-aminoalkanols. and especially the preferred 2-amino-2-methylpropanol, are surprisingly volatile ~rom cleaned surfaces considering their relatively high molecular weights.
The compositions can contain, either alone or in addition to the preferred alkanolamines, more conventional ~Ik~lin~ buffers such as ammonia; other C2 4 l S alkanolamines; alkali metal hydroxides; silicates; borates; carbonates; and/or bicarbonates. Thus, the buffers that are present usually comprise the preferred monoethanolamine and/or beta-aminoalkanol and additional conventional ~Ik~line material. The total amount of alkalinity source is typically from 0% to about 5%, preferably 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 ll.S,,more preferably from about 9.7 to about 11.3. pH is usually measured on the product.

(D) r)ETERGENT BUILDER
Detergent builders that are efficient for hard su~ace cleaners and have reduced filming/streaking characteristics at the critical levels are an essenti~l element of the present invention. Addition of the specific d~t~,.ge,lt builder tartaric acid at critical levels to the present composition improves cleaning without the problem of filminglstreaking that usually occurs when delelg~ builders are added to hard CA 02238l94 l998-05-20 surface cleaners. Through the present invention there is no longer the need to make a compromise between improved cleaning ;~nd acceptable filming/streaking results which is especially important for hard surface cleaners which are also directed at - cleaning glass. These compositions c~ nt~ininE, the detergent builder herein at the 5 levels herein. have exceptionally good cleaning properties. They also have exceptionally good shine pro~ lies, i.e., when used to clean glossy surfaces, without rinsing, they have much less tendency than, e.g., carbon~e built products to leave a dull finish on the surface and filming/streakiing.
The detergent builder is present at levels of from about 0.001% to about 0.05%. more preferably from about 0.01% to about 0.05%, and most preferably fromabout 0.025% to about 0.04%.
Typically the improvement with regard to acceptable filming/streaking results occurs most when the builder is combined with amphoteric and/or zwitterionic detergent surfactant compositions although an improvement is also seen with the less "l,_Çe.l,;d anionic or anionic/nonionic detergent surfactant compositions.

(E) AOUEOUS CO-SQLVENT SYSTFM
The balance of the formula is typic;ally water and non-aqueous polar solvents with only minim~l cleaning action, having hydrogen bonding parameters greater than about 7.7, preferably greater than about 7.8, like methanol, ethanol, isopropanol, ethylene glycol, glycol ethers having a hydrogen bonding p~r~met.~r of greater than 7.7, propylene glycol, and mixtures thereof, ~l~feldbly iso~.ol)anol, more preferably ethanol. The level of non-aqueous polar solvent is usually greater when more concentrated formulas are prepared. Typically, the level of non-aqueous polar solvent is from about 0.5% to about 40%, preferably from about 1% to about 10%, more 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 95%.

W O 97/19158 PCT~US96/17429 (F) OPTIONALIN GFUEDIENTS
The compositions herein can also contain other various adjuncts which are known to the art for detergent compositions. Preferably they are not used at levels that cause unacceptable filming/streaking.
S Non-1imiting examples of such adjuncts are: enzymes such as proteases;
hydrotropes such as sodiurn toluene sulfonate, sodium cumene sulfonate and potassium xylenç sul~onatc; aesthetic-erlhancing ingredients such as colorants ar.d perfurnes, providing they do not adversely impact on filming~streaking in the cleaning of glass. Most hard surface cleaner products contain some perfume to provide an olfactory aesthetic benefit and to cover any "chemical" odor that the product may have. The main function of a small fraction of the highly volatile, low boiling (having low boiling points), perfurne components in these perfumes is to improve the fragrance odor of the product itself~ rather than impacting on the subsequent odor of the surface being cle~n~cl However, some of the less volatile, high boiling perfume ingredients can provide a fresh and clean impression to the surfaces, and it is sometimes desirable that these ingredients be deposited and present on the dry surface. The perfumes are preferably those that are more water-soluble and/or volatile to l~n~ spotting and filming The perfumes useful herein are described in more detail in U.S. Patent 5,108,660, Michael, issued April 28, 1992, at col. 8 lines 48 to 68, and col. 9 lines 1 to 68, and col. 10 lines 1 to 24, said patent, and especia}ly said specific portion, being incorporated by reference.
,~ntib~ct~rial agents can be present, but preferably only at low levels to avoidfilming/stre~king problems. More hydrophobic ~ntib~cterial/germicidal agents, like orthoben_yl-para-chlorophenol, are avoided. If present, such materials should be kept at levels below about 0.1%.
Stabilizing ingredients can be present typically to st?hi~i7P more of the hydrophobic ingredients, e.g., perfume. The stabilizing ingredients include acetic W O 97/191~8 -17- PCT~US96/17429 acid and propionic acids. and their salts, e.g., NH4, MEA, Na, K~ etc., preferably acetic acid and the C2-C6 alkane diols, more preferably butane diol. The stabili~ing ingredients do not function in accordance with any known principle. Nonetheless. the combination of amido zwitterionic detergent surfactant with linear acyl 5 amphocarboxylate detergent surfactant, anionic d~L~ellt sllrf~rt~nt, nonionic dett:l~ e~ll surfactant, or mixtures thereof, and stabilizing ingredient can create a ~icroemulsion. The amolmt of stabilizing in~edient is typicall~r from abr~ut 0.01% to about 0.5%, preferably from about 0.02% to about 0.2~/~. The ratio of hydrophobic material, e.g., perfume that can be stabiliz:ed in the product is related to the total 10 surfactant and typically is in an arnount that provides a ratio of surfactant to hydrophobic material of from about 1:2 to about 2:1.
Concentrated compositions of the present invention can also be used in order to provide a less expensive and more ecologically sound product. Concentrations of up to IOX the original concentration, preferably up to SX, more plcr~dl)ly up to 2X
15 the original concentration can be used and can be diluted using tap water, distilled water, and/or deionized water, down to a 1X concentration.

W O 97/19lS8 ~18-The invention is illustrated by the following nonlimiting Exarnples.

EXAMPLE I
Forrnula No. (Wt. %) In~redient 1 2 3 4 5 6 7 ~PA1 2.8 2.8 2.8 E~anol -- -- -- 2.8 2.8 2.8 2.8 gp2 2.8 2.8 2.8 2.8 2.8 2.8 2.8 MEA3 0. 275 0.275 0. 30 0.075 0.07~ 0.075 0.075 Cocoarnidopropyl- 0.08 0.05 0.08 hydroxy-sultaine Sulfate (Cl2) 0.13 0.20 0.13 0.064 0.06~ 0.112 0.112 Sulfate (C14) 0.11 0.08 0.11 0.016 0.016 0.028 0.028 Tartaric Acid 0.025 0.040 0.040 0.025 0.025 0.025 0.025 Perfi~ne 0.11 0.11 0.13 0.09 0.09 0.09 0.09 Soft Water to Balance ~ BALANCE

1IsO~ allol 2Butox~ ol,a"ol 10 3Monoethanolamine CA 02238l94 l998-05-20 W O 97/19158 PCT~US96/17429 EXAMPJ_E II
Comparative e~amples with no MEA/Tartaric acid, substituting sodium bicarbonate.
,.
Formula No. (Wt. %) In~redient 8 9 l O 1 1 IPAl --Ethanol 2.8 ~.8 '~.8 2.8 Bp2 2.8 2.8 ,2.8 2.8 Cocoarnidopropyl-hydroxy-sultaine ~ ~S 0.08 0.05 0.08 Sodium Alkyl Sulfate (C12) 0.064 0.064 0.112 0.112 Sodium Alkyl Sulfate (Cl4) 0.016 0.016 0.028 0.028 NaHCO3 0.04 0.04 0.04 0.04 Perfume 0.09 0.09 0.09 0.09 Soft Water to Balance ~ ~3ALANCE- 5 1 Tsopropanol 2Butoxypropanol 3Monoethanolamine ~ nd Result Wipe Test Procedure:
Multiple sprays of the product to be tested are appl;ed to a 2ft. x 3ft. glass window (which can be soiled with body oils from a handprint) and wiped with two 15 paper towels to near dryness, cimt~l~ting actual consumer usage of the product.
Gradin~:
Expert ~udges are employed to evaluate the specific areas of product application for amount of filming/streaking, with the aid of a floodlight to cim~ te a sunbearn. A numerical value describing the quality of the end result is ~ccignP~ to 20 each product. For the test results reported here a 0-6 scale is used, in which 0 = good end result with no film/strealc, and 6 = very poor end result.

W O 97/19158 PCT~US96/17429 End Result Wipe Grade Forrnula (0 = best, 6- worst) 0.74 0.60 3 0.76 0.95 1.23 6 1.07 7 1.25 8 1.35 9 1.74 1 0 1 .4g Il 1.90

Claims (5)

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 0.01% to 2.0%, by weight of the composition, of detergent surfactant selected from the group consisting of C6-C20 alkyl sulfates, alkyl ethoxy ether sulfates, alkyl benzene sulfonates, olefin sulfonates, and mixtures thereof;

(2) from 0.02% to 15%, by weight of the composition. of detergent surfactant having the generic formula:

R1-[C(O)-N(R2)-(CR32)n1]mN(R4)2(+)-(CR32)p1-Y(-) wherein each R1 is an alkyl, or alkylene, group containing from 10 to 18 carbon atoms; each (R2) and (R3) is selected from the group consisting of hydrogen, methyl, ethyl, propyl, hydroxy substituted ethyl or propyl and mixtures thereof; each (R4) is selected from the group consisting of hydrogen and hydroxy groups, with no more than one hydroxy group in any (CR32)p1 moiety; m is 0 or 1; each n1 and p1 is a number from 1 to 4; and Y is a carboxylate or sulfonate group;

(3) 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, wherein said solvent comprises no more than 0.4%, by weight of the composition, of mono- or sesquiterpenes;

(C) from 0.05% to 10%, by weight of the composition, of alkaline material;

(D) from 0.001% to 0.05%, by weight of the composition, of tartaric acid detergent builder; and (E) the balance being an aqueous co-solvent system comprising any organic co-solvent having a hydrogen bonding parameter of greater than 7.8.

2. The composition of Claim 1 wherein component (A) is detergent surfactant selected from the group consisting of:
(1) from 0.01 to 1.0%, by weight of the composition, of a C6-C20 alkyl sulfate detergent surfactant;
(2) from 0.01% to 1.0%, by weight of the composition, of detergent surfactant having the generic formula:

R5-[C(O)-N(R6)-(CH2)n]- N(CH3)2(+)-(CR7)3-SO3(-) wherein each R5 is an alkyl, or alkylene, group containing from 10 to 15 carbon atoms; each (R6)is selected from the group consisting of hydrogen, methyl, ethyl, propyl, hydroxy substituted ethyl or propyl and mixtures thereof; each (R7) is selected from the group consisting of hydrogen and hydroxy groups wherein one of the R7 groups between the (+) and the (-) charge centers is a hydroxy group and the remaining R7 groups are hydrogen with no more than one hydroxy group in the (C R72)3 moiety and n is a number from 1 to 4; and (3) mixtures thereof.

3. The composition according to any of the preceding Claims containing sufficient alkaline material comprising alkanolamine selected from the group consisting of monoethanolamine, beta-amino-alkanol, containing from three to sixcarbons, and mixtures thereof, to give a pH of from 9.5 to 12, preferably from 9.7 to 12, more preferably from 9.7 to 11.3.

4. The composition according to any of the preceding Claims wherein the level of tartaric acid is from 0.01% to 0.05%, preferably from about 0.025% to 0.04% by weight of the composition.

5. The composition according to any of the preceding Claims wherein said solvent (B) is selected from the group consisting of monopropyleneglycolmonopropyl ether, dipropyleneglycolmonobutyl ether, monopropyleneglycolmonobutyl ether, ethyleneglycolmonohexyl ether, ethyleneglycolmonobutyl ether, diethyleneglycolmonohexyl ether, monoethyleneglycolmonobutyl ether, and mixtures thereof; preferably monopropyleneglycolmonobutyl ether.