LIQUID HARD SURFACE DETERGENT COMPOSITIONS CONTAINING ZWITTERIONIC DETERGENT SURFACTANT AND MONOETHANOLAMINE AND/OR BETA-AMINOALKANOL

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: LIQUID HARD SURFACE-DETERGENT COMPOSITIONS CONTAINING ZWITTERIONIC DETERGENT SURFACTANT AND MONOETHANOLAMINE AND/OR BETA-AMINOAL ANOL FIELD OF THE INVENTION This invention pertains to liquid detergent compositions f use in cleaning hard surfaces. Such compositions typicall contain detergent surfactants, solvents, builders, etc. BACKGROUND OF THE INVENTION The use of solvents and organic water-soluble syntheti detergents at low levels for cleaning glass are known. General purpose household cleaning compositions for har surfaces such as mgtal , glass, ceramic, plastic and linoleu surfaces, are commercially available in both powdered and liqui form. Liquid detergent compositions are disclosed in Australia Pat. Application 82/88168, filed Sept. 9, 1982, by The Procter' Gamble Company; U.K. Pat. Application GB 2,166,153A, file Oct. 24, 1985, by The Procter & Gamble Company; and U.K. Pat Application GB 2,160 t -887A, filed June 19, 1985, by Bristol-Myer Company, all of said published applications being incorporate herein by reference. .These liquid detergent compositions compris certain organic solvents, surfactant, and optional builder and/o abrasive. The prior . art, however, fails to teach, or recognize the advantage of the specific organic solvents/buffers disclose hereinafter, in liquid hard surface cleaner formulations. Liquid cleaning compositions have the great advantage tha they can be applied,, t,o hard surfaces in neat or concentrated for so that a relatively high level of surfactant material and organi solvent is delivered directly to the soil. Moreover, it is rather more straightforward task to incorporate high concentra tions of anionic or nonionic surfactant in a liquid rather than granular composition. For both these reasons, therefore, liqui cleaning compositions have the potential to provide superior soa scum, grease, and ofl soil removal over powdered cleaning com positions. Nevertheless, liquid cleaning compositions, and especiall compositions prepared for cleaning glass, still suffer a number o drawbacks which can limit their consumer acceptability. They hav to have good spotting/filming properties. In addition, they ca suffer problems of product form, in particular, inhomogeneity lack of clarity, or inadequate viscosity characteristics, o excessive "solvent" odor for consumer use. An object of the present invention is to provide detergen compositions which provide good glass cleaning without excessiv filming and/or streaking. SUMMARY OF THE INVENTION The present invention relates to an aqueous, liquid, har surface detergent composition comprising: (a) zwitterionic deter gent surfactant, containing a cationic group, preferably a quat ernary ammonium group, and an anionic group, preferably a car boxylate, sulfonate, or sulfate group, more preferably a sulfonat group; (b) solvent/buffer system that comprises either mono ethanolamine, beta-a inoalkanol which contains from about three t about six carbon atoms, or mixtures thereof, preferably mono ethanola ine; (c) optional detergent builder; and the balanc being (d) aqueous solvent system and, optionally, minor ingre dients. The composition preferably does not contain amounts o materials, like conventional detergent builders, etc., tha deposit on the surface being cleaned and cause unacceptabl spotting/filming. The compositions can be formulated at usag concentrations, or as concentrates, and can be packaged in container having means for creating a spray to make application t hard surfaces more convenient. All percentages, parts, and ratios herein are "by weight unless otherwise stated. DETAILED DESCRIPTION OF THE INVENTION In accordance with the present invention, it has been foun that superior aqueous liquid detergent compositions for cleanin shiny surfaces such as glass contain zwitterionic detergen surfactant (containing both cationic and anionic groups in sub stantially equivalent proportions so as to be electrically neutral at the pH of use, typically at least ' about 9.5, preferably a least about 10) and monoethanolamine and/or certain beta-amino alkanol compounds. The Detergent Surfactant The aqueous, liquid hard surface detergent compositio (cleaners) herein contain from about 0.001% to about 15% of sui able zwitterionic detergent surfactant containing a cationi group, preferably a quaternary ammonium group, and an anioni group, preferably carboxylate, sulfate and/or sulfonate grou more preferably sulfonate. Successively more preferred ranges zwitterionic detergent surfactant inclusion are from about 0.0 to about 10% of surfactant, and from about 0.1% to about 5% surfactant. Zwitterionic detergent surfactants, as mentioned herei before, contain both a cationic group and an anionic group and a in substantial electrical neutrality where the number of anioni charges and cationic charges on the detergent surfactant molecul are substantially the same. Zwitterionic detergents, whi typically contain both a quaternary ammonium group and an anioni group selected from sulfonate and carboxylate groups are desirabl since they maintain their amphoteric character over most of the range of interest for cleaning hard surfaces. The sulfonate gro is the preferred anionic group. Preferred zwitterionic detergent surfactants have the generi formula: R3-[C(0)-N(R4)-(CR5 2 )n3 m N(R6)2( + )-(CR5 2 )p-Y(-) wherein each y is preferably a carboxylate (C00~) or sulfona (Sθ3~) group, preferably sulfonate; wherein each R3 is a hydr carbon, e.g., an alkyl, or alkylene, group containing from about to about 20, preferably from about 10 to about 18, more preferab from about 12 to about 16 carbon atoms; wherein each (R 4 ) either hydrogen, or a short chain alkyl, or substituted alky containing from one to about four carbon atoms, preferably grou selected from the group consisting of methyl, ethyl, propy hydroxy substituted ethyl or propyl and mixtures thereof, prefe ably methyl; wherein each (R5) is selected from the group co sisting of hydrogen and hydroxy groups; wherein (R*>) is like except preferably not hydrogen; wherein m is 0 or 1; and where each n and p are a number from 1 to about 4, preferably from 2 about 3, more preferably about-3; there being no more than about one hydroxy group in any (CR 5 2) moiety. The R 3 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 R 3 groups. The R* groups can also be connected to form ring structures. Preferred hydrocarbyl a ido- alkylene sulfobetaine (HASB) detergent surfactants wherein - 1 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 hydrocarbylamidoalkylene betaines and, especially, hydrocarbylamidoalkylene sulfobetaines 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 onoethanol- amine and/or specific beta-amino alkanol as disclosed herein. A more preferred specific detergent surfactant is a Cιo-14 fatty acylamidopropylene(hydroxypropylene)sulfόbetaine, e.g., the detergent surfactant available from the Sherex Company as a 40% active product under the trade name "Varion CAS Sulfobetaine." The level of zwitterionic detergent surfactant, e.g., HASB, in the composition is typically from about 0.001% to about 15%, preferably from about 0.05% to about 10%, more preferably from about 0.2% to about 5%. 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 0.1% to about 0.25%, 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% to about 5%. It is an advantage of the zwitterionic detergent, e.g., HASB, 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.g., below about 1%. Other zwitterionic detergent surfactants are set forth Col. 4 of U.S. Pat. No. 4,287,080, Siklosi, incorporated herein reference. Another detailed listing of suitable zwitterion detergent surfactants for the detergent compositions herein can found in U.S. Pat. No. 4,557,853, Collins, issued Dec. 10, 198 incorporated by reference herein. Commercial sources of su surfactants can be found in McCutcheon's EMULSIFIERS A DETERGENTS, North American Edition, 1984, McCutcheon Division, Publishing Company, also incorporated herein by reference. The above patents and reference also disclose other deterge surfactants, e.g., anionic, and nonionic detergent surfactant that can be used in small amounts in the composition of th invention as cosurfactants.. Typical of these are the alkyl- a alkylethoxylate- (polyethoxylate) sulfates, paraffin sulfonate olefin sulfonates, alkoxylated (especially ethoxylated) alcoho and alkyl phenols, alpha-sulfonates of fatty acids and of fat acid esters, and the like, which are well-known from the dete gency art. When the pH is above about 9.5, detergent surfactan that are amphoteric at a lower pH are desirable anionic deterge cosurfactants. For example, detergent surfactants which a c 12"Cl8 acylamido alkylene a ino alkylene sulfonates, e.g compounds having the formula R-C(0)-NH-(C2H4)-N(C2H4θH CH2CH(0H)CH2S03M wherein R is an alkyl group containing from abo 9 to about 18 carbon atoms and M is a compatible cation a desirable cosurfactants. These detergent surfactants are avai able as Miranol CS, OS, JS, etc. The CTFA adopted name for su surfactants is cocoamphohydroxypropyl sulfonate. It is preferr that the compositions be substantially free of alkyl naphthale sulfonates. In general, detergent surfactants useful herein contain hydrophobic group, typically containing an alkyl group in t C9-C18 range, and, optionally, one or more linking groups such ether or amido, preferably amido groups. The anionic deterge surfactants can be used in the form of their sodium, potassium alkanolammonium, e.g., triethanolammonium salts; the nonioni generally contain from about 5 to about 17 ethylene oxide group C12-C18 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 Cs-Cis alkyl benzene sulfo¬ nate (LAS), particularly C11-C12 LAS; the sodium salt of 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 available examples 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 Corporation; the sodium and potassium salts of coconut fatty acids (coconut soaps); the condensation product of a straight-chain primary alcohol containing from about 8 carbons to about 16 carbon atoms and having an average carbon chain length of from about 10 to about 12 carbon atoms with from about 4 to about 8 moles of ethylene oxide per mole of alcohol; an amide having one of the preferred formulas: 0 II wherein Rl is a straight-chain alkyl group 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 atoms; a zwitterionic surfactant having one of the preferred formulas set forth hereinafter; or a phosphine 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. M0N0ETHAN0LAMINE AND/OR BETA-AMIN0ALKAN0L ■ Monoethandlamine and/or beta-aminoalkanol compounds serve primarily as solvents when the pH is above about 10.0, and especially above about 10.7. They also provide alkaline bufferin capacity during use. However, the most unique contribution the make is to improve the spotting/filming properties of hard surfac cleaning compositions containing zwitterionic detergent surfac 5 tant, whereas they do not provide any substantial improvement i spotting/filming when used with conventional anionic or ethoxy lated nonionic detergent surfactants. The reason for the improve ment is not known. It is- not simply a pH effect, since th improvement is not seen with conventional alkalinity sources lO Other similar materials that are solvents do not provide the sam benefit and the effect can be different depending upon the othe materials present. When perfumes that have a high percentage o terpenes are incorporated, the benefit is greater for the beta alkanolamines, and they are often preferred, whereas the ono ^ ethanolamine is usually preferred. Monoethanolamine and/or beta-alkanolamine are used at a leve of from about 0.05% to about 10%, preferably from about 0.2% t about 5%. For dilute compositions they are typically present at level of from about 0.05% to about 2%, preferably from about 0.1 20 t 0 a bout 1.0%, more preferably from about 0.2% to about 0.7%. Fo concentrated compositions they are typically present at a level o from about 0.5% to about 10%, preferably from about 1% to abou 5%. Preferred beta-aminoalkanols have a primary hydroxy group 25 Suitable beta-aminoalkanols have the formula: R R R - C C - OH 30 NH2* R wherein each R is selected from the group consisting of hydroge and alkyl groups containing from one to four carbon atoms and th total of carbon atoms in the compound is from three to six preferably four. The amine group is preferably not attached to " primary carbon atom. More preferably the amine group is attache to a tertiary carbon atom to minimize the reactivity of the amin group. Specific* preferred beta-aminoalkanols are 2-amino,l butanol; 2-amiπo,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- aminoalkanols preferably have boiling points below about 175*C. Preferably, the boiling point is within about 5'C of 165'C. Such beta-aminoalkanols are excellent materials for hard surface cleaning in general and, in the present application, have certain desirable characteristics. The beta-aminoalkanols are surprisingly better than, e.g., onoethanolamine for hard surface detergent compositions that contain perfume ingredients like terpenes and similar materials. However, normally the monoethanolamine is preferred for its effect in improving the spotting/filming performance of compositions containing zwitterionic detergent surfactant. The improvement in spotting/filming of hard surfaces that is achieved by combining the monoethanolamine and/or beta-aminoalkanol was totally unexpected. Good spotting/filming, i.e., minimal, or no, spotting/film- ing > 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-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 Cosol ent In order to obtain good cleaning without any appreciable amount of detergent builder, one can use a cosolvent that has cleaning activity in addition to the monoethanolamine and/or beta- aminoalkanol. The cosolvents employed in the solvent/buffer system in the hard surface cleaning compositions herein can be any of the well-known "degreasing" solvents commonly used in, for - 9 - example, the dry cTe'aning industry, in the hard surface clean industry and the etalworking industry. A useful definition of such solvents can be derived from t solubility parameters as set forth in "The Hoy," a publication Union Carbide, incorporated herein by reference. The most usef parameter appears to be the hydrogen bonding parameter which calculated by the formula wherein -γH is the hydrogen bonding parameter, a is the aggregati number, (Log α - 3.39066 Tb/T c - 0.15848 - Log M) , and d γT is the solubility parameter which is obtained from the formul 1/2 γT = (AH 25 - RT)d M where ΔH25 is the heat of vaporization at 25*C, R is the g constant (1.987 cal/mole/deg) , T is the absolute temperature °K, Tb is the boiling point in β K, T c is the critical temperatu in * K, d is the density in g/ml , and M is the molecular weight. For the compositions herein, hydrogen bonding parameters a preferably less than about 7.7, more preferably from about 2 about 7, and even more preferably from about 3 to about Solvents with lower numbers become increasingly difficult solubilize in the compositions and have a greater tendency cause a haze 013 glϊss. Higher numbers require more solvent provide good grea-sy/oily soil cleaning. Cosolvents are typically used at a level of from about 1% about 30%, preferably from about 2% to about 15%, more preferab from about 4% to about 8%. Dilute compositions typically ha cosolvents at a level of from about 1% to about 10%, preferab from about 3% to about 6%. Concentrated compositions contain fr about 10% to about 30%, preferably from about 10% to about 20% cosolvent. Many of such solvents comprise hydrocarbon or halogenated hydrocarbon moieties of the alkyl or cycloalkyl type, and have, a boiling point well above room temperature, i.e., above about 20'C. The formulator of compositions of the present type will be guided in the selection of cosolvent partly by the need to provide good grease-cutting properties, and partly by aesthetic consid- erations. For example, kerosene hydrocarbons function quite well for grease cutting in the present compositions, but can be mal¬ odorous. 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 Cβ-Cg alkyl aromatic solvents, especially the Cδ-Cg alkyl benzenes, 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 100'C, especially alpha-olefins, preferably 1-decene or 1-dodecene, are excellent grease removal solvents. Generically, the glycol ethers useful herein have the formula R6 θ(R7θ) m H wherein each Rδ is an alkyl group which contains from about 3 to about 8 carbon atoms, each R? is either ethylene or propylene, and m is a number from 1 to about 3. The most pre¬ ferred glycol ethers are selected from the group consisting of monopropyleneglycolmonopropyl ether, dipropyleneglycolmonobutyl ether, monopropyleneglycolmonobutyl ether, diethyleneglycolmono- hexyl ether, onoethyleneglycolmonohexyl ether, onoethylenegly¬ colmonobutyl ether, 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 g/100 g of water at 20 β C. Some examples of suitable diol solvents and their solubil- ities in water are shown in Table 1. TABLE 1 Solubility of Selected Diols in 20*C Water Solubility Diol fq/100o H?0 1,4-Cyclohexanedimethanol 20.0* 2,5-Dimethyl-2,5-hexanediol 14.3 2-Phenyl-l,2-propanediol 12.0* Phenyl-l,2-ethanediol 12.0* 2-Ethyl-l,3-hexanediol 4.2 2,2,4-Trimethyl-l,3-pentanediol 1.9 l,2-0ctanediol 1.0* ♦ Determined via laboratory measurements. All other values are from published literature. The diol solvents are especially preferred because, in add tion to good grease cutting ability, they impart to the comp sitions an enhanced ability to remove calcium soap soils fr surfaces such as bathtub and shower stall walls. These soils a particularly difficult to remove, especially for compositio which do not contain an abrasive. The diols containing 8- carbon atoms are preferred. The most preferred diol solvent 2,2,4-trimethyl-l,3-pentanediol . Solvents such as pine oil, orange terpene, benzyl alcoho n-hexanol, phthalic acid esters of C1-4 alcohols, butoxy propano Butyl Carbitol ® and l(2-n-butoxy-l-methylethoxy)propane-2-ol (al called butoxy propoxy propanol or dipropylene glycol monobut ether), hexyl diglycol (Hexyl Carbitol®), butyl triglycol, dio such as 2,2,4-trimethyl-l,3-pentanediol, and mixtures thereof, c be used. The butoxy-propanol solvent should have no more th about 20%, preferably no more than about 10%, more preferably more than about 7%, of the secondary isomer in which the buto group is attached to the secondary atom of the propanol f improved odor. The Cobuffer/Alkalinitv-Source The solvent/buffer system is formulated to give a pH in t product and, at least initially, in use of from about 9.5 to abo 13, preferably from about 9.7 to about 12, more preferably fr about 9.7 to about 11.5. pH is usually measured on the produc The buffering system comprises monoethanolamine and/or beta- aminoalkanol and, optionally, but preferably, cobuffer and/or alkaline .material .selected from the group consisting of: ammonia; other G2-C4 alkanola ines; alkali metal hydroxides; silicates; borates; carbonates; and/or bicarbonates; and mixtures thereof. The preferred cobuffering/alkalinity materials are alkali metal hydroxides. The level of the cobuffer/alkalinity-source is from 0% to about 5%, preferably from 0% to about 5%. Monoethanolamine and/or beta-aminoalkanol buffering material, in the system is important for spotting/filming. It is surprising that mono¬ ethanolamine and/or beta-aminoalkanol provides improved spotting/- filming when used with the zwitterionic detergent surfactant. The Aqueous Solvent System The balance of the formula is typically water and non-aqueous polar solvents with only minimal cleaning action like ethanol, ethanol , isopropanol, ethylene glycol, propylene glycol, and mixtures thereof. The level 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 40%, 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 95%. Optional Ingredients 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 spotting/filming. Nonlimiting examples of such adjuncts are: Enzymes such as proteases; 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/- filming in the cleaning of glass. The perfumes are prefer¬ ably those that are more water-soluble and/or volatile to minimize spotting and filming. Antibacterial agents can be present, but preferably only at low levels to avoid spotting/filming problems. More hydrophobic antibacterial/ger icidal agents, like orthobenzyl-para-chlor phenol , are avoided. If present, such materials should be kept levels below about 0.1%. Detergent Builder An optional ingredient for general cleaning purposes, is fr 0% to about 30%, preferably from about 1% to about 15%, mo preferably from about 1% to about 12%, of detergent builder. F use on glass and/or other shiny surfaces, a level of builder from about 0.1% to about 0.5%, preferably from about 0.1% to abo 0.2%, is useful. While any of the builders or inorganic salts c be used herein, some examples of builders for use herein a sodium nitrilotriacetate, potassium pyrophosphate, potassi tripolyphosphate, sodium or potassium ethane-1-hydroxyl-1,1-di phosphonate, the nonphosphorous chelating agents described in t copending U.S. Pat. Application of Culshaw and Vos, Ser. N 285,337, filed Dec. 14, 1988, said application being incorporat herein by reference (e.g., carboxymethyltartronic acid, oxydi malonic acid, tartrate monosuccinic acid, oxydisuccinic aci tartrate disuccinic acid, and mixtures thereof), sodium citrat sodium carbonate, sodium sulfite, sodium bicarbonate, and forth. Other suitable builders are disclosed in U.S. Pat. N 4,769,172, Siklosi, issued Sept. 6, 1988, and incorporated here by reference, and chelating agents having the formula: CH2C00M R - N ^ CH2C00M wherein R is selected from the group consisting of: -CH2CH2CH2OH; -CH2CH(0H)CH3; -CH2CH(0H)CH20H; -CH(CH2θH)2; -CH3; -CH2CH2OCH3; -C-CH3; -CH2-C-NH2; 0 0 -CH2CH2CH2OCH3; -C(CH20H)3; and mixtures thereof; and each M is hydrogen or an alkali metal ion. Chemical names of the acid form of some chelating agen useful herein include: N(3-hydroxypropyl)imino-N,N-d ' iacetic acid (3-HPIDA); N(-2-hydroxypropyl)imino-N,N-diacetic acid (2-HPIDA); N-glycerylimino-N,N-diacetτc acid (GLIDA); dihydroxyisopropylimino-(N,N)-diacetic acid (DHPIDA) ; methylimino-(N,N)-diacetic acid (MIDA); 2-methoxyethylimino-(N,N)-diacetic acid (MEIDA); amidoiminodiacetic acid (also known as sodium amidonitrilo- triacetic, SAND); acetamidoiminodiacetic acid (AIDA); 3-methoxypropylimino-N,N-diacetic acid (MEPIDA); and tris(hydroxymethyl)methylimino-N,N-diacetic acid (TRIDA). Methods of preparation of the iminodiacetic derivatives herein are disclosed in the following publications: Japanese Laid Open publication 59-70652, for 3-HPIDA; DE-OS-2542 708, for 2-HPIDA and DHPIDA; Chem. ZVESTI 34(1) p. 93-103 (1980), Mayer, Riecanska et al., publication of Mar. 26, 1979, for GLIDA; C.A. 104(6)45062 d for MIDA; and Biochemistry 5, p. 467 (1966) for AIDA. The levels of builder present in the wash solution used for glass should be less than about 0.5%, preferably less than about 0.2%. Therefore, dilution is highly preferred for cleaning glass, while full strength use is preferred for general purpose cleaning. Other effective detergent builders, e.g., sodium citrate, sodium ethylenediaminetetraacetate, etc., can also be used, preferably at lower levels, e.g., from about 0.1% to about 1%, preferably from about 0.1% to about 0.5%. Inclusion of a detergent builder improves cleaning, but harms spotting and filming and has to be 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. Perfumes 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), perfume 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 cleaned. However, some of the less volatile, high boiling- perfume ingredients can provide fresh and clean impression to the surfaces, and it is sometime desirable that these ingredients be deposited and present on th dry surface. It is- a special advantage of this invention tha perfume ingredient's are readily solubilized in the compositions b the acylamidoal ylene detergent surfactant. Other similar deter gent surfactants will- not solubilize as much perfume, especiall substantive perfume, or maintain uniformity to the same lo temperature. The perfume ingredients and compositions of this inventio are the conventional ones known in the art. Selection of an perfume component, or amount of perfume, is based solely o aesthetic considerations. Suitable perfume compounds and compo sitions can be found in the art including U.S. Pat. Nos. 4,145,184, Brain and Cummins, issued Mar. 20, 1979; 4,209,417 Whyte, issued June 24, 1980; 4,515,705, Moeddel , issued May 7 1985; and 4,152,272, Young, issued May 1, 1979, all of sai patents being incorporated herein by reference. Normally, the ar recognized perfume "compositions are not ver substantive a described hereinafter to minimize their effect on hard surfaces. In general, the degree of substantivity of a perfume i roughly proportional to the percentages of substantive perfum material used. Relatively substantive perfumes contain at leas about 1%, preferably at least about 10%, substantive perfum materials. Substantive perfume materials are those odorous compound that deposit on surfaces via the cleaning process and are detect able by people with normal olfactory acuity. Such material typically have vapor pressures lower than that of the averag perfume material. Also, they typically have molecular weights o about 200 or above, and are detectable at levels below those o 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' or lower. Many of the more moderately volatile perfume ingre dients are also lost substantially in the cleaning process. Th moderately volatile perfume ingredients are those having boiling points of from about 250 β C to about 300°C. The less volatile, high boiling, perfume ingredients referred to hereinbefore are those having boiling points of about 300°C or higher. A signifi- cant portion of even these high boiling perfume ingredients, considered to be substantive, is lost during the cleaning cycle, and it is desirable to have means to retain more of these ingre¬ dients on the dry surfaces. Many of the perfume ingredients, along with their odor character, and their physical and chemical properties, such as boiling point and molecular weight, are given in "Perfume and Flavor Chemicals (Aroma Chemicals)," Steffen Arctander, published by the author, 1969, incorporated herein by reference. Examples of the highly volatile, low boiling, perfume ingre- dients are: anethole, benzaldehyde, benzyl acetate, benzyl alcohol, benzyl formate, iso-bornyl acetate, camphene, cis-citral (neral), citronellal, citronellol, citronellyl acetate, para- cymene, decanal, dihydro!inalool, dihydromyrcenol , dimethyl phenyl carbinol, eucalyptol, geranial, geraniol, geranyl acetate, geranyl nitrile, cis-3-hexenyl acetate, hydroxycitronellal, d-limonene, 1inalool, 1inalool oxide, linalyl acetate, linalyl propionate, methyl anthranilate, alpha-methyl ionone, methyl nonyl acetalde- hyde, methyl phenyl carbinyl acetate, laevo-menthyl acetate, menthone, iso- enthone, yrcene, myrcenyl acetate, myrcenol, nerol, neryl acetate, nonyl acetate, phenyl ethyl alcohol, alpha- pinene, beta-pinene, gam a-terpinene, alpha-terpineol, beta-ter- pineol, terpinyl acetate, and vertenex (para-tertiary-butyl cyclohexyl acetate). Some natural oils also contain large per¬ centages of highly volatile perfume ingredients. For example, lavandin contains as major components: 1inalool; linalyl acetate; geraniol; and citronellol. Lemon oil and orange terpenes both contain about 95% of d-limonene. Examples of moderately volatile perfume ingredients are: amyl cinnamic aldehyde, iso-amyl salicylate, beta-caryophyllene, cedrene, cinnamic alcohol, coumarin,. dimethyl benzyl carbinyl acetate, ethyl vanillin, eugenol, iso-eugenol, flor acetate, heliotropine, 3-cis-hexenyl sal.icylate, hexyl salicylate, lilial (para-tertiarybutyl-alpha-methyl hydrocinnamic aldehyde), gamma methyl ionone, nerolidol, patchouli alcohol, phenyl hexanol, beta selinene, trichloromethyl phenyl ,carbinyl acetate, triethy citrate, vanillin, and veratraldehyde. Cedarwood terpenes ar composed mainly of alpha-cedrene, beta-cedrene, and other C15H2 sesquiterpenes. Examples of the less volatile, high boiling, perfume ingre dients are: benzophenone, benzyl salicylate, ethylene brassylate, galaxolide (1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclo penta-gama-2-benzopyran), hexyl cinnamic aldehyde, lyral (4-(4 hydroxy-4-methyl ρentyl)-3-cyclohexene-10-carboxaldehyde), methyl cedrylone, methyl dihydro jas onate, methyl-beta-naphthyl ketone musk indanone, musk ketone, musk tibetene, and phenylethyl phenyl acetate. Selection of any particular perfume ingredient is primaril dictated by aesthetic considerations, but more water-solubl materials are preferred, as stated hereinbefore, since suc materials are less likely to adversely affect the good spotting/ filming properties of the compositions. If the terpene types o perfume ingredients are used, the beta-aminoalkanols are preferre 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 rinsing The compositions can be formulated to be used at ful strength, where the product is sprayed onto the surface to b cleaned and then wiped off with a suitable material like cloth, 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. Ingredient Propylene Glycol Mono- butylether Isopropanol Cocoa idopropyl (Hydroxy propyl)sulfobetaine Monoethanolamine 10 l-amino-2-propanol 1.0 2-amino-l-butanol 1.0 2-amino-2-methyl-1-butan Perfume Deionized Water Ingredient 1 20 Lauryl-dimethyl-3- sulfopropylbetaine 0.20 Cocoyl-dimethyl-2-hydroxy- 3-sulfopropylbetaine 0.20 Lauryl-dimethyl-betaine 0.20 25 Cocoamidipropyl-dimethyl- betaine Cocoamidopropyl-dimethyl-2- hydroxy-3-sulfopropylbetaine Sodium Alkyl (-C13) Sulfate 30 2-Amino-2-methyl-l-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. *A11 pH's adjusted to about 10.9 EXAMPLE M Continued 10 15 20 ♦ All pH's adjusted to about 10.9 25 30 35 EXAMPLE ri (Conti nued) Formula No.* (Wt.% Ingredient 7 8 _9_ Lauryl-dimethyl-3- 5 sulfopropylbetaine - - - Cocoyl-dimethyl-2-hydroxy- 3-sulfopropylbetaine Lauryl-dimethyl-betaine . . . Cocoamidipropyl-dimethyl- 10 betaine 0.15 0.18 0.15 Cocoamidopropyl-dimethyl-2- hydroxy-3-sulfopropylbetaine - Sodium Alkyl (-C13) Sulfate 2-amino-2-methyl-l-propanol 0.5 15 Monoethanolamine - 0.5 0.5 Propylene Glycol Mono- butylether 3.0 4.0 Ethylene Glycol Monobutylether - - 3.0 20 Isopropanol 3.0 2.0 3.0 Deionized Water and Minors (e.g., Perfume) q.s. q.s. q.s. *A11 pH's adjusted to about 10.9 25 30 35 EXAMPLE IT. (Continued) Formula No.* (Wt.%) Ingredient 10 11 12 Lauryl-dimethyl-3- sulfopropylbetaine Cocoyl-dimethyl-2-hydroxy- 3-sulfopropylbetaine Lauryl-dimethyl-betaine Cocoa idipropyl-dimethyl- betaine Cocoamidopropyl-dimethyl-2- hydroxy-3-sulfopropylbetaine 0.19 0.15 0.18 Sodium Alkyl (--C13) Sulfate 2-amino-2-methyl-1-propanol 0.5 1.0 Monoethanolamine 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. *A11 pH's adjusted to about 10.9 The following example shows the Filming/Streaking performan for various formulations including the preferred zwitterionic alkanolamine combinations. Ingredient Ralufon® DL Monoethanolamine Isopropanol Propylene Glycol Mono- butylether Sodium Hydroxide Deionized Water q.s. q.s. q.s. Ralufon® DL (Raschig Corp.) is Lauryl-dimethyl- ammonium-3-sulfopropyl 3-(1auryl ,dimethyl ,ammonium)- propylsulfonate) *pH adjusted to 10.8 with NaOH, this matches the pH of the products with monoethanolamine in them. EXAMPLE III (Continued) Formula No.* (Wt.%) Ralufon ® DL (Raschig Corp.) is Lauryl-dimethyl-ammonium- 3-sulfopropyl 3-(1auryl ,dimethyl ,ammoniurn)-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. Filming/Streaking 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. Grading : Expert judges are employed to evaluate the specific areas o product application for amount of filming/streaking. A numerica value describing the amount of filming/streaking is assigned t each product. For the test results reported here a 0-10 scale wa used. 0 - No Filming/Streaking 10 » Poor Filming/Streaking Room temperature and humidity have been shown to influenc filming/streaking. Therefore these variables are always recorded Filming/Streaking Stress Test on Glass Windows (Four Replications at 73 * F and 53% Relative Humidity) Formula Mean No. Rating 1 3.8 2 0.3 3 0.4 4 1.0 5 5.4 6 7.3 7 8.2 The least significant difference between mean ratings is 0.8 a 95% confidence level.

Claims: CLAIMS: 1. An aqueous liquid hard surface detergent composition com¬ prising: (a) zwitterionic detergent surfactant, preferably at a level of from about 0.001% to about 15%, more preferably from about 0.02% to about 10%, and preferably zwitterionic detergent surfactant which has the formula: R3-[C(0)-N(R4)-(CR5 2 )n-]mN(R 6 )2^)-(CR 5 2)p-Y(-) wherein each R 3 is an alkyl, or alkylene, group containing from about 8 to about 20, preferably from about 10 to about 18, carbon atoms, each (R4) and (R^) is selected from the group consisting of hydrogen, methyl, ethyl, propyl, hydroxy substituted ethyl or propyl and mixtures thereof, each (R 5 ) is selected from the group consisting of hydrogen and hydroxy groups, with no more than about one hydroxy group in any (CR52) moiety; is 0 or 1, preferably 1; and each n and p is a number from 1 to about 4, and Y is sulfonate or carboxylate group, preferably a sulfonate group, said zwitter¬ ionic detergent surfactant being more preferably hydrocarbyl- amidoal ylenesulfobetaine detergent surfactant; (b) optional solvent/buffer system that preferably comprises monoethanolamine and/or beta-aminoalkanol containing from three to about six carbon atoms, at a level of from about 0.05% to about 10%, preferably from about 0.2% to about 5%, said beta-aminoalkanol preferably being selected from the group consisting of: 2-amino,2-methyl- propanol ; 2-amino,l-butanol ; or mixtures thereof, said solvent buffer system preferably comprising monoethanolamine, and when m is 0, said solvent/buffer system is present in an effective amount to reduce spotting/filming, and said solvent/buffer system pref¬ erably containing solvent that has a hydrogen bonding parameter of less than about 7.7 and buffering system to provide the desired pH, preferably from about 9.5 to about 13; and (c) the balance being ah aqueous solvent system and/or minor ingredients. 2. The composition of Claim 1 wherein said zwitterionic detergent surfactant (a) comprises hydrocarbyl-amidoal ylene- sulfobetaine which has the formula: R3-C(0)-N(R4)-(CR52) n -N(R6)2( + )-(CR5 2 ) p -S03(-) wherein each R 3 is an alkyl, or alkylene, group containing from about 10 to about 18, preferably from about 12 to about 16, carbon atoms, each (R 4 ) and R 6 ) is selected from the group consisting of hydrogen, methyl, ethyl, propyl, hydroxy substituted ethyl or propyl and mixtures thereof, with R4 preferably being hydrogen and R 5 being methyl, each (R 5 ) 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 (CR 2) moiety and preferably one hydroxy group being present, and n and p preferably being 3. 3. The composition of Claim I wherein said zwitterionic detergent surfactant (a) comprises hydrocarbyl-amidoalkylene- betaine which has the formula: R3-C(0)-N(R4)-(CR5 2 ) n -N(Rδ)2( + )-(CR52) n -C00(-) wherein each R is an alkyl, or alkylene, group containing from about 10 to about 18, preferably from about 12 to about 16, 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 with each R 4 being hydrogen and each R6 being methyl; each (R 5 ) 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 (CR 5 ) moiety. 4. The composition of any of the above claims wherein said R3 group contains from about 12 to about 16 carbon atoms, R 4 is hydrogen, each Rδ is methyl, when the zwitterionic detergent contains a sulfonate group one of the R5 groups between the (+) and the (-) charge centers is a hydroxy group and the remaining R 5 groups are hydrogen, and each n and p is 3. 5. The composition of any of the above claims containing an effective amount of at least one cosurfactant, preferably anionic detergent surfactant, more preferably selected from the group consisting of C12-C18 alkyl sulfates, C12-C18 paraffin sulfonates, C12-C18 acylamidoalkylene amino alkylene sulfonate and mixtures thereof. 6. The composition of any of the above claims containing sufficient buffer/alkalinity source, preferably material selected from the group consisting of: ammonia, alkanolamines, alkali metal hydroxides, alkali metal silicates, alkali metal borates, alkali metal carbonates, alkali metal bicarbonates, and mixtures thereof, preferably said monoethanolamine and/or beta-aminoalkanolamine, and/or alkali metal hydroxide, preferably sodium hydroxide, to give the desired pH, preferably from about 9.5 to about 13, more preferably from about 9.7 to about 12. 7. The composition of any of the above claims wherein said solvent/buffering system comprises from about 0.5% to about 20%., preferably from about 1% to about 15%, of organic solvent having a hydrogen bonding parameter of from about 2 to about 7, preferably from about 3 to about 6, preferably solvent selected from the group consisting of alkyl and cycloalkyl hydrocarbons and halo- hydrocarbons; alpha olefins; benzyl alcohol; pine oil; glycol ethers, preferably having the formula Rlθ(R2θ) m H wherein each Rl is an alkyl group which contains from about 3 to about 8 carbon atoms, each R is selected from the group consisting of ethylene or propylene, and is a number from 1 to about 3, preferably selected from the group consisting of monopropyleneglycolmono- propyl ether, dipropyleneglycolmonobutyl ether, onopropylene- τjlycolmonobutyl ether, diethyleneglycolmonohexyl ether, mono- ethyleneglycolmonohexyl ether, and mixtures thereof; diols containing 6 to 16, preferably 8 to 12, carbon atoms, preferably 2,2,4-trimethyl-l,3,-pentanediol ; and mixtures thereof. 8. The composition of any of the above Claims containing at least one non-aqueous polar cosolvent having a hydrogen bonding parameter of more than about 7.7. 9. The composition of any of the above Claims packaged in a package that comprises a means for creating a spray. 10. The process of cleaning hard surfaces comprising spraying said surfaces with the composition of Claim 9, preferably where the composition has a concentration of component (a) in water of from about 0.02% to about 1% and the hard surface is glass.

Inventors: MICHAEL DANIEL WAYNE, MICHAEL, DANIEL, WAYNE
Applicants: PROCTER & GAMBLE, THE PROCTER & GAMBLE COMPANY
Application year: 1991
Main classification: C11D7
IPC codes: C11B9, C11D1, C11D3, C11D17