NZ236922A - Aqueous hard surface detergents containing a zwitterionic surfactant and monoethanolamine and/or beta-aminoalkanol - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number £36922 236922 Pricriiy DctEr(s): &V.V39,.A9.'):39..., AT.3: 5P,, A*,-, V?»: Av.'?•;??, -jlHz.- so Co.i.■ ? • ■ *-S\V\*A. f'ms;' & VJPAV*, . M».«P5Ui=?.., Public? . jn Di :c: ...? .7. AMN. .TO P.O. Journal, No: .'?»P7 NEW ZEALAND PATENTS ACT, 1953 No.: Date: l^fiL^ Ik? a air"i 5? »' i a COMPLETE SPECIFICATION LIQUID HARD SURFACE DETERGENT COMPOSITIONS CONTAINING ZWITTERIONIC DETERGENT SURFACTANT AND MONOETHANOLAMINE AND/OR BETA-AMINOALKANOL X/ We, THE PROCTER & GAMBLE COMPANY, a corporation organized under the laws of the State of Ohio and the United States of America, located at One Procter & Gamble Plaza, Cincinnati, Ohio 45202, United States of America hereby declare the invention for which $•/ we pray that a patent may be granted to «e-/us, and the method by which it is to be performed, to be particularly described in and by the following statement: - (followed by page la) 236922 - la.— LIQUID HARD SURFACE DETERGENT COMPOSITIONS CONTAINING ZWITTERIONIC DETERGENT SURFACTANT AND MONOETHANOLAMINE AND/OR BETA-AMINOALKANOL FIELD OF THE INVENTION This invention pertains to liquid detergent compositions for use in cleaning hard surfaces. Such compositions typically 10 contain detergent surfactants, solvents, builders, etc.

BACKGROUND OF THE INVENTION The use of solvents and organic water-soluble synthetic detergents at low levels for cleaning glass are known.

General purpose household cleaning compositions for hard 15 surfaces such as metal, glass, ceramic, plastic and linoleum surfaces, are commercially available in both powdered and liquid form. Liquid detergent compositions are disclosed in Australian Pat. Application 82/88168, filed Sept. 9, 1982, by The Procter & Gamble Company; U.K. Pat. Application GB 2,166,153A, filed 20 Oct. 24, 1985, by The Procter & Gamble Company; and U.K. Pat. Application GB 2,160,887A, filed June 19, 1985, by Bristol-Myers Company, all of said published applications being incorporated herein by reference. These liquid detergent compositions comprise certain organic solvents, surfactant, and optional builder and/or 25 abrasive. The prior art, however, fails to teach, or recognize, the advantage of the specific organic sol vents/buffers disclosed hereinafter, in liquid hard surface cleaner formulations.

Liquid cleaning compositions have the great advantage that they can be applied to hard surfaces in neat or concentrated form 30 so that a relatively high level of surfactant material and organic solvent is delivered directly to the soil. Moreover, it is a rather more straightforward task to incorporate high concentrations of anionic or nonionic surfactant in a liquid rather than a granular composition. For both these reasons, therefore, liquid 35 cleaning compositions have the potential to provide superior soap scum, grease, and oily soil removal over powdered cleaning compositions. 236922 Nevertheless, liquid cleaning compositions, and especially compositions prepared for cleaning glass, still suffer a number of drawbacks which can limit their consumer acceptability. They have to have good spotting/filming properties. In addition, they can suffer problems of product form, in particular, inhomogeneity, lack of clarity, or inadequate viscosity characteristics, or excessive "solvent" odor for consumer use.

An object of the present invention is to provide detergent compositions which provide good glass cleaning without excessive filming and/or streaking.

SUMMARY OF THE INVENTION The present invention relates to an aqueous, liquid, hard surface detergent composition comprising: (a) zwitterionic detergent surfactant, containing a cationic group, preferably a quaternary ammonium group, and an anionic group, preferably a car-boxylate, sulfonate, or sulfate group, more preferably a sulfonate group; (b) solvent/buffer system that comprises either mono-ethanolamine, beta-aminoalkanol which contains from about three to about six carbon atoms, or mixtures thereof, preferably mono-ethanolamine; (c) optional detergent builder; and the balance being (d) aqueous solvent system and, optionally, minor ingredients. The composition preferably does not contain amounts of materials, like conventional detergent builders, etc., that deposit on the surface being cleaned and cause unacceptable spotting/filming. The compositions can be formulated at usage concentrations, or as concentrates, and can be packaged in a container having means for creating a spray to make application to hard surfaces more convenient.

All percentages, parts, and ratios herein are "by weight" unless otherwise stated.

DETAILED DESCRIPTION OF THE INVENTION In accordance with the present invention, it has been found that superior aqueous liquid detergent compositions for cleaning shiny surfaces such as glass contain zwitterionic detergent surfactant (containing both cationic and anionic groups in substantially equivalent proportions so as to be electrically neutral at the pH of use, typically at least about 9.5, preferably at least about 10) and monoethanolamine and/or certain beta-ami no- 236 9 2 2 alkanol compounds.

The Detergent Surfactant The aqueous, liquid hard surface detergent compositions (cleaners) herein contain from about 0.001% to about 15% of suit-5 able zwitterionic detergent surfactant containing a cationic group, preferably a quaternary ammonium group, and an anionic group, preferably carboxylate, sulfate and/or sulfonate group, more preferably sulfonate. Successively more preferred ranges of zwitterionic detergent surfactant inclusion are from about 0.02% 10 to about 10% of surfactant, and from about 0.1% to about 5% of surfactant.

Zwitterionic detergent surfactants, as mentioned hereinbefore, contain both a cationic group and an anionic group and are in substantial electrical neutrality where the number of anionic 15 charges and cationic charges on the detergent surfactant molecule are substantially the same. Zwitterionic detergents, which typically contain both a quaternary ammonium group and an anionic group selected from sulfonate and carboxylate groups are desirable since they maintain their amphoteric character over most of the pH 20 range of interest for cleaning hard surfaces. The sulfonate group is the preferred anionic group.

Preferred zwitterionic detergent surfactants have the generic formula: R3-[C(0)-N(R4)-(CR52)n]mN(R6)2(+)-(CR52)p-Y(-) 25 wherein each y is preferably a carboxylate (COO") or sulfonate (SO3-) group, preferably sulfonate; wherein each R3 is a hydrocarbon, e.g., an alkyl, or alkylene, group containing 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 (R^) is 30 either hydrogen, or a short chain alkyl, or substituted alkyl, containing from one to about four carbon atoms, preferably groups selected from the group consisting of methyl, ethyl, propyl, hydroxy substituted ethyl or propyl and mixtures thereof, preferably methyl; wherein each (R5) is selected from the group con-35 sisting of hydrogen and hydroxy groups; wherein (R*>) is like r4 except preferably not hydrogen; wherein m is 0 or 1; and wherein each n and p are a number from 1 to about 4, preferably from 2 to 2 3 6 9 2 2 about 3, more preferably about 3; there being no more than about one hydroxy group in any (CR52) moiety. The R3 groups can be branched and/or unsaturated, and such structures can provide spotting/filming benefits, even when used as part of a mixture 5 with straight chain alkyl R3 groups. The R^ groups can also be connected to form ring structures. Preferred hydrocarbyl amido-alkylene sulfobetaine (HASB) detergent surfactants wherein m = 1 and y is a sulfonate group provide superior grease soil removal and/or filming/streaking and/or "anti-fogging" and/or perfume 10 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 monoethanol-15 amine and/or specific beta-amino alkanol as disclosed herein.

A more preferred specific detergent surfactant is a Cio-14 fatty acylamidopropylene(hydroxypropylene)sulfobetaine, e.g., the detergent surfactant available from the Sherex Company as a 40% active product under the trade name "Varion CAS Sulfobetaine." 20 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 25 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 surfactant. For removal of difficult to remove soils like grease, the 30 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 35 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%. 23692 Other zwitterionic detergent surfactants are set forth at Col. 4 of U.S. Pat. No. 4,287,080, Siklosi, incorporated herein by reference. Another detailed listing of suitable zwitterionic detergent surfactants for the detergent compositions herein can be 5 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 EMUISIFIERS AND DETERGENTS, North American Edition, 1984, McCutcheon Division, MC Publishing Company, also incorporated herein by reference. 10 The above patents and reference also disclose other detergent surfactants, e.g., anionic, and nonionic detergent surfactants, that can be used in small amounts in the composition of this invention as cosurfactants.. Typical of these are the alkyl- and alkylethoxylate- (polyethoxylate) sulfates, paraffin sulfonates, 15 olefin sulfonates, alkoxylated (especially ethoxylated) alcohols and alkyl phenols, alpha-sulfonates of fatty acids and of fatty acid esters, and the like, which are well-known from the deter-gency art. When the pH is above about 9.5, detergent surfactants that are amphoteric at a lower pH are desirable anionic detergent 20 cosurfactants. For example, detergent surfactants which are C12-C18 acylamido alkylene amino alkylene sulfonates, e.g., compounds having the formula R-C(0)-NH-(C2H4)-N(C2H40H)~ CH2CH(0H)CH2S03M wherein R is an alkyl group containing from about 9 to about 18 carbon atoms and M is a compatible cation are 25 desirable cosurfactants. These detergent surfactants are available as Miranol CS, OS, JS, etc. The CTFA adopted name for such surfactants is cocoamphohydroxypropyl sulfonate. It is preferred that the compositions be substantially free of alkyl naphthalene sulfonates.

In general, detergent surfactants useful herein contain a hydrophobic group, typically containing an alkyl group in the Cg-Cis range, and, optionally, one or more linking groups such as ether or amido, preferably amido groups. The anionic detergent surfactants can be used in the form of their sodium, potassium or 35 alkanolammonium, e.g., triethanolammonium salts; the nonionics generally contain from about 5 to about 17 ethylene oxide groups. 236 9 2 2 Ci2~Ci8 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 sulfonate (LAS), particularly Cji-Cj2 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 Rl - C - N(R2)2 wherein R1 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.

MONOETHANOLAMINE AND/OR BETA-AMINOALKANOL Monoethanolamine and/or beta-aminoalkanol compounds serve primarily as solvents when the pH is above about 10.0, and 236 92 especially above about 10.7. They also provide alkaline buffering capacity during use. However, the most unique contribution they make is to improve the spotting/filming properties of hard surface cleaning compositions containing zwitterionic detergent surfactant, whereas they do not provide any substantial improvement in spotting/filming when used with conventional anionic or ethoxy-lated nonionic detergent surfactants. The reason for the improvement is not known. It is not simply a pH 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 materials present. When perfumes that have a high percentage of terpenes are incorporated, the benefit is greater for the beta-alkanolamines, and they are often preferred, whereas the mono-ethanolamine is usually preferred.

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 compositions 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 about 0.7%. For concentrated compositions they are typically present at a level of from about 0.5% to about 10%, preferably from about 1% to about 5%.

Preferred beta-aminoalkanols have a primary hydroxy group. Suitable beta-aminoalkanols have the formula: R R I I R - C - C - OH I I NH2 R wherein each R is selected from the group consisting of hydrogen and alkyl groups containing from one to four carbon atoms and the total of carbon atoms in the compound is from three to six, preferably four. The amine group is preferably not attached to a primary carbon atom. More preferably the amine group is attached to a tertiary carbon atom to minimize the reactivity of the amine group. Specific preferred beta-aminoalkanols are 2-amino,l- 23692 butanol; 2-amino,2-methylpropanol; and mixtures thereof. The most preferred beta-aminoalkanol is 2-amino,2-methylpropanol since it has the lowest molecular weight of any beta-aminoalkanol which has the amine group attached to a tertiary carbon atom. The beta-5 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., monoethanolamine 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 15 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-20 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 25 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 30 considering their relatively high molecular weights.

The Cosolvent 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-35 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 236922 9 - example, the dry cleaning industry, in the hard surface cleaner industry and the metal working industry.

A useful definition of such solvents can be derived from the solubility parameters as set forth in "The Hoy," a publication of Union Carbide, incorporated herein by reference. The most useful parameter appears to be the hydrogen bonding parameter which is calculated by the formula "1/2 7H - 7T or - 1 a wherein 7H is the hydrogen bonding parameter, a is the aggregation number, (Log a = 3.39066 Tb/Tc - 0.15848 - Log M) , and 15 d 7T is the solubility parameter which is obtained from the formula . 1/2 yT = (AH25 - RT)d L M where AH25 is the heat of vaporization at 25°C, R is the gas constant (1.987 cal/mole/deg), T is the absolute temperature in "K, Tb is the boiling point in °K, Tc is the critical temperature in °K, d is the density in g/ml, and M is the molecular weight.

For the compositions herein, hydrogen bonding parameters are 25 preferably less than about 7.7, more preferably from about 2 to about 7, an'd 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 cause a haze on glass. Higher numbers require more solvent to 30 provide good greasy/oily soil cleaning.

Cosolvents are typically used at a level of from about 1% to about 30%, preferably from about 2% to about 15%, more preferably from about 4% to about 8%. Dilute compositions typically have cosolvents at a level of from about 1% to about 10%, preferably 35 from about 3% to about 6%. Concentrated compositions contain from about 10% to about 30%, preferably from about 10% to about 20% of cosolvent. 236 9 22 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 5 guided in the selection of cosolvent partly by the need to provide good grease-cutting properties, and partly by aesthetic considerations. For example, kerosene hydrocarbons function quite well for grease cutting in the present compositions, but can be malodorous. Kerosene must be exceptionally clean before it can be 10 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 C5-C9 alkyl aromatic solvents, especially the C5-C9 alkyl 15 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 0(R70}mH wherein each R*> 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 preferred glycol ethers are selected from the group consisting of 25 monopropyleneglycolmonopropyl ether, dipropyleneglycolmonobutyl ether, monopropyleneglycolmonobutyl ether, diethyleneglycolmono-hexyl ether, monoethyleneglycolmonohexyl ether, monoethylenegly-colmonobutyl ether, and mixtures thereof.

A particularly preferred type of solvent for these hard 30 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.

Some examples of suitable diol solvents and their solubil-35 ities in water are shown in Table 1. 236 9 2 2 TABLE 1 Solubility of Selected Diols in 20"C Water Solubility Diol (q/lOOq H20 1,4-Cyclohexanedimethanol .0* 2,5-Dimethyl-2,5-hexanediol 14.3 2-Phenyl-1,2-propanediol 12.0* Phenyl-1,2-ethanediol 12.0* 2-Ethyl-l,3-hexanediol 4.2 2,2,4-Trimethyl-1,3-pentanediol 1.9 1,2-Octanediol 1.0* ♦Determined via laboratory measurements.

All other values are from published literature. ^5 The diol solvents are especially preferred because, in addi tion to good grease cutting ability, they impart to the compositions an enhanced ability to remove calcium soap soils from surfaces such as bathtub and shower stall walls. These soils are particularly difficult to remove, especially for compositions 20 which do not contain an abrasive. The diols containing 8-12 carbon atoms are preferred. The most preferred diol solvent is 2,2,4-trimethyl-1,3-pentanediol.

Solvents such as pine oil, orange terpene, benzyl alcohol, n-hexanol, phthalic acid esters of C1-4 alcohols, butoxy propanol, 25 Butyl Carbitol® and 1(2-n-butoxy-l-methylethoxy)propane-2-ol (also called butoxy propoxy propanol or dipropylene glycol monobutyl ether), hexyl diglycol (Hexyl Carbitol®), butyl triglycol, diols such as 2,2,4-trimethyl-1,3-pentanediol, and mixtures thereof, can be used. The butoxy-propanol solvent should have no more than 30 about 20%, preferably no more than about 10%, more preferably no more than about 7%, of the secondary isomer in which the butoxy group is attached to the secondary atom of the propanol for improved odor.

The Cobuffer/Alkalinitv-Source 35 The solvent/buffer system is formulated to give a pH in the product and, at least initially, in use of from about 9.5 to about 13, preferably from about 9.7 to about 12, more preferably from about 9.7 to about 11.5. pH is usually measured on the product. 236922 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 C2-C4 alkanolamines; alkali metal hydroxides; silicates; borates; carbonates; and/or bicarbonates; and mixtures thereof. The preferred cobuffering/alkal inity materials are alkali metal hydroxides. The level of the cobuffer/alkalinity-source is from 0% to about 5%, preferably from 0% to about 5%. Monoethanol amine and/or beta-aminoalkanol buffering material, in the system is 10 important for spotting/filming. It is surprising that monoethanol amine 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 15 polar solvents with only minimal cleaning action like methanol, 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 20 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 25 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 30 sulfonate and potassium xylene sulfonate; and Aesthetic-enhancing ingredients such as colorants and perfumes, providing they do not adversely impact on spotting/-filming in the cleaning of glass. The perfumes are preferably those that are more water-soluble and/or volatile to 35 minimize spotting and filming.

Antibacterial agents can be present, but preferably only at low levels to avoid spotting/filming problems. More hydrophobic 236 9 2 2 ant i bacteri al/germi ci dal agent's, like orthobenzyl-para-chloro-phenol, are avoided. If present, such materials should be kept at levels below about 0.1%.

Detergent Builder An optional ingredient for general cleaning purposes, is from 0% to about 30%, preferably from about 1% to about 15%, more preferably from about 1% to about 12%, of detergent builder. For use on glass and/or other shiny surfaces, a level of builder of from about 0.1% to about 0.5%, preferably from about 0.1% to about 0.2%, is useful. While any of the builders or inorganic salts can be used herein, some examples of builders for use herein are sodium nitrilotriacetate, potassium pyrophosphate, potassium tripolyphosphate, sodium or potassium ethane-1-hydroxy!-1,1-di-phosphonate, the nonphosphorous chelating agents described in New Zealand Patent Application No. 225759, said application being incorporated — herein by reference (e.g., carboxymethyltartronic acid, oxydi-malonic acid, tartrate monosuccinic acid, oxydisuccinic acid, tartrate disuccinic acid, and mixtures thereof), sodium citrate, sodium carbonate, sodium sulfite, sodium bicarbonate, and so forth.

Other suitable builders are disclosed in U.S. Pat. No. 4,769,172, Siklosi, issued Sept. 6, 1988, and incorporated herein by reference, and chelating agents having the formula: CH2COOM R - N CH2COOM wherein R is selected from the group consisting of: -CH2CH2CH2OH; -CH2CH(OH)CH3; -CH2CH(0H)CH2OH; -CH(CH2OH)2; -CH3; -CH2CH2OCH3; -C-CH3; -CH2-C-NH2; tl tl 0 0 -CH2CH2CH2OCH3; -C(CH2OH)3; and mixtures thereof; and each M is hydrogen or an alkali metal ion.

Chemical names of the acid form of some chelating agents useful herein include: N(3-hydroxypropyl)imino-N,N-diacetic acid (3-HPIDA); N(-2-hydroxypropyl)imino-N,N-diacetic acid (2-HPIDA); 236 9; 14 - N-glycerylimino-N,N-diacetic acid (GLIDA); dihydroxyisopropylimino-(N,N)-diacetic acid (DHPIDA); methylimino-(N,N)-diacetic acid (MIDA); 2-methoxyethylimino-(N,N)-diacetic acid (MEIDA); amidoiminodiacetic acid (also knowrTas sodium amidonitrilo- triacetic, SAND); acetamidoiminodiacetic acid (AIDA); 3-methoxypropylimino-N,N-diacetic acid (MEPIDA); and tris(hydroxymethyl)methyl imino-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-25 42 708* for 2-HPIDA and DHPIDA; Chem. ZVESTI 34(1) p. 93-103 (1980), Mayer, Riecanska et alT, 15 publication of Mar. 25, 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 20 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%, 25 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. 30 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 35 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 * available upon request 2369 the less volatile, high boiling perfume ingredients can provide a fresh and clean impression to the surfaces, and it is sometimes desirable that these ingredients be deposited and present on the dry surface. It is a special advantage of this invention that 5 perfume ingredients are readily solubi1ized in the compositions by the acylamidoalkylene detergent surfactant. Other similar detergent surfactants will not solubi1ize as much perfume, especially substantive perfume, or maintain uniformity to the same low temperature.

The perfume ingredients and compositions of this invention are the conventional ones known in the art. Selection of any perfume component, or amount of perfume, is based solely on aesthetic considerations. Suitable perfume compounds and compositions can be found in the art including U.S. Pat. Nos.: 15 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 said patents being incorporated herein by reference. Normally, the art recognized perfume compositions are not very substantive as 20 described hereinafter to minimize their effect on hard surfaces.

In general, the degree of substantivity of a perfume is roughly proportional to the percentages of substantive perfume material used. Relatively substantive perfumes contain at least about 1%, preferably at least about 10%, substantive perfume 25 materials.

Substantive perfume materials are those odorous compounds that deposit on surfaces via the cleaning process and are detectable by people with normal olfactory acuity. Such materials typically have vapor pressures lower than that of the average 30 perfume material. Also, they typically have molecular weights of about 200 or above, and are detectable at levels below those of the average perfume material.

Perfumes can also be classified according to their volatility, as mentioned hereinbefore. The highly volatile, low boiling, 35 perfume ingredients typically have boiling points of about 250*C or lower. Many of the more moderately volatile perfume ingredients are also lost substantially in the cleaning process. The 236922 moderately volatile perfume ingredients are those having boiling points of from about 250°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 significant 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 ingredients 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 ingredients are: anethole, benzaldehyde, benzyl acetate, benzyl alcohol, benzyl formate, iso-bornyl acetate, camphene, cis-citral (neral), citronellal, citronellol, citronellyl acetate, para-cymene, decanal, dihydrolinalool, dihydromyrcenol, dimethyl phenyl carbinol, eucalyptol, geranial, geraniol, geranyl acetate, geranyl nitrile, cis-3-hexenyl acetate, hydroxycitronellal, d-limonene, linalool, linalool oxide, linalyl acetate, linalyl propionate, methyl anthranilate, alpha-methyl ionone, methyl nonyl acetalde-hyde, methyl phenyl carbinyl acetate, laevo-menthyl acetate, menthone, iso-menthone, myrcene, myrcenyl acetate, myrcenol, nerol, neryl acetate, nonyl acetate, phenyl ethyl alcohol, alpha-pinene, beta-pinene, gamma-terpinene, alpha-terpineol, beta-ter-pineol, terpinyl acetate, and vertenex (para-tertiary-butyl cyclohexyl acetate). Some natural oils also contain large percentages of highly volatile perfume ingredients. For example, lavandin contains as major components: linalool; 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, he!iotropine, 3-cis-hexenyl salicylate, hexyl salicylate, lilial 236 9 (para-tertiarybutyl-alpha-methyl hydrocinnamic aldehyde), gamma-methyl ionone, nerolidol, patchouli alcohol, phenyl hexanol, beta-selinene, trichloromethyl phenyl carbinyl acetate, triethyl citrate, vanillin, and veratraldehyde. Cedarwood terpenes are 5 composed mainly of alpha-cedrene, beta-cedrene, and other Cj5H24 sesquiterpenes.

Examples of the less volatile, high boiling, perfume ingredients are: benzophenone, benzyl salicylate, ethylene brassylate, galaxolide (l,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclo-10 penta-gama-2-benzopyran), hexyl cinnamic aldehyde, lyral (4-(4-hydroxy-4-methyl pentyl)-3-cyclohexene-10-carboxaldehyde), methyl cedrylone, methyl dihydro jasmonate, methyl-beta-naphthyl ketone, musk indanone, musk ketone, musk tibetene, and phenylethyl phenyl acetate.

Selection of any particular perfume ingredient is primarily dictated by aesthetic considerations, but more water-soluble materials are preferred, as stated hereinbefore, since such materials are less likely to adversely affect the good spotting/-filming properties of the compositions. If the terpene types of 20 perfume ingredients are used, the beta-aminoalkanols are preferred for product stability.

These compositions have exceptionally good cleaning properties. They can also be formulated to have good "shine" properties, i.e., when used to clean glossy surfaces, without rinsing. 25 The compositions can be formulated to be used at full strength, where the product is sprayed onto the surface to be cleaned and then wiped off with a suitable material like cloth, a paper towel, etc. They can be packaged in a package that comprises a means for creating a spray, e.g., a pump, aerosol pro-30 pell ant and spray valve, etc.

The invention is illustrated by the following Examples. 236922 EXAMPLE I Ingredient Propylene Glycol Mono- butyl ether Isopropanol Cocoamidopropyl (Hydroxy- propyl )sul fobetaine Monoethanolamine 1-amino-2-propanol 2-amino-l-butanol 2-amino-2-methyl -1-butanol Perfume Deionized Water Formula No.

(Vt.%) 1 2.0 5.0 0.15 1.0 0.20 q.s. 2.0 5.0 1.0 0.20 q.s. 2.0 5.0 0.15 0.15 1.0 0.20 q.s. 2.0 5.0 0.15 1.0 0.20 q.s. *pH adjusted to about 11.3 EXAMPLE II Ingredient Lauryl-dimethyl -3- sul fopropylbetaine Cocoyl-dimethyl-2-hydroxy- 3-sulfopropylbetaine Lauryl-dimethyl-betaine Cocoamidipropyl-dimethyl - betaine Cocoamidopropyl-dimethyl-2-hydroxy-3-sulfopropylbetai ne Sodium Alkyl (-C13) Sulfate 2-Amino-2-methyl -1-propanol Monoethanolamine Propylene Glycol Mono- butylether Isopropanol Deionized Water and Minors (e.g., Perfume) Formula No.* (Wt.%) 0.20 0.5 3.0 3.0 q.s. 0.20 0.5 3.0 3.0 q.s. 0.20 0.5 3.0 3.0 q.s.

*A11 pH's adjusted to about 10.9 2369 EXAMPLE II (Continued) Formula No.* (Ut.%) Ingredient Lauryl-dimethyl-3- sulfopropylbetaine Cocoyl-dimethyl-2-hydroxy- 3-sulfopropylbetaine Lauryl-dimethyl-betaine Cocoamidipropyl-dimethyl -betaine Cocoamidopropyl-dimethyl-2- hydroxy-3-sulfopropylbetaine Sodium Alkyl (—C13) Sulfate 2-Amino-2-methyl-1-propanol Monoethanolamine Propylene Glycol Mono- butyl ether Isopropanol Deionized Water and Minors (e.g., Perfume) 0.20 0.5 3.0 3.0 q.s.

*A11 pH's adjusted to about 10.9 0.20 0.5 3.0 3.0 q.s. 0.18 0.02 0.5 3.0 3.0 q.s. 236922 EXAMPLE H (Continued) Formula No.* Ingredient Lauryl-dimethyl-3- sulfopropyl betaine Cocoyl-dimethyl-2-hydroxy- 3-sulfopropylbetaine Lauryl-dimethyl -betaine Cocoamidipropyl-dimethyl - betaine Cocoamidopropyl-dimethyl-2- hydroxy-3-sulfopropylbetai ne Sodium Alkyl (-C13) Sulfate 2-amino-2-methyl -1-propanol Monoethanolamine Propylene Glycol Mono- butyl ether Ethylene Glycol Monobutylether Isopropanol Deionized Water and Minors (e.g., Perfume) (Wt.%) 0.15 0.5 3.0 3.0 q.s.

*A11 pH's adjusted to about 10.9 8 0.18 0.5 4.0 2.0 q.s, 0.15 0.5 3.0 3.0 q.s. 236922 EXAMPLE IT (Continued) Formula No.* Ingredient Lauryl-dimethyl-3- sulfopropylbetaine Cocoyl-dimethyl-2-hydroxy- 3-sulfopropylbetaine Lauryl-dimethyl-betaine Cocoamidipropyl-dimethyl - betaine Cocoamidopropyl-dimethyl-2- hydroxy-3-sulfopropylbetaine Sodium Alkyl (-C13) Sulfate 2-amino-2-methyl-1-propanol Monoethanolamine Propylene Glycol Mono- butyl ether Ethylene Glycol Monobutylether Isopropanol Deionized Water and Minors (e.g., Perfume) 0.19 0.5 4.0 2.0 q.s, *A11 pH's adjusted to about 10.9 11 0.15 0.5 3.0 3.0 q.s. fWt.%) 12 0.18 1.0 3.0 3.0 q.s.

The following example shows the Filming/Streaking performance for various formulations including the preferred zwitterionic/-alkanolamine combinations.

EXAMPLE III Ingredient Ralufon® DL Monoethanolamine Isopropanol Propylene Glycol Mono- butyl ether Sodium Hydroxide Deionized Water Formula No.* (Wt.%) 1 0.20 q.s. 2 0.20 0.5 q.s. 3 0.20 0.5 3.0 q.s. 236 92 Ralufon® DL (Raschig Corp.) is Lauryl-dimethyl-ammonium-3-sulfopropyl 3-(lauryl.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.%1 Ingredient 4 5 6 7 Ralufon® DL 0.20 0.20 0.20 0.20 Monoethanolamine 0.5 Isopropanol 3.0 Propylene Glycol Mono- butylether 3.0 - 3.0 3.0 Sodium Hydroxide - * - * Deionized Water q.s. q.s. q.s. q.s Ralufon® DL (Raschig Corp.) is Lauryl-dimethyl-ammonium-20 3-sulfopropyl 3-(lauryl,dimethyl,ammonium)-propyl - sulfonate) *pH adjusted to 10.8 with NaOH, this matches the pH of the products with monoethanol amine 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 35 allowed to dry for ten minutes before grading by expert judges. 23 6 9 2 2 Grading: Expert judges are employed to evaluate the specific areas of product application for amount of filming/streaking. A numerical value describing the amount of filming/streaking is assigned to 5 each product. For the test results reported here a 0-10 scale was used. 0 = No Filming/Streaking 10 = Poor Filming/Streaking Room temperature and humidity have been shown to influence 10 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.

Ratina 1 3.8 2 0.3 3 0.4 4 1.0 .4 6 7.3 7 8.2 The least significant difference between mean ratings is 0.8 at 95% confidence level. 236922

Claims (14)

WHAT WE CLAIM IS:

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

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

3. The composition of Claim 2 which contains from 0.001% to 15% of said detergent surfactant (a) and wherein the anionic group in said detergent surfactant (a) is a sulfonate group.

4. The composition of Claim 3 wherein the level of said detergent surfactant (a) in the total composition comprises from 0.02% to 10% hydrocarbyl-amido-alkylenesulfobetaine which has the formula: R3-C(0) -N(R4) -(CR52) n-N(R6) 2 (+)-(CR52)p-S03 (_) wherein each R3 is an alkyl, or alkylene, group containing frcm substan- 4 6 tially 10 to substantially 18 carbon atoms, each (R ) and (R ) is selected from the group consisting of hydrogen, methyl, ethyl, propyl, hydroxy substituted ethyl or propyl and mixtures thereof, each (R ) is selected frcm the group consisting of hydrogen and hydroxy groups, and each n and p is a number frcm 1 to substantially 4; with no 5 more than substantially one hydroxy group in any (CR moiety.

5. The composition of Claim 2 wherein the level of said detergent surfactant (a) in the total composition comprises from 0.001% to 15% hydrocarbyl-amido-alkylenebetaine which has the formula: R3-C(0) -N(R4) - (CR52) n-N(R6) 2 (+) -(CR52)p-000(") wherein each R3 is an alkyl, or alkylene, group containing frcm substan- 4 6 tially 10 to substantially 18 carbon atoms, each (R ) and (R ) is selected frcm the group consisting of hydrogen, methyl, ethyl, propyl, hydroxy substituted ethyl or propyl and mixtures thereof, each 5 . (R ) is selected frcm the group consisting of hydrogen and hydroxy groups, and each n and p is a number from 1 to 4; with" no more than substantially one hydroxy group in any (CR^„) moiety. - O " 1 V ' 23692 -25-

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

7. The composition of Claim 1 wherein the level of said detergent surfactant (a) in the total composition comprises from 0.001% to 15% zwitterionic detergent surfactant which has the formula: R3-[C(0) -N(R4) - (CR52) n-]mN (R6) 2 (+) -(CR52) p-Y(_) wherein each R3 is an alkyl, or alkylene, group containing frcm substan- 4 6 tially 9 to substantially 18 carbon atoms, each (R ) and (R ) is selected frcm the group consisting of hydrogen, methyl, ethyl, propyl, hydroxy 5 substituted ethyl or propyl and mixtures thereof, each (R ) is selected from the group consisting of hydrogen and hydroxy groups, with no more than substantially one hydroxy group in any (CR"^) moiety; m is 0 or 1; each n and p is a number from 1 to 4; and Y is a carboxylate or sulfonate group.

8. Ihe composition of Claim 7 wherein Y is a sulfonate group, 3 4 said R group contains from 9 to 15 carbon atoms, R 6 5 is hydrogen, each R is methyl, one of the R groups between the (+) and the (-) charge centers is a hydroxy group and the • • 5 remaining R groups are hydrogen, and each n and p is 3.

9. The composition of Claim 7 containing at least one cosur-factant.

10. The composition of Claim 1 wherein the level of said detergent surfactant (a) in the total composition comprises from 0.02% to 10% hydrocarbyl-amido-alkylenebetaine which has the formula: R3-C(0) -N(R4) - (CR52) n-N(R6) 2 (+) -(CR52) p-QOO(_) wherein each R3 is an alkyl, or alkylene, group containing frcm substan- 4 6 tially 10 to substantially 18 carbon atoms, each (R ) and (R ) is selected from the group consisting of hydrogen, methyl, ethyl, propyl, hydroxy substituted ethyl or propyl and mixtures thereof, each 5 . (R ) is selected from the group consisting of hydrogen and hydroxy groups, and each n and p is a number frcm 1 to 4; with no more than substantially one hydroxy group in any (CR ) moiety. \:: -2 MAY 1994 236922 -26

11. The composition of Claim 1 wherein the solvent buffer system additionally contains sufficient cobuffer/alkalinity-source to give a pH of from 9.5 to 13.

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

13. The composition of Claim li wherein the cofcuffer/alkalinity-source is an alkali metal hydroxide to give a pH of from 9.7 to 11.3.

14. An aqueous liquid hard surface detergent composition according to any one of claims 1 to 13 substantially as herein described with reference to the foregoing examples. A. J. PARK SON 2-2 MAY 1994