AU7342691A

AU7342691A - Liquid hard surface detergent compositions containing zwitterionic detergent surfactant and monoethanolamine and/or beta-aminoalkanol

Info

Publication number: AU7342691A
Application number: AU73426/91A
Authority: AU
Inventors: Daniel Wayne Michael
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1990-01-29
Filing date: 1991-01-22
Publication date: 1991-08-21
Anticipated expiration: 2011-01-22
Also published as: MY107342A; AU659994B2; EP0513240A4; KR927003772A; EP0513240B1; CN1054265A; WO1991011505A1; JPH05503547A; NZ236922A; BR9105962A; MX173001B; CA2074823C; AR245202A1; CA2074823A1; DE69129981D1; EP0513240A1; CN1036073C; ES2119773T3; DE69129981T2

Description

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 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 surfaces such as mgtal , glass, ceramic, plastic and linoleum surfaces, are commercially available in both powdered and liquid form. Liquid detergent compositions are disclosed in Australian Pat. Application 82/88168, filed Sept. 9, 1982, by The Procter & Gamble Company; U.K. Pat. Application GB 2,166,153A, filed Oct. 24, 1985, by The Procter & Gamble Company; and U.K. Pat . Application 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 abrasive. The prior art, however, fails to teach, or recognize, the advantage of the specific organic solvents/buffers disclosed hereinafter, in liquid hard surface cleaner formulations.

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 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 cleaning compositions have the potential to provide superior soap scum, grease, and oflj soil removal over powdered cleaning compositions. 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 carboxylate, sulfonate, or sulfate group, more preferably a sulfonate group; (b) solvent/buffer system that comprises either monoethanolamine, beta-aminoalkanol which contains from about three to about six carbon atoms, or mixtures thereof, preferably monoethanolamine; (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-amino alkanol compounds.

The Detergent Surfactant

The aqueous, liquid hard surface detergent compositions (cleaners) herein contain from about 0.001% to about 15% of suitable 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% to about 10% of surfactant, and from about 0.1% to about 5% of surfactant.

Zwitterionic detergent surfactants, as mentioned herein- before, 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 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 thepH 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(O)-N(R⁴)-(CR⁵ ₂)_n]_mN(R⁶)₂(+)-(CR⁵ ₂)_p-γ(-) 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 (R⁴) is 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 co sisting of hydrogen and hydroxy groups; wherein (R⁶) 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 about 3, more preferably about -3; there being no more than about one hydroxy group in any (CR⁵ ₂) 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 with straight chain alkyl R³ groups. The R⁴ groups can also be connected to form ring structures. Preferred hydrocarbyl amidoalkylene 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 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 monoethanolamine and/or specific beta-amino alkanol as disclosed herein.

A more preferred specific detergent surfactant is a C_10-14 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 surfactant. 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 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 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 Company, also incorporated herein by reference.

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, 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 cosurfactants. For example, detergent surfactants which are C₁₂-C₁₈ acylamido alkylene amino alkylene sulfonates, e.g., compounds having the formula R-C(O)-NH-(C₂H₄)-N(C₂H₄OH)- CH₂CH(OH)CH₂SO₃M wherein R is an alkyl group containing from about 9 to about 18 carbon atoms and M is a compatible cation are desirable cosurfactants. These detergent surfactants are 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 herei n contai n a hydrophobic group, typically containing an alkyl group in the C₉-C₁₈ range, and, optionally, one or more linking groups such as ether or amido, preferably amido groups. The anionic detergent surfactants can be used in the form of their sodium, potassium or alkanolammonium, e.g., triethanolammonium salts; the nonionics generally contain from about 5 to about 17 ethylene oxide groups. C₁₂-C₁₈ paraffin-sulfonates and alkyl sulfates, and the ethoxylated 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 C₈-C₁₈ alkyl benzene sulfonate (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

R¹ - 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 alkylcarboxylate and FC-170-C, a mixture of fluorinated alkyl polyoxyethylene 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 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 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 ethoxylated 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- alkanol amines, and they are often preferred, whereas the monoethanolamine is usually preferred.

Monoethanol amine and/or beta-alkanol amine 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% t_{0 a}bout 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

R - C C - OH

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,1- 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 betaaminoalkanols preferably have boiling points below about 175ºC. Preferably, the boiling point is within about 5ºC of 165ºC.

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 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-aminoalkanols 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 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- 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 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 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 wherein γH is the hydrogen bonding parameter, a is the aggregation number,

(Log α = 3.39066 T_b/T_c - 0.15848 - Log M) , and

d

γT is the solubility parameter which is obtained from the formula γT =

where ΔH₂₅ is the heat of vaporization at 25ºC, R is the gas constant (1.987 cal/mole/deg), T is the absolute temperature in °K, Tb is the boiling point in ºK, T_c is the critical temperature in ºK, 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, 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 cause a haze on glϊss. Higher numbers require more solvent to 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 from about 3% to about 6%. Concentrated compositions contain from about 10% to about 30%, preferably from about 10% to about 20% of 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 20ºC.

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 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 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-C₉ alkyl aromatic solvents, especially the C₆-C₉ 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 100ºC, especially alpha-olefins, preferably 1-decene or 1-dodecene, are excellent grease removal solvents.

Generically, the glycol ethers useful herein have the formula R⁶ O(R⁷O)_mH wherein each R⁶ is an alkyl group which contains from about 3 to about 8 carbon atoms, each R⁷ is either ethylene or propyl ene, and m is a number from 1 to about 3. The most preferred glycol ethers are selected from the group consisting of monopropyleneglycolmonopropyl ether, dipropyleneglycolmonobutyl ether, monopropyleneglycolmonobutyl ether, diethyleneglycolmonohexyl ether, monoethyleneglycolmonohexyl ether, monoethyleneglycolmonobutyl 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 20ºC.

Some examples of suitable diol solvents and their solubilities in water are shown in Table 1. TABLE 1

Solubility of Selected Diols in 20ºC Water

Solubility

Diol fq/100o H₂O

1,4-Cyclohexanedimethanol 20.0*

2,5-Dimethyl-2,5-hexanediol 14.3

2-Phenyl-1,2-propanediol 12.0*

Phenyl-1,2-ethanediol 12.0*

2-Ethyl-1,3-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. The diol solvents are especially preferred because, in addition 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 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 C_1-4 alcohols, butoxy propanol, Butyl Carbitol® and 1(2-n-butoxy-1-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 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/Alkalinity-Source

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. The buffering system comprises monoethanol amine and/or betaaminoalkanol 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/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 monoethanolamine 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 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 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 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 minimize spotting and filming.

Antibacterial agents can be present, but preferably only at low levels to avoid spotting/filming problems. More hydrophobic antibacterial/germicidal agents, like orthobenzyl-para-chlorophenol, 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-hydroxyl-1,1-di2 phosphonate, the nonphosphorous chelating agents described in the copending U.S. Pat. Application of Culshaw and Vos, Ser. No. 285,337, filed Dec. 14, 1988, said application being incorporated herein by reference (e.g., carboxymethyltartronic acid, oxydimalonic 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(OH)CH₂OH;

-CH(CH₂OH)₂; -CH₃; -CH₂CH₂OCH₃; -C-CH₃; -CH₂-C-NH₂;

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); 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 known as sodium amidonitrilotriacetic, 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 ethyl enediaminetetraacetate, 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 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 perfume ingredients are readily solubilized in the compositions by the acylamidoalkylene detergent surfactant. Other similar detergent surfactants will not solubilize 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. : 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 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 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 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, perfume ingredients typically have boiling points of about 250ºC or lower. Many of the more moderately volatile perfume ingredients are also lost substantially in the cleaning process. The moderately volatile perfume ingredients are those having boiling points of from about 250ºC 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, paracymene, decanal, dihydro! inalool, 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 acetaldehyde, methyl phenyl carbinyl acetate, laevo-menthyl acetate, menthone, iso-menthone, myrcene, myrcenyl acetate, myrcenol, nerol, neryl acetate, nonyl acetate, phenyl ethyl alcohol, alphapinene, beta-pinene, gamma-terpinene, alpha-terpineol, beta-terpineol, 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, heliotropine, 3-cis-hexenyl salicylate, hexyl salicylate, lilial (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 composed mainly of alpha-cedrene, beta-cedrene, and other C₁₅H₂₄ sesquiterpenes.

Examples of the less volatile, high boiling, perfume ingredients 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 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 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.

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 propell ant and spray valve, etc.

The invention is illustrated by the following Examples. EXAMPLE I

F ormul a No . * (Wt .%)

Ingredient 1 2 3 4

Propylene Glycol Mono- butylether 2.0 2.0 2.0 2.0

Isopropanol 5.0 5.0 5.0 5.0

Cocoamidopropyl (Hydroxy

propyl)sulfobetaine 0. 15 0.15 0.15 0. 15

Monoethanolamine 1.0 - - -

1-amino-2-propanol - 1.0 - -

2-amino-1-butanol - - 1.0 -

2-amino-2-methyl-1-butanol - - - 1.0

Perfume 0.20 0.20 0.20 0.20

Deionized Water q.s . q.s . q.s. q.s .

*pH adjsted to ab out 11.3

EXAMPLE II

Formul a No .* fWt.%)

Ingredient 1 2 3

Lauryl-dimethyl-3- sulfopropylbetaine 0.20 - -

Cocoyl-dimethyl-2-hydroxy- 3-sulfopropylbetaine - 0.20 -

Lauryl -dimethyl-betaine - - 0.20

Cocoamidipropyl-dimethyl- betaine - - -

Cocoamidopropyl-dimethyl-2- hydroxy-3-sul fopropyl betaine - - -

Sodium Alkyl (-C₁₃) Sulfate - - -

2-Amino-2-methyl-1-propanol - - -

Monoethanol amine 0.5 0.5 0.5

Propylene Glycol Mono- butylether 3.0 3.0 3.0

Isopropanol 3.0 3.0 3.0

Deionized Water and Minors

(e.g., Perfume) q.s. q.s. q.s.

*All pH's adjusted to about 10.9 EXAMPLE ll (Continued)

Formula No.* (Wt.%)

Ingredient 4 5 6

Lauryl-dimethyl-3- sulfopropylbetaine - - -

Cocoyl-dimethyl-2-hydroxy-

3-sulfopropylbetaine - - -

Lauryl-dimethyl-betaine - - -

Cocoamidipropyl-dimethyl- betaine 0.20 - -

Cocoamidopropyl-dimethyl-2- hydroxy-3-sulfopropylbetaine - 0.20 0.18

Sodium Alkyl (-C₁₃) Sulfate - - 0.02

2-Amino-2-methyl-1-propanol - - -

Monoethanol amine 0.5 0.5 0.5

Propylene Glycol Mono- butylether 3.0 3.0 3.0

Isopropanol 3.0 3.0 3.0

Deionized Water and Minors

(e.g., Perfume) q.s. q.s. q.s.

*All pH's adjusted to about 10.9

EXAMPLE ll (Conti nued)

Formula No.* (Wt.%)

Ingredient 7 8 9

Lauryl-dimethyl-3- sulfopropylbetaine - - -

Cocoyl-dimethyl-2-hydroxy-

3-sulfopropylbetaine - - - Lauryl-dimethyl-betaine - - - Cocoamidipropyl-dimethyl- betaine 0.15 0.18 0.15

Cocoamidopropyl-dimethyl-2- hydroxy-3-sulfopropylbetaine - - - Sodium Alkyl (-C₁₃) Sulfate - - - 2-amino-2-methyl-1-propanol 0.5 - - Monoethanolamine - 0.5 0.5

Propylene Glycol Monobutylether 3.0 4.0 - Ethylene Glycol

Monobutylether - - 3.0 Isopropanol 3.0 2.0 3.0 Deionized Water and Minors

(e.g., Perfume) q.s. q.s. q.s.

*All pH's adjusted to about 10.9

EXAMPLE II (Continued)

Formula No.* (Wt.%)

Ingredient 10 11 12

Lauryl-dimethyl-3- sulfopropylbetaine

Cocoyl-dimethyl-2-hydroxy- 3-sulfopropylbetaine

Lauryl-dimethyl-betaine

Cocoamidipropyl-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 Monobutylether 4.0 - 3.0

Ethylene Glycol Monobutylether - 3.0 -

Isopropanol 2.0 3.0 3.0

Deionized Water and Minors

(e.g., Perfume) q.s. q.s. q.s.

*All pH's adjusted to about 10.9

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

EXAMPLE III

Formul a No.* (Wt.%)

Ingredient 1 2 3 Ralufon^® DL 0.20 0.20 0.20 Monoethanolamine - 0.5 0.5 Isopropanol - - 3.0

Propylene Glycol Monobutylether - - - Sodium Hydroxide - - - Deionized Water q.s. q.s. q.s. 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.%)

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

Sodi um Hydroxide - * - *

Deionized Water q.s. q.s. q.s. q.s

Ralufon^® DL (Raschig Corp.) is Lauryl-dimethyl-ammonium- 3-sul fopropyl 3- (lauryl,dimethyl,ammoniurn)-propyl- sulfonate)

*pH adjusted to 10.8 with NaOH, thi s 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 allowed to dry for ten minutes before grading by expert judges. Grading :

Expert judges are employed to evaluate the specific areas off product application for amount of filming/streaking. A numerical value describing the amount of filming/streaking is assigned to each product. For the test results reported here a 0-10 scale was used.

0 = No Filming/Streaking

10 = Poor Filming/Streaking

Room temperature and humidity have been shown to influence filming/streaking. Therefore these variables are always recorded.

Filming/Streaking Stress Test on Glass Windows (Four Replications at 73ºF 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 at 95% confidence level.

Claims

CLAIMS:

1. An aqueous liquid hard surface detergent composition comprising: (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(O)-N(R⁴)-(CR⁵ ₂)_n-]_mN(R⁶)₂(+)-(CR⁵ ₂)_p-Y(-) wherein each R³ 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 (R⁶) is selected from the group consisting of hydrogen, methyl, ethyl, propyl, hydroxy substituted ethyl or propyl and mixtures thereof, each (R⁵) is selected from the group consisting of hydrogen and hydroxy groups, with no more than about one hydroxy group in any (CR⁵ ₂) moiety; m 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 zwitterionic detergent surfactant being more preferably hydrocarbyl- amidoalkylenesulfobetaine detergent surfactant; (b) optional solvent/buffer system that preferably comprises monoethanol amine 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,1-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 preferably 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-amidoalkylenesulfobetaine which has the formula:

R³-C(O)-N(R⁴)-(CR⁵ ₂)_n-N(R⁶)₂(+)-(CR⁵ ₂)_p-SO₃(-) wherein each R³ 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, with R⁴ preferably being hydrogen and R⁵ being methyl, each (R⁵) is selected from the group consisting of hydrogen and hydroxy groups, and each n and p is a number from 1 to about 4; with no more than about one hydroxy group in any (CR⁵ 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(O)-N(R⁴)-(CR⁵ ₂)_n-N(R⁶)2(+)-(CR⁵ ₂)_n-COO(-) wherein each R³ 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 R⁴ being hydrogen and each R⁶ being methyl; each (R⁵) is selected from the group consisting of hydrogen and hydroxy groups; and each n and p is a number from 1 to about 4; with no more than about one hydroxy group in any (CR⁵ ₂) moiety.

4. The composition of any of the above claims wherein said R³ group contains from about 12 to about 16 carbon atoms, R⁴ is hydrogen, each R⁶ 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 R⁵ 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, alkanol amines, alkali metal hydroxides, alkali metal silicates, alkali metal borates, alkali metal carbonates, alkali metal bicarbonates, and mixtures thereof, preferably said monoethanol amine and/or beta-aminoalkanol amine, 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 R¹O(R²O)_mH wherein each R¹ is an alkyl group which contains from about 3 to about 8 carbon atoms, each R² is selected from the group consisting of ethylene or propyl ene, and m is a number from 1 to about 3, preferably selected from the group consisting of monopropyleneglycolmonopropyl ether, dipropyleneglycolmonobutyl ether, monopropyleneglycolmonobutyl ether, diethyleneglycolmonohexyl ether, monoethyl eneglycolmonohexyl ether, and mixtures thereof; diols containing 6 to 16, preferably 8 to 12, carbon atoms, preferably 2,2,4-trimethyl-1,3,-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.