WO1996034933A1

WO1996034933A1 - Glass cleaner compositions having linear alkyl sulfate surfactants

Info

Publication number: WO1996034933A1
Application number: PCT/US1996/005561
Authority: WO
Inventors: Ronald Anthony Masters; Charles Albert Hensley; Lori Boden Mitchell; Michael Stephen Maile; Nicola John Policicchio; Todd Christian Severson
Original assignee: The Procter & Gamble Company
Priority date: 1995-05-05
Filing date: 1996-04-23
Publication date: 1996-11-07
Also published as: CA2220131A1; DE69604660T2; DE69604660D1; EP0823937B1; DK0823937T3; ATE185591T1; CA2220131C; AR001845A1; BR9608216A; ES2136988T3; MX9708503A; CO4700538A1; GR3032284T3; AU5564296A; EP0823937A1

Abstract

The present invention relates to an aqueous, liquid hard surface detergent composition having excellent surface lubricity and filming/streaking characteristics. Said composition comprises less than about 1 %, by weight of the composition, of a C8-C18 linear alkyl sulfate detergent surfactant wherein more than about 30 %, by weight of said surfactant, has a C14 chainlength, is essentially free of unreacted fatty alcohol and alkanolamine compounds and is suitable for cleaning glass.

Description

Glass cleaner compositions having linear alkyl sulfate surfactants.

FIELD OF INVENTION

This invention pertains to glass cleaning compositions, preferably clear liquid detergent compositions, for use in cleaning glass and, preferably, other hard surfaces. BACKGROUND OF THE INVENTION It has recently been discovered that there is a strong consumer preference for liquid cleaning compositions, especially compositions prepared for cleaning glass, that impart a smooth "gliding" feel, based on good surface lubricity, as the cleaning implement wipes and dries.

At first glance, the task of making a cleaning composition that feels slippery, or imparts a smooth "gliding" feel while it is being used seems fairly straightforward. One would think it possible to use a wax or a silicone, as is known in the art, to provide good lubricity. However, it is also well known that liquid cleaning compositions, and especially compositions prepared for cleaning glass, need exceptionally good filming/streaking properties. Because good filming/streaking properties are required especially for glass cleaners, the levels of surfactants and other actives must be kept low in order to achieve this benefit. Therefore, the level of surfactant is too low to solubilize and/or stabilize waxes or silicones in the product, especially when a hydrophobic perfume is also present.

Also, it is known in the art that water-sheeting and anti-spotting benefits are preferred in glass cleaning compositions. These water-sheeting and anti-spotting benefits are typically achieved by providing a composition which leaves behind a hydrophilic residue. Waxes and silicones are extremely hydrophobic and therefore are entirely incompatible with this requirement.

It has been discovered that long chain, i.e., C14 or longer, alkyl sulfate detergent surfactants provide the desired amount of surface lubricity as the composition is wiped dry on glass as well as contributing detergency and providing acceptable filming/streaking results and product clarity. Furthermore, the long-chain alkyl sulfate surfactants are soluble in water and help to reinforce the surface hydrophilicity that is required in order to obtain water-sheeting and anti-spotting benefits.

SUMMARY OF THE INVENTION The present invention relates to detergent compositions, preferably glass cleaning compositions, that impart good surface lubricity and cleaning without leaving objectionable levels of filming and/or streaking. Preferably said compositions contain an effective amount of substantive material which provides the glass with long lasting higher hydrophilicity and are in the form of an aqueous, liquid, hard surface detergent composition having improved cleaning and good spotting characteristics after rewetting, comprising:

(A) less than about 1%, by weight of the composition, of a linear alkyl sulfate detergent surfactant having the general formula:

R-O-SO3 M wherein M is a suitable counter ion; R is an alkyl group having a chain length of from about Cg to about Cjg or mixtures thereof; wherein more than about 30%, by weight of said surfactant, of said surfactant has a C14 chainlength;

(B) from about 0.5% to about 30%, by weight of the composition, of a hydrophobic solvent having a hydrogen bonding parameter of from about 2 to

7.7;

(C) the balance being an aqueous solvent system selected from the group consisting of water and non-aqueous polar solvents having a hydrogen bonding parameter of greater than 7.7; and wherein said composition is essentially free of unreacted fatty alcohol and alkanolamine compounds and wherein said composition is suitable for cleaning glass. DETAILED DESCRIPTION OF THE INVENTION The present invention relates to detergent compositions, preferably aqueous, liquid hard surface detergent compositions having excellent surface lubricity and filming/streaking characteristics, comprising:

R-O-SO3 M wherein M is a suitable counter ion; R is an alkyl group having a chain length of from about Cg to about C_jg or mixtures thereof; wherein more than about 30%, by weight of said surfactant, of said surfactant has a C14 chainlength; (B) from about 0.5% to about 30%, by weight of the composition, of a hydrophobic solvent having a hydrogen bonding parameter of from about 2 to 7.7;

(C) the balance being an aqueous solvent system selected from the group consisting of water and non-aqueous polar solvents having a hydrogen bonding parameter of greater than 7.7; and wherein said composition is essentially free of unreacted fatty alcohol and alkanolamine compounds and wherein said composition is suitable for cleaning glass. (A) THE LONG CHAIN ALKYL SULFATE PRIMARY SURFACTANT The aqueous, liquid hard surface detergent compositions herein contain less than about 1%, by weight of the composition, preferably from about 0.01% to about 1%, more preferably from about 0.02% to about 0.3%, by weight of the composition, of one or more chainlengths of a linear alcohol sulfate detergent surfactant having the general formula: R - O - SO3 M wherein M is any suitable counterion, preferably sodium, potassium, etc.; and wherein R is an alkyl group with a chainlength of from about Cg to about C_jg and mixtures thereof, preferably from about C12 to about Cjg and mixtures thereof, more preferably from about C14 to about C^g and mixtures thereof, and wherein R is Cj4 in more than about 30%, preferably more than about 35%, more preferably more than about 40?/o, by weight of the alkyl sulfate. The entire alkyl sulfate surfactant can contain R of C14 and longer chainlength(s), but more than 30%, by weight of the alkyl surfactant must be a C14 chainlength. Compositions containing only alkyl sulfate surfactants with higher chainlengths, i.e., Cj^i provide good surface lubricity benefits. However, these chain lengths, without the required amount of C14 chainlengths, exhibit poor filming/streaking properties. On the other hand, compositions which are solely made up of lower-chain alkyl sulfate surfactants, i.e., Cg-12 alkyl sulfate surfactants, provide acceptable filming/streaking properties but show poor surface lubricity properties. The presence of the C14 chainlength at levels of more than about 30%, by weight of the alkyl sulfate surfactant, in combination with other chainlengths, or alone, provide a product with both excellent surface lubricity properties and excellent filming/streaking properties. Particularly preferred compositions contain from about 0.05% to about 0.25%, by weight of the composition, of a C 12/14 blend in which the C γ to C 14 weight ratio is from about 1:10 to about 2: 1, preferably from about 1:5 to about 1.5: 1, and more preferably from about 1 :3 to about 1: 1. This combination has been found to provide sufficient surface lubricity while avoiding objectionable filming/streaking. The alcohol sulfate detergent raw materials selected are essentially free from unreacted fatty alcohol wherein the term "essentially free" is defined as having less than about 2%, by weight of the composition, preferably less than about 1.8%, and more preferably less than about 1.5%, by weight of the composition of unreacted fatty alcohol in a nominally 30% active raw material.

A more preferred alkyl sulfate surfactant is a mixture of Stepanol WA-Extra®, available from the Stepan Company, with extra C14 alkyl sulfate added such that the C 12/ 14 ratio is nearly 1:1.

Concentrated compositions can also be used in order to provide a less expensive product. When a higher concentration is used, i.e., when the level of alkyl sulfate surfactant used is from about 0.10% to about 2.5%, by weight of the composition, it is preferable to dilute the composition before using it to clean a hard surface, especially glass. Dilution ratios of the alkyl sulfate concentrate(s) to water can range, preferably, from about 1: 1 to 1: 10, more preferably from about 1 : 1.5 to 1 :5, and most preferably from about 1 :2 to 1:5. (B) THE OPTIONAL CO-SURFACTANTS

The aqueous, liquid hard surface detergent compositions of the present invention can contain optional co-surfactants. Suitable co-surfactants which can be used are as follows: (1) The Amphocarboxylate Detergent Surfactant

The aqueous, liquid hard surface detergent compositions (cleaners) herein can contain from 0% to about 0.5%, by weight of the composition, preferably from about 0.01% to about 0.5%, more preferably from about 0.02% to about 0.2%, and even more preferably from about 0.03% to about 0.08%, by weight of the composition, of C_f5-io short chain amphocarboxylate detergent surfactant. It has been found that these amphocarboxylate, and, especially glycinate, detergent surfactants provide good cleaning with superior filming/streaking for detergent compositions that are used to clean both glass and/or relatively hard-to-remove soils. Despite the short chain, the detergency is good and the short chains provide improved filming/streaking, even as compared to most of the zwitterionic detergent surfactants described hereinafter. Depending upon the level of cleaning desired and/or the amount of hydrophobic material in the composition that needs to be solubilized, one can either use only the amphocarboxylate detergent surfactant, or can combine it with cosurfactant, preferably said zwitterionic surfactants. The "amphocarboxylate" detergent surfactants herein preferably have the generic formula:

R-N(Rl)(CH2)_nN(R2)(CH₂)pC(O)OM wherein R' is a Cg.io hydrophobic moiety, typically a fatty acyl moiety containing from about 6 to about 10 carbon atoms which, in combination with the nitrogen atom forms an amido group, R is hydrogen (preferably) or a Cι_2 alkyl group, R^ is a Cι_3 alkyl or, substituted C1.3 alkyl, e.g., hydroxy substituted or carboxy methoxy substituted, preferably, hydroxy ethyl, each n is an integer from 1 to 3, each p is an integer from 1 to 2, preferably 1, and each M is a water-soluble cation, typically an alkali metal, ammonium, and or alkanolammonium cation. Such detergent surfactants are available, for example: from Witco under the trade name Rewoteric AM-V®, having the formula C₇H! 5C(O)NH(CH₂)2N(CH2CH2OH)CH₂C(O)O(-) Na(⁺)i

Mona Industries, under the trade name Monateric 1000®, having the formula

C7H 1₅C(O)NH(CH2)2N(CH2CH2OH)CH₂CH2C(O)O(-) Na(⁺); and Lonza under the trade name Amphoterge KJ-2®, having the formula

^C7,9^H15, 19^c(0)NH(CH2)2N(CH2CH₂OCH2C(O)O(-)Na(⁺))CH₂C(O)O(-) Na(⁺)-

(2) Zwitterionic Detergent Surfactant

The aqueous, liquid hard surface detergent compositions (cleaners) herein can contain from about 0% to about 1%, by weight of the composition, 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. A more preferred range of zwitterionic detergent surfactant inclusion is from about 0.005% to about 0.3% of surfactant, a most preferred range is from about 0.01% to about 0.2%, by weight of the composition. 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 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 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)-(CR52)_nl]_mN(R6)2(⁺)-(CR52)pl-Y(-) wherein each Y is preferably a carboxylate (COO") or sulfonate (SO3") group, more preferably sulfonate; wherein each R^ 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 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 (R^) is selected from the group consisting of hydrogen and hydroxy groups with no more than one hydroxy group in any (CR^p group; wherein (R°) is like R^ except preferably not hydrogen; wherein m is 0 or 1; and wherein each nl and p are an integer from 1 to about 4, preferably from 2 to about 3, more preferably about 3. The R^ groups can be branched, unsaturated, or both and such structures can provide filming/streaking benefits, even when used as part of a mixture with straight chain alkyl R^ groups. The R^ groups can also be connected to form ring structures such as imidazoline, pyridine, etc. 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 sulfobetaines, and, to a lesser extent hydrocarbylamidoalkylene betaines are excellent for use in hard surface cleaning detergent compositions, especially those formulated for use on both glass and hard- to-remove soils. They are even better when used with monoethanolamine and/or specific beta-amino alkanol as disclosed herein.

A more preferred specific detergent surfactant is a C10-14 fatty acylamidopropylene(hydroxypropylene)sulfobetaine, e.g., the detergent surfactant available from the Witco Company as a 40% active product under the trade name "REWOTERIC AM CAS Sulfobetaine®." 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 0.0% to about 1%, preferably from about 0.005% to about 0.5%, more preferably from about 0.01% to about 0.25%, by weight of the composition, of detergent surfactant. For removal of difficult to remove soils like grease, the level can, and should be, higher, typically from about 0% to about 10%, preferably from about 0.005% to about 2%, by weight of the composition. Concentrated products will typically contain from about 0% to about 10%, preferably from about 0.005% to about 5%, by weight of the composition. 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.

(3) The Optional Anionic Detergent Surfactants

The detergent compositions, preferably aqueous, liquid hard surface detergent compositions, herein can contain as the cosurfactant, preferably, from about 0.0% to about 2.0%, more preferably from about 0.005% to about 0.99% of suitable anionic detergent surfactant other than the essential alkyl sulfate detergent surfactant. While it is understood that the longer chain alkyl sulfate surfactants disclosed herein are considered the primary surfactant system, additional co- surfactants can be added including alkyl sulfate surfactants of even lower chain lengths. The optional anionic surfactants are suitably water-soluble alkyl or alkylaryl compounds, the alkyl having from about 6 to about 20 carbons, and including a sulfate or sulfonate substituent group, but excluding the essential alkyl sulfate detergent surfactant. Depending upon the level of cleaning desired one can use only the essential anionic detergent surfactant, or, more preferably, the anionic detergent surfactant can be combined with a cosurfactant, preferably an amphoteric cosurfactant. Nonionic surfactants, e.g., ethoxylated alcohols and/or alkyl phenols, can also be used as cosurfactants but are not preferred.

The anionic detergent surfactants herein preferably have the generic formula:

R⁹-(R1⁰)O-I-SO₃(-)M(⁺) wherein R⁹ is a C6-C20 alkyl chain, preferably a C -Cig alkyl chain; Rl°, when present, is a C6-C20 alkylene chain, preferably a Cg-Cig alkylene chain, a C6H4 phenylene group, or O; and M is the same as before.

The patents and references disclosed hereinbefore and incorporated by reference also disclose other detergent surfactants, e.g., anionic, and, less preferably, nonionic detergent surfactants, that can be used in small amounts, preferably as cosurfactants for the essential alkyl sulfate detergent surfactant and preferred amphoteric/zwitterionic detergent cosurfactant. The cosurfactant level can be small in relation to the primary surfactant. Typical of these are the alkyl- and alkylethoxylate- (polyethoxylate) sulfates, paraffin sulfonates, olefin sulfonates, alkoxylated (especially ethoxylated) alcohols and alkyl phenols, alkyl phenol sulfonates, alpha-sulfonates of fatty acids and of fatty acid esters, and the like, which are well-known from the detergency art. When the pH is above about 9.5, detergent surfactants that are amphoteric at a lower pH are desirable anionic detergent cosurfactants. For example, detergent surfactants which are Ci2-C g 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 herein contain a hydrophobic group, typically containing an alkyl group in the Cc-Cιg 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, not preferred, generally contain from about 5 to about 17 ethylene oxide groups.

Some suitable surfactants for use herein in small amounts are one or more of the following: sodium linear Cg-Cig alkyl benzene sulfonate (LAS), particularly 1 l" i2 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

R7 — C — N(R8)₂ wherein R⁷ 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 R^ 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 alkyl carboxylate 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.

(4) Mixtures Mixtures of amphocarboxylate, zwitterionic detergent surfactants, and/or anionic detergent surfactants as discussed hereinbefore, can be present in the present invention.

When a co-surfactant is added to the composition of the present invention, the total surfactant level can be from about 0.01% to about 5%, by weight of the total composition however, the alkyl surfactant should be present at a level less than 1%, by weight of the composition. The ratio of zwitterionic detergent surfactant to amphocarboxylate detergent surfactant is typically from about 3: 1 to about 1 :3, preferably from about 2: 1 to about 1:2, more preferably about 1: 1. The ratio of the primary C14 alkyl sulfate detergent surfactant to cosurfactant, or cosurfactants, is typically from about 3 : 1 to about 1 :1. (C) HYDROPHOBIC SOLVENT

In order to improve cleaning in liquid compositions, one can use a hydrophobic solvent that has cleaning activity. The solvents employed in the hard surface cleaning compositions herein can be any of the well-known "degreasing" solvents 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:

1/2 a • 1 γH - γT a

wherein γH is the hydrogen bonding parameter, a is the aggregation number, (Log α = 3.39066 TyT_c - 0.15848 - Log M), and d γT is the solubility parameter which is obtained from the formula:

where ΔH25 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, T_D is the boiling point in °K, T_c 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 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 glass. Higher numbers require more solvent to provide good greasy/oily soil cleaning.

Hydrophobic solvents are typically used at a level of from about 0.5% to about 30%, preferably from about 2% to about 15%, more preferably from about 3% to about 8%. Dilute compositions typically have solvents at a level of from about 1% to about 10%, preferably from about 3% to about 6%. Concentrated compositions contain from about 10% to about 30%, preferably from about 10% to about 20% of solvent.

Many of such solvents comprise hydrocarbon or halogenated hydrocarbon moieties of the alkyl or cycloalkyl type, and have a boiling point well above room temperature, i.e., above about 20°C.

The formulator of compositions of the present type will be guided in the selection of cosolvent partly by the need to provide good grease-cutting properties, and partly by aesthetic 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 Cβ-Co. alkyl aromatic solvents, especially the Cg-Cα alkyl benzenes, preferably octyl benzene, exhibit excellent grease removal properties and have a low, - 11 - 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 RU O-(R 2θ-)_mlH wherein each R! 1 is an alkyl group which contains from about 3 to about 8 carbon atoms, each R12 is either ethylene or propylene, and ml 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, ethyleneglycolmonohexyl ether, ethyleneglycolmonobutyl 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 20°C.

Solvents such as pine oil, orange terpene, benzyl alcohol, n-hexanol, phthalic acid esters of C 1.4 alcohols, butoxy propanol, Butyl Carbitol® and l(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-l,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.

(D) OPTIONAL ALKALINITY SOURCE

The compositions of this invention can contain an optional alkalinity source. Suitable compounds which can be used include but are not limited to alkali metal hydroxides, i.e., sodium, potassium, etc., and carbonates or sodium bicarbonates. The alkalinity source can be present at a level of 0% to about 0.2%, by weight of the composition. Typically said alkalinity source is present at a level of from about 0.001% to about 0.1%, preferably from about 0.005% to about 0.05%, by weight of the composition. It is undesirable to use alkanolamine compounds as an alkalinity source in the present invention. Said alkanolamine compounds interfere with the surface lubricity benefit achieved by the long-chain alkyl sulfate surfactants. Said composition is therefore essentially free of alkanolamine compounds. "Essentially free" as defined herein means less than about 0.5%, preferably less than about 0.1%, more preferably less than about 0.01%.

(E) OPTIONAL SOLUBLE CARBONATE AND/OR BICARBONATE SALTS Water-soluble alkali metal carbonate and/or bicarbonate salts, such as sodium bicarbonate, potassium bicarbonate, potassium carbonate, cesium carbonate, sodium carbonate, and mixtures thereof, are added to the composition of the present invention in order to improve the filming/streaking when the product is wiped dry on the surface, as is typically done in glass cleaning. Preferred salts are sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, their respective hydrates, and mixtures thereof. Solubilized, water-soluble alkali metal carbonate and bicarbonate salts are typically present at a level of from about 0% to about 0.5%, preferably from about 0.001% to about 0.1%, more preferably from about 0.005% to about 0.05%, by weight of the composition. The pH in the composition, at least initially, in use is from about 7 to about 1 1, preferably from about 7.5 to about 10.5, more preferably from about 8 to about 10. pH is typically measured on the product.

(F) OPTIONAL SUBSTANTIVE MATERIAL THAT INCREASES HYDROPHILICITY OF GLASS

An optional but preferred ingredient of this invention is the substantive material that improves the hydrophilicity of the surface being treated, especially glass. This increase in hydrophilicity provides improved appearance when the surface is rewetted and then dried. The water "sheets" off the surface and thereby rninimizes the formation of, e.g., "rainspots" that form upon drying. Many materials can provide this benefit, but the preferred materials are polymers that contain hydrophilic groups, especially carboxylate or sulfonate groups. Other materials that can provide substantivity and hydrophilicity include cationic materials that also contain hydrophilic groups and polymers that contain multiple ether linkages. Cationic materials include cationic sugar and or starch derivatives and the typical block copolymer detergent surfactants based on mixtures of polypropylene oxide and ethylene oxide are representative of the polyether materials. The polyether materials are less substantive, however.

The preferred polycarboxylate polymers are those formed by polymerization of monomers, at least some of which contain carboxylic functionality. Common monomers include acrylic acid, maleic acid, ethylene, vinyl pyrrollidone, methacrylic acid, methacryloylethylbetaine, etc. The preferred polysulfonate polymers are those based upon a polystyrene backbone. Preferred polymers for substantivity are those having higher molecular weights. For example, polyacrylic acid having molecular weights below about 10,000 are not particularly substantive and therefore do not normally provide hydrophilicity for three rewettings with all compositions, although with higher levels and or certain surfactants like amphoteric and/or zwitterionic detergent surfactants, molecular weights down to about 1000 can provide some results. In general, the polymers should have molecular weights of more than 10,000, preferably more than about 20,000, more preferably more than about 300,000, and even more preferably more than about 400,000. It has also been found that higher molecular weight polymers, e.g., those having molecular weights of more than about 3,000,000, are extremely difficult to formulate and are less effective in providing anti-spotting benefits than lower molecular weight polymers. Accordingly, the molecular weight should normally be, especially for polyacrylates, from about 20,000 to about 3,000,000; preferably from about 20,000 to about 2,500,000; more preferably from about 300,000 to about 2,000,000; and even more preferably from about 400,000 to about 1,500,000. An advantage for some polycarboxylate polymers is the detergent builder effectiveness of such polymers. Surprisingly, such polymers do not hurt filming/streaking and like other detergent builders, they provide increased cleaning effectiveness on typical, common "hard-to-remove" soils that contain particulate matter. Some polymers, especially polycarboxylate polymers, thicken the compositions that are aqueous liquids. This can be desirable. However, when the compositions are placed in containers with trigger spray devices, the compositions are desirably not so thick as to require excessive trigger pressure. Typically, the viscosity under shear should be less than about 200 cp, preferably less than about 100 cp, more preferably less than about 50 cp. It can be desirable, however, to have thick compositions to inhibit the flow of the composition off the surface, especially vertical surfaces.

Examples of suitable materials for use herein include poly(vinyl pyrrolidone/acrylic acid) sold under the name "Acrylidone"® by ISP, polystyrene sulfonic acid and polystyrene sulfonate salts sold under the name "Versaflex"® by National Starch, and poly(acrylic acid) sold under the name "Accumer"® by Rohm & Haas.

The level of substantive material should normally be from about 0% to about 1.0%, preferably from about 0.01% to about 0.5%, more preferably from about 0.02% to about 0.2%, by weight of the composition. In general, lower molecular weight materials such as lower molecular weight poly(acrylic acid), e.g., those having molecular weights below about 10,000, and especially about 2,000, do not provide good anti-spotting benefits upon rewetting, especially at the lower levels, e.g., about 0.02%. One should use only the more effective materials at the lower levels. In order to use lower molecular weight materials, substantivity should be increased, e.g., by adding groups that provide improved attachment to the surface, such as cationic groups, or the materials should be used at higher levels, e.g., more than about 0.05%.

(G) 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, glycol ethers having a hydrogen bonding parameter of greater than 7.7, propylene glycol, and mixtures thereof, preferably ethanol. The level of non-aqueous polar solvent is usually greater when more concentrated formulas are prepared. Typically, the level of non-aqueous polar solvent is from about 0.5% to about 40%, preferably from about 1% to about 10%, more preferably from about 2% to about 8% (especially for "dilute" compositions) and the level of water is from about 50% to about 99%, preferably from about 75% to about 95%. (H) 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 filming/streaking. Non-limiting examples of such adjuncts are:

Enzymes such as proteases;

Hvdrotropes 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 filming/streaking in the cleaning of glass. Most hard surface cleaner products contain some perfume to provide an olfactory aesthetic benefit and to cover any "chemical" odor that the product may have. The main function of a small fraction of the highly volatile, low boiling (having low boiling points), 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. The perfumes are preferably those that are more water-soluble and or volatile to rninimize streaking and filming. The perfumes useful herein are described in more detail in U.S. Patent 5, 108,660, Michael, issued April 28, 1992, at col. 8 lines 48 to 68, and col. 9 lines 1 to 68, and col. 10 lines 1 to 24, said patent, and especially said specific portion, being incorporated by reference.

Antibacterial agents can be present, but preferably only at low levels to avoid filming/streaking problems. More hydrophobic antibacterial geimicidal agents, like orthobenzyl-para-chlorophenol, are avoided. If present, such materials should be kept at levels below about 0.1%.

Stabilizing ingredients can be present typically to stabilize more of the hydrophobic ingredients, e.g., perfume. The stabilizing ingredients include acetic acid and propionic acids, and their salts, e.g., NH4, MEA, Na, K, etc., preferably acetic acid and the C2-C6 alkane diols, more preferably butane diol. The stabilizing ingredients do not function in accordance with any known principle. Nonetheless, the combination of amido zwitterionic detergent surfactant with linear acyl amphocarboxylate detergent surfactant, anionic detergent surfactant, nonionic detergent surfactant, or mixtures thereof, and stabilizing ingredient can create a microemulsion. The amount of stabilizing ingredient is typically from about 0.01% to about 0.5%, preferably from about 0.02% to about 0.2%. The ratio of hydrophobic material, e.g., perfume that can be stabilized in the product is related to the total surfactant and typically is in an amount that provides a ratio of surfactant to hydrophobic material of from about 1:2 to about 2:1. Other detergent builders that are efficient for hard surface cleaners and have reduced filming/streaking characteristics at the critical levels can also be present in the compositions of the invention. Addition of specific detergent builders at critical levels to the present composition further improves cleaning without the problem of filming streaking that usually occurs when detergent builders are added to hard surface cleaners. There is no need to make a compromise between improved cleaning and acceptable filming/streaking results, which is especially important for hard surface cleaners which are also directed at cleaning glass. These compositions containing these specific additional detergent builders have exceptionally good cleaning properties. They also have exceptionally good "shine properties, i.e., when used to clean glossy surfaces, without rinsing, they have much less tendency than, e.g., carbonate built products to leave a dull finish on the surface and filming/streaking.

Suitable additional optional detergent builders include salts of ethylenediaminetetraacetic acid (hereinafter EDTA), citric acid, nitrilotriacetic acid (hereinafter NT A), sodium carboxymethylsuccinic acid, sodium N-(2- hydroxypropy -iminodiacetic acid, and N-diethyleneglycol-N,N-diacetic acid (hereinafter DID A). The salts are preferably compatible and include ammonium, sodium, potassium and or alkanolammonium salts. The alkanolammonium salt is preferred as described hereinafter. A preferred detergent builder is NTA (e.g., sodium), a more preferred builder is citrate (e.g., sodium or monoethanolamine), and a most preferred builder is EDTA (e.g., sodium). These additional optional detergent builders, when present, are typically at levels of from about 0.01% to about 0.5%. more preferably from about 0.02% to about 0.3%, most preferably from about 0.02% to about 0.15%. The levels of these additional builders present in the wash solution used for glass should be less than about 0.2%. Therefore, typically, dilution is highly preferred for cleaning glass, while full strength is preferred for general purpose cleaning, depending on the concentration of the product.

Typically the best filming streaking results occurs most when the builder is combined with amphoteric and/or --witterionic detergent surfactant compositions although an improvement is also seen with anionic or anionic/nonionic detergent surfactant compositions.

The invention is illustrated by the following nonlimiting Examples.

Static Friction Height Test A 12" x 12" pane of glass is sprayed with product (one spray from a standard spray device) and wiped to near dryness with one paper towel. A 550 gram plexiglass block is wrapped with a paper towel by taking one sheet and folding it twice into a square. The towel is taped to the bottom of the block so it is stretched taut with no wrinkles or creases and no tape is on the bottom surface that will be in contact with the glass. The block is placed on the glass toward one end. The end of the glass is raised slowly until the block begins to move. The distance that the glass was raised is measured. The higher the height, the higher the friction and the static friction height. A normal dry clean glass has a high coefficient of friction (0.9-1.0), and therefore a high static friction height (greater than 5 inches with this method).

End Result Wipe Test Procedure: Five sprays of the product to be tested are applied to a 2ft. x 3ft. glass window (which can be soiled with body oils from a handprint) and wiped with two paper towels to near dryness, simulating actual consumer usage of the product. Grading:

Expert judges are employed to evaluate the specific areas of product application for amount of filming/streaking, with the aid of a floodlight to simulate a sunbeam. A numerical value describing the quality of the end result is assigned to each product. For the test results reported here a 0-6 scale is used, in which 0 = good end result with no film/streak, and 6 = very poor end result.

EXAMPLE I

INGREDIENT 1 2 3 4 5

Wt.% Wt.% Wt.% Wt.% Wt.%

Butoxypropanol 2.8 2.8 2.8 2.8 2.8

Ethanol 2.8 2.8 2.8 2.8 2.8

Polystyrene Sulfonate

(Versaflex® 7000) ^] 0.10 0.10 0.10 0.10 0.10

Sodium Octyl Sulfate 0.05 0.05 0.05 0.05 0.05

Sodium Dodecyl Sulfate 0.06 — — 0.06 —

Sodium Tetradecyl Sulfate 0.06 0.06 0.06 — —

Sodium Hexadecyl/octadecyl

Sulfate — — 0.04

1 Available from National Starch

The above formulas were tested according to the above methods for static friction height and end result wipe, with the results as follows (average of 3 replicates with standard deviation):

Static Friction Height End Result Wipe Grade

Formula finches) (0 = best. 6= worst) 1 1.82 + 0.06 0.75 ± 0.00

2 1.82 + 0.06 0.83 ± 0.11

3 1.52 ± 0.06 0.83 ± 0.11

4 2.44 ± 0.06 0.75 ± 0.17

5 2.46 ± 0.05 0.92 ± 0.11 Relative Humidity = 30%

As can be seen by the above example, formulas 1-3 of the present invention provide lower static friction height than formulas 4-5 which are outside the scope of the present invention while maintaining good end results. For relatively low and constant surfactant levels (about 0.1 to 0.2%) which are consistent with good end result, the C14 and longer chainlengths provide the most smoothness (lowest static friction height). Qualitative evaluation shows that Formulas 1-3 provide noticeably improved surface lubricity while wiping to dryness than do Formulas 4-5. EXAMPLE II

INGREDIENT 6 7 8 9

Wt.% Wt.% Wt.% Wt.%

Butoxypropanol 2.8 2.8 2.8 2.8

Ethanol 2.8 2.8 2.8 2.8

Poly(vinylpyrrolidone/acrylate) 0.025 0.025 — —

Sodium Hydroxide 0.04 0.04 — —

Sodium Dodecyl Sulfate 0.20 — — —

Sodium Tetradecyl Sulfate 0.08 0.05 0.05 0.02

Stepanol WA-extra

(70/30 blend C12/14 alkyl sulfate)² — — 0.10 0.10

Sodium Bicarbonate — 0.015 — 0.015

Sodium Carbonate — 0.005 — 0.005

Fragrance 0.03 0.03 0.07 0.07

End Result Wipe Grade

(Relative Humidity = 35%) 1.8 0.56 0.80 0.55

End Result Wipe Grade

(Relative Humidity = 54%) NA NA 1.65 1.00 ^Available from the Stepan Co.

The above example shows that the addition of a small amount of carbonate provides for a modest improvement in the end result wipe grade, both for formulas which contain a polymer for hydrophilic surface modification and for those which do not. The improvement is even more pronounced at higher humidities.

Claims

What is Claimed is:

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

(A) less than 1%, preferably from 0.01% to 0.9%, more preferably from 0.02% to 0.3%, by weight of the composition, of a linear alkyl sulfate detergent surfactant having the general formula:

R-O-SO3 M wherein M is a suitable counter ion; R is an alkyl group having a chain length of from Cg to Cig or mixtures thereof; preferably from C12 to Cig, more preferably from C14 to C g wherein more than 30%, preferably more than 35%, more preferably more than 40%, by weight of said surfactant, of said surfactant has a C 4 chainlength;

(B) from 0.5%) to 30%, by weight of the composition, of a hydrophobic solvent having a hydrogen bonding parameter of from 2 to 7.7;

(C) the balance being an aqueous solvent system selected from the group consisting of water and non-aqueous polar solvents having a hydrogen bonding parameter of greater than 7.7; and wherein said composition is essentially free of unreacted fatty alcohol and alkanolamine compounds and wherein said composition is suitable for cleaning glass.

2. The composition of Claim 1 wherein R is an alkyl group having a chainlength of a C 2/14 blend having a C 2 to C 4 weight ratio of from 1: 10 to 2: 1.

3. The composition of Claim 1 further comprising up to 4.9%, by weight of the composition of a co-surfactant selected from the group consisting of:

(A) amphocarboxylate detergent surfactants;

(B) zwitterionic detergent surfactants;

(C) anionic detergent surfactants; and

(D) mixtures thereof.

4. The composition of Claim 1 further comprising from 0% to 0.5%, preferably from 0.001% to 0.1%, more preferably from 0.005% to 0.5%, by weight of the composition of solubilized, water-soluble alkali metal carbonate salt, bicarbonate salt, or mixtures thereof

5. The composition of Claim 4 wherein said salt is selected from the group consisting of sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, their respective hydrates, and mixtures thereof.

6. The composition of Claim 1 further comprising from 0% to 1.0% of a substantive material that increases hydrophilicity of glass.

7. The composition of Claim 6 wherein said substantive material is polycarboxylate polymer, preferably having a molecular weight of from 1,000 to 3,000,000, more preferably having a molecular weight of 20,000 to 2,500,000, most preferably having a molecular weight of from 400,000 to 1,500,000.

8. A liquid, aqueous hard surface detergent composition having both excellent surface lubricity characteristics and excellent filming/streaking characteristics, comprising:

(A) from 0.01% to 0.9%, by weight of the composition, of a linear alkyl sulfate detergent surfactant having the formula:

R-O-SO3 M wherein M is a sodium counterion; R is an alkyl group having a chainlength consisting of a C 12/14 blend having a Ci2 to C 4 weight ratio of from 1: 10 to 2: 1 and wherein more than 30% of said alkyl sulfate surfactant is comprised of a C 4 chainlength;

(B) from 0.005% to 0.9%, by weight of the composition, of a C14 alkyl sulfate co-surfactant;

(C) from 0.001% to 0.1%, by weight of the composition, of sodium carbonate;

(D) from 0.5% to 30%, by weight of the composition, of butoxypropanol;

(E) the balance being a mixture of ethanol and water; and wherein said composition is essentially free of unreacted fatty alcohol and alkanolamine compounds and wherein said composition is suitable for cleaning glass.

9. The process of cleaning glass, comprising:

(A) spraying the composition of Claim 1 onto a glass surface using a spraying device; and

(B) wiping said surface to near dryness.