CA2224461C - Cleaning composition and method for the cleaning of delicate surfaces - Google Patents

Abstract

Compositions are disclosed which are suitable for the safe cleaning of delicate surfaces, i.e. marble and painted and lacquered surfaces, e.g. lacquered wooden floors. The compositions disclosed herein comprise at least one surfactant, they are formulated in the mildly acidic to mildly alkaline pH range, they comprise a builder or a combination of builders, and positive divalent ions in amounts so as to saturate the builder in the composition.

Description

WO 96/41856 PCTlUS96107030 W, Cleaning Composition and Method for the Cleaning of Delicate Surfaces Technical Field The present invention relates to hard surface cleaning compositions. The compositions herein are specifically designed for the safe cleaning of marble and painted and lacquered surfaces, especially painted and lacquered wood.
Backgiround A wide variety of cleaning compositions for hard surfaces have been disclosed in the prior art. Most of these compositions are concerned only with performance, on a wide variety of stains and in a wide variety of conditions. And most hard surfaces are rather resistant to the point that it is generally not a concern that these surfaces may be permanently damaged by the cleaning composition.
However marble and lacquered surfaces are two types of surfaces which do require particular attention, when formulating cleaning compositions for their cleaning. Indeed, marble is mainly composed of calcium carbonate, and is therefore incompatible with cleaning compositions which would be acidic to neutral and/or which would comprise a builder. Indeed, acidity would "dissolve" marble, while the builder, whose function is specifically to bind ions which are present in water and dirt particles, would also bind the calcium in the marble, thereby turning the surface from very shiny to dull, as the introduced surface irregularities lower the reflectance of the surface.
More surprisingly, we have found that most cleaning products formulated at neutral pH, containing builders andlor avionics, also damage marble. Thus the formulation of an alkaline, builder free composition would seem indicated in the present circumstances.
However, the formulation of an alkaline composition does not accommodate the cleaning of lacquered and painted surfaces, such as painted metal surfaces, or lacquered and painted wooden surfaces e.g. lacquered wooden floors. As used herein, lacquers are typically made out of polyurethanes or

2 polyacrylates or mixtures of both, and paint is mainly pigmented polyacrylates, polyvinylacetates or alkydresins. Indeed such surfaces are permanently damaged by alkalinity. Specifically, alkalinity would destroy the t lacquer and therefore give the lacquered surface the appearance of dullness or a colour change. Thus it would appear that formulating a cleaning composition which is suitable for cleaning both marble and lacquered surfaces is hindered by incompatible pH requirements.
Also, the absence of a builder, which is desirable for preserving the marble, is somewhat incompatible with a good performance for the cleaning of greaselparticulate soil. Indeed, it has been observed that dirt comprises Ca2+, Mg2+ and/or metal ions which, in turn, most probably bind the charged ends of the fat molecules in grease, thereby forming a dirt-grease complex which is difficult to removal. The presence of a builder which binds the metal ions loosens the complex and therefore helps its removal.
Thus it is an object of the present invention to formulate a liquid composition which is suitable for the cleaning of both marble and painted and lacquered surfaces, and which provides good cleaning performance, in particular which performs well on grease removal.
In response to this object, we have formulated a liquid composition which comprises at least one surfactant, which is formulated at a mildly acidic to mildly alkaline pH , which comprises a builder, and positive divalent ions in amounts so as to saturate the builder in the composition.
Indeed, we have found that in the present compositions, the mildly acidic to neutral pH does damages neither marble nor lacquers. Also, the builder saturated with the positive divalent ions prevents the damage on marble, while it still displays its building action, as evidenced by improved grease cleaning performance.
t Cleaning composition which are said to be for delicate surfaces are described in EP 511 091, CN 1055198 (title) and CN 10 32 360 (title).

3 Summary of the Invention The present invention encompasses a liquid cleaning composition which comprises at least one surfactant, which is formulated in the mildly acidic to mildly alkaline pH range, which comprises a builder and positive divalent ions in an amount so as to saturate the builder in the composition.
The present invention further encompasses a method of cleaning marble or lacquered surfaces, where an effective amount of the composition is applied to clean said marble or lacquered surfaces, and said composition is removed.
Detailed description of the invention The compositions herein are liquid compositions. They are typically aqueous and typically comprise from 10 % to 99 % by weight of the total composition, preferably from 15 % to 95 %, most preferably from 30 % to 92 of water.
As a first essential characteristic, the compositions herein comprise at least one surfactant. The surfactant herein is required for cleaning. Suitable surfactants for use herein include anionic, nonionic, cationic and amphoteric surfactants. Non limiting examples of surfactants useful herein typically include the conventional alkyl benzene sulphonates ("LAS"), typically C11-C1g LAS, alkyl sulphonates, typically Cg-C1g alkyl sulphonates and primary, branched-chain and random alkyl sulphates ("AS"), typically C1p-C20 AS, the secondary (2,3) alkyl sulphates, typically C1 p-C1 g ones, of the formula CH3(CH2)X(CHOSOg-M'~') CH3 and CH3 (CH2)y(CHOS03-M+) CH2CH3 where x and (y+1 ) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulphates such as oleyl sulphate, the alkyl alkoxy sulphates ("AEXS"), especially C10-C1g AEXS, especially EO 1-7 ethoxy sulphates, alkyl alkoxy carboxylates, especially the C1 p-C1 g ones, especially EO 1-5 ethoxycarboxylates, the glycerol ethers, preferably the C10-C1g ones, the alkyl polyglycosides and their corresponding sulphated polyglycosides, and alpha-sulphonated fatty acid esters, preferably the C10-C1 g ones. If desired, the conventional nonionic and amphoteric surfactants such as the alkyl ethoxylates ("AE") preferably C12-C1g AE, including the so-called WO 96/41856 PCT/(TS96/07030

4 narrow peaked alkyl ethoxylates and alkyl phenol alkoxylates, especially the Cg-C12 ones, especially ethoxylates and mixed ethoxy-propoxy, betaines and sulfobetaines ("sultaines"), preferably the C12-C1 g ones, amine oxides, typically the C1 p-C1 g ones, and the like, can also be included in the overall compositions. The N-alkyl polyhydroxy fatty acid amides, typically C10-C1g ~l ones, can also be used. Typical examples include the C12-C1g N-methylglucamides, see WO 9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C1 p-C1 g N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl gfucamides, preferably C12-C1g ones, can be used for low sudsing. C1p-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C1p-C1g soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts.
The compositions herein comprise from 0.1 % to 90 % by weight of the total composition, preferably from 5 % to 85 %, most preferably from 5 % to 70 of at least one surfactant. The preferred surfactants for use herein are the nonionic surfactants or mixtures of avionics and nonionics, for their cleaning action on grease. It is another benefit of the present invention that anionic surfactants can be used herein without damaging marble. Indeed, it has been observed that anionic surfactants usually also damage marble probably because, like builders, they bind with the calcium in the marble.
However the compositions of the present invention can surprisingly afford the presence of anionic surfactants for improved cleaning without having to suffer any negative on safety to marble.
As a second essential characteristic, the compositions herein comprise a builder. The compositions herein comprise from 0.1 % to 20 %, preferably from 0.2 % to 10 %, most preferably from 0.3 % to 6 % by weight of the total composition of builder, or mixtures thereof.
Suitable builders for use herein include polycarboxylates and polyphosphates, and salts thereof.
Suitable and preferred polycarboxylates for use herein are organic polycarboxylates where the highest LogKa, measured at 25°C/0.1 M ionic strength is between 3 and 8, wherein the sum of the LogKCa + LogKMg, measured at 25°C/0.1 M ionic strength is higher than 4, and wherein LogKCa ~ogKMg ~ 2 units, measured at 25°C/0.1 M ionic strength.
Such suitable and preferred polycarboxylates include citrate and complexes of the formula CH(A)(COOX)-CH(COOX)-O-CH(COOX)-CH(COOX)(B) wherein A is H or OH; B is H or -O-CH(COOX)-CH2(COOX); and X is H or a salt-forming canon. For example, if in the above general formula A and B
are both H, then the compound is oxydissuccinic acid and its water-soluble salts. If A is OH and B is H, then the compound is tartrate monosuccinic acid ('T'MS) and its water soluble salts. If A is H and B is -O-CH(COOX)-CH2(COOX), then the compound is tartrate diauccinic add (TDS) and its water soluble salts. Mixtures of these builders are espedally preferred for use heroin. Parnculariy TMS to TDS, these builders are disclosed in U.S.
Patent 4,683,071, issued to Bush et al., on May 5, 1987.
Still other ether potycarboxylates suitable for use heroin indude copolymers of malefic anhydride with ethylene or 'vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisutfonic acid, and carboxymethyloxyaucanic sad.
Other useful polycarboxyiate builders induds the ether hydroxypolycart~oxyistes represented by the structure HO-(C(R)(COOM)~C(R)(COOM)-Ojn~H
wherein M is hydn~gen or a canon wherein the resultant salt is water soluble, prefersbly an alka~ metal, ammonium or substituted ammonium canon, n is from about 2 to about 15 (preferably n is from about 2 to about 10, more pn averages from about 2 to about 4) and each R is the same or diffensnt and selected from hydn~gen, Cl.d alkyl or C1-4 substituted alkyl (preferably R is hydrogen).
Suitable ether polycauboxylates also include cydic compounds, particularly aljcydic compounds, such as those described in U.S. Patents 3,923,679;
3,835,163; 4,158,635; 4,120,874 and 4,102,903.

Preferred amongst those cyclic compounds are dipicolinic acid and chelidanic acid.
Also suitable polycarboxyiates for use herein are mellitic acid, succinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, benezene pentacarboxylic acid, and carboxymethyioxysuccinic acid, and soluble salts thereof.
Still suitable carboxyiate builders herein include the carboxylated carbohydrates disclosed in U.S. Patent 3,723,322. Diehl, issued March 28, 1973.
Other suitable carboxylates for use herein, but which are less preferred because they do not meet the above criteria are alkali metal, ammonium and substituted ammonium sans of polyacetic ands. Examples of polyacetic acid builder salts are sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamine, tetraacetic sad and nitriiotriacetic sad.
Other suitable but less preferred poiyc;arboxyiates are those also known as alkyiiminoacetic builders such as methyl imino diacstic sad, alanine diacetic sad, methyl giyane diacetic acid, hydroxy propylene imino diacetic acid and other alkyl imino acetic acid builders.
Also suitable in the compositions of the present invention aro the 3,3-dicarboxy-4-oxa~1,8-hexanediotes and the related compounds disclosed in U.S. Patent 4,588,9&1, Bush, issued January 28, 1988.
Useful sucanic aad builders indude the C5-C20 alkyl suacinic adds and saib thereof. A particularly profiernsd compound of this type is dodecenylsucanic sad. Alkyl sucanic aads typically are of the genera!
formula R-CH(COOH)CH2(COOH) i.e., derivabw~s of sucanic sad, wheroin R is hydrocarbon, e.g., C~0-C20 alkyl or alkenyl, preferably C12-Cog or wheroin R may be substituted with hydroxyl, sutfo, sutfoxy or suifone substituents, ail as described in the above-ment'roned patents.
The succinats builders are preferably used in the form of their water-soluble salts, including the sodium, potassium, ammonium and alkanolammonium salts.

Specific examples of succinate builders include : lauryisuccinate, myristylsuccinate, paimitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application '0 200 263, published November 5, 1986.
Examples of useful builders also include sodium and potassium carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclo-hexanehexacarboxylate, cia-cyclopentane-tetracarboxylate, water-soluble polyacrylates and the copolymers of malefic anhydride with vinyl methyl ether or ethylene.
Other suitable polycarhoxylates are the polyacetal carboxyiates disdoaed in U.S. Patent 4,144,226, Cnrtchfield et al., issued Mardi 13, 1979.
These polyaceml carboxylates can be prepared by bringing together, under polymerization conditions, an eater of glyoxylic sad and a polyerization initiator. The resulting polyacetal carboxyiate eater is then attached to chemically stable end groups to stabilize the polyacetal carboxylate ~ against rapid depoNmerization in alkaline solution, converted to the corresponding sale, and added to a surfactant.
Polycarboxylats builders are also disclosed in U.S. Patent 3,308,087, Diehl, issued March 7, 1987. Such materials indude the wabr-soluble salts of homo- and copolymers of aliphatic carboxylic scids suds as malefic acid, itaoonic add, mesaconic acad, fumaric acid, aconi~ticc add, dda~onic sad and methylsnemalonic sad.
Suitable polyphosphonates for use herein are the aUcali metal, ammonium and alkanolsmmonium salts of polyphosphates (exemplified by the tripolyphospha~es, pyrophosphates, and glsssy polymer>c meta-phosphates), phosphonates. The most preferred builder for use heroin is citrate.
As a third essentisi ingredient, the compositions herein comprise positive divalent ions in amounts so as to saturate the bulkier present in the composition. By "saturate", it is meant herein that there should be enough ions to bind substantially all the builder present in the composition, i.e. at least 75% of the builder, preferably at least 80%, most preferably at least 90% or all of the builder. Thus, for a 100% saturation, the ions should be present most preferably in a molar ratio of builder ions to builder of at least X:2, where X is the maximum potential number of negative charges carried per mole of builder. For instance, if said builder is citrate, then said molar ratio should be at least 3:2, because each mole of citrate can carry 3 negative changes. For the purpose of the present invention and the amount of ions needed therein, the form in which the carboxylate or phosphate groups in the builder are present is not critical. In other words, at certain pH
values between 6 to 8 where some of the carboxylate or phosphate groups in the builder are in their protonated form, the preferred X:2 ratio still applies.
The ions can be introduced in the compositions in any form. As far as Mg is concerned, MgCl2 has been found to be commercially attractive. However MgS04, Mg Phosphates and MgN03 are also suitable source of Mg ions for the compositions herein. Without wishing to be bound by theory, we speculate that the ions herein somehow prevent the builder from binding with the calcium in the marble, without preventing the builder from performing in the cleaning operation.
Suitable positive divalent ions for use herein include Mg2+, Ba2+, Fe2~', Ca2+, Zn2+ and Ni2+. Most Preferred are Mg2+ and Ca2+, or mixtures thereof.
As a fourth essential characteristic, the compositions herein are formulated in a mildly acidic to mildly alkaline range. Accordingly, the compositions herein preferably have a pH between 6 and 9, more preferably between 6.5 and 8, and most preferably between 7 and 7.5. At lower pH, the composition would damage marble while, at higher pH, it would damage lacquers. Interestingly, even in neutral pH in which the compositions herein can be formulated, damage to marble would be observed in the absence of the saturated citrate. The pH of the compositions herein can be adjusted by any of the means well known to the man skilled in the art, such as addition of NaOH, KOH, MEA,TEA,MDEA,K2C03,Na2C03 and the like, or citric acid, sulphuric acid, nitric acid, hydrochloric acid , malefic acid, acetic acid and the like.

WO 96/41856 PCTlIJS96/0?030 Particularly preferred compositions herein comprise an effective amount of a carbonate of the formula XHC03 or, if the builder used is not a phosphate-type builder, a phosphate of the formula XaHbP04, where a+b=3 and a or b can be 0, XaHbP207 where a+b=4 and a or b can be 0, or XaHbP3010 where a+b=5 and a or b can be 0, and where X is an alkali metal, particularly K+, Na+, or NH4+. Indeed, apart from the pH adjusting effect just described, we have found that the presence of those compounds furher improves the safety of the compositions herein to delicate surfaces. Without wishing to be bound by theory, it is believed that the compounds react with the calcium on the surface of marble, to form an insoluble calcium carbonate salt at the marble/solution interface, creating a protective layer. Using these compounds in addition to the saturation technology described hereinabove provides a synergetic effect on delicate surface safety. The amount of these compounds needed in the compositions herein can be determined by trial and error, but appears to lie in the range of from 0.05%
to 0.4% by weight of the total composition, preferably from 0.05% to 0.1 %.
Caution needs to be exercised however in that we have observed that too high an amount of XHC03 may raise be dertimental to surface safety on lacquered wood.
The compositions herein can further comprise a variety of well known optional ingredients, including perfumes, dyes, alkanolamines.
The present invention further encompasses a method of cleaning marble or lacquered surfaces. In that method, an effective amount of a composition as herein before described is applied onto said marble or lacquered surface, and said composition is optionally removed.
Depending on the surface which is being cleaned, the compositions herein can be used undiluted, i.e. neat, or diluted. Typically, when used on large surfaces, such as floors, the compositions herein are used in diluted form, i.e. at dilution levels of from about 0.5% to 1.5%, depending on how concentrated the product is. In such diluted conditions, the compositions herein are applied to said surface, and left to dry, i.e. no rinsing is required.
In order to remove tough stains on these surfaces the product can also be applied neat on the surFace to remove the encrustated dirt much more easily. When used on smaller surfaces, e.g. bathroom walls which can be made out of marble, neat usage of the composition will be preferred. In neat usage, it is preferable that the composition should be removed, i.e. rinsed off after it has been applied to clean.
The present invention will be further illustrated by the following examples.
The following compositions ware made by mixing the listed ingredients in the listed proportions. These composi~ons were used neat to clean marble and dilute to clean lacquered wooden floors. Excellent cleaning and surface safety performance was observed.
Ingrediertts Compositions (weight %) CT-g,Ca.1 ~ EOg 3.0 3.0 5.0 3.2 3.2 3.2 8.0 8.0 Dobanol c~ 23-3 1.0 1. 0 1. 5 1.3 i . 3 1.5 3.0 3.5 EmpiisnNKBE21 + 2.0 2.0 2.5 1.9 1.9 2.0 5.0 8.0 NaPS 2.0 1.5 1.2 1.2 1.0 1.7 3.0 2.5 NsCS 1.2 3.0 2.2 2.0 2.0 1.5 4.0 5.0 NIgS04 0.20 0.9 0.30 0.50 1.3 2.0 1.0 3.0 Ct6ralt 0.3 1.0 0.5 0.75 1.8 3.0 1.5 8.0 NaHC03 0.08 0.1 - 0.1 - 0.2 - -Na2HP04 - - 0.1 - 0.3 - - -Na2H2PZQT - - - - - - 0.2 0.5 pH 8.0 T.5 T.0 T.25 8.0 T.4 7.5 T.2 Water and Minors up -t0 100do As used hereinabove:
-NaPS stands for Na paraffin sulphonate -NaCS stands for Na cumene sulphonate -Dobanoi~ 23-3 is a C12-13 alcohol ehtoxylated with an average ethoxylation degree of 3.
-Empilart~ KBE21 is a C 7 2-14 alcohol ethoxylated with an average ethoxylation degree of 3.

Claims (14)

WHAT IS CLAIMED IS:

1. A method of cleaning, marble or lacquered surfaces with a composition having a pH of from 6 to 9, said composition comprising from:
(a) 5% to 85% by weight of a surfactant;
(b) positive divalent ions in an amount sufficient to saturate the builder in the composition wherein said positive divalent ions are Mg2+ or Ca2+ or mixtures thereof; and (c) 0.1% to 20% by weight of an organic polycarboxylate builder wherein the highest LogKa, measured at 25° C./0.1M ionic strength is between 3 and 8, wherein the sum of the LogKCa+LogKMg, measured at 25° C./0.1M
ionic strength is higher than 4, and wherein LogKCa=LogKMg~2, measured at 25° C./0.1M ionic strength.
said method comprising the step of contacting said surface with an amount of said composition effective to clean said surface

2. A method according to claim 1 wherein said composition is formulated in a pH
range of from about 6.5 to about 8.

3. A method according to claim 2 wherein said composition is formulated in a pH
range of from about 7 to about 7.5.

4. A method according to claim 3 wherein said composition comprises from about 8% to about 70% by weight of the total composition of said surfactant.

5. A method according to claim 1 wherein said surfactant is a nonionic surfactant.

6. A method according to claim 1 wherein said surfactant is a mixture of an anionic surfactant with a nonionic surfactant.

7. A method according to claim 1 wherein said positive divalent ions are Mg2+
ions.

8. A method according to claim 1, wherein said builder is citrate.

9. A method according to claim 1 wherein said composition comprises from about 0.2% to about 10% by weight of the total composition of said builder.

10. A method according to claim 9 wherein said composition comprises from about 0.3% to about 6% by weight of the total composition of said builder.

11. A method according to claim 1 wherein the composition further comprises an effective amount for keeping the pH of said composition between 6 and 9 of a bicarbonate of the formula XHCO3 or, a phosphate of the formula Xa H b PO4, where a+b=3 and a or b can be 0, X a H b P2 O7 where a+b=4 and a or b can be 0, or X a H b P3 O10 where a+b=5 and a or b can be 0, and where X is an alkali metal or ammonium.

12. A method according to any of claims 1-10 wherein said composition further comprises a bicarbonate of the formula XHCO3 where X is an alkali metal.

13. The method of any of claims 1, 2, 5, 7, 8, 9 or 11 wherein the composition is diluted to a concentration of from 0.5 to 1.5% by weight, prior to the step of contacting to the step of contacting said surface.

14. The method according to claim 1 wherein said composition need not be rinsed from said surface.