MXPA97010064A - Cleaning composition and method for cleaning delica surfaces - Google Patents

Abstract

Compositions are described which are suitable for the safe cleaning of delicate surfaces, ie marble surfaces and painted and varnished surfaces, eg varnished wood floors, the compositions described herein comprise at least one surfactant, are formulated on a scale of slightly acidic to slightly alkaline pH, they comprise an improved detergency or a combination of detergency builders, as well as positive divalent ions in amounts such as to saturate the builder in the composition.

Description

CLEANING COMPOSITION AND PORA LINE METHOD 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 varnished surfaces, especially painted and varnished wood.

BACKGROUND A wide variety of hard surface cleaning compositions have been described in the prior art. Most of these compositions relate only to performance, over a wide variety of spots and in a wide variety of conditions. And the harder surfaces are rather resistant to the point where it is generally not a concern that these surfaces can be permanently damaged by the cleaning composition. However, marble or varnished surfaces are two types of surfaces that require particular attention, when cleaning compositions are formulated for cleaning. In fact, the marble is composed mainly of calcium carbonate and therefore is incompatible with cleaning compositions that would be acid to neutral and / or which would comprise a detergency meter. In fact, the acidity would "dissolve" the marble, while the detergency improver, whose function is specifically to bind ions that are present in water and dirty particles, would also bind the calcium in the marble, thus making the surface pass through. very glossy to opaque, since the surface irregularities introduced reduce the reflectance of the surface. Very surprisingly, it has been found that most cleaning products formulated at neutral pH, which contain builder and / or ammonium builders, also damage marble. Therefore, the formulation of an alkaline composition without detergent improver would seem indicated in the present circumstances. However, the formulation of an alkaline composition is not adapted to the cleaning of varnished and painted surfaces, such as painted metal surfaces, or varnished and painted wood surfaces, e.g., varnished wood floors. As used herein, varnishes are typically made of fluoroethanes or polyacrylates or mixtures of both, and the paint is primarily polyacrylates, polyvinyl acetates or pigmented alkyladic reams. In fact, those surfaces are permanently damaged by alkalinity. Specifically, alkalinity would destroy the lacquer and therefore give the varnished surface the appearance of opacity or a change in color. This would make it appear that the formulation of a cleaning composition that is suitable for cleaning marble and varnished surfaces is impeded by incompatible pH requirements. Also, the absence of a builder, which is desirable for preserving marble, is to some degree incompatible with good performance for cleaning grease / particulate dirt. In fact, it has been observed that dirt comprises Ca2 +, Mg2 + and / or metal ions which in turn most likely bind the charged ends of the fat molecules in the fat, thus forming a dirt / fat complex that is difficult to remove . The presence of a builder that binds the metal ions releases the complex and therefore aids its removal. Therefore, an object of the present invention is to formulate a liquid composition which is suitable for cleaning marble surfaces as well as painted and varnished surfaces, and which provides good cleaning performance, in particular having good performance on the removal of grease. In response to this object, a liquid composition comprising at least one surfactant, which is formulated at a slightly acidic and slightly alkaline pH, comprising a detergency builder, and positive divalent ions in amounts such as to saturate has been formulated. the detergency builder in the composition.

In fact, it has been found that in the present compositions, the slightly acidic to neutral pH does not damage the marble or the varnishes. Also, the detergency builder saturated with the positive divalent ions prevents damage to the marble, while displaying its improved detergency action, as evidenced by the improved grease cleaning performance. Cleaning compositions which are said to be for delicate surfaces are described in EP 511 091, CN 1055198 (title) and CN 10 32 360 (title).

BRIEF DESCRIPTION OF THE INVENTION The present invention includes a liquid cleaning composition comprising at least one surfactant, which is formulated on the slightly acid to slightly alkaline pH scale, comprising a detergent builder and positive divalent ions in an amount to saturate the buffer. of detergency in the composition. The present invention further comprises a method of cleaning marble or varnished surfaces, wherein an effective amount of the composition is applied to clean said marble or varnished 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 with respect to the total composition, preferably from 15% to 95%, most preferably from 30% to 92% of water. As a first essential feature, the compositions herein comprise at least one surfactant. The surfactant here 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 conventional alkylbenzene sulfonates ("LAS" s), typically Cii-Ciß LAS / alkylsulphonates, typically β-Ciß alkylsulphates, and primary C 10 -C 20 alkylsulphonates ("AS") , branched chain and random, typically secondary alkylsulfates (2,3) of Cio-Ciß of the formula CH3 (CH2) * (CH0S03-M +) CH3 and CH3 (CH2) and (CH0S03-M +) CH2CH3 where xy (and + 1) are integers of at least 7, preferably at least about 9, and M is a cation of solubilization in water, especially sodium, unsaturated sulaphthates such as oleyl sulfate, the alkylalkoxysulfates of C? OC? ß ("AEXS" especially EO 1-7 ethoxysulfates), Cι-Ciß alkylalkoxycarboxylates (especially the EO 1-5 ethoxycarboxylates), the Cι-Ciß glycol ethers, the Cι-Ciß alkyl polyglycosides and their corresponding sulphated polyglycosides, and alphasulfonated fatty acid esters of C12 -C18. If desired, conventional amphoteric and nonionic surfactants such as alkyl ethoxylates ("AE") preferably C12-C18 AE, including so-called narrow-chain alkyl ethoxylates and C6-C12 alkyl enolalycoxylates (especially ethoxylates and ethoxy / mixed propoxy) ), betaines and sulfobetaines ("sultaines"), preferably C12-C18, amine oxides, typically Cio-Ciß, and the like, can also be included in the overall compositions. N-alkyl polyhydroxolic fatty acid amides, typically from Cι-Ciß, can also be used. Typical examples include C 12 -C 18 N-rnethylglucarnines, see 10,96,154. Other surfactants derived from sugar include the N-alkoxy polyhydric fatty acid amides, such as N- (3-methoxypropyl) glucarnine from Cι-Ciß- The N-propyl to N-hexylglucarnides, preferably from C 12 -C 18, can be used for low foaming. Conventional C10-C20 soaps can also be used. If high spunation is desired, branched-chain Cio-Ciß soaps can be used. Mixtures of anionic and nonionic surfactants are especially useful. Other useful conventional surfactants are listed in standard texts. The compositions herein comprise from 0.1% to 90% by weight with respect to the total composition, preferably from 5% to 85%, most preferably from 5% to 70% of at least one surfactant. Preferred surfactants for use herein are nonionic surfactants or mixtures of anionic and nonionic, for their cleansing action on fats. Another benefit of the present invention is that the anionic surfactants can be used without damaging the marble. In fact, it has been observed that anionic surfactants generally also damage marble, probably because, like detergent builders, they bind with calcium in marble. However, the compositions of the present invention can surprisingly allow the presence of anionic surfactants for improved cleaning without having to suffer any negative effect on safety for the marble. As a second essential feature, 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 with respect to the total detergency builder composition, or mixtures thereof. Suitable detergency builders for use herein include polycarboxylates and polyphosphates, and salts thereof. Suitable and preferred polycarboxylates for use herein are organic polycarboxylates wherein the highest LogKa, measured at 25 ° C / 0.1M ionic strength is between 3 and 8, where the sum of LogKCa + LogKMg, measured at 25 ° C /0.1M ionic strength is greater than 4, and where LogKCa = LogKMg ± 2 units, measured at 25 ° C / 0.1M ionic strength. Said suitable and preferred polycarboxylates include citrate and form complexes of the formula CH (A) (C0OX) ~ CH (C0OX) -0-CH (C00X) -CH (C0OX) (B) wherein A is H or OH; B is H or -O-CH (COOX) -CH2 (COOX); and X is H or a salt-forming cation. For example, without the above general formula A and B are both H, then the compound is acid OXJ, disuccimco and its water soluble salts. If A is OH and B is H, then the compound is tartrate monosuccimic acid (TMS) and its water soluble salts. If A is H and B is -O-CH (COOX) -CH2 (COOX), then the compound is tartrate disuccinic acid (TDS) and its water soluble salts. Mixtures of these detergency builders are especially preferred for use here. Particularly TMS to TDS, these detergency enhancers are described in the U.S. Patent. No. 4,663,071, issued to Bush et al., May 5, 1987. Other etherpolycarboxylates suitable for use herein include copolymers of rnaleic anhydride with ethylene or vinyl ether, 1, 3,5-tr? H? Drox? Benzene-2, , 6-tr? Sulfonic acid and carboxymethyloxy succimic acid. Other useful polycarboxylate detergent builders include the hydroxypolycarboxylate ether represented by structure: H0-CC (R) (C00M) -C (R) (C00M) -0] "- H wherein h is hydrogen or a cation wherein the salt The resultant is soluble in water, preferably an alkali metal, ammonium or substituted ammonium cation, n is from 2 to about 15 (preferably n is from about 2 to about 10, most preferably n averages from about 2 to about 4) and each R is the same or different and is selected from hydrogen, C 1-4 alkyl or substituted C 1-4 alkyl (preferably R is hydrogen). Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Pat. 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903, all of which are incorporated herein by reference. Preferred among those cyclic compounds are dipicolinic acid and chelidanic acid. Polycarboxylates also suitable for use herein are rhnelitic acid, succinic acid, polyrnaleic acid, benzene 1, 3,5-tricarboxylic acid, benzenecarboxylic acid and carboxymethyloxysuccinic acid, and soluble salts thereof. Suitable carboxylate builders herein include the carboxylated carbohydrates described in the U.S. Patent. No. 3,723,322, Diehl, issued March 28, 1973, incorporated herein by reference. Other carboxylates suitable for use herein, but which are less preferred because they do not meet the above criteria are alkali metal, ammonium and substituted ammonium salts of polyacetic acids. Examples of polyacetic acid detergent builder salts are sodium, potassium, lithium, ammonium or substituted ammonium salts of ethylenediaminetetraacetic acid and nitrilotriacetic acid. Other suitable but less preferred polycarboxylates are those known as alkylaminoacetic detergency builders such as rnethylnirinodiacetic acid, alanindiacetic acid, rnethylglycliciacetic acid, hydroxypropylene-n-n-diacetic acid and other detergents of alkyl-arninoacetic acid. Also suitable in the compositions of the present invention are the 3,3-dicarboxy-4-oxa-1, 6-hexanediotes and the related compounds described in the U.S. Patent. No. 4,566,984, Bush, issued January 28, 1986, incorporated herein by reference. Useful succinic acid detergency builders include the C5-C20 alkylsuccinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Alkylsuccinic acids are typically of the general formula R-CH (C00H) CH2 (COOH), ie, succinic acid derivatives, wherein R is hydrocarbon, e.g., C? Or C al alkyl or alkenyl, preferably of C 12 -C 16 or wherein R can be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents, all described in the aforementioned patents. The succinate detergency builders are preferably used in the form of their water soluble salts, including sodium, potassium, ammonium and alkanolaronium salts. Specific examples of succinate detergency builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate and the like. Lauryl succinates are the preferred detergency builders of this group, and are described in European Patent Application No. 86200690.5 / 0 200 263, published November 5, 1986. Examples of useful detergency builders also include carboxymethylmalonatonate, carboirnethyloxy-succinate , cis-cyclohexanehexacarboxylate, sodium and potassium cis-cyclopentane-tetracarboxylate, water-soluble polyacrylates and rnaleic anhydride copolymers with vinylmethyl ether or ethylene. Other suitable polycarboxylates are the polyacetal carboxylates described in the U.S. Patent. No. 4,144,226, Crutchfield et al., Issued March 13, 1979, incorporated herein by reference. These polyacetal carboxylates can be prepared by coupling, under polymerization conditions, a glyoxylic acid ester and a polymerization initiator. The polyacetal carboxylate ester is then fixed to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution, to convert to the corresponding salt and to be added to a surfactant.

Polycarboxylate detergent builders are also described in the U.S. Patent. No. 3,308,067, Diehl, issued March 7, 1967, incorporated herein by reference. Such materials include water-soluble salts of furnace and copolymers of aliphatic carboxylic acids such as rnaleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid, and rnethylenemalonic acid. The polyphosphonates suitable for use herein are the alkali metal, ammonium and alkanolarnmonium salts of poly phosphates (illustrated by tripolisphosphates, pyrophosphates and vitreous polyrheric methylated phosphatides), phosphonates. The most preferred builder for use herein is citrate. As a third essential ingredient, the compositions herein comprise positive divalent ions in amounts such as to saturate the detergency builder present in the composition. By "saturating" is meant herein that there must be sufficient ions to bind substantially all of the detergency builder present in the composition, ie, at least 75% of the builder, preferably at least 80%, most preferably at least 90% of all detergency improvement. Thus, for a 100% saturation, the ions should be present very preferably in a molar ratio of builder ions to the detergency builder of at least X: 2, where X- is the maximum potential number of buffers. Negative charges carried by a detergency builder. For example, said detergent detergent is citrate, wherein said molar ratio should be at least 3: 2, because each citrate roller can carry 3 negative charges. For the purpose of the present invention and the amount of ions required therein, the manner in which the carboxylate or phosphate groups in the detergency builder are present is not critical. In other words, at certain pH values in 6 to 8 where some of the carboxylate or phosphate groups in the builder are in their protonated form, the preferred X: 2 ratio is applied. The ions can be introduced into the compositions in any form. As regards Mg, it has been found that MgCl 2 is commercially attractive. However, MgSO 4, Mg phosphates and MgN 3 - are also a suitable source of Mg ions for the compositions herein. Without wishing to be limited by theory, it is speculated that the ions of the present prevent in some way that the detergent improver is bound to calcium in the marble, without preventing the detergent from making its effect in the cleaning operation. Positive divalent ions suitable for use herein include Mg +, Ba +, Fe2 +, Ca2 +, Zn2 + and N? 2+. Very preferred are Mg2 + and Ca2 +, or mixtures thereof. As a fourth essential feature, the compositions herein are formulated on a slightly acidic to slightly alkaline scale. Accordingly, the compositions herein preferably have a pH between 6 and 9, most preferably between 6.5 and 8, and most preferably between 7 and 7.5. At a lower pH, the composition would damage the marble while at a higher pH, it would damage the varnishes. Interestingly, even at a neutral pH at which the compositions herein can be formulated, damage to the marble is observed in the absence of saturated citrate. The pH of the compositions herein can be adjusted by any means well known to those skilled in the art, such as addition of NaOH, KOH, MEA, TEA, MDEA, K2C03, Na2C03 and the like, citric acid, sulfuric acid , nitric acid, hydrochloric acid, rnaleic acid, acetic acid and the like. Particularly preferred compositions herein comprise an effective amount of a carbonate of the formula XHCO3 or if the detergency builder used is not a phosphate-type builder, a phosphate of the formula aHbP0 «, where a + b = 3 and a or b can be 0, X »HbP2? -y where a + b = 4 and a can be 0, or XßHbP3 or where a + b = 5 and a or b can be 0, and in where X is an alkali metal, particularly K +, Na + or NH "+. In fact, in addition to the pH adjustment effect just described, it has been found that the presence of those compounds further improves the safety of the compositions herein for delicate surfaces. Without wishing to be bound by theory, it is believed that the compounds react with calcium on the surface of the marble, to form an insoluble calcium carbonate salt on the adjoining marble / solution surface, creating a protective layer. Using these compounds in addition to the saturation technology described above provides a synergistic effect on delicate surface security. The amount of these compounds needed in the compositions herein can be determined by trial and error, but appears to lie on the scale of 0.05% to 0.4% by weight with respect to the total composition, preferably from 0.05% to 0.1%. Caution is necessary however, since it has been observed that too high an amount of XHCO3 can be detrimental to the safety of the surface on varnished wood. The compositions herein may further comprise a variety of well-known optional ingredients, including perfumes, colorants, alkanolamine. The present invention further comprises a method for cleaning marble or varnished surfaces. In that method, an effective amount of a composition as described above is applied to said marble or varnished surface, and said composition is optionally removed. Depending on the surface being cleaned, the compositions herein may be used undiluted, i.e., in net form, or may be used diluted. Typically, when used on large surfaces such as floors, the compositions herein are used in diluted form, ie, at dilution levels of about 0.5% to 1.5%, depending on how concentrated the product is. In said dilute conditions, the compositions herein are applied to the surface and allowed to dry, i.e., no rinsing is required. In order to remove difficult stains on these surfaces, the product can also be applied neatly on the surface to remove the earth in a crust form in a much easier way. When used on small surfaces, eg, bath walls that may be made of marble, the net use of the composition will be preferred. During net use, it is preferable that the composition be removed, that is, rinsed after having been applied for cleaning. The present invention will be further illustrated by the following examples.

EXAMPLES The following compositions are made by mixing the ingredients listed in the listed proportions. These compositions were used in net form to clean marble and in diluted form to clean varnished wood floors. Excellent cleaning performance and surface safety was observed.

Ingredients Compositions (% by weight) C7-9, C9-11 EOß 3.0 3.0 5.0 3.2 3.2 3.2 8.0 8.0 DobanolR 23 -3 1.0 1.0 1.5 1.3 1.3 1.5 3.0 3.5 Ernpilan KBE 21 + 2.0 2.0 2.5 1.9 1.9 2.0 5.0 6.0 NaPS 2.0 1.5 1.2 1.2 1.0 1.7 3.0 2.5 NaCS 1.2 3.0 2.2 2.0 2.0 1.5 4.0 5.0 Mg 04 0.20 0.9 0.30 0.50 1.3 2.0 1.0 3.0 Cit ato 0.3 1.0 0.5 0.75 1.8 3.0 1.5 6.0 NaHC03 0.06 0.1 • - 0.1 - 0.2 - - Na2HP04 - - 0.1 - 0.3 - - ~ Na2H2P207 - - - - - - 0.2 0.5 pH 8.0 7.5 7.0 7.25 8.0 7.4 7.5 7.2 Water and minor compounds 1lasta 100% As previously used: -NaPS represents Naf paraffinsulfonate. -NaCS represents Na ensulphonate. -DobanolR 23-3 is an ethoxylated C12-12 alcohol with an average degree of ethoxylation of 3. -Ernpilan KBE21 is an ethoxylated C12-14 alcohol with an average degree of ethoxylation of 3.

Claims (18)

1. NOVELTY OF THE INVENTION
3. A liquid cleaning composition comprising at least one surfactant, which is formulated at a slightly acidic to slightly alkaline pH, comprising a detergency builder, and positive divalent ions in amounts such as to saturate the builder in the composition. 2. A composition according to claim 1, further characterized in that it is formulated on a pH scale of about 6 to about 9. 3. A composition according to claim 2, further characterized because it is formulated on a scale of pH preferably from about 6.5 to about 8.
4. 4. A composition according to claim 3, further characterized in that it is formulated on a scale of pH nu and preferably of about 7 to about 7.5.
5. 5. A composition according to claim 1, further characterized in that it comprises from about 0.1% to about 90% by weight with respect to the total composition of said surfactant.
6. 6. A composition according to claim 5, further characterized in that it preferably comprises from about 5% to about 85% by weight with respect to the total composition of said surfactant.
7. 7. A composition according to claim 6, further characterized in that it preferably comprises from about 8% to about 70% by weight with respect to the total composition of said surfactant.
8. 8. A composition according to claim 1, further characterized in that said surfactant includes a nonionic surfactant.
9. 9. A composition according to claim 8, further characterized in that said surfactant is a mixture of an ammonium surfactant with a nonionic surfactant.
10. 10. A composition according to claim 1, further characterized in that said positive divalent ions are Mg24 ions.
11. 11. A composition according to claim 1, further characterized in that it comprises an effective amount of a carbonate of the formula XHCO3 wherein X is an alkali metal.
12. 12. A composition according to claim 1, further characterized in that said detergent builder is a polycarboxylate builder or a polyphosphate builder.
13. 13. A composition according to claim 12, further characterized in that said polycarboxylate detergent builder is an organic polycarboxylate wherein LogKa as measured at 25 ° C / 0.1M of ionic strength is between 3 and 8, wherein the sum of LogKa + LogMg, measured at 25 ° C / 0.1M ionic strength is greater than 4, and where LogKCa = LogMg ± 2 units preferably 1.5 units, measured at 25 ° C / 0.1M ionic strength.
14. 14. A composition according to claim 13, further characterized in that said detergency builder is c treatment.
15. 15. A composition according to claim 1, further characterized in that it comprises from about 0.1% to about 20% by weight with respect to the total composition of said builder.
16. 16. A composition according to claim 15, further characterized in that it preferably comprises from about 0.2% to about 10% by weight with respect to the total composition of said detector improver.
17. 17. A composition according to claim 16, further characterized in that it preferably comprises from about 0.3% to about 6% by weight with respect to the total composition of said detergency builder.
18. 18. A method of cleaning marble or varnished surfaces, wherein an effective amount of a composition according to claims 1-17 is applied to clean said marble or varnished surfaces, and said composition is optionally removed.