JPH11507688A - Cleaning compositions and methods for cleaning delicate surfaces - Google Patents

Abstract

  (57) [Summary] Disclosed are compositions that are suitable for safe cleaning of delicate surfaces, ie, marble and paint / lacquered surfaces, for example, lacquered wood floors. The compositions disclosed herein comprise at least one surfactant, are formulated in a mildly acidic to mildly alkaline pH range, and serve to saturate the builder or combination of builders and builders in the composition. It contains an amount of positive divalent ions.

Description

DETAILED DESCRIPTION OF THE INVENTION         Cleaning compositions and methods for cleaning delicate surfaces                                 Technical field   The present invention relates to hard surface cleaning compositions. The composition, in particular, Marble and paint / lacquered surfaces, especially paint / lacquered wood Intended for safe cleaning.                                 Background art   Various cleaning compositions for hard surfaces have been disclosed in the prior art. . Most of these compositions have only performance for various stains under various conditions. Related. And most hard surfaces have these surfaces exposed to the cleaning composition. To the point that is generally not a problem that can be permanently damaged You.   However, marble and lacquered surfaces may not be There are two types of surfaces that require particular attention when formulating a skinning composition. In fact, marble consists mainly of calcium carbonate, and therefore is acidic to neutral And / or incompatible with cleaning compositions that will contain builders It is. In fact, acidity "dissolves" marble while functioning as water and dirt particles Builders, which specifically bind the ions present in the particles, also bind to the calcium in the marble. Will thereby make the surface very brilliant to matte. The reason is This is because the introduced surface irregularities lower the reflectivity of the surface. More amazing In addition, the present inventors have developed a neutral solution containing a builder and / or an anionic surfactant. Most cleaning products formulated at pH have also been found to damage marble. That is, the formulation of the alkaline composition without builder is not suitable for the current situation. It is pointed out.   However, the formulation of the alkaline composition is based on lacquered / painted surfaces, e.g. For example, painted metal surfaces or lacquered / painted wood surfaces, for example Not compatible with cleaning lacquered wood floors. The lacquer used here is Typically prepared from polyurethane or polyacrylate or a mixture of both. And paints are primarily pigmented polyacrylates, polyvinyl acetate Or an alkyd resin. In fact, such surfaces can be permanently damaged by alkalinity. Be damaged. In particular, alkalinity destroys lacquer and hence lacquer It will give the painted surface a matte appearance or discoloration. Thus, marble and lacquer -Formulate a cleaning composition that is suitable for cleaning both the painted surface This seems to be hampered by incompatible pH requirements.   Also, the absence of desirable builders for preserving marble is due to grease / particle contamination. Somewhat incompatible with good performance for cleaning. In fact, the dirt, maybe -Grease that is difficult to remove by attaching the charged end of the fat molecule in the source Ca forming a complex²⁺, Mg²⁺Observed to contain metal ions Was done. The presence of builders that bind metal ions loosens the complex, Well, this helps to get rid of it.   That is, an object of the present invention is to provide both marble and paint / lacquered surfaces. It is suitable for cleaning and gives good cleaning performance. It is to formulate a liquid composition which is often accomplished in the past.   To this end, the present inventors have included at least one surfactant, Builders and compositions formulated at mildly acidic to mildly alkaline pH Liquid comprising an amount of positive divalent ions to saturate builders therein The composition was formulated.   In fact, we have found that in the present compositions, mild acidic to neutral pH We found that neither the marble nor the lacquer was damaged. Also saturated with positive divalent ions Builder has improved grease screen while preventing marble damage Still show the building action as evidenced by the building performance.   Cleaning compositions which are said to be for delicate surfaces are described in EP 511 No. 091, CN 1055198 (title) and CN 10 No. 32360 (title).                                Disclosure of the invention   The present invention comprises at least one surfactant, which is intended to be mildly acidic to mildly acidic. Is formulated in a highly alkaline pH range, the builder and the builder in the composition A liquid cleaning set comprising an amount of positive divalent ions to saturate Includes products.   The invention further provides for applying an effective amount of the composition to clean a marble or lacquered surface. Marble or lacquering characterized by cleaning and removing said composition Includes surface cleaning methods.                      BEST MODE FOR CARRYING OUT THE INVENTION   The composition is a liquid composition. They are typically aqueous and typically Typically, 10-99% by weight of the total composition, preferably 15-95% by weight, most preferably Or 30 to 92% by weight of water.   As a first essential feature, the composition comprises at least one surfactant. The surfactant of the present invention is required for cleaning. Suitable for use here Surfactants include anionic surfactants, nonionic surfactants, and cationic surfactants. Surfactants and amphoteric surfactants are included. Non-limiting surfactants useful here By way of example, typically, conventional alkyl benzene sulfonates ("LAS") , Typically C₁₁~ C₁₈LAS, alkyl sulfonates, typically C₈~ C₁₈ Alkylsulfonates and primary, branched and random alkyl sulfates ("AS"), typically C_Ten~ C₂₀AS, secondary (2,3) alkyl sulf , Typically of the formula CH_Three(CH_Two)_x(CHOSO_Three ^-M⁺) CH_ThreeAnd CH_Three (CH_Two)_y(CHOSO_Three ^-M⁺) CH_TwoCH_Three(Where x and (y + 1) are small M is an integer of at least about 7, preferably at least about 9, and M is a water-soluble cation, Is sodium)_Ten~ C₁₈, Unsaturated sulfates, such as Il sulfate, alkyl alkoxy sulfate ("AE_xS "), especially C_{1 0} ~ C₁₈AE_xS, especially EO1-7 ethoxysulfate, alkylalkoxyca Ruboxylate, especially C_Ten~ C₁₈, Especially EO1-5 ethoxycarboxylate Glycerol ether, preferably C_Ten~ C₁₈Stuff, alkyl polygly Cosides and their corresponding sulfated polyglycosides, and α-sulfonated fatty acids Esters, preferably C_Ten~ C₁₈One. If desired, the usual non-a On- and amphoteric surfactants such as alkyl ethoxylates ("A E "), preferably C₁₂~ C₁₈AEs, such as so-called narrow peaked alkyl esters Toxylates and alkylphenol alkoxylates, especially C₆~ C₁₂Nomo Especially ethoxylates and mixed ethoxy / propoxy, betaine and sulphate Hobetaine ("sultaine"), preferably C₁₂~ C₁₈Of, amine oxide , Typically C_Ten~ C₁₈And the like can be incorporated into the entire composition. N-alkyl Lihydroxy fatty acid amide, typically C_Ten~ C₁₈Can also be used. Typical A typical example is C₁₂~ C₁₈N-methylglucamide is exemplified. WO 9th and 2nd See 06,154. Other sugar-derived surfactants include C_Ten~ C₁₈N- ( N-alkoxy polyhydroxy fatty acids such as 3-methoxypropyl) glucamide Amides are mentioned. From N-propylglucamide to N-hexylglucamide , Preferably C₁₂~ C₁₈Can be used for low foaming. Normal C_Ten~ C 20 soaps may also be used. If high foaming is desired, the branched C_Ten~ C₁₆Soap May be used. Mixtures of anionic and nonionic surfactants, especially Useful. Other common useful surfactants are standard Is described in the text.   The composition may comprise from 0.1 to 90% by weight of the total composition, preferably from 5 to 85% by weight, most preferably Also preferably comprise from 5 to 70% by weight of at least one surfactant. Used here Preferred surfactants are non-ionic due to their cleaning action on the grease. On-surfactants or mixtures of anionic and non-ionic surfactants You. According to the invention, it is possible that anionic surfactants can be used here without damaging the marble. Is another benefit. In fact, anionic surfactants are usually The marble was also observed to be damaged as it binds to the calcium in the marble. I However, the compositions of the present invention surprisingly have a negative impact on marble safety. Anionic surfactant for improved cleaning without disturbing The presence of the agent can be provided.   As another essential feature, the composition comprises a builder. The composition is a total composition 0.1-20% by weight, preferably 0.2-10% by weight, most preferably 0.3% ビ ル ダ ー 6% by weight of builder or a mixture thereof.   Builders suitable for use herein include polycarboxylates and polycarboxylates. Rephosphates, and salts thereof.   Preferred polycarboxylates suitable for use herein are organic polycarboxylates. Xylate (Max LogKa measured at 25 ° C / 0.1M ionic strength is 3-8 Yes, between LogKCa and LogKMg measured at 25 ° C / 0.1M ionic strength Sum is greater than 4 and LogKCa = Lo measured at 25 ° C./0.1 M ionic strength gKMg ± 2 units).   Such preferred preferred polycarboxylates include citrate and 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) -CH_Two(COOX), where X is H or salt-forming Is on) Complex. For example, in the above general formula, A and B are both H If so, the compound is oxydisuccinic acid and its water-soluble salts. A is OH, B Is H, the compound is tartrate monosuccinic acid (TMS) and its It is a water-soluble salt. A is H, B is -O-CH (COOX) -CH_Two(COOX) If present, the compound is tartrate disuccinic acid (TDS) and its water-soluble salts It is. Mixtures of these builders are particularly preferred for use herein. Especially In the case of TMS vs. TDS, these builders will be U.S. Pat. No. 4,663,071 issued to U.S. Pat.   Still other ether polycarboxylates suitable for use herein include: A copolymer of maleic anhydride and ethylene or vinyl methyl ether, 5-trihydroxybenzene-2,4,6-trisulfonic acid, and carboxy Methyloxysuccinic acid is exemplified.   Other useful polycarboxylate builders include structures       HO- [C (R) (COOM) -C (R) (COOM) -O]_n-H Wherein M is hydrogen or a cation (the resulting salt is water-soluble), preferably alkali A metal, ammonium or substituted ammonium cation, wherein n is from about 2 to about 15; (Preferably, n is about 2 to about 10, more preferably n is about 2 to about 4 on average) , Each R is the same or different and is hydrogen, C_{1 ~Four}Alkyl or C_{1 ~Four}Substituted alkyl (Preferably, R is hydrogen)] And ether hydroxy polycarboxylate represented by the following formula:   Preferred ether polycarboxylates include cyclic compounds, especially alicyclic compounds. Formula compounds, for example, US Pat. No. 3,923,679, 3,835,1 No. 63, No. 4,158,635, No. 4,120,874 And 4,102,903 (all of which are incorporated herein by reference. Transfer).   Of the cyclic compounds, dipicolinic acid and chelidanoic acid are preferred.   Also, polycarboxylates suitable for use herein include melitic acid, succinic Acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, benzenepentaca With rubonic acid, and carboxymethyloxysuccinic acid, and their soluble salts is there.   Still suitable carboxylate builders here include March 28, 1973 Issued U.S. Pat. No. 3,723,322, which is hereby incorporated by reference. And carboxylated carbohydrates disclosed in US Pat.   Suitable for use here, but less preferred because it does not meet the above criteria Other carboxylates are alkali metal salts, ammonium salts of polyacetic acid and It is a substituted ammonium salt. An example of a polyacetic acid builder salt is ethylenediaminetetravinegar Sodium, potassium, lithium and ammonium salts of acids and nitrilotriacetic acid And substituted ammonium salts.   Other suitable but less preferred polycarboxylates are alkyl esters Known as minoacetic acid builder, for example, methyliminodiacetic acid, alaninediamine Acetic acid, methylglycine diacetate, hydroxypropylene iminodiacetic acid and other Luquilimino acetate builder.   Also, US Patent No. 4,566,984 issued to Bush on January 28, 1986. 3,3-dicarboxy-4-O disclosed in US Pat. Kisa-1,6-hexanediolate and related compounds are suitable in the compositions of the present invention. is there. Useful succinic acid builders include C5 to C20 alkyl succinic acids and the like. These salts are mentioned. A particularly preferred compound of this type is dodecenyl succinic acid is there. Alkyl succinic acids typically have the general formula R-CH (COOH) CH_Two(COOH), that is, a derivative of succinic acid Where R is a hydrocarbon such as C_Ten~ C₂₀Alkyl or alkenyl, preferred Or C₁₂~ C₁₆Or R is a hydroxyl, sulfo as described in said patent. May be substituted with a sulfo, sulfoxy or sulfone substituent).   Succinate builders are preferably sodium salts, potassium salts, ammonium salts. It is used in the form of a water-soluble salt, including umium salts and alkanolammonium salts.   Specific examples of succinate builders include lauryl succinate, myris succinate Chill, palmityl succinate, 2-dodecenyl succinate (preferred), succinic acid 2 -Pentadecenyl and the like. Lauryl succinate is a preferred bisene of this group. And European Patent Application No. 86200690. issued Nov. 5, 1986. 5/0 200 263.   Examples of useful builders include sodium and potassium carboxy. Methyl oxymalonate, carboxymethyloxysuccinate, cis-cyclo Hexane hexacarboxylate, cis-cyclopentanetetracarboxylate, water Soluble polyacrylate and maleic anhydride with vinyl methyl ether or ethyl And salts of copolymers with ren.   Other suitable polycarboxylates are known as Clutch®, issued March 13, 1979. U.S. Pat. No. 4,144,226, which is incorporated herein by reference. Polyacetal carboxylate disclosed in (1). These polyacetals Carboxylates can be produced as follows. Glyoxyl The acid ester and the polymerization initiator are put together under polymerization conditions. Next, the obtained port Riacetal carboxylates can be attached to chemically stable end groups to Stabilizes tar carboxylate against rapid depolymerization in alkaline solution , Converted to the corresponding salt and added to the surfactant.   Polycarboxylate Builder is a US-based deal issued March 7, 1967. It is also disclosed in Japanese Patent No. 3,308,067 (herein incorporated by reference). ing. Such substances include maleic acid, itaconic acid, mesaconic acid, and fumaric acid. Aliphatic carboxylic acids such as luic acid, aconitic acid, citraconic acid, and methylenemalonic acid And water-soluble salts of copolymers.   A suitable polyphosphonate for use herein is polyphosphoric acid (tripolyphosphonate). Examples by phosphate, pyrophosphate, and glassy polymeric metaphosphate C), alkali metal salts, ammonium salts and alkanol ammonium phosphonic acids Is a sodium salt. The most preferred builder to use here is the site rate is there.   As a third essential component, the present composition saturates builders present in the composition Of positively charged divalent ions. "Saturated" refers to substantially all of the Builders, ie at least 75% of the builders, preferably at least Also sufficient to bind 80%, most preferably at least 90% or all It means here that ions should be. Thus, the 100% saturation field If so, the ions are most preferably at least a builder ion to builder molar ratio. Also X: 2 (where X is the maximum potential number of negative charges carried per mole of builder) ). For example, if the builder is site rate If so, the molar ratio should be at least 3: 2. The reason is that This is because each mole of the salt can carry three negative charges. Object of the invention and there For the amount of ions required, the carboxylate or phosphate in the builder The form in which the fate group is present is not critical. In other words, carbo in the builder Certain p-types of 6-8 wherein some of the xylate or phosphate groups are in a protonated form At H values, the preferred X: 2 ratio still applies.   The ions can be introduced into the composition in any form. As far as Mg is concerned, MgCl_Two Have been found to be commercially attractive. However, MgSO_Four, Mg phosphate and MgNO_ThreeIs also a suitable Mg ion source for the present composition. You. While not intending to be limited by theory, the present inventors assume that ON means that the builder will not perform the cleaning operation It is presumed to prevent binding to calcium in marble.   Positive divalent ions suitable for use herein include Mg²⁺, Ba²⁺, Fe²⁺ , Ca²⁺, Zn²⁺And Ni²⁺Is mentioned. Mg²⁺And Ca²⁺Or it These mixtures are most preferred.   A fourth essential feature is that the composition is mildly acidic to mildly alkaline. It is prescribed within the potash range. Therefore, the present composition is preferably pH 6-9, More preferably, it has 6.5 to 8, most preferably 7 to 7.5. Lower pH In the composition, the composition will damage marble, while at higher pH Would damage the lacquer. Interestingly, while we can formulate this composition Even at neutral pH, marble damage is observed in the absence of saturated citrate Will. The pH of the composition can be adjusted by any means known to those skilled in the art, for example, NaO H, KOH, MEA, TEA, MDEA, K2CO3, Na2CO3, etc. Can be adjusted by adding citric acid, sulfuric acid, nitric acid, hydrochloric acid, maleic acid, acetic acid, etc. You.   Particularly preferred compositions of the present invention comprise an effective amount of a compound of the formula XHCO_ThreeThe carbonate also If the builder used is not a phosphate builder, the formula X_aH_bPO_Four( Wherein a + b is 3 and a or b can be 0), X_aH_bP_Two O₇Wherein a + b is 4 and a or b can be 0, and Is X_aH_bP_ThreeO_Ten(Where a + b is 5 and a or b is 0) (X is an alkali metal, especially K⁺, Na⁺Or NH_Four ⁺In Including). In fact, in addition to the pH-adjusting effect, the present inventors Further enhances the safety of this composition against delicate surfaces I found it to improve. Although not intended to be limited by theory, The material reacts with calcium on the surface of the marble to form insoluble carbon at the marble / solution interface. It is thought to form a calcium acid salt and form a protective layer. These compounds are Using it in addition to Japanese technology has a synergistic effect on delicate surface safety give. The amount of these compounds required in the composition is determined by trial and error 0.05-0.4% by weight of the total composition, preferably 0.05-0.1% by weight It seems to be in the range of the amount%. However, we have found that too much XHC O_ThreeObserved that it would be detrimental to the surface safety on lacquered wood, Care must be taken.   The composition comprises a variety of well-known optional ingredients including fragrances, dyes, and alkanolamines. May be further included.   The invention further encompasses a method for cleaning marble or lacquered surfaces. So The method of claim 1, wherein the effective amount of the composition as described above comprises the marble or lacquer. Applied on a painted surface, the composition is optionally removed.   Depending on the surface to be cleaned, the composition may be undiluted, ie, neat (neat). ) Or dilution. Typically used on large surfaces such as floors When present, the composition may be in diluted form, i.e., depending on how concentrated the product is. , Used at dilution levels of about 0.5% to 1.5%. In such a diluted state The composition is applied to the surface and allowed to dry, i.e. no rinsing is required. Not. To remove unwanted stains on these surfaces, the product must be Can be applied neat to remove skin-forming dirt much more easily You. Use on smaller surfaces, for example, bathroom walls, which can be made from marble At times, neat use of the composition may be preferred. For neat use, the composition The object should be removed after it has been applied for cleaning, ie rinsing It should preferably be dropped.   The invention is further illustrated by the following examples.                                    An example   The following compositions were prepared by mixing the indicated ingredients in the indicated proportions. These compositions are used neat to clean marble, lacquer -Diluted used to clean painted wood floors. Excellent cleaning And surface safety performance was observed.   NaPS as used above means Na paraffin sulfonate,   NaCS means cumene sulfonate Na, C12-13 alcohol,   Empilan KBE21 was ethoxylated with an average degree of ethoxylation of 3. C12-14 alcohol.

Claims (1)

[Claims] 1. It comprises at least one surfactant, is formulated at a mildly acidic to mildly alkaline pH, and comprises a builder and an amount of a positive divalent ion to saturate the builder in the composition. , Liquid cleaning compositions. 2. The composition according to claim 1, wherein the composition is formulated in a pH range of 6-9, preferably 6.5-8, most preferably 7-7.5. 3. Composition according to any one of the preceding claims, comprising from 0.1 to 90%, preferably from 5 to 85%, most preferably from 5 to 70% by weight of the total composition of said surfactant. . 4. The composition of any one of the preceding claims, wherein the surfactant comprises a nonionic surfactant. 5. The composition according to claim 4, wherein the surfactant is a mixture of an anionic surfactant and a nonionic surfactant. 6. The composition according to any one of the preceding claims, wherein said positive divalent ion is Mg2 ⁺ or Ca2 ⁺ or a mixture thereof. 7. If the effective amount of the carbonate of formula XHCO ₃ or the builder is not a phosphate builder, the formula X _a H _b PO ₄ (where a + b can be 3 and a or b can be 0), X _a H _b P ₂ O ₇ (wherein, a + b can be and is and a or b 4 0), or in _{X a H b P 3 O 10} ( wherein, a + b is 5 and a or The composition according to the preceding claim, further comprising a phosphate (b can be 0), wherein X is an alkali metal, especially K ⁺ , Na ⁺ or NH ₄ ⁺ . 8. The composition according to the preceding claim, wherein the builder is a polycarboxylate builder or a polyphosphate builder. 9. The polycarboxylate builder is an organic polycarboxylate (the maximum LogKa measured at 25 ° C / 0.1 M ionic strength is 3 to 8, and the sum of LogKCa and LogKMg measured at 25 ° C / 0.1 M ionic strength is 4%. 9. The composition of claim 8, wherein the composition is higher and measured at 25 [deg.] C / 0.1 M ionic strength is Log KCa = Log KMg ± 2 units. 10. 10. The composition of claim 9, wherein the builder is a citrate. 11. The composition according to any of the preceding claims, comprising 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 said builder. Composition. 12. Cleaning a marble or lacquered surface by applying an effective amount of a composition according to any one of the preceding claims and optionally removing said composition, Cleaning method.