MXPA98009179A

MXPA98009179A - Limpi compositions

Info

Publication number: MXPA98009179A
Application number: MXPA/A/1998/009179A
Authority: MX
Inventors: Trani Marina; Rigoni Monica
Original assignee: The Procter & Gamble Company
Priority date: 1996-05-03
Filing date: 1998-11-03
Publication date: 1999-04-06

Abstract

A cleaning composition providing effective cleaning and gloss performance is provided, said composition comprising a surfactant system consisting of an alkyl sulfate and a betaine or sulphobetaine surfactant in a weight ratio of alkyl sulfate to bataine or sulfobetaine of 5.5. : 1 to 100: 1 and wherein the pH of the composition is at least 4, preferably the composition comprises a solvent for improved cleaning performance and brightness of the composition

Description

CLEANING COMPOSITIONS TECHNICAL FIELD OF THE INVENTION The present invention relates to a cleaning composition that provides an effective cleaning and gloss performance on surfaces »especially hard surfaces.

BACKGROUND OF THE INVENTION The formulation of compositions that provide glossy cleaned surfaces is a problem known in the art by the for ulator of a cleaning composition. Very particularly, the problem of providing glossy surfaces is commonly compromised by residues of the compositions left on said surfaces and which appear as veins upon completion of the evaporation of the water. The problem of residuals is even more noticeable when the composition is used to clean surfaces made of shiny materials, such as glossy ceramic mosaics, windows and mirrors, or materials such as PVC coated with urethane, which is widely used. in North America. Furthermore, currently * many products are formulated or can be used as products that do not require rinsing. In such conditions or with such products, the problem of residuality has become more acute. Accordingly, there is a need for a composition that provides effective cleaning performance but also provides the cleaned surfaces with a glossy effect without leaving residues. Numerous solutions in the art have been proposed to solve this need, including the use of an acid * magnesium ions or the use of certain solvents as described in WO 95/21229, EP 0 639 ß33 or E.U. 3 »ß39,234. The applicant has now surprisingly discovered that this need can also be satisfied by formulating a composition comprising a surfactant system consisting of an alkyl sulfate surfactant and a betaine or a sulfabetaine surfactant at specific ratios and wherein the pH of the composition is at least 4. This discovery is especially surprising since it has been discovered that the use of surfactants of allylsulfate, which provide an effective cleaning "forms crystals after drying" which results in waste splashes on the cleaned surface; while on the other hand the use of surfactants of betaine or sulfabetaine, also effective cleaning components »leaves amorphous residues that result in a greasy film on the surface. Surprisingly, the use of a mixture of an alkylsulfate and a betaine or a sulphobetaine surfactant in specific ratios not only provides an effective cleaning of the surfaces, but also causes the said residues to appear less or even appear no more. The Applicant has further discovered that the addition of solvents to this surfactant system provides an improved benefit of gloss and cleanliness. Therefore, an advantage of the invention is to provide a composition that provides effective cleaning and gloss performance on surfaces. Another advantage of the invention is to provide a composition with effective disinfection performance. A major advantage of the invention is to provide a composition that is not aggressive to the skin.

BRIEF DESCRIPTION OF THE INVENTION The present invention relates to a cleaning composition comprising a surfactant system consisting of an alkyl sulfate and a betaine to a sulphobetaine-type active agent in a weight ratio of alkyl sulfate to betaine or sulfobetaine of 5.5? 1 to 100%, and wherein the pH of the composition is at least 4. In a preferred embodiment of the invention, the composition comprises a solvent for improved cleaning performance and gloss of the composition. In another preferred embodiment of the invention, the composition further comprises a peroxygen bleach to provide the composition with effective disinfection performance.

DETAILED DESCRIPTION OF THE INVENTION An essential feature of the invention is a system of a tenoactive agent. Said system comprises an alkylsulfate and a betaine or a sulphobetaine surfactant at specific weight ratios of alkyl sulfate to betaine or to a sulphobetaine surfactant.

The alkyl sulfate surfactants to be used herein are those of the formula R0S03-M * "wherein R represents an alkyl group containing from 6 to 24 carbon atoms" preferably 6 to 16 and most preferably 14 to 14 carbon atoms " M represents a cation soluble in water. The alkyl group may be in straight or branched configuration and preferably in straight confi ruration. Alkulsulfate is commercially available from Rhone Poulenc under the trade name Rhodapan * or Albright & Wilson under the trade name EMPICQL. "A commercial alkyl sulfate that is preferred to use here is EMPILE 0137 / A.

Betaine to a sulphobetaine surfactant The composition according to the present invention comprises a betaine or a sulphobetaine surfactant or derivatives thereof, or mixtures thereof. A further advantage of the invention is the smooth action profile of said betaine and / or sulfobetaine surfactants. Accordingly, the compositions herein can be particularly suitable for cleaning delicate surfaces such as delicate clothing or surfaces in contact with food and / or babies. Furthermore, the betaine and / or sulfobetaine surfactants are also extremely gentle to the skin and thus contribute to the user's convenience of using the compositions of the present invention. The betaine / sulphobetaine surfactants suitable for use in the compositions of the present invention are betaine / sulfobetaine in which the molecule contains both basic and acid groups which form an inner salt which gives the molecule both cationic and anionic hydrophilic groups on the a wide range of pH values. Some common examples of these detergents are described in the US patents. Nos. 2,082,275, 2,702 * 279 and 2,255,082, incorporated herein by reference. Preferred betaine or sulfobetaine surfactants have the formula? R2 I R1 N * (CH2) n Y "! R3 wherein R1 is an alkylaryl radical containing from about 1 to about 24 carbon atom * preferably about 8 to 18 and most preferably about 12 to 14 * where R2 and R3 contain from 1 to 3 carbon atoms and preferably 1 carbon atom * wherein n is an integer from 1 to 10 * preferably from 1 to 6 and most preferably is 1 * Y is selected from the group consisting of carboxy radicals. and sulphonium lo * and wherein the sum of the radicals R1 »R2 and R3 is from about 14 to about 24 carbon atoms» or mixture of them.Examples of particularly suitable betaine surfactants include alkylamine Idimeti Ibetaine C12- C18 such as cacobetaine and alkyldimeti Ibetaine of C10-C6, such as lauri Ibetaine, Cocobetaine and lauri Ibetaine are commercially available from Seppic and Albright &ilson respectively * under the trade name of Onyl 2651"and Emp i gen BB / Lm respectively. Typically, the compositions herein comprise at least 0.0057. by weight of the total composition of said betaine or sulfobetaine surfactant "or derivatives thereof" or mixtures thereof "preferably of 0.017. to 10% and most preferably 0.17. to 57 .. Weight ratios of amine oxide to betaine or sulfabetaine are an important feature of the invention. Thus * out-of-scale ratios »such as those in which the betaine or sulphobetaine surfactant is in higher proportion than the amine oxide» will not provide the benefit of cleanliness and shine »but only the benefit of cleaning leaving still greasy residues. On the other hand »a ratio above 100? 1 of amine oxide to betaine or sulphobetaine surfactant would result in a surface showing crystalline spill waste. Thus, an important feature is that the alkylsulfate and the betaine or sulfobetaine surfactant are present in the composition in a weight ratio of alkyl sulfate to betaine of 5.5? 1 to 100? 1 »preferably 10? 1 to 50? 1. For a more optimal cleaning and gloss performance, a weight ratio of alkyl sulfate to betaine of 15 is preferred? 1 to 30? 1.

Etí Another important feature of the invention is the pH of the composition. Accordingly, it has been found that compositions comprising the specific surfactant system mentioned above and having a pH below 4 produce a precipitate in the solution. The pH of the composition is measured at 20 ° C when the composition is a solid composition. Accordingly, an essential feature of the invention is that the pH of the composition is at least 4. Preferably, the compositions according to the present invention are liquid and aqueous cleaning compositions. Said aqueous compositions preferably have a pH as such of not more than 12 *, most preferably from 4 to 10. The pH of the compositions can be adjusted using organic or organic acids * or alkalizing agents.

Additional components The composition of the invention may optionally contain additional components such as peroxygen bleach solvents, chelators and mixtures thereof.

When used, the solvents will advantageously give an improved cleaning performance and gloss to the composition. Suitable solvents for incorporation into the compositions according to the present invention include propylene glycol derivatives such as n-butoxypropanal or n-butoxypropoxypropanol »CARBIT0L solvents? soluble in water or solvents CELL0S0LVE * soluble in water. The solvent CARBITOL11 * solvents in water are compounds of the class 2- (2-alkoxyethoxy> ethanol in which the alkoxy group is derived from ethyl * propyl or butyl.) A water-soluble carbitol which is preferred is 2- (2 -butoxyethoxy (ethanol also known as butylcarbonate) Water-soluble CELL0S0LVE * solvents are compounds of class 2-oxyethoxyethanol, with 2-butoxyethoxyethanol being preferred Other suitable solvents are benzyl alcohol, ethanol, isopropyl alcohol and diols such as 2-hydroxyethanol. -III-3-hexanediol and 2 * 2'-trimethyl-1'-pentanediol and mixtures thereof The solvents which are preferred to be used here are N-butoxypropoxypropanol * butyl carbitol1 * and mixtures thereof. more preferred is to use here is butyl carbitol. * Solvents may typically be present in the undiluted composition of the invention at a level of from 0.01% to 10% by weight »preferably 3% to 7% by weight of the composition.

Peroxygen bleach Another suitable additional component to be used here is a peroxygen bleach. The peroxygen bleach "especially hydrogen peroxide" persulfate and the like »in the compositions of the present invention advantageously contributes to the disinfecting properties of said compositions. In this way, without trying to be limited by theory * it is believed that said peroxygen bleach can attack the vital function of the cells of my microorganisms * for example * it can inhibit the assembly of ribosome units within the cytoplasm of the microorganism cells. Likewise * said peroxygen bleach such as hydrogen peroxide »is a strong oxidant that generates hydroxyl free radicals that attack proteins and nucleic acids. Furthermore, the presence of said peroxygen bleach, especially hydrogen peroxide, provides strong stain removal benefits that are particularly noticeable, for example, in laundry and hard surface cleaning applications. As used herein, a "hydrogen peroxide source" refers to any compound that produces hydrogen peroxide when said compound comes into contact with water. Water-soluble sources of hydrogen peroxide suitable for use herein include percarbonates »persilicate * persulfate such as monopersulfate» perborates and peroxyacids such as di-peroxy dodecanoic acid (DPDA), peristaltic magnesium acid and mixtures thereof. A hydrogen peroxide, or a water-soluble source of hydrogen peroxide, which you prefer is preferred » or mixtures thereof. A peroxygen bleach that is most preferred is hydrogen peroxide. In addition to the peroxygen bleach other kinds of peroxides may be used as an alternative to hydrogen peroxide and sources thereof or in combination with hydrogen peroxide and sources thereof. Suitable classes include diali peroxides * diacyl peroxides * preformed percarboxylic acids and organic and inorganic peroxides. Typically * the compositions herein may comprise at least 0.01% by weight of the total composition of said peroxygen bleach or mixtures thereof * preferably from 0.1% to 15% and most preferably from 1% to 10%. The following disinfection test method can be applied to measure the disinfection properties of the composition? M all ti * test rje, tft ipfnir ciQ? The disinfecting properties of a composition can be measured by the bactericidal activity of said composition. A test method for evaluating the bactericidal activity of a composition is described in European Standard prEN 1276 »CEN / TC 216 N 59» of November 1995, issued by the European Committee for the Regulation * Brussels. European Standard prEN 1276 »CEN / TC 216 N 59 specifies a test method and requirements for the minimum bactericidal activity of a disinfectant composition. The test is passed if the bacterial colonies forming units (cfu) are reduced from IO "7" cfu (initial level) to 10 * cfu (final level after contact with the disinfectant product) * that is to say »a reduction of 10ß in viability.

Guelatadore agents »Chelating agents are also additional components that may be suitable for use here. Preferred chelating agents are those selected from the group of inophosphonates. The indophosphonate compounds suitable for use herein include alkaline metal or no tri-tetramethylene phosphonate * eti lendia, nitrate methylene phosphonates and diethyl lactate, non-pentane-methyl-phosphonates. The phosphonate compounds may be present either in their acid form or as saltse of different cations on some or all of their acid functionalities. The inofasphonate chelator that I prefer to use here is diethylenetria inopentamethylenephosphonate. Said foefonate chelator is commercially available from Monsanto under the trade name DEQUEST *. Such chelating agents * especially the phosphonate chelating agents such as diethylenetriaminepenta ethylene phosphonates are particularly preferred in the compositions according to the present invention park have been found to contribute more to the disinfecting properties of hydrogen peroxide. Typically * the compositions according to the present invention may comprise up to 5% by weight of the total composition of a chelating agent »or mixtures thereof» preferably from 0.002% to 3% by weight »and most preferably from 0.002% to 1.5% by weight of the composition.

Gori uf Pff op jorm? Gff The compositions herein may further comprise a variety of other optional compounds including compound antimicrobials such as Eugenol ™ commercially available for example from Sigma »Systems - Bioinduetriee (SBl) - Manheimer Inc.» detergency builders »pH regulators * bactericides» enzymes »hydrotropes» dyes »stabilizers * bleach activators, dirt suspending agents * dye transfer agents, brighteners» perfumes * powder anti-dust agents * dispersants »dye transfer inhibitors» pigments »Perfumes and colorants.

FORM OF FORMULATION OF THE COMPOSITIONS The compositions according to the present invention can be formulated as either solids or liquids. In case the compositions are formulated as solids they will be mixed with a suitable solvent, typically water, before being used. In liquid form * the compassions are preferably formulated * but not necessary as aqueous compositions. Liquid compositions are preferred here for the convenience of u.sub.o.

Packaging Form of the Compositions The compositions herein can be packaged in a variety of suitable detergent packages known to those skilled in the art. The liquid compositions herein can be desirably packaged in manually operated spray supply containers which are usually made of synthetic organic polymer plastics. Accordingly * the present invention also encompasses liquid cleaning compositions of the invention packaged in a sprinkler * preferably in a trigger sprinkler. In fact »di The surfactant will allow uniformly applying to a relatively large area of a surface to be cleaned the liquid cleaning compositions suitable for use in accordance with the present invention, thus contributing to the cleaning properties of said compositions. These sprinklers are particularly suitable for cleaning vertical surfaces. Suitable sprinklers for use in accordance with the present invention include manually operated foam trigger sprinklers sold for example by Special ty Packaging Products »Inc. or Continental Spravers» Inc. These types of sprinklers are described, for example, in E.U. 4 »701, 311 to Dunnining and others and E.U. 4,646 * 973 and E.U. 4 * 538 * 745 both to Focarracci. It is particularly preferred to use in the present sprinklers such as T 8500R commercially available from Continental Spray International or T 8100 * commercially available from Canyon, Northern Ireland. In said sprinkler »the liquid composition is divided into fine liquid droplets resulting in a spray which is directed on the surface to be treated. In fact, in said sprinkler, the composition contained in the body of said sprinkler is directed through the head of the sprinkler, half of the energy communicated to a pumping mechanism by the user while said user activates said pumping mechanism. Very particularly * in said head of the sprinkler the composition is forced against an obstacle »v.gr. a grid or a cone or the like »thus providing shocks that help to atomize the liquid composition» that is, to assist in the formation of liquid droplets. The compositions of the present invention can also be incorporated in the form of rags. By "rags" it is tried here to say disposable towels * eg "paper towels" that incorporate a composition according to the present invention. Accordingly, the present invention also encompasses disposable * paper towels * that incorporate a liquid composition according to the present invention. In the preferred embodiment, said rags are impregnated * most preferably moistened with said liquid compositions. Preferably, said rags are packed in a plastic box. The advantage of this method is a faster use of a cleaning composition by the user * even outside the home * that is to say * there is no need to empty the liquid compositions according to the present invention on the surfaces to be treated and dry them with a towel. In other words * the rags allow the cleaning of surfaces in one step. The present invention encompasses a method for cleaning surfaces in which a composition according to the present invention is applied on said surfaces. By "surface" is meant here any surface that includes hard surfaces such as bathroom, kitchen, floors, tables, refiners, walls, mosaics, washing surfaces and the like. In the surface cleaning process according to the present invention * said compositions can be applied to the surface to be disinfected in concentrated form or in diluted form. By "far to diluted" it is tried here to say that the compositions to be used in the cleaning process of the present * are either in a solid or liquid form * can be diluted by the user typically up to 1000 times their weight of water » preferably up to 300 times * very preferably 80 to 30 times its weight of water and most preferably 60 to 40 times. In a preferred embodiment of the process of the present invention wherein said composition is applied to a surface to be cleaned * such as a hard surface * in its diluted pharma * it is not necessary to rinse the surface after the composition has been applied * in fact * no visible residue remains on the surface. The invention is illustrated in the case of non-limiting examples * in which all percentages are on a weight basis unless indicated otherwise. The test methods applied to measure the cleaning benefit and san shine as follows? Cleaning test method Normal varnished plates were soiled by applying a particle / grease material on them and then cooking them. The tested compositions were then applied on a sponge and then placed on a Gardner machine. The Gardner machine measured the number of strokes needed to achieve 95-99% clean plates. The yield was measured as such (ie, undiluted) and after a 1.5% dilution in water.

Five milliliters of the test product was applied on one side of a moistened sponge. The moistened sponge was applied in a movement with uniform pressure from the top to the bottom of a black mosaic previously cleaned with isopropyl alcohol. The mosaic with the product (s) aplicads (s) was allowed to dry for ten minutes before being evaluated by expert judges. The control reference is made by repeating the previous test with a moistened sponge but without the tested product. Expert judges were used to evaluate the specific area of product application to verify the amount of film / grain removed. A numerical value that describes the amount of film / grain is assigned to each product. For the test results, use a 0-4 scale. 0 = There is no difference between the tested product and the control reference »that is to say * poor film removal / streaking performance of the tested product. 4 = There is a clear difference between the product and the control reference * eß say * there is no peel / grain formation with the tested product. In the examples, the abbreviated component identifications have the following meanings? alkyl sulfate? Empicol 0137 / A betaine '< Cocoalquildimeti Ibetaine available from Albright & Wilßon under the name of E pi in BB / LR butyl carbitol *! 2- (2-butoxyethane) ethanol E EMPLO j Was the following composition prepared according to the present invention by mixing the listed ingredients in the proportioned portions? EEMPLO Z The following compositions are in accordance with the invention? 0 ! 0 0

Claims

NOVELTY OF THE I VENTION CLAIMS 1. - A cleaning composition comprising a component of a surfactant consisting of an alkyl sulfate and a betaine or sulphobetaine surfactant in a weight ratio of alkyl sulfate to betaine or sulfobetaine of about 5.5? 1 to approximately 100? 1 and wherein the pH of the composition is at least about 4.
2. A cleaning composition according to claim 1 further characterized in that said ratio of alkyl sulfate to betaine or sulfobetaine is about 10? 1 Approximately 50? 3. A cleaning composition according to claim 2, characterized in that said ratio of alkyl sulfate to betaine or sulfobetaine is approximately 15? 1 to approximately 30? 4. A cleaning composition according to claim 1 or 2"further characterized in that said alkyl sulfate is according to the formula R0S03 ~ M * wherein R represents an alkyl group containing from about 6 to about 24 carbon atoms and where M represents a cation soluble in water. 5. A cleaning composition according to claim 4 * characterized in that R represents an alkyl group containing from about 6 to about 16 carbon atoms. 6. A cleaning composition according to claim 5, further characterized in that R represents an alkyl group containing from about 8 to about 14 carbon atoms. 7. A cleaning composition according to claim 4 * further characterized in that said betaine or eulfobetaine surfactant ee according to the formula? R2 R1 NI * (CH2) n Y "I R3 wherein Ri is an alkyla radical containing from about 1 to about 24 carbon atoms, preferably 8 to 18" wherein R2 and R3 contain from about 1 to about 3 and carbon atoms "wherein n is an integer from 1 to 10" Y is selected from the group consisting of carbaxyl and sulphanilyl radicals "and wherein the sum of the radicals R1» R2 and R3 is approximately 14 to about 24 carbon atoms »or mixtures of the isomers 8.- A cleaning composition according to claim 7» further characterized in that said composition further comprises a solvent 9.- A cleaning composition according to claim 8 »further characterized because said solvent is selected from the group consisting of propylene glycol derivatives »class 2- (2-alkoxyethoxy) ethanol» class 2-alkoxyethoxyethanol * benzyl alcohol, ethanol »isopropyl alcohol» diols and mixtures thereof, sele preferably based on the polypropylene glycol derivatives and the 2- (2-alkoxyethoxy) ethanal class. 10. A cleaning composition according to claim 1 »further characterized in that said composition further comprises a peroxygen bleach. 11. A rag incorporating a cleaning composition according to claim 1. 12. A cleaning composition according to claim 1, further characterized in that said composition is packed in a sprinkler, preferably in a trigger sprinkler. . 13. A method for cleaning a surface applying a composition comprising a seventh surfactant which connects an alkylsulfate and a betaine or sulphobetaine surfactant at a weight ratio of alkyl sulfate to betaine or sulfobetaine of approximately 5.5. ? 1 to approximately 100? 1"and wherein the pH of the composition is at least about 4. 14. A method for cleaning a surface according to claim 11" further characterized in that said composition is diluted to approximately 1,000 times its weight of water before of being applied to said surface. 15.- A procedure to clean a surface according to claim 14 »further characterized in that said composition is diluted to approximately 300 times its weight of water before being applied to said surface. 16. A method for cleaning a surface according to claim 15 »further characterized in that said composition is diluted approximately 80 to about 30 times its weight of water before being applied to said surface. 17. A method for cleaning a surface according to claim 16 »further characterized in that said composition is diluted to approximately 60 to about 40 times its weight of water before being applied on said surface. 18. A method according to claim 14, further characterized in that said surface is not rinsed after said composition has been applied. 19. A method for providing cleanliness and gloss to surfaces that are clean by applying a cleaning composition comprising a sulfate alkylate and a betaine surfactant or β-β-betabetaine system. Such a composition has a pH of at least about 4. 20.- A method in accordance with the claim 19"further characterized in that said composition further comprises a solvent. 21. A cleaning composition comprising a solvent and a surfactant system consisting of an alkylsulfate and a betaine or sulphobetaine surfactant in a weight ratio of alkylsulfate to betaine or sulfobetaine of about 5.5? 1 to approximately 100? 1 and wherein the pH of the composition is at least about 4. 22. A cleaning composition according to claim 1 or 2 »further characterized in that said alkyl phosphate is according to the formula R0S03-M * wherein R represents a group at uyl containing from about 6 to about 24 carbon atoms and wherein M represents a cation soluble in water. 23. A cleaning composition according to claim 22 »further characterized in that R represents an alkyl group containing from about 6 to about 16 carbon atoms. 24. A cleaning composition according to claim 22 »further characterized in that said betaine or sulphobetaine surfactant ee according to the formula R2 I Rl N * (CH2) n Y" i R3 wherein Rl is a radical alkyl containing from about 1 to about 24 carbon atoms * preferably 8 to 18"where R2 and R3 contain from about 1 to about 3 carbon atoms where n is an integer of 10 and A group consisting of carboxyl and sulfonyl radicals and wherein the sum of the radicals R 1 and R 3 is approximately 14 to about 24 carbon atoms or mixtures thereof. claim 1 further characterized in that said solvent is selected from the group consisting of derivatives of prapi lengl icol * class 2- (2-alkoxyethoxy) ethanol * class 2-alkoxyethoxyethanal * benzyl alcohol * ethanol * isopropyl alcohol * d ioles and mixes of them. 26. A cleaning composition according to claim 25 * further characterized in that said solvent is selected from the propylene glycol derivatives and the class 2- (2-alkoxyethoxy) ethanol. 27. A cleaning composition according to claim 1 * further characterized in that said composition further comprises a peroxygen bleach. 28. A rag incorporating a cleaning composition according to claim 1. 29. A cleaning composition according to claim 1 * further characterized in that said composition is packed in a sprinkler * preferably in a trigger sprinkler. 30. - A method for cleaning a surface by applying to said surface a composition comprising a surfactant agent consisting of an alkylsulfate and a betaine or sulphobetaine surfactant in a weight ratio of alkyl sulfate to betaine or sulfobetaine of about 5.5? 1 to approximately 100? 1 and wherein the pH of the composition is at least about 4. 31.- A method for cleaning a surface according to claim 28 »further characterized in that said composition is diluted up to about 1 * 000 times its weight of water before being applied to said surface. 32. A method for cleaning a surface according to claim 31 »further characterized in that said composition is diluted to approximately 300 times its weight of water before being applied to said surface. 33. A method for cleaning a surface according to claim 32 »further characterized in that said composition is diluted up to about 80 to about 30 times its water weight before being applied to said surface. 34. A method for cleaning a surface according to claim 33 »further characterized in that said composition is diluted to about 60 to about 40 times ßu water pe before being applied to said surface. 35. - A method according to claim 31 »characterized in that said surface is not rinsed after said composition has been applied.