US3741914A - Cleaning polishing composition - Google Patents

Abstract

CLEANING AND POLISHING COMPOSITIONS DRYABLE TO A BRIGHT SURFACE WITHOUT REQUIRING BUFFING, COMPRISING: A CONTINUOUS AQUEOUS PHASE, A DISPERSED, NON-BOLATILE, WATER-INSOLUBLE, SOLID FILM-FORMING POLYMER CAPABLE OF BEING DEPOSITED IN A SMOOTH, BRIGHT, PROTECTIVE FILM UPON EVAPORATION OF THE AQUEOUS PHASE AND HAVING A MOLECULAR WEIGHT OF FROM BOUT 5 MILLION TO ABOUT 15 MILLION, A PLASTICIZER FOR SAID POLYMER, A CLEANING AGENT, AND SUFFICIENT BASE TO ADJUST THE PH OF THE FORMULATION TO FORM ABOUT 8 TO ABOUT 12.

Description

United States Patent 3,741,914 CLEANING POLISHING COMPOSITION Lawrence R. Parks, Cincinnati, Ohio, assignor to The Procter & Gamble Company, Cincinnati, Ohio No Drawing. Filed June 26, 1969, Ser. No. 836,935 Int. Cl. C11d 1/50, N12 US. Cl. 252-545 8 Claims ABSTRACT OF THE DISCLOSURE Cleaning and polishing compositions dryable to a bright surface without requiring buffing, comprising: a continuous aqueous phase; a dispersed, non-volatile, water-insoluble, solid film-forming polymer capable of being deposited in a smooth, bright, protective film upon evaporation of the aqueous phase and having a molecular weight of from about 5 million to about 15 million; a plasticizer for said polymer; a cleaning agent; and sufiicient base to adjust the pH of the formulation to from about 8 to about 12.

CROSS REFERENCE TO RELATED APPLICATIONS Similar applications have been disclosed in the copending applications of Donald T. Hooker et al., Ser. No. 681,920, filed Nov. 9, 1967, now abandoned for Cleaning Polishing Composition and of Franklin Dale Moore, Ser. No. 785,734, filed Dec. 20, 1968, now abandoned for Cleaning Polishing Composition.

FIELD OF THE INVENTION This invention relates to an aqueous cleaning and polishing composition which when applied to a substrate, e.g., a tile floor, is capable of effectively removing dirt and providing a thin layer of film-forming polymer as a smooth, bright, protective layer on said substrate. More particularly, this invention relates to compositions of this type comprising a specific mixture of ingredients which give an excellent film and an alkaline cleaning agent. These compositions maintain acceptably low viscosities during storage and have acceptable removability.

PRIOR ART The type of was cleaner which is exemplified by the compositions of this invention is highly desirable. Since such compositions can 'be utilized to clean a floor while simultaneously applying a polish coating, significant amounts of time and effort can be saved by using such compositions.

Typical prior art compositions of this type are disclosed in Canadian Patent 688,573 and in the copending applications of Donald T. Hooker et a1. and Franklin Dale Moore referred to hereinbefore. Prior art compositions, however, do not achieve the superior results, especially in the area of maintenance of an acceptable low viscosity while providing acceptable detergency, which can be attained with the compositions of this invention.

SUMMARY OF THE INVENTION The compositions of this invention are superior to the compositions of the prior art and provide many advantages which will become apparent hereafter from the specification.

The compositions of this invention are cleaning and polishing compositions dryable to a bright surface without requiring buffing, comprising: a continuous aqueous phase; a dispersed, non-volatile, water-insoluble, solid film-forming polymer having a molecular weight of from about 5 million to about 15 million capable of being deposited in a smooth, bright, protective film upon evaporation of the aqueous phase; a plasticizer for said poly- "ice mer; from about 0.25% to about 1% of a cleaning agent; and sufiicient base to adjust the pH of the formulation to from about 8 to about 12.

More specifically, the compositions of this invention consist essentially of:

(1) From about 5% to about 30% of a film-forming polymer which contains monomers selected from the group consisting of styrene, lower alkyl methacrylates wherein said alkyl group contains from 1 to about 12 carbon atoms, lower alkyl acrylates wherein said alkyl group contains from 1 to about 12 carbon atoms, and acrylonitrile or methacrylonitrile, the amount of styrene varying from 0 to about 60% by weight of the polymer, the amount of alkyl methacrylates varying from 0 to about by weight of the polymer, the amount of alkyl acrylates varying from about 0% to about 50% by weight of the polymer but no more than about 30% when the alkyl group contains 4 or more carbon atoms and the amount of acrylonitrile and/or methacrylonitrile varying from 0 to about 30% by weight of the polymer, the total amount of styrene and alkyl methacrylates being from about 40% to 90% by weight of the polymer, and the molecular weight of the polymer varying from about five million to about fifteen million;

(2) From about 2% to about 75% based on the weight of the film-forming polymer of a plasticizer for said polymer;

(3) From about 0 to about 0.02% of a fluorochemical leveling agent;

(4) From about 0.25 to about 1% of a water soluble cleaning agent;

(5) From about 60% to about of water; and

(6) Sufficient base to adjust the pH of the composition to from about 8 to about 12.

THE FILM-FORMING POLYMER The polymers described hereinafter are the primary film-forming ingredient in the cleaning and polishing compositions of this invention. These polymers are primarily responsible for film performance including properties such as hardness, gloss, and durability, and they also contribute to the chemical resistance of the film.

It has also been discovered that a proper selection of molecular weights for these polymers contributes greatly to the maintenance of a properly low viscosity, e.g., preferably less than about 1'0 centipoises, for the polish formulation. When an alkaline material is present, as is normally required in good cleaning compositions, compositions containnig such polymers having molecular weights of from less than one million to about four million tend to increase in viscosity on storage. This can be unacceptable because low viscosity products are needed for proper levelling. Now it has been discovered that such polymers having molecular weights from about five million to about fifteen million are remarkably resistant to the effects of alkaline materials with respect to viscosity. Accordingly, compositions containing these higher molecular weight polymers can be used more easily to formulate cleaning polishing compositions containing a wide variety of alkaline builder materials at surprisingly higher levels than are possible with similar cleaning polishing compositions containing polymers having molecular weights below about five million. The compositions of this invention also have surprisingly good removability.

These polymers are formed from polymerizable ethylenically unsaturated monomers. The monomers comprise styrene, lower alkyl methacrylates wherein the alkyl group contains from 1 to about 12 carbon atoms (preferably from 1 to about 6 carbon atoms) lower alkyl acrylates wherein the alkyl group contains from 1 to about 12 carbon atoms (preferably from 1 to about 6 carbon atoms), and acrylonitrile and/or methacrylonitrile. Styrene, by

itself, forms a polymer which is too hard and brittle and which lacks resiliency without excessive plasticization. However, styrene is relatively inexpensive and it is desirable to use it in relatively large amounts. The lower alkyl methacrylates also cause the polymer to be hard and relatively brittle. The styrene and methyl methacrylate is essentially interchangeable. The alkyl acryates, on the other hand, cause the polymer to be soft. By balancing the amounts of styrene, alkyl methacrylate and alkyl acrylate, it is possible to prepare a polymer which has a good balance of hardness and flexibility. The other monomers, acrylonitrile and/or methacrylonitrile are added to the polymer to prevent plasticizers in the substrate, e.g., tile, from passing into or through the film and making it tacky. Acrylonitrile and methacrylonitrile decrease the permeability of the film to these plasticizers.

As discussed hereinbefore the styrene normally constitutes from to about 60%, preferably from about 20% to about 60% by weight of the polymer. It is possible to prepare a desirable polymer without styrene, but there will normally be some styrene in the polymer. The amount of alkyl methacrylate constitutes from O to about 90%, preferably from about 20% to about 60%, by weight of the polymer. The total amount of styrene and alkyl methacrylate in the polymer should range from about 40% to about 90% preferably from about 40% to about 70% by Weight of the polymer. The alkyl acrylate constitutes from about 0% to about 50% preferably from about 20% to about 40% by weight of the polymer but not more than about 30% when the alkyl group contains 4 or more carbon atoms. R is possible to prepare a polymer without alkyl acrylate, but such a polymer will require more plasticizer. The acrylonitrile constitutes from 0% to about 30%, preferably from about 10% to about 20% by weight of the polymer. The polymer can also contain small amounts of other monomers such as methacrylic acid to improve removability. Within the above limits it is possible to formulate polymers which have a proper balance of hardness and flexibility. The preferred molecular weight is from about 5 million to about million.

Suitable examples of alkyl methacrylates include methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, 2-ethyl hexyl, and cyclohexyl methacrylates. Suitable alkyl acrylates include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, 2-ethyl hexyl, and cycohexl acrylates, the polymer should contain no more than about 30% butyl or higher alkyl acrylates, since these acrylates soften the polymer more than the short chain alkyl acrylates.

THE PLASTICIZER In order to make the fihn more plastic and resilient, there should be present in the composition a plasticizer for the film forming polymer. The plasticizer is used in amounts from about 2% to 75%, preferably from about 5% to about 25%, based on the weight of the film-forming polymer. Suitable plasticizers include tributoxy ethyl phosphate, 2-pyrrolidine, polyethylene glycol dibenzoate, dibutyl phthalate, diethylene glycol monoethyl ether, dieth'- ylene glycol diacetate, diacetin, tricresyl phosphate, butyl phthalyl butyl glycolate, methyl phthalyl ethyl glycolate, trimethylene glycol di-Z-ethyl hexoate, trimethyelne glycol di-Z-ethyl butyrate, and ethylene glycol. Other plasticizers which are known in the art to be useful as plasticizers for acrylic ester copolymers can also be used such as those described in Plasticization and Plasticizer Processes, Advances in Chemistry Series Number 48, N. A. Platzer (1965). This book is incorporated herein by reference. A preferred plasticizer is tributoxy ethyl phosphate which is primarily a leveling agent as described hereinafter.

When the alkyl groups in the methacrylates and/or acrylates contain 4 or more carbon atoms, less plasticizer is required.

4 THE CLEANING AGENT The cleaning agent of this invention is selected from the group consisting of zwitterionic detergents, nonionic detergents, anionic detergents and alkaline detergency builders. Preferred cleaning agents include ethane-l-hydroxy-l,1,2-triphosphonic acid, ethane-1-hydroxy-l,2,2- triphosphonic acid, ethane-1,l,2-triphosphonic acid, ethane-l-hydroxy-1,1-diphosphonic acid, ethane-l-amino-1,1- diphosphonic acid, ethane-2-carboxy-1,l-diphosphonic acid, ethane-1,Z-dicarboxy-1,2-diphosphonic acid, the water-soluble salts of said acids, and mixtures thereof as disclosed in the copending application of Donald T. Hooker et al. Ser. No. 681,920, filed Nov. 9, 1967, which is incorporated herein by reference. It will be recognized that though the acids are added to the composition they will be converted into salts by the base which is added to the composition to adjust the pH to from about 8 to about 12, preferably from about 8.5 to about 9.5. The cleaning agents of this invention are much more effective at pHs above about 9. Suitable salts include the alkali metal salts, especially sodium and potassium, ammonium, triethanolammonium, diethanolammonium, morpholinium, and other substituted ammonium salts, etc. It will be recognized that the salts will be ionized in solution and that it does not matter which particular salt is added so long as the composition contains the proper cations to permit forming a stable composition. In general, the more Water-soluble cations such as ammonium and potassium are preferred but, for economy, sodium salts are preferred. Preferably, from about 0.25% to about 0.75% of these phosphonate cleaning agents are used.

The above phosphonate cleaning agents provide superior performance.

Other preferred cleaning agents of this invention are the alkyl benzene sulfonates wherein the alkyl groups contain from about 7 to about 10 carbon atoms. These cleaning agents are disclosed in the copending application of Franklin Dale Moore, Ser. No. 785,734, filed Dec. 20, 1968 which is incorporated herein by reference.

These cleaning agents are the water-soluble salts of alkyl benzene sulfonates wherein said alkyl groups contain from about 7 to about 10 carbon atoms. The alkali metal, ammonium and substituted ammonium salts are preferred, e.g., sodium, potassium, ammonium, triethanolammonium, and morpholinium salts. The alkyl benzene sulfonates include heptyl benzene sulfonate, actyl benzene sulfonates, nonyl benzene sulfonates, and decyl benzene sulfonates. The alkyl groups can be derived from any source.

These specific alkyl benzene sulfonates are unique in that they provide superior cleaning in this type of composition as compared with other alkyl benzene sulfonates having either more or less carbon atoms in the alkyl chain or as compared with other conventional surface active detergent materials. In addition, the alkyl benzene sulfonate cleaning agents of this invention do not adversely affect the good gloss properties of the compositions of this invention. Preferably from about 0.75 to about 1.25% of the cleaning agent is used.

It is difficult to provide a cleaning and polishing composition of the type described herein that has superior cleaning without raising the viscosity above what is considered an acceptable value, i.e., an absolute viscosity of about 10 centipoises. Conventional hardsurface cleaning agents such as sodium carbonate, sodium nitrilotriacetate, and potassaium pyrophosphate can also be used but not in very large amounts without raising the viscosity to unacceptable values. Accordingly, the phosphonate and alkyl benzene sulfonate cleaning agents are preferred.

Other suitable cleaning agents are those disclosed in US. Pat. 3,422,137, especially at column 6, line 52 to column 13, line 62.

THE BASE Any base which gives water-soluble cations can be used. Suitable bases include: sodium, potassium, ammonium, triethanolammonium, diethanolammonium, monoethanolammonium and morpholinium hydroxides and the corresponding compounds such as sodium, sodium oxide, etc. which will give these hydroxides in water.

THE WATER Water constitutes from about 60% to about 95% preferably from about 70% to about 90% by weight of the composition. The water is preferably either distilled, deionized, or softened.

THE LEVELING AGENTS Although a cleaning and polishing composition can be formulated with the ingredients described hereinbefore, it is preferable that the composition contain a leveling agent. Excellent anionic fluorochemical leveling agents, e.g., FC-128, are described in Green, US. Pat. 2,937,098. These fluorochemical leveling agents can be used in amounts up to about 0.02%, preferably from about .004% to about 0.01% by weight of the composition. Tributoxy ethyl phosphate and various well-known nonionic surface active agents can also be used as leveling agents in the composition of this invention at levels up to about 2.0%, preferably from about 0.6% to about 1.0%

The cleaning and polishing composition of this invention generally and preferably contains optional components which add to the desirability and utility of this composition. Among these optional ingredients are ethylene glycol which can be added in amounts up to about 5%, preferably less than about 3%, and monoand dialkyl ethers of diethylene glycol wherein the alkyl group contains from 1 to about 4 carbon atoms, e.g., Carbitol, which can be added to the composition of this invention in amounts up to about 5%, preferably less than about 3%, to help control the drying characteristics (coalescence) of the polish film, as well as to control freezethaw characteristics of the aqueous cleaning and polishing composition. The ethylene glycol and ethers of diethylene glycol also act as plasticizers.

Other optional components include alkali soluble resins containing carboxyl groups and having a molecular weight of up to about 10,000, such as (1) condensation type resins having an acid number ranging from about 120 to about 220, (2) addition type resins having an acid number from about 140 to about 300 containing at least two ethylenically unsaturated monomers, and (3) mixtures of said condensation type resins and addition type resins. Examples of these resins are set forth in Us. Pat. 3,308,078 in columns 13, 14, 15 and 16. This patent is incorporated herein by reference.

Polyethylene waxes can also be added to the composition of this invention. These polyethylene waxes add durability and flexibility to the floor polish composition of this invention. These polyethylene waxes are commercially available and examples of these commercial products include A-C polyethylene 629, A-C polyethylene 729, A-C polyethylene 630 and Epolene E.

In general these polyethylene waxes comprise mildly oxidized polyethylene in which oxygen has been introduced into the molecule, presumably in the form of carboxyl groups, without materially altering the molecule in other respects. They are generally characterized by an essentially polyethylenic structure formed of recurring methylene groups, by a molecular weight between about 1000 and about 5000, by an oxygen content between about 1% and about 17%, by a hardness equal to a penetration of not more than 1.5 mm. as measured by standard ASTM method D-525, by a toughness equal to at least 2 foot pounds per linear inch as measured by a standard ASTM method D-256-47-P, and by a low ratio of saponification number to acid number.

The compositions can also contain up to about 2% of a nonionic detergent which acts as a dispersing agent for the polymer. Preferably the compositions contain from about /z% to about 1% of this nonionic detergent. The nonionic detergent improves freeze-thaw recovery and aids in preventing coagulation of the polymer dispersion by mechanical action. However, excess nonionic detergent can break down the dispersion and cause coagulation during storage or shipment. Preferred nonionic detergents have the formula wherein R is either an alkyl group containing from about 10 to about 18 carbon atoms or an alkyl phenyl group wherein the alkyl group contains from about 8 to about 16 carbon atoms and wherein n is a number from about 4 to about 40, preferably from about 8 to about 15.

The compositions can also contain up to about 3%, preferably from about /2% to about 1%% of conventional water-soluble anionic detergent, e.g., coconut or tallow alkyl sulfates, dodecyl benzene sulfonates, etc. These anionic detergents normally accompany the polymer since they are used in the preparation of the polymer by the emulsion polymerization process. These anionic detergents normally contain an alkyl group containing from about 10 to about 18 carbon atoms and either a sulfonate or sulfate group neutralized with an alkali metal or ammonium hydroxide. Suitable nonionic and anionic detergents are described in Canadian Patent 688,573 which is incorporated herein by reference.

The preferred cleaning and polishing compositions of this invention which contain these optional ingredients consist essentially of:

(1) From about 5% to about 30% of a film-forming polymer which contains monomers selected from the group consisting of styrene, lower alkyl methacrylates wherein said alkyl group contains from 1 to about 6 carbon atoms, lower alkyl acrylates wherein said alkyl group contains from 1 to about 6 carbon atoms, and acrylonitrile or methacrylonitrile, the amount of styrene varying from 0 to about 60% by weight of the polymer, the amount of alkyl methacrylate varying from 0 to about 60% by weight of the polymer, the amount of alkyl acrylate varying from about 10% to about 50% by weight of the polymer but no more than about 30% when the alkyl group contains 4 or more carbon atoms and the amount of acrylonitrile or methacrylonitrile varying from 0 to about 30% by weight of the polymer, the total number of styrene and alkyl methacrylates being from about 40% to about 70% by weight of the polymer, and the molecular weight of the polymer varying from about five to about ten million;

(2) From about 2% to about 75% based on the weight of the film-forming polymer of a plasticizer for said polymer; (3) From 0 to about 0.02% of a fluorochemical levelmg agent;

(4) From 0 to about 5% of the hereinbefore described resin acids;

(5) From 0 to about 5% of the hereinbefore described polyethylene;

(6) From 0 to about 5% of monoand/or dialkyl ether or diethylene glycol wherein the alkyl group contains from 1 to about 4 carbon atoms;

-(7) From 0 to about 5% ethylene glycol;

(8) From about 0.1% to about 3% of a cleaning agent selected from the group consisting of ethane-l-hydroxy- 1,2,2-triphosphonic acid, ethane-l-hydroxy 1,1,2-triphosphonic acid, ethane-l-hydroxy 1,1-diphosphonic acid, ethane-1-amino-1,1-diphosphonic acid, ethane-Z-carboxy- 1,1-diphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, water-soluble salts of said acids, alkylbenzene sulfonates wherein the alkyl group contains from 7 to 10 carbon atoms, and mixtures thereof;

(9) From about 70% to about 90% water; and

(10) Sufficient base to raise the pH of the composition to from about 8 to about 12.

In addition to the ingredients already named, small amounts of other materials can also be used in the compositions of this invention. Pigments and/or dyes, bactericides (e.g., phenyl mercuric acetate), perfumes, optical whiteners, insecticides, antioxidants, and corrosion inhibitors can be present in small amounts, e.g., less than about 1%. The corrosion inhibitor is desirable if the product is marketed in an aerosol can.

PREPARATION OF THE COMPOSITION It is generally preferred that the following mixing sequence be followed.

The polymer emulsion is placed in a mixing tank equipped with a stirring apparatus. An aqueous solution of the resin component and an aqueous emulsion of the polyethylene are separately prepared. The resin solution is slowly added to the polymer emulsion. Subsequently, the polyethylene emulsion is added. The monoand/or dialkyl ethers of diethylene glycol, the ethylene glycol, tributoxy ethyl phosphate and fluorochemical leveling agent are each diluted with at least an equal weight amount of water and added to the above emulsion. A separate aqueous solution of the cleaning agent(s) is prepared. The pH of this solution is adjusted to 10 with caustic and the solution is added to the aqueous emulsion and mixed. This mixture is then adjusted to a pH of at least '9 with, e.g., ammonium hydroxide to form the cleaning and polishing composition of this invention.

CASTING THE POLISH FILM The cleaning and polishing composition of this invention can be used on most floor coverings such as linoleum, vinyl tile and vinyl asbestos tile. It is not suitable for use on wood. The polish film is cast by merely applying the liquid composition to the floor in a well-known manner, e.g., with a sponge or applicator. As the polish film is cast, the iioor is cleaned due to the high pH of the composition, the presence of surfactant, and/or the sequestering and cleaning capacity of, e.g., the watersoluble salts of ethane-1-hydroxy-1,l,2-triphosphonic acid; ethane-l-hydroxy-1,2,2-triphosphonic acid; ethane- 1-amino-1,l-diphosphomc acid; ethane-2-carboxy-1,1-diphosphonic acid; ethane-1,2-dicarboxy-1,2-diphosphonic acid; and/or ethane-1-hydroxy-1,1- diphosphonic acid; and/ or other alkaline builder materials.

The cleaning and polishing composition of this invention can be used on almost any surface, but it is not recommended for use on unsealed wood surfaces and flat or semigloss painted surfaces. Suitable surfaces on which the cleaning and polishing composition can be used include: sheet vinyl; vinyl tile; vinyl asbestos tile; asphalt tile; sheet linoleum; linoleum tile; inlaid linoleum; ceramic tile; sealed wood; terrazzo; slate; stone; concrete; Formica; porcelain; marble; plastic; and imitation wood paneling.

The above invention can be better understood by reference to the following examples.

Example I of 214 F., a hardness of 5.5, an acid number of 15, and a viscosity at C. of 340 cps.

A small portion of the water and the copolymer are premixed. Aqueous solutions/ dispersions of the resin acid, the polyethylene and the minor ingredients are then added sequentially. The partially neutralized ethane-l-hydroxy- 1,1-diphosphonic acids are added next and then aqueous ammonia is added to adjust the pH. Additional water is then added to adjust the formula to the indicated percentages.

A series of compositions was also prepared in which the Rhoplex -B-2l7 was replaced, at the same level, by copolymers having the same monomer mixture, but different molecular weights. The methacrylic acid was added near the end of the polymerization reaction. The viscosity in centipoises was measured immediately after each composition was prepared, after standing 24 hours at F. and after standing 48 hours at 140 F. The results were as follows:

MOLECULAR WEIGHT DETERMINATION The viscosities of the complex interpolymcrs of styrene, methyl methacrylate, acrylonitrile, butyl acrylate and methacrylic acid herein were determined in methyl ethyl ketoue solvent. It was discovered that the reduced viscosity in this solvent was almost independent of concentration, i.e., methyl ethyl ketone is essentially a theta solvent. A theta solvent is one which does not interact thermodynamically with the polymer and does not cause any expansion of the polymer coil. The intrinsic viscosity (n) of a polymer in a theta solvent is related to the molecular weight (viscosity average M,., which is near the weight average) by the following equation:

For theta solvents k is often near 1X10- as discussed in F. W. Billmeyer, Textbook of Polymer Science, John Wiley & Sons, New York, 1962, p. 84. This is the value used in the above equation for the work reported here. The viscosities were obtained with a Brookfield viscometer.

As can be seen from the above data, polymers having molecular weights of -5 10 or higher can be used to prepare high pH cleaning and polishing compositions of the type described herein whose viscosities do not increase with time to a point where the product becomes difficult to use, e.g., 10.

When, in the above compositions, the following alkyl methacrylates are substituted either wholly or in part (e.g., a 1:1 ratio) for the methyl methacrylates in the copolymer, substantially equivalent results are obtained in that the compositions are good cleaning and polishing compositions: methyl, ethyl, propyl, isopropyl, butyl,

pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, 2-ethyl hexyl, and cyclohexyl methacrylates.

When, in the above compositions, the following alkyl acrylates, either wholly or in part (e.g., a 1:1 ratio) are substituted for the butyl acrylate in the copolymer, substantially equivalent results are obtained in that the compositions are good cleaning and polishing compositions: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, 2-ethyl hexyl, and cyclohexyl acrylates.

When, in the above compositions, the following plasticizers are substituted either wholly or in part (e.g., a 1:1 ratio), for the tributoxy ethyl phosphate, substantially equivalent results are obtained in that the compositions are good cleaning and polishing compositions and the film is plasticized: 2-pyrrolidine, polyethylene glycol dibenzoate, dibutyl phthalate, diethylene glycol monoethyl ether, diethylene glycol diacetate, diacetin, tricresyl phosphase, butyl phthalyl butyl glycolate, trimethylene glycol di-Z-ethyl hexoate, trimethylene glycol di-2-ethyl butyrate, and ethylene glycol.

When, in the above compositions, the following cleaning agents are substituted, either wholly or in part for the ethane 1 hydroxy-l-diphosphonic acid, substantially equivalent results are obtained in that the compositions are good cleaning and polishing compositions: ethane-1- hydroxy-l,l,2-triphosphonic acid; ethane-1-hydroxy-1,2,2- triphosphonic acid; ethane-1,1,2-triphosphonic acid; ethane-1-amino-1,l-diphosphonic acid; ethane-2-carboxy-l,1- diphosphonic acid; ethane-1,2-dicarboxy-1,2-diphosphonic acid; octyl benzene sulfonate; decyl benzene sulfonate, and mixtures thereof.

When, in the above compositions, the following bases are substituted either wholly or in part (e.g., a 1:1 molar ratio) for the ammonia on an equivalent basis, substantially equivalent results are obtained in that the compositions are good cleaning and polishing compositions: sodium, potassium, triethanolammonium, diethanolammonium, monoethanolammonium and morpholinium hydroxides.

When, in the above compositions, the following anionic and/or nonionic detergents are present either to replace the nonionic detergent or as additional ingredients at a level of about /s% of nonionic and 1% anionic detergent substantially equivalent results are obtained in that the compositions are good cleaning and polishing compositions: sodium, potassium, ammonium, triethanolammonium and morpholinium coconut alkyl sulfate, tallow alkyl sulfate, heptyl benzene sulfonate, octyl benzene sulfonate, dodecyl benzene sulfonate, decyl benzene sulfonate, and dodecyl alkane sulfonate; coconut alcohol polyethoxylate containing about 15 moles of ethylene oxide per mole of coconut alcohol, and nonyl phenol polyethoxylate containing about 15 moles of ethylene oxide per mole of nonyl phenol.

All parts, percentages and ratios herein are by weight unless otherwise specified.

What is claimed is:

1. Cleaning and polishing compositions dryable to a bright surface without requiring bufling consisting essentially of from about 5% to about 30% of film-forming eopolymer which contains styrene, lower alkyl methacrylates wherein said alkyl group contains from 1 to about 12 carbon atoms, lower alkyl acrylates wherein said alkyl group contains from 1 to about 12 carbon atoms and acrylonitrile, the amount of styrene varying from about 20% to about by weight of the polymer, the amount of alkyl methacrylates varying from about 20% to about 60% by weight of the polymer, the amount of alkyl acrylates varying from about 20% to about 40% by weight of the polymer but no more than about 30% when the alkyl group contains 4 or more carbon atoms and the amount of acrylonitrile varying from about 10% to about 20% by weight of the polymer, the total amount of styrene and alkyl methacrylates being from about 40% to about by weight of the polymer and the molecular weight of the polymer varying from about five million to about fifteen million;

from about 2% to about based on the weight of the film-forming polymer of a plasticizer for said polymer;

from 0.25 to about 1% of a water-soluble cleaning agent selected from the group consisting of ethane-1- hydroxy-1,2,2-triphosphonic acid, ethane-l-hydroxy- 1,1,2-triphosphonic acid, ethane 1 hydroxy-1,1-diphosphonic acid, ethane-l-amino 1,1 diphosphonic acid, ethane-Z-carboxy-l,l-diphosphonic acid, ethane-l,2-dicarboxy-1,2-diphosphonic acid, alkyl benzene sulfonic acids containing 7 to 10 carbon atoms in the alkyl chain, water-soluble salts of said acids, and mixtures thereof;

from about 60% to about Water; and

sufficient base to adjust the pH of the composition to from about 8 to about 12.

2. The composition of claim 1 wherein said alkyl groups contain from 1 to 6 carbon atoms.

3. The composition of claim 1 containing up to about 2% of a nonionic detergent having the formula wherein R is selected from the group consisting of an alkyl group wherein the alkyl group contains from about 8 to about 16 carbon atoms and wherein n is a number from 4 to about 40.

4. The cleaning and polishing compositions of claim 1 consisting essentially of:

from about 5% to about 30% of a film-forming copolymer which contains styrene, lower alkyl methacrylates wherein said alkyl group contains from 1 to about 6 carbon atoms, lower alkyl acrylates wherein said alkyl group contains from 1 to about 6 carbon atoms, acrylonitrile and methacrylonitrile, the amount of styrene varying from about 20% to about 60% by weight of the polymer, the amount of alkyl methacrylate varying from about 20% to about 60% by weight of the polymer, the amount of alkyl acrylate varying from about 20% to about 40% by weight of the polymer but no more than about 30% when the alkyl group contains 4 or more carbon atoms and the amount of acrylonitrile and methacrylonitrile varying from about 10% to about 20% by weight of the polymer, the total amount of styrene and alkyl methacrylates being from about 40% to about 70% by weight of the polymer, and the molecular weight of the polymer varying from about five million to about ten million; from about 2% to about 75 based on the weight of the film-forming polymer of a plasticizer for said polymer; from 0 to about 5% of a polyethylene wax comprising a mildly oxidized polyethylene having a molecular weight of from about 1,000 to about 5,000, an oxygen content of from about 1% to about 17%, a hardness equal to a penetration of not more than about 1.5 mm. as measured by standard ASTM Method D-5-25, a toughness equal to at least 2 foot pounds per linear inch as measured by a standard ASTM method -D-25647-P, and a low ratio of saponification number to acid number. from 0 to about 5% of an ether of diethylene glycol selected from the group consisting of monoalkyl and dialkyl ethers wherein the alkyl groups contain from 1 to about 4 carbon atoms; from 0 to about 5% ethylene glycol;

from about 0.1% to about 1% of a cleaning agent selected from the group consisting of ethane-l-hydroxy-1,2,2-triphosphonic acid, ethane-l-hydroxy-l, 1,2-triphosphonic acid, ethane-l-hydroxy-l,l-diphosphonic acid, ethane-l-amino-1,1-diphosphonic acid, ethane-2-carboxy-1,l-diphosphonic acid, ethane-1,2- dicarboxy-1,2-diphosphonic acid, alkyl benzene sulfonic acids containing 7 to carbon atoms in the alkyl chain, Water-soluble salts of said acids, and mixtures thereof;

from about 70% to about 90% water; and

sufficient base to raise the pH of the composition to from about 8 to about 12.

5. The composition of claim 1 wherein the plasticizer is selected from the group consisting of tributoxy ethyl phosphate, Z-pyrrolidine, polyethylene glycol dibenzoate, dibutyl phthalate, diethylene glycol monoethyl ether, diethylene glycol diacetate, diacetin, tricresyl phosphate, butyl phthalyl butyl glycolate, methyl phthalyl ethyl glycolate, trimethylene glycol di-2-ethy1 hexoate, trimethylene glycol di-Z-ethyl butyrate, and ethylene glycol.

6. The composition of claim 1 wherein the base is selected from the group consisting of sodium, potassium, ammonium, triethanolammonium, diethanolammonium, monoethanolammonium and morpholinium hydroxides and the corresponding compounds which will give these hydroxides in water.

7. The composition of claim 1 having a pH of from about 8.5 to about 9.5.

8. The composition of claim 1 containing up to about 3% of an alkali metal or ammonium sulfonate or sulfate detergent having an alkyl group of from about 10 to about 18 carbon atoms.

References Cited UNITED STATES PATENTS OTHER REFERENCES Chem. Absts., vol. 51, p. 1879a; vol. 57, pp. 7403-5.

-Rohm & Haas Publications, Floor Polish Formulations, May 1963 and November 1964.

Weyna, P. L. et al.: Soap & Chem. Specialties, Metal Chelates in Floor Polishes, pp. 43-46 and 88, July 1967.

LEON D. ROSDOL, Primary Examiner P. E. WILLIS, Assistant Examiner US. Cl. X.R. 252550, 8