GB2416773A

GB2416773A - Aqueous acidic hard surface cleaning compositions and process for cleaning

Info

Publication number: GB2416773A
Application number: GB0417476A
Authority: GB
Inventors: James Chi-Cheng Feng; Farid Ahmad Nekmard
Original assignee: Reckitt Benckiser LLC
Current assignee: Reckitt Benckiser LLC
Priority date: 2004-08-06
Filing date: 2004-08-06
Publication date: 2006-02-08
Also published as: AR050449A1; GB0417476D0; WO2006013319A1

Abstract

Aqueous acidic hard surface cleaning compositions comprise urea salts, preferably urea salts formed in situ in the cleaning composition, one or more detersive surfactants and optionally one or more further constituents such as organic solvents. The pH is 1.5 or less. The salt is preferably urea hydrochloride formed in situ by reaction of urea and hydrochloric acid. Anionic, nonionic and amphoteric surfactant may be present. A process of cleaning a hard surface using the composition is also claimed.

Description

B- - -

241 6773

IMPROVEMENTS IN CLEANING COMPOSITIONS

The present invention relates to hard surface cleaning compositions, methods for their manufacture as well as methods for their use. More particularly the present invention relates to largely aqueous hard surface cleaning compositions which are acidic in nature, methods for their manufacture and methods for their use in the treatment of inanimate hard surfaces.

Cleaning compositions are commercially important products and enjoy a wide field of utility in assisting in the removal of dirt and grime from surfaces, especially those characterized as useful with "hard surfaces". Hard surfaces are those which are frequently encountered in lavatories such as toilets, shower stalls, bathtubs, bidets, sinks, etc., as well as countertops, walls, floors, etc. In such lavatory environment various forms of undesirable residues are known to form including hard water stains as well as "soap scum stains". Hard water stains are mineral stains caused by the deposition of salts, such as calcium or magnesium salts, frequently present in hard water. Soap scum stains are residues of fatty acid soaps such as those which are based on alkali salts of low fatty acids, which precipitate in hard water due to the presence of metal salts therein, leaving an undesirable residue upon such surfaces.

The prior art has provided a number of acidic hard

surface cleaning compositions.

US 5985929 describes a cold chemical sterilant composition including a monohydric alcohol, an urea salt, a e bee see ëe e e e e e e e see e e e e e e e e e e e e e e e e e e e ee e e e e e e e e polyhydric alcohol, a surface active agent and water. The composition is not recited to have good cleaning efficacy against limescale or soapacum stains.

US 6340660 describes a water based urea hydrochloride cleaning solution containing amphoteric and/or nonionic surfactant, a butyne based corrosion inhibitor, and an ethanol amine is suggested for cleaning stainless steel and aluminum surfaces which is corrosive to neither aluminum nor polycarbonate glazed acrylic surfaces. The urea hydrochloride present in an amount of 15% to 70% by volume in the recited compositions wherein it is used as a stabilizing constituent.

A Material Safety Data Sheet the Spartan Chemical Co. Inc. for a product, "CLEAN ON THE GO ACID BATHROOM AND SHOWER CLEANER" which appears to necessarily include 50- 60%wt. of urea hydrochloride.

While prior art formulations may provide some benefit, nonetheless many of these prior art compositions however suffer one or more shortcomings such as poor long term storage stability, or comprising relatively high amounts of strong acids necessary to provide their cleaning efficacy.

It is to such shortcomings, as well as to further shortcomings known to the art with such compositions to which the present invention is directed.

Accordingly there is a real and continuing need in the art for improved acidic hard surface treatment compositions which provide a cleaning benefit, particularly for the cleaning of soapacum and limescale stains as are commonly encountered in lavatory and other environments.

... ... ...

. . . . . . . . . . . . . . . It is therefore among the objects of the invention to provide an improved acidic hard surface treatment compositions which provide a cleaning benefit, particularly for the cleaning of soapscum and limescale stains as are S commonly encountered in lavatory and other environments which is easy to apply and which is effective in the removal of such stains.

A further object of the invention to provide a readily pourable and readily pumpable cleaning composition which features the benefits described above.

It is a further object of the invention to provide a process for cleaning and/or sanitization of hard surfaces, which process comprises the steps of providing the composition as outlined above, and applying an effective amount to a hard surface, particularly for the purpose of removing undesired soapscum and/or limescale stains or deposits present thereon.

These and other objects of the invention will be more apparent from a reading of the specification and of the claims attached.

According to a first aspect of the invention there is provided an aqueous, acidic hard surface cleaning composition which provides a cleaning benefit to a hard surface which comprises the following constituents: (a) a urea salt; (b) one or more detersive surfactants; (c) optionally, one or more organic solvents; (f) water.

wherein the aqueous compositions are at an highly acidic pH, namely a pH of 1.5 or less, preferably at a pH of about ... ..

. . . . . . . : ë .. :e .e...

1 or less, more preferably at a pH of about 0.5 or less, and most preferably at a pH of about 0.3 or less and wherein the aqueous compositions are efficacious in the solubilization and removal of limescale deposits, viz., stains, on hard surfaces.

The compositions described above may include one or more further optional constituents including but not limited to: pH buffering agents, perfumes, perfume carriers, colorants, germicides, thickeners, fungicides, antioxidants, anti-corrosion agents, etc., which are not found to deleteriously affect the cleaning properties of the inventive compositions.

Preferred compositions according to the invention are largely aqueous, comprising at least 80%wt. water, and are readily pourable and pumpable. Particularly preferred compositions all exhibit good storage stability, particularly under accelerated ageing testing.

According to a further aspect of the invention, there is provided a process for cleaning or sanitization of hard surfaces, which process comprises the step of providing the composition as outlined above, and applying an effective amount to a hard surface requiring such treatment.

The present inventive compositions comprise a salt form of urea, which is formed in situ, in the aqueous compositions of the present invention by reaction of urea with a chemical compound which provides a counterion. Non- limiting examples of such chemical compounds which may provide a counterion include many known organic acids as well as inorganic acids, non-limiting examples of which include acetic acid, hydroxyacetic acid, gluconic acid, * . .. . . . . . . . . . . . . . . . s lactic acid, citric acid, sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, and the like. Of these, inorganic acids, particularly hydrochloric acid are preferred.

The urea salt is preferably selected from the group consisting of urea monosulfate, urea hydrochloride and urea acetate or mixtures thereof. More preferably the urea salt is an organic salt form of urea, such as urea hydrochloride which may be formed by the in-situ reaction of urea with hydrochloric acid under acidic conditions in an aqueous medium. Most preferably the urea salt is a urea hydrochloride.

The urea salt is necessarily present in the inventive compositions in amounts of from 0.1%wt. to about 15%wt., IS but is preferably present in amounts of from 1-10%wt., more preferably from about 2.5 - 10%wt, and most preferably is present in amounts of from about 5 - 10%wt. based on the total weight of the compositions of which they form a part.

Compositions of the invention include one or more detersive surfactants, which may be one or more of anionic, nonionic, cationic, zwitterionic and amphoteric surfactants.

Nonlimiting examples of suitable nonionic surfactants which may be used in the present invention include: (1) The polyethylene oxide condensates of alkyl phenols. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration with ethylene oxide, the ethylene oxide being present in an amount equal to 5 to 25 . . moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds can be derived, for example, from polymerized propylene, diisobutylene and the like.

Examples of compounds of this type include nonyl phenol condensed with about 9.5 moles of ethylene oxide per mole of nonyl phenol; dodecylphenol condensed with about 12 moles of ethylene oxide per mole of phenol; dinonyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol and diisooctyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol.

(2) The condensation products of aliphatic alcohols with from about 1 to about 60 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Examples of such ethoxylated alcohols include the condensation product of myristyl alcohol condensed with about 10 moles of ethylene oxide per mole of alcohol and the condensation product of about 9 moles of ethylene oxide with coconut alcohol (a mixture of fatty alcohols with alkyl chains varying in length from about 10 to 14 carbon atoms). One example of such a nonionic surfactant is available as Empilan KM 50.

(3) Alkoxy block copolymers, and in particular, compounds based on ethoxy/propoxy block copolymers.

Polymeric alkylene oxide block copolymers include nonionic surfactants in which the major portion of the molecule is made up of block polymeric C2C4 alkylene oxides. Such nonionic surfactants, while preferably built up from an alkylene oxide chain starting group, and can have as a starting nucleus almost any active hydrogen containing ... . .

. . c group including, without limitation, amides, phenols, thiols and secondary alcohols.

Other nonionic surfactants containing the characteristic alkylene oxide blocks are those which may be generally represented by the formula (A): HO-(EO)X(PO)y(EO)z-H (A) where EO represents ethylene oxide, PO represents propylene oxide, y equals at least 15, (EO)x+y equals 20 to 50% of the total weight of said compounds, and, the total molecular weight is preferably in the range of about 2000 to 15,000. These surfactants are available under the PLURONIC tradename from BASE or Emulgen from Kao.

Another group of nonionic surfactants can be represented by the formula (B): R-(EO,PO) a (EO, PO) b-H (B) wherein R is an alkyl, aryl or aralkyl group, where the R group contains 1 to 20 carbon atoms, the weight percent of EO is within the range of 0 to 45% in one of the blocks a, b, and within the range of 60 to 100% in the other of the blocks a, b, and the total number of moles of combined EO and PO is in the range of 6 to 125 moles, with 1 to 50 moles in the PO rich block and 5 to 100 moles in the EO rich block. e ë

.e . . . . Further nonionic surfactants which in general are encompassed by Formula B include butoxy derivatives of propylene oxide/ethylene oxide block polymers having molecular weights within the range of about 2000-5000.

Still further nonionic surfactants containing polymeric butoxy (BO) groups can be represented by formula (C) as follows: RO-(BO) n (EO) x-H (C) wherein R is an alkyl group containing I to 20 carbon atoms, n is about 5-15 and x is about 5-15.

Also further nonionic block copolymer surfactants, which also include polymeric butoxy groups, are those which may be represented by the following formula (D): HO- (EO) x (BO), (EO) yH (D) wherein n is about 515, preferably about 15, x is about 5-15, preferably about 15, and y is about 5-15, preferably about 15.

Still further nonionic block copolymer surfactants include ethoxylated derivatives of propoxylated ethylene diamine, which may be represented by the following formula: H(EO)y(PO)x\ / (PO)x(Eo)yH CH2 CH2 (E) H(EO)y(PO) x (PO)x(EO)yH . e .e e where (EO) represents ethoxy, (PO) represents propoxy, the amount of (PO)x is such as to provide a molecular weight prior to ethoxylation of about 300 to 7500, and the amount of (EO)y is such as to provide about 20% to 90% of the total weight of said compound.

Particularly preferred nonionic block copolymers include those based on a polymeric ethoxy/propoxy units which may also be used include those presently commercially available in the Plurafac series of block copolymers (ex.

BASF) These are described to be nonionic surfactants based on ethoxy/propoxy block copolymers, conveniently available in a liquid form from its supplier.

One particularly preferred nonionic surfactant is PlurafaC SL-62 which is described to be a nonionic surfactant based on alkoxylated linear alcohols. In certain preferred embodiments of the inventive composition the sole nonionic surfactant present is a nonionic surfactant as described with reference to Plurafac SL-62.

Other examples of non-ionic surfactants include linear alcohol ethoxylates. The linear alcohol ethoxylates which may be employed in the present invention are generally include the C6-cls straight chain alcohols which are ethoxylated with about 1 to 13 moles of ethylene oxide.

Exemplary and particularly non-ionic surfactants include Alfonic0 810-4.5, which is described in product literature from Sasol North America Inc. as having an average molecular weight of 356, an ethylene oxide content of about 4.85 moles (about 60 wt.), and an HLB of about 12; Alfonic 810-2, which is described in product . . . . . . . . . . * a e e. e literature from Sasol North America Inc. as having an average molecular weight of 242, an ethylene oxide content of about 2.1 moles (about 40 wt.%), and an HLB of about 12; and Alfonic 610-3.5, which is described in product literature from Sasol North America Inc. as having an average molecular weight of 276, an ethylene oxide content of about 3. 1 moles (about 50 wt.%), and an HLB of 10.

Product literature from Sasol North America Inc. also identifies that the numbers in the alcohol ethoxylate name designate the carbon chain length (numbers before the hyphen) and the average moles of ethylene oxide (numbers after the hyphen) in the product. These examples are typically C6 -Cl1 straight-chain alcohols which are ethoxylated with from about 3 to about 6 moles of ethylene oxide.

Other examples of ethoxylated alcohols include the Neodol 91 series nonionic surfactants available from Shell Chemical Company which are described as C,-Cll ethoxylated alcohols. The Neodol 91 series non-ionic surfactants of interest include Neodol 91-2.5, Neodol 91-6, and Neodol 918. Neodol 91-2.5 has been described as having about 2.5 ethoxy groups per molecule; Neodol 91-6 has been described as having about 6 ethoxy groups per molecule; and Neodol 91-8 has been described as having about 8 ethoxy groups per molecule. Another example includes a Cll linear primary alcohol ethoxylate averaging about 9 moles of ethylene oxide per mole of alcohol, available, for example, under the commercial name of Neodol 1-9.

eTaa ear . .e . . Further examples of ethoxylated alcohols include the Rhodasurf DA series non-ionic surfactants available from Rhodia which are described to be branched isodecyl alcohol ethoxylates. Rhodasurf DA-530 has been described as having 4 moles of ethoxylation and an HLB of lo. 5; Rhodasurf DA- 630 has been described as having 6 moles of ethoxylation with an HLB of 12.5; and Rhodasurf DA-639 is a 90% solution of DA-630...DTD: Further examples of ethoxylated alcohols include those from Tomah Products (Milton, WI) under the TomadolX tradename with the formula RO(CH2CH2O)H where R is the primary linear alcohol and n is the total number of moles of ethylene oxide. The ethoxylated alcohol series from Tomah include 91-2.5; 91-6; 91-8 - where R is linear C9/Clo/Cll and n is 2.5, 6, or 8; 1-3; 1-5; 1-7; 1-73B; 1-9; where R is linear Cll and n is 3, 5, 7 or 9; 23-1; 23-3; 23-5; 23-6.5 where R is linear Cl2/Cl3 and n is l, 3, 5, or 6.5; 25-3; 25-7; 25-9; 25-12 - where R is linear C12/cl3/cl4/ C15 and n is 3, 7, 9, or 12; and 45-7; 45-13 where R is linear Cl4/ Cl5 and n is 7 or 13.

Other examples of nonionic surfactants include primary and secondary linear and branched alcohol ethoxylates, such as those based on C6-Cle alcohols which further include an average of from 2 to 80 moles of ethoxylation per mol of alcohol. These examples include the Genapol UD series from Clariant, described as tradenames Genapol UD 030, Clloxo-alcohol polyglycol ether with 3 EO; Genapol UD, 050 Cll- oxo-alcohol polyglycol ether with 5 EO; Genapol UD 070, Cll- oxo-alcohol polyOlycol ether with 7 EO; Genapol UD 080, Cll oxo-alcohol polyglycol ether with 8 EO; Genapol UD 088, Cll ., . , . . . a oxo-alcohol polyglycol ether with 8 EO; and Genapol UD 110, c11-Oxo-alcohol polyglycol ether with 11 EO.

Further useful nonionic surfactants include those having a formula RO (CH2CH2o) nH wherein R is a mixture of linear, even carbon-number hydrocarbon chains ranging from C12H25 to C16H33 and n represents the number of repeating units and is a number of from about 1 to about 12.

Surfactants of this formula are presently marketed under the Genapol tradename. available from Clariant, Charlotte, N.C., include the 26-L series of the general formula RO (CH2CH2o) nH wherein R is a mixture of linear, even carbon- number hydrocarbon chains ranging from C12H25 to C16H33 and n represents the number of repeating units and is a number of from 1 to about 12, such as 26-L-1, 26-L-1.6, 26-L-2, 26-L 3, 26-L-5, 26-L-45, 26-L-50, 26-L-60, 26-L-60N, 26-L-75, 26-L-80, 26-L-98N, and the 24-L series, derived from synthetic sources and typically contain about 55% C12 and 45% C14 alcohols, such as 24-L-3, 24-L-45, 24-L-50, 24-L-60, 24-L-60N, 24-L-75, 24-L-92, and 24-L-98N. From product literature, the single number following the "LN corresponds to the average degree of ethoxylation (numbers between 1 and 5) and the two digit number following the letter "LN corresponds to the cloud point in C of a 1.0 wt.% solution in water.

Additional examples of useful alcohol ethoxylates are Clo oxo -alcohol ethoxylates available from BASF under the Lutensol ON tradename. They are available in grades containing from about 3 to about 11 moles of ethylene oxide (available under the names Lutensol ON 30; Lutensol ON 50; s c c e.c Bbl ace e e e e a eC e c e C a e c e c e e e e a a ee a a e Lutensol ON 60; Lutensol ON 65; Lutensol ON 66; Lutensol ON 70; Lutensol ON 80; and Lutensol ON 110).

Another class of nonionic surfactants include amine oxide compounds which may be defined as one or more of the S following of the four general classes: (1) Alkyl di (lower alkyl) amine oxides in which the alkyl group has about 6-24, and preferably 8-18 carbon atoms, and can be straight or branched chain, saturated or unsaturated. The lower alkyl groups include between 1 and 7 carbon atoms, but preferably each include 1 - 3 carbon atoms.. Examples include octyl dimethyl amine oxide, lauryl dimethyl amine oxide, myristyl dimethyl amine oxide, and those in which the alkyl group is a mixture of different amine oxides, such as dimethyl cocoamine oxide, dimethyl (hydrogenated tallow) amine oxide, and myristyl/palmityl dimethyl amine oxide; (2) Alkyl di (hydroxy lower alkyl) amine oxides in which the alkyl group has about 6-22, and preferably 8-18 carbon atoms, and can be straight or branched chain, saturated or unsaturated. Examples include bis-(2 hydroxyethyl) cocoamine oxide, bis-(2-hydroxyethyl) tallowamine oxide; and bis-(2-hydroxyethyl) stearylamine oxide; (3) Alkylamidopropyl di(lower alkyl) amine oxides in which the alkyl group has about 10-20, and preferably 12-16 carbon atoms, and can be straight or branched chain, saturated or unsaturated. Examples are cocoamidopropyl dimethyl amine oxide and tallowamidopropyl dimethyl amine oxide; and * .eve as* * . . ..

* * * * * . . . . .. . . (4) Alkylmorpholine oxides in which the alkyl group has about 10-20, and preferably 12-16 carbon atoms, and can be straight or branched chain, saturated or unsaturated.

While these amine oxides recited above may be used, preferred are amine oxides which may be represented by the following structural representation: R1 R2 1 O R1 wherein each R1 independently is a straight chained C1-C4 alkyl group; and, R2 is a straight chained C6-C22 alkyl group or an alkylamidoalkylene having the formula R3-C NH (CH2) where R3 is Cs-C20 alkyl or (CH2t-OH where n is 1 to 5 and p is 1 to 6; additionally, R2 or R3 could be ethoxylated (1 to 10 moles EO/mol) or propoxylated (1 to 10 moles of PO/mol).

Each of the alkyl groups may be linear or branched, but most preferably are linear. Examples include Ammonyx LO which is described to be as a 30%wt. active solution of ee.ë.e a e :::: ::: ë e.

ë e lauryl dimethyl amine oxide; Ammonyx CDO Special, described to be a about 30%wt. active solution of cocoamidopropylamine oxide, as well as Ammonyx MO, described to be a 30%wt. active solution of myristyldimethylamine oxide, all available from Stepan Company (Northfield, IL) with similar materials also available from Lonza under the Barlox trademark.

Further useful nonionic surfactants include condensates of alkylene oxides, particularly ethylene oxide with sorbitan fatty acid esters. Such materials are presently commercially available under the tradename TWEENS from Imperial Chemical Industries and include polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleates which are available in a variety of grades, and with differing amounts of polyoxylethylene groups per molecule.

Once class of particularly useful nonionic surfactants are alkyl polySlycosides. Suitable alkyl polyglycosides are known nonionic surfactants which are alkaline and electrolyte stable. Alkyl mono and polyglycosides are prepared generally by reacting a monosaccharide, or a compound hydrolyzable to a monosaccharide with an alcohol such as a fatty alcohol in an acid medium. Various glycoside and polyglycoside compounds including alkoxylated glycosides and processes for making them are disclosed in U.S. Patent No. 2,974,134; U.S. Patent No.3,219,656; U.S. Patent No. 3,598,865; U.S. Patent No. 3,640,998; U.S. ecc.ecce C . C C C C C . Patent No. 3,707,535; U.S. Patent No. 3,772,269; U.S. Patent No. 3,839,318; U.S. Patent No. 3,974,138; U.S. Patent No. 4,223, 129; and U.S. Patent No. 4,528,106, the contents of which are herein incorporated by reference.

A preferred group of alkyl glycoside surfactants suitable for use in the practice of this invention may be represented by formula I below: RO-(R1 ON-(G)XZb I wherein: R is a monovalent organic radical containing from about 6 to about 30, preferably from about 8 to about 18 carbon atoms; R1 is a divalent hydrocarbon radical containing from about 2 to about 4 carbon atoms; O is an oxygen atom; y is a number which has an average value from about O to about 1 and is preferably 0; G is a moiety derived from a reducing saccharide containing 5 or 6 carbon atoms; and x is a number having an average value from about 1 to (preferably from 1.1 to 2); z i s O2M1, o _o-C-R2 O(CH2), CO2M1, OSO3M1, or O(CH2)SO3M1; R2 is (CH23CO2M1 or CH=CHCO2M1; (with the proviso that Z can be O2M1 only if Z is in place of a primary hydroxyl group in which the primary hydroxyl-bearing carbon atom, e . . . . . . . . .. . . . . . . -CH2OH, is oxidized to form a o C-OM1 group); b is a number of from 0 to 3x+1 preferably an average of from 0.5 to 2 per glycosal group; p is l to lo, Ml is H+ or an organic or inorganic cation, such as, for example, an alkali metal, ammonium, monoethanolamine, or calcium.

As defined in Formula I above, R is generally the residue of a fatty alcohol having from about 8 to 30 and preferably 8 to l8 carbon atoms.

Most preferably, the inventive compositions include an alkylpolYglycoside compound according to the structure:

OH CH2

O- R

_ OH x wherein: R is an alkyl group, preferably a linear alkyl chain, which comprises C8 to Cl6 alkyl groups; x is an integer value of from 0 3, inclusive.

.e see e e e e ëe e e e e e.. e Examples of preferred and particularly preferred alkylglycosides as described above include, for example, APG 325 CS which is described as being a 50% C,-Cll alkyl polyglycoside, also commonly referred to as D glucopyranoside, (commercially available from Henkel Corp, Ambler PA) and Glucopon 625 CS which is described as being a 50% C1O-Cl6 alkyl polyglycoside, also commonly referred to as a D- glucopyranoside, (available from Henkel Corp., Ambler PA), as well as other materials sold under the Glucopon tradename. Particularly preferred alkypolyglycosides include materials presently sold as Glucopon 425N, and Glucopon 425N/HH...DTD: Non limiting examples of anionic surfactants which may be included in the concentrate compositions include for example, alkali metal salts, ammonium salts, amine salts, or aminoalcohol salts of one or more of the following compounds (linear and secondary): alcohol sulfates and sulfonates, alcohol phosphates and phosphonates, alkyl sulfates, alkyl ether sulfates, sulfate esters of an alkylphenoxy polyoxyethylene ethanol, alkyl monoglyceride sulfates, alkyl sulfonates, olefin sulfonates, paraffin sulfonates, beta-alkoxy alkane sulfonates, alkylamidoether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkyl ether sulfonates, ethoxylated alkyl sulfonates, alkylaryl sulfonates, alkyl benzene sulfonates, alkylamide sulfonates, alkyl monoglyceride sulfonates, alkyl carboxylates, alkyl sulfoacetates, alkyl ether carboxylates, alkyl alkoxy carboxylates having 1 to 5 moles of ethylene oxide, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkylamide sulfosuccinates, alkyl . ... ..

e ë e . . . . . .. . . . sulfosuccinamates, octoxynol or nonoxynol phosphates, alkyl phosphates, alkyl ether phosphates, taurates, N-acyl taurates, fatty taurides, fatty acid amide polyoxyethylene sulfates, isethionates, acyl isethionates, and sarcosinates, acyl sarcosinates, or mixtures thereof.

Generally, the alkyl or acyl radical in these various compounds comprise a carbon chain containing 12 to 20 carbon atoms.

Exemplary and particularly useful anionic surfactants include diphenyl oxide disulfonates and alkyl diphenyl ether disulfonates, including those which are commercially available in anionic surfactant compositions from the Dow Chemical Co. These are available as Dowfax materials of which those which conform to the following general structure are particularly useful:

R :+

SO3X SO3X wherein: X represents a counterion, desirably an alkali metal or ammonium counterion, yet more desirably is lithium, potassium or sodium, especially sodium, and, R represents a hydrogen of a hydrophobic alkyl group, desirably a linear or branched C6-C16 alkyl group which may be straight chained or branched, may be optionally substituted but desirably are unsubstituted C6-C12 straight chained alpha olefins, or is tetrapropylene. c....

. . . ..

. e a.

. . of these, particularly useful are those available as Dowfax 3B2 which is described as being a sodium salt according to the general structure depicted above and wherein R is a C6 olefin; and, Dowfax 2Al which is described as being a sodium salt according to the general structure depicted above and wherein R is tetrapropylene.

Examples of the foregoing anionic surfactants are available under the following tradenames: Rhodapon, Stepanol@, Hostapur, Surfing, Sandopan@, Neodox@, Biosoft@, and Inanely.

A further class of useful anionic and particularly preferred anionic surfactants are alkyl ethersulfates and salts thereof, especially one or more alkyl ethersulfates which may be represented by the following general formula: o R (CH2CH2O)n-O-S-O- X+

O

wherein R is a C8 - Cls alkyl group, n is an integer from l to 30, and X represents an counterion selected from alkali metals and ammonium. Of these alkyl ethersulfates, especially preferred are those wherein R is aCl2-Cl5 group, n is 4, and X is a sodium cation or is an ammonium cation.

Such alkyl ether sulfates may be produced by known methods, or in the alternative are commercially available under the trade name Steol (Stepan Co., Northbrook, IL).

Exemplary useful amphoteric surfactants include alkylampho(mono)acetates having the formula . . a . . . . . . . . CH2COO RCONHCH2CH2-N-H CH2CH2OH as well as one or more alkylampho(di)acetates according to the formula/ae s CH2COO RCONHCH2CH2 NtH2COOH I or CH2CH2OH

COCOS

RCONHCH2CH2-l-H CH2CH2O-CH2COOH as well as alkylampho(mono)propionates according to the formula CH2CH2COO RCONHCH2CH2 N-H CH2CH2OH as well as one or more alkylampho(di)propionates according to the formula/ae e . ë e . . . . e e e CH2CH2COO RCONHCH2CH2 1CH2CH2COOH I or CH2CH2OH CH2CH2COO RCONHCH2CH2 N-H CH2CH2O-CH2CH2COOH In the above formulae, R represents a C8 to C24 alkyl group, and is preferably a Cl0 to C16 alkyl group.

S Further useful amphoteric surfactants include sultaines, including compounds which may be represented by the following formula: CH3 OH RCONHCH2CH2CH2-iN<3CH2CHCH2SO3e CH3 as well as alkylaminodipropionates, including compounds which may be represented by the following formula: CH2CH2COO R-N(3 H CH2CH2COOH In the above formulae, R represents a C8 to C24 alkyl group, and is preferably a C10 to C16 alkyl group.

Examples of these useful and preferred amphoteric surfactants can be found under the tradename MIRANOL from e.e.. ..

. a. . . e . . Rhodia (Cranbury, NJ). Some examples include MIRANOL C2M- Conc. NP, described to be disodium cocoamphodiacetate; MIRANOL FA-NP, described to be sodium cocoamphotacetate; MIRANOL DM, described to be sodium steroamphoacetate; MIRANOL CS cone., described to be sodium cocoamphohydroxypropyl sulfonate; MIRANOL HMA, described to be sodium lauroamphoacetate; MIRANOL C2M, described to be cocoamphodiprioponic acid; MIRANOL C2M-SF, described to be disodium cocoamphodiproprionate; MIRANOL CM-SF Conc., described as being cocoamphopropriate; MIRATAINE H2C-HA, described as sodium lauiminodiproprionate; MIRATAINE H2C- HA, described to be sodium lauriminodipropionate; MIRATAINE CBS, described to be a cocoaminopropoxy hydroxyl sultaine; MIRANOL Ultra L-32, described as sodium lauroamphoacetate; and MIRANOL Ultra C-37, described as sodium cocoamphoacetate. Other amphoteric surfactants are also available under the tradename AMPHOTERGE from Lonza (Fair Lawn, NJ) such as AMPHOTERGE K described to sodium cocoamphoproprionate; AMPHOTERGE K-2, described as disodium cocoamphodiproprionate; AMPHOTERGE W. described to be sodium cocoamphoacetate; and AMPHOTERGE W-2, described to be disodium cocoamphodiacetate.

Further exemplary amphoteric surfactants include one or more water soluble betaine surfactants which may be represented by the general formula: iCH3 R1-N-R2-COO CH3 . . . . . . . . e. . . . wherein: R1 is an alkyl group containing from 8 to 18 carbon atoms, or the amido radical which may be represented by the following general formula:

O H 11 1

R-C-N -(cH2)a-R2 wherein R is an alkyl group having from 8 to 18 carbon atoms, a is an integer having a value of from 1 to 4 inclusive, and R2 is a C1-C4 alkylene group. Examples of such water soluble betaine surfactants include dodecyl dimethyl betaine, as well as cocoamidopropylbetaine.

Particularly preferred detersive surfactants, and particularly preferred systems of detersive surfactants are exemplified by one or more of the following examples. The one or more detersive surfactants are present in amounts up to 10%wt., preferably are present in amount of 0.1 - 8%wt., more preferably 0.5 - 5%wt., and most preferably 1 3.5%wt. based on the total weight of the composition of which they form a part.

In certain preferred embodiments the inventive compositions comprise one or more non-aqueous solvents as a necessary constituent. Examples of nonaqueous solvents which can be used in minor amounts in the inventive compositions include those which are at least partially water-miscible such as alcohols, (e.g., low molecular weight alcohols, such as, for example, ethanol, propanol, isopropanol, and the like), glycols (such as, for example, ethylene glycol, propylene glycol, hexylene glycol, and the like), water-miscible ethers (e.g. diethylene glycol . ëe.e e . e. a . . diethylether, diethylene glycol dimethylether, propylene glycol dimethylether), water-miscible glycol ether (e.g. propylene glycol monomethylether, propylene glycol mono ethylether, propylene glycol monopropylether, propylene glycol monobutylether, propylene glycol monohexyl ether, ethylene glycol monobutylether, dipropylene glycol monomethylether, dipropylene glycol monobutylether, diethyleneglycol monobutylether), lower esters of monoalkylethers of ethyleneglycol or propylene glycol (e.g. propylene glycol monomethyl ether acetate) all commercially available such as from Union Carbide (Danbury, CT), Dow Chemical Co. (Midland, MI) or Hoechst (Germany). Mixtures of several organic solvents can also be used.

Preferred non-aqueous solvents which can be used in minor amounts in the inventive compositions are glycol ethers. Exemplary useful glycol ethers are those having the general structure Ra-O-Rb-OH, wherein Ra is an alkyl of 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, or an aryl of at least 6 carbon atoms, and Rb is an alkylene of 1 to 8 carbons, preferably 1 to 3 carbons, or is an ether or polyether containing from 2 to 20 carbon atoms. Exemplary glycol ethers include propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol isobutyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol phenyl ether, propylene glycol phenol ether, dipropylene glycol monobutyl ether and mixtures thereof Specific examples of more preferred glycol ether solvents include propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl . . ... ... ...

. .. . . . . . ether, propylene glycol isobutyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol phenyl ether, propylene glycol phenol ether, and mixtures thereof. Particularly preferred organic solvents, as well as particularly preferred organic solvent systems are exemplified by one or more of the following examples.

When present, the organic solvents are present in amounts up to 10%wt., preferably are present in amount of 0.001 - 5%wt., more preferably 0.01 2%wt., based on the total weight of the composition of which they form a part.

According to particularly preferred embodiments the inventive compositions comprise not more 2%wt, preferably not more than 1% glycol ethers when present as it has been observed by the present inventors that the accelerated ageing stability of the compositions are deleteriously affected when glycol ethers are present in amount in excess of 1%wt. According to certain preferred embodiments glycol ethers are absent from the inventive compositions.

According to further preferred embodiments organic solvents are wholly absent from the inventive compositions.

Other conventional additives known to the art but not expressly enumerated here may also be included in the compositions according to the invention. By way of non limiting example without limitation these may include: chelating agents, coloring agents, light stabilizers, fragrances, thickening agents, hydrotropes, pH adjusting agents, pH buffers. Many of these materials are known to the art, per se, and are described in McCutcheon's Detergents and Emulsifiers, North American Edition, 1998; i.. .

. . . . . . . . . . . . r Kirk- Othmer, Encyclopedia of Chemi cal Technology, 4th Ed., Vol. 23, pp. 478-541 (1997), the contents of which are herein incorporated by reference. Such optional, i.e., non- essential constituents should be selected so to have little or no detrimental effect upon the desirable characteristics of the present invention, namely the blooming behavior, cleaning efficacy, disinfectant activity, and low toxicity as provided by the inventive compositions. Generally the total weight of such further conventional additives may comprise up to 15% by weight, preferably up to 10% by weight of a composition formulation.

As is noted above, the compositions according to the invention are aqueous in nature. Water is added to order to provide to 100% by weight of the compositions of the invention. The water may be tap water, but is preferably distilled and is most preferably deionized water, or soft' water. If the water is tap water, it is preferably substantially free of any undesirable impurities such as organics or inorganics, especially minerals salts which are present in hard water which may thus undesirably interfere with the operation of the constituents present in the aqueous compositions according to the invention.

According to one particularly preferred embodiment of the invention there is provided an aqueous, acidic hard surface cleaning composition which provides a cleaning benefit to a hard surface which comprises (preferably consists essentially of) the following constituents: (a) a urea salt formed in situ in the composition; ..

, . . . . . . 1 b (b) one or more detersive surfactants selected from diphenyl oxide disulfonates, linear primary alcohol ethoxylates, and alkylpolyglcosides (c) one or more organic solvents; (d) water, and (e) optionally one or more optional constituents selected from fragrances, dyes and coloring agents, wherein the aqueous compositions are at highly acid pH, namely a pH of 1.5 or less, preferably at a pH of about 1, more preferably at a pH of about 0.5, and most preferably at a pH of about 0.3 or less and wherein the aqueous compositions are efficacious in the solubilization and remove of limscale deposits, viz., stains, or hard surfaces. Most desirably the urea salt is urea hydrochloride.

According to one particularly preferred embodiment of the invention there is provided an aqueous, acidic hard surface cleaning composition which provides a cleaning benefit to a hard surface which comprises (preferably consists essentially of) the following constituents: (a) a urea salt formed in situ in the composition; (b) one or more detersive surfactants selected from diphenyl oxide disulfonates, alcohol ethoxylates, and alkylpolyglcosides; (c) one or more organic solvents; (d) water, and (e) optionally one or more optional constituents selected from fragrances, dyes and coloring agents, wherein the aqueous compositions are at highly acid pH, namely a pH e ce. she as a e ee a e 1 8 et 8 e e I 1 La Be I e of 1.5 or less, preferably at a pH of about 1, more preferably at a pH of about 0.5, and most preferably at a pH of about 0.3 or less and wherein the aqueous compositions are efficacious in the solubilization and removal of limescale deposits, viz., stains, on hard surfaces. Most desirably the urea salt is urea hydrochloride.

According to a further particularly preferred embodiment of the invention there is provided an aqueous, acidic hard surface cleaning composition which provides a cleaning benefit to a hard surface which comprises (preferably consists essentially of) the following constituents: (a) a urea salt formed in situ in the composition; (b) as the sole detersive surfactants, one or more nonionic surfactants based on alcohol ethoxylates with at least one further surfactants selected from diphenyl oxide disulfonates, and alkylpolyglcosides; (c) one or more organic solvents; (d) water, and (e) optionally one or more optional constituents selected from fragrances, dyes and coloring agents, wherein the aqueous compositions are at highly acid pH, namely a pH of 1.5 or less, preferably at a pH of about 1, more preferably at a pH of about 0.5, and most preferably at a pH of about 0.3 or less are efficacious in the solubilization and removal of limscale deposits, viz., stains, on hard surfaces. Most desirably the urea salt is urea hydrochloride.

e . . . . . * In particularly preferred embodiments, the inventive compositions are shelf stable aqueous cleaning and disinfecting composition which do not undesirably degrade when subjected to an elevated temperature over an extended period of time. More specifically, the inventive compositions do not suffer precipitation or phase separation when a sample composition is subjected to an accelerated ageing testing at 120 F, for a two week, preferably a four week test period. As is known to the art, such a test is a harsh test, and a useful indicator of the long term shelf stability of the tested sample composition.

In further particularly preferred embodiments, the preferred embodiments of the invention exhibit excellent freeze/thaw stability characteristics with little or no discoloration of the composition following at least 2, preferably at least 3 freeze thaw cycles. Most preferably the light transmittance loss subsequent to the at least 2, preferably at least 3 freeze thaw cycles is not more than 7%, preferably not more than 5% of the original light transmittance of a sample of the inventive composition prior to subsequent freeze/thaw cycles.

The inventive compositions may be produced according to any of a number of methods. In general terms, the components can be added in any order although it may be preferred to add first a major proportion of the water, then any detersive surfactants present, followed by the remaining constituents and ultimately the remaining balance of water required to produce 100%wt. of the composition.

Preferably the addition of the constituents to the water is e a. . . . . done under continuous stirring so to ensure homogeneity of the final composition.

Preferably however, the compositions are produced by first supplying the urea to a major proportion of the water, followed by the acid constituent which is used to form the urea salt under stirring, at any convenient temperature, e.g. room temperature (20 C, 60 F) and thereafter the surfactants are added, and ultimately the remaining constituents including fragrance, and any remaining balance of water needed 100%wt. of the compositions.

The compositions of the present invention can be used as a ready to use composition, supplied in a pour bottle or trigger bottle having a trigger pump spray device, from which it may be dispensed in a ready-to-use form. The compositions of the present invention exhibit good cleaning properties against dirt and stains commonly found in household, commercial and residential settings, particularly in lavatory settings wherein limescale, soap scum stains and rust stains are frequently encountered.

Examples of hard surfaces to which the invention can be applied include surfaces composed of refractory materials such as: glazed and unglazed tile, porcelain, ceramics as well as stone including marble, granite, and other stones surfaces; glass; metals; plastics e.g. polyester, vinyl; Fiberglas, Formica@, Corian and other hard surfaces known to the industry. Hard surfaces which are to be particularly denoted are lavatory fixtures such as shower stalls, bathtubs and bathing appliances (racks, shower doors, shower bars) toilets, bidets, wall and ë .

s. . . . ..

. . . flooring surfaces especially those which include refractory materials and the like. Further hard surfaces which are to be denoted include painted surfaces and those associated with kitchen environments and other environments associated S with food preparation, including cabinets and countertop surfaces as well as walls and floor surfaces especially those which include refractory materials, plastics, Formica, Corian and stone. As noted the compositions are particularly useful in the cleaning and maintenance of hard surfaces and articles upon which limescale, soap scum stains and rust stains are prone to form or collect.

Whereas the present invention is intended to be produced and provided in the "ready-to-use" form described above, nothing in this specification shall be understood as to limit the use of the composition according to the invention with a further amount of water to form a cleaning solution therefrom. In such a proposed diluted cleaning solution, the greater the proportion of water added to form said cleaning dilution, the greater may be the reduction of the rate and/or efficacy of the thus formed cleaning solution in the cleaning of a hard surface. Accordingly, longer residence times upon the soil to effect their loosening and/or the usage of greater amounts may be necessitated. Such further diluted cleaning compositions may be easily prepared by diluting measured amounts of the compositions in further amounts of water by the consumer or other end user in certain weight ratios of composition: water, and optionally, agitating the same to ensure even distribution of the composition in the water. The aqueous compositions according to the invention may be used without . . e. e further dilution, but may also be used with a further aqueous dilution, i.e., in composition:water concentrations of 1:0, to extremely dilute dilutions such as 1:10,000.

Desirably however, in order to ensure disinfection the compositions should be used "as is", that is to say without further dilution. However, aqueous dilutions, i.e., composition:water of concentrations of 1:1-10 may provide good cleaning efficacy, but may require longer contact times in order to provide a satisfactory cleaning effect.

The actual dilution selected is in part determinable by the degree and amount of dirt and grime to be removed from a surface(s), the amount of mechanical force imparted to remove the same, as well as the observed efficacy of a particular dilution. Generally better results and faster removal is to be expected at lower relative dilutions of the composition and the water, with the best results expected when the inventive compositions are used without further dilution with water.

The composition of the present invention, whether as described herein or in a concentrate or super concentrate form, can also be applied to a hard surface by using a wet wipe. The wipe can be of a woven or non-woven nature.

Fabric substrates can include nonwoven or woven pouches, sponges, in the form of abrasive or non-abrasive cleaning pads. Such fabrics are known commercially in this field, and are often referred to as wipes. Such substrates can be resin bonded, hydroentanged, thermally bonded, meltblown, needlepunched or any combination of the former.

The nonwoven fabrics may be a combination of wood pulp fibers and textile length synthetic fibers formed by well . . . e . e known dry-form or wet-lay processes. Synthetic fibers such as rayon, nylon, orlon and polyester as well as blends thereof can be employed. The wood pulp fibers should comprise about 30 to about 60 percent by weight of the nonwoven fabric, preferably about 55 to about 60 percent by weight, the remainder being synthetic fibers. The wood pulp fibers provide for absorbency, abrasion and soil retention whereas the synthetic fibers provide for substrate strength and resiliency.

The substrate of the wipe may also be a film forming material such as a water soluble polymer. Such self supporting film substrates may be sandwiched between layers of fabric substrates and heat sealed to form a useful substrate. The free standing films can be extruded utilizing standard equipment to devolatilize the blend.

Casting technology can be used to form and dry films, or a liquid blend can be saturated into a carrier and then dried in a variety of known methods.

The compositions of the present invention are absorbed onto the wipe to form a saturated wipe. The wipe can then be sealed individually in a pouch which can then be opened when needed or a multitude of wipes can be placed in a container for use on an as-needed basis. The container, when closed, is sufficiently sealed to prevent evaporation of any components from the compositions.

The following examples illustrate the superior properties of the formulations of the invention and particular preferred embodiments of the inventive compositions. The terms "parts by weight" or "percentage weight" are used interchangeably in the specification and # # he in the following Examples wherein the weight percentages of each of the individual constituents are indicated in weight percent based on the total weight of the composition, unless indicated otherwise.

While described in terms of the presently preferred embodiments, it is to be understood that the present disclosure is to be interpreted as by way of illustration, and not by way of limitation, and that various modifications and alterations apparent to one skilled in the art may be made without departing from the scope and spirit of the present invention. Examples 'provided below are to be understood as merely illustrative of the instant invention, and not are not be understood as limiting the present inventive concept.

Examples

The following examples illustrate the formulation and performance of various compositions of the invention, as well as certain particularly preferred embodiments of the invention. These exemplary formulations described in more detail in Tables lA-lJ below were formulated generally in accordance with the following protocol. Unless indicated otherwise, the weight percentages indicated the "as supplied" weights of the named constituent.

Into a suitably sized vessel, a measured amount of water was provided at room temperature, and under constant stirring was added the following sequence: urea, acid constituent, surfactants and the balance of the remaining constituents. All of the constituents were supplied at room temperature, and any remaining amount of water was . . . . - . . e ..

e e added thereafter. Mixing, which generally lasted from 5 minutes to 120 minutes was maintained until the particular exemplary formulation appeared to be homogeneous. The exemplary compositions were readily pourable, and retained S well mixed characteristics (i.e., stable mixtures) upon standing for extend periods. Particularly preferred compositions of the invention demonstrated good stability under accelerated ageing testing as described previously.

. . . . . _, . -- N N - o m I V di, CD.- -.m, , O, O, 0111 - V tl _. - 1 __ o _ O _. I _I p3, o, ua, , rn, r, om v N. Ir' O _ Ul N O O O o' . V r,0\ Ul 0\, O, U) N O N O I V O _. . _ o _ O - 1 I =1 _ 1D N O O V 0. . N_ _. N O O O I V a:, , . . N, _. N O N O I V r _ oN ul aY N, , 1) N O O V r _ N _ o N _ _, N O O O I V 11 N l O N l I 10 N o l O I V N _ o N _- In, O o I V [] N -o N NO O O I V N N _ o --- N O O I V 0 m 0 rl N= U O U V . . . . . . . N- r NIT __ o_ o O. V N- r cl l l l 00 0. v ' ' ' ' .

_ _ _ _ N O V

to _ -N _1 l l O O O it, N - r N _ _ O l O O V [13. . , , __, O -1 _ _m 0\ U. 111 _ _.

:1f . . .. . . . . . . . . . . . .. . . . . . Table 1C = = = = = = = = = E27 E28 E29 E30 E31 E32 E33 E34 E35 HCl (30.9%) 6.4 6.4 6.4 6.4 __ __ __ __ __ HCl (32.01%) __ __ __ __ 6.2 6. 2 6.2 6.2 6.2 5 5 5 5 urea 3.2 3.2 3.2 3.2 3.2 3.2 3.2 3.2 3.2 g g g g g g I_g. g TOMADOL 91-6 0.5 1.0 __ 1.0 __ 1.0 0.5 __ __ MIRATAINE CBS 2.0 2. 0 2.0 2.0 2.0 2.0 a.o 2.0 2.0 (43.5%) MIRANOL CS cone. 1.0 1.0 1.0 1.0 1. 0 1.0 1.0 1.0 1.0 (45%) DOWANOL DPnB 2.0 2.0 2.0 1.0 2.0 1.0 1.0 1.0 1.0 DOWANOL DPM __ __ 1.0 __ __ __ __ __ __ fragrance 0.3 0.3 0.3 0.3 __ 0.3 0.3 0.3 0.3 (proprietary) water q.s q.s q.s q.s q.s q.s q.s q.s q.s pH of cl <1 <1 <1 <1 <1 <1 <1 <1 composition _ Table 1D = = = = = = = = E36 E37 E38 E39 E40 E41 E42 E43 HCl (32.01%) 9.8 9.8 9.8 9.8 9.8 9.8 9.8 9.8 4 4 4 4 4 4 4 4 urea 5.1 5.1 5.1 5.1 5.1 5.1 5.1 5.1 9 9 9 9 9 9 9 9 PLURAFAC SL-62 = 1.0 1.0 3.0 3.0 1.0 1.0 2.0 TOMADOL 91- 6 1.0 1.0 3.0 3.0 1.0 1.0 3.0 2.0 MIRATAINE CBS 2.0 __ __ __ __ __ __ __ eee eee .

e e e e e e eee e e e a e e e e e e ee e e e - MIRANOL CS 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 cone. (45%) DOWANOL DPnB l.0 1. 0 1.0 1.0 1.0 1.0 1.0 1.0 DOWANOL DPM __ 1.0 5.0 5.0 5.0 5.0 1.0 3.0 fragrance 0.3 0.1 0.1 0.1 0.1 0.1 0.1 0.1 (proprietary) water q.s q.s q.s q.s q.s q.s q.s q.s pH of <1 <1 <1 <1 <1 cl <1 <1 composition Table 1E = = = = = = = = E44 E45 E46 E47 E48 E49 E50 E51 HCl (32.01%) 9.8 9.8 9.8 9.8 9.8 9.8 9.8 9.8 4 4 4 4 4 4 4 4 urea 5.1 5.1 5.1 5.1 5.1 5.1 5.1 5.1 9 9 9 9 9 9 9 9 PLURAFAC SL-62 3.0 3.0 1.5 3.0 __ 3.0 __ __ TOMADOL 91- 6 3.0 1.0 1.5 __ __ __ 3.0 3.0 MIRANOL CS 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 cone. (45) DOWANOL DPnB 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 DOWANOL DPM 1.0 1. 0 3.0 1.0 5.O 5.O 5.O 1.0 fragrance 0.3 0.1 0.1 0.1 0.1 0.1 0.1 0.1 (proprietary) water q.s q.s q.s q.s q.s q.s q.s q.s pH of <1 <1 <1 <1 <1 <1 <1 <1 composition c c.e......

c c c c c c c c c c c c . .

Table 1F l l l l I -

1 E521 E53 1E54 1E55 1E56 1E57 T E58 1E59 HC1 (32.01%) 9.8 9.8 9.8 9.8 9. 8 9.8 9.8 9.8 9.8 4 4 4 4 4 4 4 4 4 urea 5.1 5.1 5.1 5.1 5.1 5.1 5.1 5.1 5.1 9 9 9 9 9 9 9 9 9 PLURAFAC SL-62 1.0 2.0 1.0 3.0 3.0 1.0 3.0 3.0 1.0 STEPANOL WAC 3.0 2.0 1.0 3.0 1.0 3.0 3.0 1.0 1.0 MIRANOL CS 1.0 1.0 1.0 1. 0 1.0 1.0 1.0 1.0 1.0 cone. (45%) DOWANOL DPnB 3.0 2.0 1.0 3.0 1.0 1.0 1. 0 3.0 3.0 fragrance 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 (proprietary) water q.s q.s q.s q.s q.s q.s q.s q.s q.s pH of <1 <1 <1 <1 <1 <1 cl <1 <1 composition

Table 1G

_

E61 E62 E63 E64 E65 E66 E67 E68 E69 E70 HCl (32.01%) 9.8 9.8 9.8 9.8 9. 8 9.8 9.8 9.8 9.8 9.8 4 4 4 4 4 4 4 4 4 4 urea 5.1 5.1 5.1 5.1 5.1 5.1 5.1 5.1 5.1 5.1 9 9 9 9 9 9 9 9 9 9 PLURAFAC SL-62 1.0 __ __ 1.0 1.0 __ 0.5 __ 1.0 __ TOMADOL 91-6 _ = = 1.0 1.0 1.0 0.5 1.0 __ __ MIRATAINE H2C- 5.0 3.0 5.0 5. 0 3.0 3.0 4.0 5.0 3.0 3.0 HA (30%) DOWANOL DPnB 1.0 1.0 3.0 3.0 3.0 3.0 2. 0 3.0 3.0 3.0 ... ... . . fragrance 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0. 1 0.1 (proprietary) water q.s q.s q.s q.s q.s q.s q.s q.s q.s q.s pH of <1 cl cl cl cl cl cl cl cl cl composition

Table 1H

E71 E72 E73 E74 E75 E76 E77 HCl (32.01%) 9.84 9.8 9.8 9.8 9.8 9.8 9.84 urea 5.19 5.1 5.1 5.1 5.1 5.1 5.19 GLUCOPON 225 3.0 3.0 3.0 __ __ __ __ ALFONIC 810-4.5 __ 1.0 1.0 3.0 3.0 3.0 3.0 STEOL CS ____ __ 10. __ __ __ 330(28.5%) 0 STEOL CS ____ __ __ 11. __ __ 130(25.3%) 26 STEOL CS ____ __ __ __ 11. __ 230(25.5%) 18 STEOL CS 460(59%) __ __ __ __ __ __ 4.83 DOWANOL DPnB _ __ 1.0 __ _ __ __ fragrance 0.1 0.1 0.1 0.1 0.1 0.1 0.1 (proprietary) water q.s. q.s q.s q.s q.s q.s q.s.

pH of composition cl <1 cl <1 <1 <1 cl . ......

. . . .e.

. .

Table 1I

E78 E79 E80 E81 E82 E83 E84 HCl (32.01% ) 9.84 9.84 9.84 9.84 9.84 9.84 9. 84 urea 5.19 5.19 5.19 5.19 5.19 5.19 5.19 GLUCOPON 425 4.0 4.0 4.0 4.0 4. 0 4.0 4.0 ALFONIC 810-4.5 3.0 3.0 3.0 3.0 3.0 3.0 3.0 isopropanol 2.0 2. 0 2.0 2.0 2.0 2.0 2.0 fragrance 0.1 0.15 0.15 0.15 0.2 0.3 0.3 (proprietary) water q.s. q.s. q.s. q.s. q.s. q.s. q.s.

pH of <1 <1 <1 <1 <1 <1 <1 composition

Table 1J = =

E85 E86 E87 E88 E89 E90 HCl (32.01%) 9.84 9.84 9.84 9.84 9.84 9.84 urea 5. 19 5.19 5.19 5.19 5.19 5.19 DOWFAX 3B2 2.5 __ __ _ _ __ __ GLUCOPON 425 __ 1.0 1.0 4.0 4.0 2.0 ALFONIC 810-4.5 2.0 3.0 1.0 1.0 3.0 2.0 isopropanol _ 2.0 2.0 2.0 2.0 2.0 fragrance 0.15 0.15 0.15 0.15 0.15 0.15 (proprietary) water q.s. q.s. q.s. q.s. q.s. q.s.

pH of <1 <1 <1 <1 <1 <1 composition The individual constituents indicated as "%wt." on the foregoing tables were used "as supplied" from their respective manufacturer or supplier. The percent actives of each individual constituent are understood to be 100%wt, a.. .e ate a* ce a a * e a a e. a a a unless otherwise indicated on the foregoing Tables 1A through 1J, or on the following Table 2 which more specifically identifies the individual constituents used.

For each composition, deionized water or 'soft water' was added in "quantum sufficient" to provide compositions having 100%wt. The identity of the particular constituents is indicated on Table 2.

Table 2

constituent Identity, %wt. active HCl (36.5%) aqueous hydrochloric acid, 36.5%wt.

active HCl HCl (32.01%) aqueous hydrochloric acid, 32.01%wt.

active HCl urea powdered, laboratory grade, 100%wt.

active PLURAFAC SL-62 EO/PO block copolymer, 100%wt. active TOMADOL 91- 6 C,-C1l linear primary alcohol ethoxylate, avg. 6 mole EO (ex. Sasol) ALFONIC 810-4.5 C8-C10 linear primary alcohol ethoxylate, avg. 4.5 mole EO (ex. Sasol) STEPANOL WAC (29%) anionic sodium lauryl sulfate, 29%wt.

active, (ex. Stepan) DOWFAX 3B2 (45%) diphenyl oxide disulfonate, 45%wt.

active, (ex. Dow Chemical Co.) 13IOSOFT D-40 sodium dodecylbenzene sulfonate (40%wt.

active) STEOL CS lauryl ether sulfate, sodium salt 330(28.5%) (28.5%wt. active) STEOL CS lauryl ether sulfate, sodium salt 130(25.3%) (28.5%wt. active)

. ... ... . ...DTD: e ae e STEOL CS lauryl ether sulfate, sodium salt 230(25.5%) (28.5%wt. active) STEOL CS 460(59%) lauryl ether sulfate, sodium salt (28.5%wt. active) MIRATAINE CBS cocoamidopropyl hydroxysultaine (43.5%) (43.5%wt. active) MIRANOL CS cone. sodium cocoamphohydroxypropyl sulfonate (45%) (45%wt. active) MIRATAINE H2C-HA sodium lauriminodipropionate (30%wt.

(30%) active) GLUCOPON 425 C-C16 alkylpolyglycosides (ex. Cognis) DOWANOL DPnB dipropylene glycol n-butyl ether, 100%wt. active, (ex. Dow Chemical Co.) DOWANOL DPM dipropylene glycol methyl ether, 100%wt.

acive (ex. Dow Chemical Co.) isopropanol laboratory grade, 100%wt. active fragrance proprietary composition of its (proprietary) respective supplier water distilled water or soft water Certain of the foregoing compositions were evaluated for their cleaning performance on various soils and stains, as well as for storage stability under accelerated ageing conditions as well as freeze/thaw stability. The performance of known art compositions were also evaluated in certain tests for purposes of comparison.

Soap scum removal evaluation: The soap scum removal characteristics of certain example formulations described on Table 1 were evaluated, as well that of several commercially available consumer L b a, products which were used as comparative examples. The test is generally in accordance with the protocols outlined in CSMA Designation DCC-16 (May 1995).

This test is described generally as follows: First, a "parent" soil is made, based on the following formulation: "Parent" soil % w/w bar soap 3.90 shampoo 0.35 clay 0.06 artificial sebum 0.15 hard water 95.54 The parent soil was produced according to the following steps: First, the bar soap was shaved into a suitable beaker, after the remaining constituents, were added in the order given above and stirred with three-blade propeller mixer. Next, the contents of the beaker was heated to 45- 50 C and mixed using a motorized three-blade propeller mixer until a smooth, lump-free suspension is achieved.

This usually required about two hours with moderate agitation. Subsequently, the contents of the beaker were filtered through a Buchner funnel fitted with Whatman #1 filter paper or equivalent. The filtrate was then resuspended in clean, deionized water, using the same amount of water used to make the soil, and this was filtered again. The (re- filtered) filtrate was uniformly dried overnight at 45 C to form a filter cake. Thereafter, the filter cake was pulverized and was suitable for immediate use, or may be stored in a sealed container for up to six months.

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As test substrates, 4 inch by 4 inch black ceramic bathroom tiles were used. Each of the tiles as thoroughtly washed (using a commercially available hand dishwashing detergent) and rinsed, then washed with isopropyl alcohol.

The washed tiles were then permitted to dry overnight at room temperature. Each tile was then weighed, and the mass recorded.

In preparation for supplying the tiles with an amount of the test soil, a test soil was prepared based on the following formulation: Test soil: %w/w "parent" soil 4.50 hard water 9.0 hydrochloric acid (O.lN) 0.77 acetone 85.73 The test soil was produced according to the following steps: The constituents indicated were introduced into a clean beaker, with the acetone being added prior to the water, and the 'parent' soil being added last. The contents of the beaker were mixed using a standard three blade laboratory mixed until the contents formed a uniform mixture, and the color changed from white to gray. This typically required 20-40 minutes, during which time the beaker should have been covered as much as possible to avoid excessive solvent loss. Next, a suitable quantity of the contents of the test soil from the beaker were provided to an artist's airbrush while the beaker was swirled to ensure a soil uniformity. (If testing required . ;2.;..

more than one day, a fresh amount of test soil was prepared daily and used for that day's testing.) Soil was applied to a number of clean, dry tiles may be placed into rows and columns in preparation for depositing of the test soil. The airbrush was operated at psi, and the test soil was sprayed to provide a visually uniform amount of soil onto the tiles. (Uniform soil suspension during application was maintained by continuous brush motion and/or swirling of test soil in the airbrush.) In this manner, approximately O.lOg-0.12g of the test soil were applied per tile. Subsequently each of the coated tiles were then allowed to air dry for approximately 30 minutes. Thereafter each tile was placed in a laboratory oven having a temperature of 205 C for 30 minutes to further treat the coated tiles. Subsequently the tiles were removed and permitted to cool to room temperature.

To evaluate cleaning, 2 tiles were treated with each tested composition in order to evaluate its efficacy in removing soap scum from the prepared tile substrates. In the test, prepared tile substrates were secured within a Gardner Abrasion Tester, and thereafter 2 grams of a test composition was applied by pipetting to the soiled surface of a tile, which was allowed to stand for 30 seconds.

Thereafter the a Gardner Abrasion Tester was cycled 10 times with a clean moistened sponge, and then the tile was immediately removed and rinsed in a stream of cold running tap water for 20 - 30 seconds. Subsequently, the rinsed tile was allowed to dry at room temperature in a rack which stood the tile on one side thereof.

The dried tested tile was then evaluated using a Tri Gloss meter at 60 degrees, and 16 readings were taken at ..e;; randomly selected points of the cleaned surface in order to determine surface reflectance. According to the reflective means, the percentage of soap scum removal from each tile was determined utilizing the following equation: % Removal = RC - RS X 100

RO - RS where

RC = Reflectance of tile after cleaning with test product RO = Reflectance of original soiled tile RS = Reflectance of soiled tile The results of this evaluation was averaged for each of the tested compositions, and the results of the evaluation are reported on the following table.

Product or composition %soap scum removal E85 85.93 E89 66.9 MR. Propre (Belgium) (ex. Procter & 65.52 Gamble Co.) Mr. Muscle (UK) (ox. SC Johnson) 59.81 Kaboom (ex. Orange Glo 74.62 International) CLR (ex. Jelmar Co.) 39.75 The reported results illustrate that compositions according to the present invention exhibited soap scum removal efficacy comparable to or superior to tested commercially available cleaning products. so

Hard water stain removal evaluation: The soap scum removal characteristics of certain example formulations described on Table 1 were evaluated, as well that of several commercially available consumer products which were used as comparative examples.

This test is described generally as follows: A "Solution A" was made, based on the following formulation: Solution A % w/w sodium bicarbonate 3. 0 anhydrous sodium 4.0 metasilicate deionized water 93.0 A "Solution B" was made, based on the following formulation: Solution B I% w/w anhydrous calcium 2.0 chloride magnesium chloride 6H2O 1.0 ethanol (95%) 24.0 deionized water 73.0 As test substrates, 4 inch by 4 inch black ceramic bathroom tiles were used. Each of the tiles was thoroughly washed (using a commercially available hand dishwashing detergent) and rinsed, then washed with isopropyl alcohol.

The washed tiles were then permitted to dry overnight at room temperature.

A number of clean, dry tiles was placed into rows and columns on a flat surface in preparation for depositing of the test soil. An airbrush was operated at approximately psi, and Solution B was sprayed onto the surface of the tiles to form a uniform coating. These tiles were immediately dried by applying a stream of heated air from the laboratory blow dryer and drying continued until white spots were visible on the surface of the tiles. Thereafter Solution A was sprayed onto the surface of the tiles to form a uniform coating on the layer of dried material deposited by Solution B. Immediately thereafter the tiles were dried by applying a stream of heated air from the laboratory blow dryer, and thereafter each tile was rinsed for a few seconds in a stream of room temperature deionized water. The surface water on the rinsed tiles was then dried by use of a laboratory blow dryer, and thereafter each tile was allowed to dry for 24 hours at room temperature.

To evaluate cleaning, 2 tiles were treated with each tested composition in order to evaluate its efficacy in removing hard water stains from the prepared tile substrates. In the test, prepared tile substrates were secured within a Gardner Abrasion Tester, and thereafter 2 grams of a test composition was applied by pipetting to the soiled surface of a tile, which was allowed to stand for 15 seconds. Thereafter the a Gardner Abrasion Tester was cycled 6 times with a clean moistened sponge, and then the tile was immediately removed and rinsed in a stream of cold running tap water for 20 - 30 seconds. Subsequently, the rinsed tile was allowed to dry at room temperature in a rack which stood the tile on one side thereof.

The dried tested tile was then evaluated using a Tri- Gloss meter at 60 degrees, and 16 readings were taken at randomly selected points of the cleaned surface in order to determine surface reflectance. According to the reflective means, the percentage of soap scum removal from each tile was determined utilizing the following equation: % Removal = RC - RS X 100

RO - RS where

Product or composition %hard water stain removal E85 36.13 E89 40.76 MR. Propre (Belgium) (ex. Procter 40.02 Gamble Co.) Mr. Muscle (UK) (ex. SC Johnson) 29.63 Kaboom (ex. Orange Glo 38.90 International) CLR (ex. Jelmar Co.) 43.29 The reported results illustrate that compositions according to the present invention exhibited hard water stain removal efficacy comparable to the tested commercially available cleaning products.

Limescale Removal Evaluation S The limescale removal characteristics of certain example formulations described on Table 1 were evaluated, as well that of several commercially available consumer products which were used as comparative examples.

Natural marble cubes (3/4 inch x 3/4 inch x 3/8 inch) were thoroughly rinsed with deionized water, then dried at 105 C for one hour and then allowed to cool to room temperature. Each of the dried marble cubes was weighed on an analytical balance, and the initial mass was recorded. For each tested composition or product, a 40 gram aliquot was provide to a clean laboratory jar. A pre- weighed, dried marble cube was immersed for 60 seconds, then removed an immediately rinsed in a stream of room temperature deionized water for 30 seconds. The treated and rinsed marble cube was then dried at 105 C for one hour, allowed to cool to room temperature and then reweighed in order to evaluate the amount of mass lost.

For each tested product or composition, five replicates (cubes) were used and the averaged result for the five replicates used to evaluate limescale efficacy for each particular composition or product was calculate, and is reported on the following table.

2".2. 22 ''. 2.

Product or composition %wt. of marble cube (lime) dissolved E85 0.52284 E89 0.48665 MR. Propre (Belgium) (ex. Procter & 0.02748 Gamble Co.) Mr. Muscle (ex. SCJohnson) 0.01893 Kaboom (ex. Orange Glo 0.49888 International) CLR (ex. Jelmar Co.) 0.32459 As can be seen from the foregoing, the examples of inventive compositions provided comparable performance, and in some cases superior performance to other commercially available consumer cleaning products with respect to limescale removal efficacy.

Rust removal evaluation: Certain compositions were evaluated for their efficacy in the removal of rust stains from hard surfaces generally in accordance with the following protocol.

A standardized test soil was prepared by combining 98%wt.

deionized water at room temperature with 2% ferric chloride which was mixed until a uniform soil composition was formed.

As substrates, a series of standard white 4 1/4 inch square ceramic tiles were used. The white surfaces of the tiles were cleaned with isopropanol and dried overnight at room temperature. The reflectance reading of each of the tiles was evaluated using a Minolta Reflectometer CR-231.

22 . c2 e.'..e Next, the dried tiles were placed on a flat surface, and using a fine mist sprayer an even coating of the uniform soil composition was applied to the exposed surfaces of the tile. Immediately after this application, a stream of heated air provided by a laboratory grade blow dryer was passed over the coated surfaces until a light brown color was observed on each of the tiles.

Subsequently a 1% NaOH aqueous solution was applied to the dried tile surfaces using a fine mist sprayer and again, thereafter the tile surfaces were dried by using the laboratory grade blow dryer as noted above. The tiles were then allowed to cool to the touch, and then each was rinsed under a stream of tap water and then again dried by using the laboratory grade blow dryer as noted above. The reflectance reading of the each of the prepared, soiled tiles was again evaluated To evaluate rust removal efficacy, 2 grams of each test composition was applied by pipetting to the soiled surface of a tile, and allowed to stand for 10 minutes.

Thereafter the tile was rinsed in a stream of cold tap water for 10 15 seconds, then the tile was placed in a Gardner Abrasion Tester and secured. A moistened sponge was placed in the holder of the Tester, and the device was cycled once. Thereafter the tile was removed and the surface reflectance, an indicator of the rust removal efficacy of the tested composition was evaluated a Minolta Reflectometer CR-231 in order to determine the change in reflectance between the original reflectance value of the soiled bathroom tile, and the reflectance of a soiled tile which was cleaned using a quantity of a tested composition in accordance with the test protocol described above.

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According to the reflective means, the percentage of rust removal was determined utilizing the following equation: % Removal = RC - RS X 100

RO - RS where

RC = Reflectance of tile after cleaning with test product RO = Reflectance of original soiled tile RS = Reflectance of soiled tile For each tile, three readings were taken and the results averaged to provide a median reading for each tile.

Two tiles were used to evaluate each of the tested compositions and the average reading for each tile, as well as the averaged reflectance reading for both tiles treated using a particular test composition is reported on the

following table.

Product or composition % rust removed E85 70.93 E89 68.56 MR. Propre (Belgium) (ex. Procter & 26.42 Gamble Co.) Mr. Muscle (UK) (ex. SC Johnson) 28.17 Kaboom (ex. Orange Glo 53.37 International) CLR (ex. Jelmar Co.) 43.77 From the foregoing, it can be seen that the compositions according to the present invention provided superior rust 2. 2;e removal performance to known art, commercially available cleaning products.

Cleaning Evaluation The cleaning characteristics of certain example formulations described on Table 1 were evaluated, as well as the cleaning efficacy of several commercially available consumer products which were used as comparative examples.

Cleaning evaluations were performed in accordance with the testing protocol outlined according to ASTM D4488 A2 Test Method, which evaluated the efficacy of the cleaning compositions in removing greasy soil on masonite wallboard samples painted with wall paint. The soil applied was a greasy soil sample containing: Test Greasy Soil %w/w

Vegetable oil 33

Vegetable shortening 33 Lard 33 Carbon black 1 which were blended together to homogeneity under gentle heating to form a uniform mixture which was later allowed to cool to room temperature. The sponge (water dampened) of a Gardner Abrasion Tester apparatus was squirted with a gram sample of a tested cleaning composition, and the apparatus was cycled 10 times. The test was replicated 2 times for each tested composition. The tiles were dried, and then the cleaning efficacy was evaluated.

Each dried tested tiles was evaluated using a Tri Gloss meter at 60 degrees, and 3 readings were taken at l22.. ;... ss

randomly selected points of the cleaned surface in order to determine surface reflectance. According to the reflective means, the percentage of soap scum removal from each tile was determined utilizing the following equation: % Removal = RC - RS X 100

RO - RS where

Product or composition soil removed (mean value) E85 60.77 E89 72.96 MR. Propre (Belgium) (ex. Procter & 73.91 Gamble Co.) Mr. Muscle (UK) (ex. SC Johnson) 70.01 Kaboom (ex. Orange Glo 70.24 International) CLR (ex. Jelmar Co.) 55.22 From the foregoing, it can be seen that the compositions according to the present invention provided 22...

comparable or superior cleaning performance to known art, commercially available cleaning products.

Room Temperature Stability evaluation: The colorfastness of certain example formulations described on Table 1 were evaluated, as well as the cleaning efficacy of a commercially available consumer product, "Kaboom", which was used as a comparative examples. The test evaluated the colorfastness of the tested compositions when stored in clear glass containers (jars) at room temperature conditions for 4 weeks under ambient light conditions (mixed fluorescent lamps, and natural daylight) on a laboratory benchtop.

Samples of the tested compositions were evaluated visually for color, as well as for W absorption within the wavelength spectrum of 800 nm nm.

The results of the visual observation of the samples is outlined on the following table: Sample: Visual appearance: E85, initial sample colorless E85, subsequent to storage at room colorless temperature for 4 weeks in clear glass jar Kaboom' trigger spray formulation colorless provided in dark purple bottle, initial sample Kaboom' trigger spray formulation golden yellow provided in dark purple bottle, subsequent to storage at room temperature for 4 weeks in clear glass jar Deionized water colorless As is apparent from the foregoing, the commercial product suffered degradation when stored in a transparent container over a four week period.

Each of the foregoing samples were evaluated W absorption within the wavelength spectrum of 800 nm - 190 nm. Except for the sample which appeared as "golden yellow" indicated on the foregoing table, which exhibited a distinctive large peak at 300 nm, which is the wavelength for yellow color, No other sample had any significant peaks in the visible light range.

As is apparent from the foregoing, the compositions according to the present invention exhibited superior lightfastness to the prior art, commercially available composition tested.

Accelerated Ageing (High Temperature Stability) evaluation: Compositions according to E85 and E89 were evaluated for their storage stability at elevated temperatures generally in accordance with the following protocol.

Samples of each formulation were held at 120 F for 4 weeks, and further samples of E85 and E89 were held at 105 F for 6 weeks. All the samples remained homogenous and are judged to exhibit good long term storage stability.

The foregoing examples below illustrate exemplary formulations as well as preferred embodiments of the invention. It is to be understood that these examples are provided by way of illustration only and that further useful formulations falling within the scope of the present invention and the claims may be readily produced by one ...e 2... ;.;..

skilled in the art without deviating from the scope and spirit of the invention.

....'... ;....

Claims

Claims: 1. Aqueous, acidic hard surface cleaning composition which

provides a cleaning benefit to a hard surface which comprises the following constituents: (a) a urea salt; (b) one or more detersive surfactants; (c) optionally, one or more organic solvents; (f) water.

wherein the aqueous compositions are at an highly acidic pH, namely a pH of 1.5 or less, preferably at a pH of about 1 or less, more preferably at a pH of about 0.5 or less, and most preferably at a pH of about 0.3 or less and wherein the aqueous compositions are efficacious in the solubilization and removal of limescale deposits, viz., stains, on hard surfaces.
2. The composition according to claim 1 wherein the urea salt is formed, in situ, in the cleaning composition.
3. Aqueous, acidic hard surface cleaning composition which provides a cleaning benefit to a hard surface which comprises (preferably consists essentially of) the following constituents: (a) a urea salt formed in situ in the composition; (b) one or more detersive surfactants selected from diphenyl oxide disulfonates, linear primary alcohol ethoxylates, and alkylpolyglcosides (c) one or more organic solvents; (d) water, and (e) optionally one or more optional constituents selected from fragrances, dyes and coloring agents, wherein the aqueous compositions are at highly acid pH, namely a pH of 1.5 or less, preferably at a pH of about 1, more preferably at a pH of about 0.5, and most preferably at a pH of about 0.3 or less and wherein the aqueous compositions are efficacious in the solubilization and remove of limscale deposits, viz., stains, or hard surfaces.
4. Aqueous, acidic hard surface cleaning composition which provides a cleaning benefit to a hard surface which comprises (preferably consists essentially of) the following constituents: (a) a urea salt formed in situ in the composition; (b) one or more detersive surfactants selected from diphenyl oxide disulfonates, alcohol ethoxylates, and alkylpolyglcosides; (c) one or more organic solvents; (d) water, and (e) optionally one or more optional constituents selected from fragrances, dyes and coloring agents, wherein the aqueous compositions are at highly acid pH, namely a pH of 1.
5 or less, preferably at a pH of about 1, more preferably at a pH of about 0.5, and most preferably at a pH of about 0.3 or less and wherein the aqueous compositions are efficacious in the solubilization and removal of limescale deposits, viz., stains, on hard surfaces 5. Aqueous acidic hard surface cleaning composition which provides a cleaning benefit to a hard surface which _ 16. ..

: . . : comprises (preferably consists essentially of) the following constituents: (a) a urea salt formed in situ in the composition; (b) as the sole detersive surfactants, one or more nonionic surfactants based on alcohol ethoxylates with at least one further surfactants selected from diphenyl oxide disulfonates, and alkylpolyglcosides; (c) one or more organic solvents; (d) water, and (e) optionally one or more optional constituents selected from fragrances, dyes and coloring agents, wherein the aqueous compositions are at highly acid pH, namely a pH of 1.5 or less, preferably at a pH of about 1, more preferably at a pH of about 0.5, and most preferably at a pH of about 0.3 or less are efficacious in the solubilization and removal of limscale deposits, viz., stains, on hard surfaces.
6. A composition according to any of claims 3 - 5 wherein the urea salt formed in situ is urea hydrochloride.
7. A composition substantially described with reference

to the Examples.
8. A process for the cleaning treatment of a hard surface in need thereof, comprising the step of: applying a cleaning effective amount of the composition according to claim 1 to said hard surface.

2, ' , . 2