WO2012042251A1

WO2012042251A1 - Adhesive lavatory treatment compositions

Info

Publication number: WO2012042251A1
Application number: PCT/GB2011/051818
Authority: WO
Inventors: Lydia Nycz; Diane Joyce Burt
Original assignee: Reckitt Benckiser Llc; Reckitt & Colman (Overseas) Limited
Priority date: 2010-10-01
Filing date: 2011-09-26
Publication date: 2012-04-05
Also published as: GB201016491D0

Abstract

A adhesive lavatory treatment compositions which are essentially anhydrous (comprise less than about 0.01%wt. water, preferably less than about 0.05% water, alternately and/or more preferably, comprise no water as an added constituent to the said compositions) and which comprise: about 1 - 25%wt, preferably about 5 - 25%wt. of an organic solvent constituent, about 5— 50%wt.of at least one surfactant, preferably an alkanolamide based nonionic surfactant; at least about 25%wt. of a primary adhesion promoter constituent based on one or more oxyalkylenated compounds which includes two or more different oxyalkylenated compounds, 0 - 5%wt. of at least one co-adhesion promoter; optionally one or more further optional constituents which may impart a further aesthetic or technical benefit to the said adhesive lavatory treatment compositions; wherein in use, the said adhesive lavatory treatment compositions may be applied and adhered to a dry ceramic surface, especially the interior sidewall in a toilet bowl or other lavatory appliance, and wherein the said adhesive lavatory treatment compositions is retained adhered to the said surface following a plurality of flushes of water impinging upon the adhered adhesive lavatory treatment compositions.

Description

ADHESIVE LAVATORY TREATMENT COMPOSITIONS

The present invention relates to adhesive lavatory treatment compositions which are adapted to be directly adhered to a art of a lavatory appliance, e.g., the inner sidewall of a toilet bowl.

An adhesive lavatory composition known to the art is that described in US Patent 6667286. Therein is disclosed a sanitary agent for direct application to a sanitary object to be cleaned comprising: an adhesion promoter selected from the group consisting of long and long-chained organic molecules, which are at least partly hydrophilic, and the hydrophilic part of the adhesion promoter interacts at least in part with the water molecules in the presence of water and becomes "sticky" which enables said agent to adhere to said sanitary object even after a large number of rinse actions; water; anionic and/or nonionic and/or amphoteric surfactants ("tensides"); and optional components selected from the group consisting of fragrances, thickeners, colorants, presei-vatives, and combinations thereof; wherein the viscosity of the agent is at least 15,000 mPas. That document recites that "The agent can be 'sticky' either through a certain water content already in the formulation to be applied or the adhesion can be obtained by a light dampening of the surface - for example, by activating the flush water - and then applying the agent.

Clearly while the compositions disclosed in US Patent 6667286 provide satisfactory performance characteristics, it is also clear that the sanitary agents necessarily require water in order to "become sticky" and thereby provide adhesion between the sanitary agent and a toilet bowl. A further review of this document reveals that the example compositions disclosed therein comprise 3 - 60%wt. of water as a necessary constituent.

Certain adhesive lavatory compositions are disclosed in EP 1 78080 Al . The compositions disclosed therein necessarily comprise at least 20%w , preferably at least 30%wt. of an adhesion promoter constituent. Thus while the ait proposes certain compositions which exhibit satisfactoiy performance under certain conditions, there remains a real and continued need in the ait for further improved lavatory treatment compositions which overcome shortcomings of prior art compositions.

The compositions of the adhesive lavatory treatment compositions address and overcome shortcomings of prior art lavatory treatment composition. These and further objects of the present invention will become apparent from a review of the following specification. Further, the compositions of the present invention exhibit excellent surface adhesion to diy surfaces, particularly to dry surfaces of lavatory appliances, e.g., toilets, bidets, urinals and the like, especially the inner sidewall of a toilet bowl.

Broadly, the present invention provides an adhesive lavatory treatment compositions which are essentially anhydrous (comprise less than about 0.01%wt. water, preferably less than about 0.05% water, alternately and/or more preferably, comprise no water as an added constituent to the said compositions) and which comprise:

about 1 - 25%wt, preferably about 5 - 25%wt. of an organic solvent constituent, which is liquid at room temperature (20°C);

about 5— 50%wt., preferably about 15— 30%wt. of at least one surfactant, which preferably is an alkanolamide based nonionic surfactant;

at least about least about 25%wt, preferably at least about 30%wt, yet more preferably at least about 40%wt. of a primary adhesion promoter constituent based on one or more oxyalkylenated compounds which includes two or more different oxyalkylenated compounds at least one of which is pasty or is solid at room temperature (20°C) and which preferably have different molecular weights, and preferably with each having a minimum molecular weight of about 500;

about 0— 5%wt. of at least one co-adhesion promoter;

optionally one or more further optional constituents which may impart a further aesthetic or technical benefit to the said adhesive lavatory treatment compositions;

wherein in use, the said adhesive lavatory treatment compositions may be applied and adhered to a dry ceramic surface, especially the interior sidewall in a toilet bowl or other lavatory appHance, and wherein the said adhesive lavatory freatment compositions is retained adhered to the said surface following a plurality of flushes of water impinging upon the adhered adhesive lavatory treatment compositions.

In a second aspect the present invention provides a viscous, extmdable adhesive lavatory treatment compositions which are essentially anhydrous (comprise less than about 0.01 %wt. water, preferably less than about 0.05 % water, alternately and/or more preferably, comprise no water as an added constituent to the said compositions) which may be applied and adhered to a dry ceramic surface, especially the interior sidewall in a toilet bowl or other lavatory appliance, and wherein the said adhesive lavatory treatment compositions is retained adhered to the said surface following a plurality of flushes of water impinging upon the adhered adhesive lavatory treatment compositions.

In a further aspect the present invention provides methods for the manufacture of the adhesive lavatory treatment compositions disclosed herein, as well as to methods for the use the disclosed adhesive lavatory treatment compositions in the treatment of lavatory appliances, and especially toilet bowls.

Further features and aspects of the present invention will become more apparent from a further reading of the present specification.

The inventive adhesive lavatory treatment compositions about 1 - 25%wt., preferably about 5 - 25%wt. of an organic solvent constituent, which is liquid at room temperature (20°C), which organic solvent constituent may be single organic solvent, or may be a mixture of blend of two or more organic solvents. By way of non-limiting example exemplary useful organic solvents which may be included are 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 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, ethylene glycol monobutylether, dipropylene glycol monomethylether, diethyleneglycol monobutylether), lower esters of monoalkylethers of ethylene glycol or propylene glycol (e.g. propylene glycol monomethyl ether acetate), and mixtures thereof. Glycol ethers having the general structure R_a-R_b-OH, wherein R_a is an alkoxy of 1 to 20 carbon atoms, or aryloxy of at least 6 carbon atoms, and Rb is an ether condensate of propylene glycol and/or ethylene glycol having from one to ten glycol monomer units. Of course, mixtures of two or more organic solvents may be used in the organic solvent constituent.

The organic solvent constituent may also be one or more polyalkylene glycols, especially polyethylene glycols, polypropylene glycols and polybutylene glycols having a molecular weight of at least about 200, preferably at least about 300 which are liquid at room temperature. Such polyalkylene glycols are preferred in certain embodiments as they show a high degree of chemical compatibility with the at oxyalkylenated compounds of the adhesion promoter constituent which is pasty or is solid at room temperature

(20°C). Of these, preferred are polypropylene glycols and polybutylene glycols which have branched alkylene moieties present within the molecule, e.g., branched

polypropylene glycols which may be represented by one or more of the following structures (a), (b), (c) and/or (d):

CH₂

I

HO(CH-CH₂0)_nH (a)

CH₃

HO(CH -CH₂-CH₂0)_nH

CH₃

HO(CH₂— CH-CH₂0)_nH (<

Examples of the foregoing, including further examples of useful polyalkylene glycols, having a molecular weight of at least about 200, preferably at least about 300 which are liquid at room temperature are commercially available within the Pluriol P series of materials (ex BASF), including Pluriol P 400 described to be a branched polypropylene glycol which is liquid at room temperature at 23 °C and having an average molecular weight of about 430, Pluriol P 600 described to be a branched polypropylene glycol which is liquid at room temperature at 23°C and having an average molecular weight of about 600, Pluriol P 900 described to be a branched polypropylene glycol which is liquid at room temperature at 23 °C and having an average molecular weight of about 900, Pluriol P 2000 described to be a branched polypropylene glycol which is liquid at room temperature at 23°C and having an average molecular weight of about 2000, and Pluriol P 4000 described to be a branched polypropylene glycol which is liquid at room temperature at 23 °C and having an average molecular weight of about 4000.

The organic solvent may also include one or more further liquids such as glycerine and paraffin oil, as well as petroleum distillates and/or petroleum products, such as mineral oil, paraffinic oils usually based on n-alkanes, naphthenic oils usually based on cycloalkanes, aromatic oils such as those based on aromatic hydrocarbons, as well as technical grade mixtures of hydrocarbons may be used as or in the organic solvent. Examples of the latter include paraffinic hydrocarbons including both linear and branched paraffinic hydrocarbons; the former are commercially available as NORPAR solvents (ex. ExxonMobil Corp.) while the latter are available as ISOPAR solvents (ex. ExxonMobil Corp.) Mixtures of branched hydrocarbons especially as isoparaffins form are also contemplated to be useful.

In accordance with certain preferred embodiments the organic solvent constituent is a single organic solvent, and preferably is a glycol ether, and other organic solvents are excluded. Especially preferably the organic solvent constituent comprises, preferably consists essentially of propylene glycol and/or a polyalkylene glycol having a molecular weight of at least about 200, preferably at least about 300 and further having branched alkylene moieties present within the molecule.

The organic solvent constituent comprises 1 - 25%wt. of the inventive compositions. Preferably, in order of increasing preference the organic solvent constituent is present in an amount of at least about 1%, 2.5%, 5%, 7%, 8%, 9%, 10%, by weight of the inventive composition of which they form a part. Preferably, in order of increasing preference the organic solvent constituent comprises not more than 25%, and in order of increasing preference, not more than about 24%, 22%, 20%, 19%, 18%, 17%, 16%, 15%, 14%, 13% and 12% weight of the inventive composition of which they form a art. Particularly preferred amounts of the organic solvent constituent are recited in one or more of the Examples, with preferred ranges of the organic solvent constituent also disclosed in the Examples.

The inventive adhesive lavatory treatment compositions also comprise about 5 - 50%wt, preferably about 15 - 30%wt. of at least one alkanol amide based nonionic surfactant compound. The at least one alkanolamide based nonionic surfactant compound(s) provide additional cleaning and concurrently also functions as a foam booster which improves the overall foaming characteristics of the inventive

compositions. Nonlimiting examples of such useful alkanolamides include one or more monoethanol amides, and diethanol amides of fatty acids having an acyl moiety which contains from about 8 to about 18 carbon atoms, and which may be represented in accordance with the formula:

i— CO— (H)_m.₁(R₂OH)₃-_m

where Ri represents a saturated or unsaturated aliphatic hydrocarbon radical of from about 7 to 21 carbon atoms, butpreferably from about 11 to 17 carbon atoms; R₂ represents a -CH₂- or -CH₂C3¾-, and m is an integer from 1 to 3, but is preferably 1. Preferably, Ri is a saturated or unsaturated aliphatic hydrocarbon radical comprising from about 11 to 17 carbon atoms, and m is 1. Specific examples of such compounds include mono-ethanol amine coconut fatty acid amide and diethanol amine dodecyl fatty acid amide. An exemplary useful and particularly preferred fatty acid amides include cocomonoethanol amide or cocodiethanolamide, which are presently commercially available as MONAMID CMA or MONAMID MDNA (ex. Mona Industries, Paterson NJ). Further exemplary useful alkanolamides which provide such functions include inter alia: cocamide MEA, cocamide DEA, soyamide DEA, lauramide DEA, oleamide MIPA, stearamide MEA, myristamide MEA, lauramide MEA, capramide DEA, ricinoleamide DEA, myristamide DEA, stearamide DEA, oleylamide DEA, tallowamide DEA, lauramide ΜΓΡΑ, tallowamide MEA, isostearamide DEA, isostearamide MEA, and mixtures thereof. Further useful alkanolamide surfactant compounds include alkanolamides, particularly fatty mono alkanolamides and fatty dialkanolamides, including one or more of those marketed under the Ninol® tradename.

A preferred alkanolamide based nonionic surfactant compound is Ninol® 40-CO (ex. Stepan Co.) which comprises at least 85%wt. of a coco fatty acid alkanolamide derived from diethanol amide and which also comprises about 8%wt. of 1, 2, 3- propanetriol (glycerine).

The inventive compositions comprise about 5 - 50%wt. of the said at least one alkanolamide based nonionic surfactant. In order of increasing preference, the at least one alkanolamide based nonionic surfactant compound at least about 5%, 7.5%, 10%, 12.5%, 15%, 16%, 17%, 18%, 19%, 20% by weight, based on the total weight of the inventive composition. In order of increasing preference, the at least one alkanolamide based nonionic surfactant compound of not more than about 50%, 45%, 40%, 35%, 32%, 30%, 29%, 28%, 27%, 26%, and 25% by weight, based on the total weight of the inventive composition of which the at least one alkanolamide based nonionic surfactant forms a part. Particularly preferred amounts of the at least one alkanolamide based nonionic surfactant are recited in one or more of the Examples.

In addition to the above required at least one alkanolamide based nonionic surfactant, the compositions may optionally but in certain cases preferably also include one or more further additional surfactants. Such may be selected from known art anionic surfactants, further nonionic surfactants other than the required alkanolamide based nonionic surfactant constituent, cationic surfactants, amphoteric surfactants and/or zwitterionic surfactants. One or more further nonionic surfactants are especially preferred. Virtually all known art nonionic surfactants may be included in the further optional nonionic surfactant constituent of the invention. Non-limiting and illustrative examples of suitable nonionic surfactants include, inter alia, condensation products of alkylene oxide groups with an organic hydrophobic compound, such as an aliphatic compound or with an alkyl aromatic compound. Many nonionic synthetic organic detergents generally are the condensation products of an organic aliphatic or alkyl aromatic hydrophobic compound and hydrophilic ethylene oxide groups. Practically any hydrophobic compound having a carboxy, hydroxy, amido, or amino group with a free hydrogen attached to the nitrogen can be condensed with ethylene oxide or with the polyhydration product thereof, polyethylene glycol, to form a water soluble nonionic detergent. Further, the length of the polyethenoxy hydrophobic and hydrophilic elements may be varied to adjust these properties. Illustrative examples of such nonionic surfactants include the condensation product of one mole of an alkyl phenol having an alkyl group containing from 6 to 12 carbon atoms with from about 5 to 25 moles of an alkylene oxide. Another example of such a nonionic surfactant is the condensation product of one mole of an aliphatic alcohol which may be a primary, secondary or tertiary alcohol having from 6 to 18 carbon atoms with from 1 to about 10 moles of alkylene oxide. Preferred alkylene oxides are ethylene oxides or propylene oxides which may be present singly, or may be both present.

Illustrative examples of nonionic surfactants include primary and secondary linear and branched alcohol ethoxylates, such as those based on C₆-Ci₈ alcohols which further include an average of from 2 to 80 mols of ethoxylation per mol of alcohol. Examples include the Genapol® series of linear alcohol ethoxylates from Clariant Corp., (Charlotte, NC.) The 26-L series is based on the formula RO(CH₂CH₂0)_nH wherein R is a mixture of linear, even carbon-number hydrocarbon chains ranging from Ci₂H₂₅ to Ci6H₃₃ and n represents the number of repeating units and is a number of from 1 to about 12. Further examples of useful nonionic surfactants include secondary Ci₂-Ci₅ alcohol ethoxylates, including those which have from about 3 to about 10 moles of ethoxylation. Such are available in the Tergitol® series of nonionic surfactants (ex. Dow Chemical, Midland, MI). Further exemplary nonionic surfactants include linear primary Cn-Cis alcohol ethoxylates, including those which have from about 3 to about 10 moles of ethoxylation. Such are available in the Tomadol® series of nonionic surfactants (ex. Tomah

Industries.). Still further exemplary nonionic surfactants include C₈-Ci₆ alcohol alkoxylates typically having between about 1-15 moles of ethoxylation, as available in the Tomadol® series of nonionic surfactants (ex. Air Products Inc.) Such include Tomadol® 91-2.5, 91-6, 1-3, 1-7, 23-1, 23-6.5, 25-3, 25-9, 25-12, 45-7 and 45-13 surfactant products. Further useful as the nonionic surfactant constituent are the series of plant derived alcohol based nonionic surfactants commercially available in the

Tomadol® L series, e.g., Tomadol® L80, L124, L130 and LI44 surfactant products. An exemplary and preferred series of nonionic surfactants include those presently marketed in the Tomadol® 400, 600, 900, 1200 series of surfactants. Such are recited as being environmentally fiiendly nonionic surfactants particularly well suited as replacements for nonyl phenol ethoxylate based nonionic surfactants. Specific examples include:

Further examples of usefiil nonionic surfactants include C₆-Ci5 straight chain alcohols ethoxylated with about 1 to 13 moles of ethylene oxide, particularly those which include about 4 to about 7 moles of ethylene oxide.

Further examples of useful nonionic surfactants include alkyl glycoside surfactants including those which may be represented by formula I below:

RO— (RiOJy-iOxZb I

wherein:

R is a monovalent organic radical containing from about 6 to about 30, preferably from about 8 to about 18 carbon atoms;

R] 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 0 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 5 (preferably from 1.1 to 2); Z is 0₂M

O I I

— 0-C-R2

0(CH₂), C0₂M', OSO₃M¹, or 0(CH₂)S0₃M'; R₂ is (CH₂)C0₂M' or

CE CHCO2M¹; (with the proviso that Z can he 0₂M^] only if Z is in place of a primary hydroxyl group in which the primary hydro xyl-bearing

carbon atom,

— CH₂OH, is oxidized to form a

group);

b is a number of from 0 to 3 +l preferably an average of from 0.5 to 2 per glycosal group;

p is 1 to 10,

M¹ is H⁺ or an organic or inorganic cation, such as, for example, an alkali metal, ammonium, mono ethanol amine, 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 18 carbon atoms. Examples of such

alkylglyco sides as described above include, for example, APG™ 325 CS GLYCOSIDE which is described as being a 50% C9-C1₁ 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% Ci₀-C₁₆ alkyl polyglycoside, also commonly referred to as a D-glucopyranoside.

Additional examples of suitable nonionic surfactants are 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 C₂-C₄ alkylene oxides. Such nonionic surfactants, while preferably built up from an alkylene oxide chain stalling group, and can have as a starting nucleus almost any active hydrogen containing group including, without limitation, amides, phenols, thiols and secondary alcohols. Yet further useful nonionic surfactant compounds useful in the nonionic surfactant constituent include one or more amine oxide compounds. Exemplary useful amine oxide surfactant compounds include:

alkyl di(Ci-C₇) 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 of such compounds include lauryl dimethyl amine oxide, myristyl dimethyl amine oxide, and those in which the alkyl group is a mixture of different amine oxide, dimethyl cocoamine oxide, dimethyl (hydrogenated tallow) amine oxide, and myristyl/palmityl dimethyl amine oxide;

alkyl di(hydroxy C_\-Ci) 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 of such compounds include bis(2-hydroxyethyl) cocoamine oxide, bis(2-hydiOxyethyl) tallowamine oxide; and bis(2-hydroxyethyl) stearylamine oxide;

alkylamidopropyl di(Ci-C₇) 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 of such compounds include cocoamidopropyl dimethyl amine oxide and tallowamidopropyl dimethyl amine oxide; and

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.

Particularly prefened are alkyl di(Ci-C₂) amine oxides in which the alkyl group has about 10-14, and preferably has 12 carbon atoms, which are preferably saturated. Especially preferred is lauryl dimethyl amine oxide which in preferred embodiments is present to the exclusion of other amine oxides.

Non-limiting examples of useful anionic surfactants include one or more of:

alcohol sulfates and sulfonates, alcohol phosphates and phosphonates, alkyl ester sulfates, alkyl diphenyl ether sulfonates, alkyl sulfates, alkyl ether sulfates, sulfate esters of an alkylphenoxy polyoxyethylene ethanol, alkyl monoglyceride sulfates, alkyl sulfonates, alkyl ether sulfates, alpha-olefin sulfonates, beta-alkoxy alkane sulfonates, alkyl ether sulfonates, ethoxylated alkyl sulfonates, alkylaryl sulfonates, alkylaryl sulfates, alkyl monoglyceride sulfonates, alkyl carboxylates, alkyl ether carboxylates, alkyl alkoxy c arboxyl at es having 1 to 5 moles of ethylene oxide, alkylpolyglycolethersulfates

(containing up to 10 moles of ethylene oxide), sulfosuccinates, octoxynol or nonoxynol phosphates, taurates, fatty taurides, fatty acid amide polyoxyethylene sulfates, acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, alkylpolysaccharide sulfates, alkylpolyglucoside sulfates, alkyl polyethoxy carboxylates, and sarcosinates or mixtures thereof.

Further examples of anionic surfactants include water soluble salts or acids of the formula (ROS0₃)_xM or (RS0₃)_xM wherein R is preferably a C₆-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a Cio-C₂₀ alkyl component, more preferably a Ci₂-C₁₈ alkyl or hydroxyalkyl, and M is H or a mono-, di- or tri-valent cation, e. g., an alkali metal cation (e. g., sodium, potassium, lithium), or ammonium or substituted ammonium (e. g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like) and x is an integer, preferably 1 to 3, most preferably 1. Materials sold under the Hostapur and Biosoft trademarks are examples of such anionic surfactants.

Further examples of anionic surfactants include alkyl-diphenyl-ethersulphonates and alkyl-carboxylates. Other anionic surfactants can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono- , di-and ri-iethanolamine salts) of soap, C₆-C₂o linear alkylbenzenesulfonates, C₆-C₂₂ primary or secondary alkanesulfonates, C₆-C₂4 olefmsulfonates, sulfonated

polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e. g., as described in British patent specification No. 1 ,082, 179, C₆-C₂4 alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl ester sulfates such as Cw-ie methyl ester sulfates; acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C]₂- Cis monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C₆-Ci4 diesters), acyl sarcosinates, sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described below), branched primary alkyl sulfates, alkyl polyethoxy carboxylates such as those of the formula RO(CH₂CH₂0)_kCH₂COO^_M⁺ wherein R is a C₈-C₂₂ alkyl, k is an integer from 0 to 10, and is a soluble salt-forming cation. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U. S. Patent No. 3,929,678 to Laughlin, et al. at column 23, line 58 through column 29, line 23, the contents of which are herein incorporated by reference.

Also useful as the anionic surfactant constituent are carboxylates such as alkyl carboxylates which include those which may be represented by the general formula:

R-COO^'M⁺

wherein R is a straight or branched hydrocarbon chain containing from about 9 to 21 carbon atoms, and M is a metal or ammonium ion; polyalkoxycarboxylates,

representative of which are polyethoxycarboxylates which may be represented by the general formula:

R-[-OCH₂CH₂-]_n-CH₂COO^" M⁺

wherein R is a straight chained or branched hydrocarbon chain which may include an aryl moiety, but is desirably a straight chained or branched hydrocarbon chain; and n is an integer value of from 1 - 24.

Exemplary useful optional cationic surfactants include quaternary ammonium compounds and salts thereof include quaternary ammonium germicides which may be characterized by the general structural formula:

where at least one or R[, R₂, R₃ and R4 is a alkyl, aryl or alkylaryl substituent of fiom 6 to 26 carbon atoms, and desirably the entire cation portion of the molecule has a molecular weight of at least 165. The alkyl substituents may be long-chain alkyl, long-chain alkoxyaryl, long-chain alkylaryl, halogen-substituted long-chain alkylaryl, long-chain alkylphenoxyalkyl, arylalkyl, etc. The remaining substituents on the nitrogen atoms other than the abovementioned alkyl substituents are hydrocarbons usually containing no more than 12 carbon atoms. The substituents Ri, R₂, R₃ and R4 may be straight-chained or may be branched, but are preferably straight-chained, and may include one or more amide, ether or ester linkages. The counterion X may be any salt-forming anion which permits water solubility of the quaternary ammonium complex. Exemplary counterions include halides, for example chloride, bromide or iodide, or methosulfate.

Exemplary useful amphoteric surfactants include alkylbetaines, particularly those which may be represented by the following structural formula:

RN(CH₃)₂CH₂COO- wherein R is a straight or branched hydrocarbon chain which may include an aryl moiety, but is preferably a straight hydrocarbon chain containing from about 6 to 30 carbon atoms. Further exemplary useful amphoteric surfactants include amidoalkylbetaines, such as amidopropylbetaines which may be represented by the following structural formula:

RCONHCH₂CH₂CH₂N⁺(CH₃)2CH₂COO^" wherein R is a straight or branched hydrocarbon chain which may include an aryl moiety, but is preferably a straight hydrocarbon chain containing from about 6 to 30 carbon atoms.

When present, such one or more further optional additional surfactants may be present in amounts which provide a useful technical benefit, e.g., foaming, cleaning, to the adhered lavatory treatment compositions but at the same time, do not unduly detract from the adhesive properties and/or useful technical benefits which are provided. When present, the cumulative amount of further surfactant compounds may form up to about 50%wt. of the present inventive compositions. Preferably, and in order of increasing preference the cumulative amount of such optional further surfactant compounds may be present in amounts of from 0.01 - 50%wt., preferably 0.5 - 20%wt. In certain inventive embodiments, the sole surfactant present in the adhesive lavatoiy treatment compositions are the least one alkanolamide based nonionic surfactant compound, to the exclusion of other detersive surfactants, namely other nonionic, anionic, cationic, amphoteric and/or zwitterionic surfactants.

In certain further inventive embodiments, the sole surfactant present in the adhesive lavatory treatment compositions are the least one alkanolamide based nonionic surfactant compound, and optionally one or more different further nonionic surfactants, but to the exclusion of other detersive surfactants, namely anionic, cationic, amphoteric and/or zwitterionic surfactants.

The inventive compositions necessarily further comprise at least about 25%wt, preferably at least about 30%wt., yet more preferably at least about 40%wt. of a primary adhesion promoter constituent based on one or more oxyalkylenated compounds which includes two or more different oxyalkylenated compounds which preferably have different molecular weights. At least one of the two oxyalkylenated compounds is pasty or is a solid at room temperature (20°C). These oxyalkylenated compound(s) typically comprise ethylene oxide groups ("EO") (oxyetnylenated compounds), or propylene oxide groups ("PO") (oxypropylenated compounds) or both ("EO/PO")

(oxyethylenated/oxypropylenated compounds). A plurality of oxyalkylenated compound(s) may be used in the primary adhesion promoter constituent of the adhesive lavatory treatment compositions, and are present in preferred embodiments of the invention. Preferably the oxyalkylenated compounds of the primary adhesion promoter have a (weight average) molecular weight of at least about 500, more preferably at least about 2000.

Exemplary suitable oxyalkylenated compounds may be selected from:

polyethylene glycols, polyethylene glycol esters and/or polypropylene glycol esters, polyethylene glycol ethers and/or polypropylene glycol ethers, alkoxyiated acyl derivatives, ethoxylated acyl polyol derivatives, oxyalkylenated (especially)

oxyet ylenated triesters of glycerol and of fatty acids, and mixtures thereof, each having a minimum molecular weight of about 500 to a maximum molecular weight of about 50,000. Non-limiting examples of suitable polyethylene glycols which may be used in the composition of the invention include ethylene oxide polycondensates having a number of ethylene oxide (EO) units of greater than 50, and preferably greater than about 200. The ethylene oxide number preferably range from about 50 to about 25,000 and preferably from about 200 to about 10,000. Non-limiting examples of such polyethylene glycols include polyethylene glycol comprising 7,000 EO (CTFA name: PEG-7M), polyethylene glycol comprising 75 EO (CTFA name: PEG-75), polyethylene glycol comprising 20,000 EO (CTFA name: PEG-20M), and polyethylene glycol comprising 150 EO (CTFA name: PEG-150).

Non-limiting examples of suitable polyethylene glycol esters and/or

polypropylene glycol esters include condensates of polyethylene glycol and/or polypropylene glycol with one or more fatty acids. These compounds typically have the formula:

wherein:

each of R and R' independently represent: hydrogen or a saturated or unsaturated, linear or branched, hydroxylated or non-hydro xylated alkyl chain containing from 1 to 30 carbon atoms, preferably from 12 to 22 carbon atoms, or an aryl chain, with the proviso that R and R' are not simultaneously hydrogen,

a = 0 - 5000

b = 0— 5000, and preferably a + b is greater than or equal to 10, preferably at least 25, still more preferably at least 50.

Non-limiting examples of polyethylene glycol acid esters and/or polypropylene glycol acid esters include polyethylene glycol distearate (150 EO), PEG-150 dibehenate, polyethylene glycol palmitostearate (120 EO), the copolymer of polyethylene glycol (30 EO) and of 12-hydroxystearic acid, and polyethylene glycol stearate (40 EO). Examples of compounds according to the foregoing formula wherein R and R' are both hydrogen, such compound may be polyoxyethylene polyoxypropylene copolymers. Non-limiting examples of polyethylene glycol ethers and/or polypropylene glycol ethers include condensates of polyethylene glycol and/or polypropylene glycol with one or more fatty alcohols. These compounds typically conform to the formula:

R- -CH₂C¾0- -CH2CH2CH2O- -R' wherein:

each of R and R' represent, independently of each other, hydrogen or a saturated or unsaturated, linear or branched, hydroxylated or non-hydroxylated alkyl chain containing from 1 to 30 carbon atoms, preferably from 12 to 22 carbon atoms, or an aryl chain, with the proviso that R and R' are not simultaneously hydrogen.

a = 0 - 300

b = 0 - 300, and preferably a + b is greater than or equal to 10, preferably at least 25, still more preferably at least 50.

Non-limiting examples of such polyethylene glycol ethers include

oxyethylenated (30 EO) cetyl alcohol, oxyethylenated (15 EO) oleyl alcohol,

oxyethylenated (50 EO) oleyl alcohol, oxyethylenated (10 EO) behenyl alcohol, oxyethylenated (30 EO) behenyl alcohol, oxyethylenated (12 EO) lauryl alcohol, oxyethylenated (23 EO) lauryl alcohol, oxyethylenated (20 EO) 2-octyldodecyl alcohol, oxyethylenated (20 EO) isocetyl alcohol, oxyethylenated (10 EO) oleyl alcohol, oxyethylenated (20 EO) oleyl alcohol, oxyethylenated (100 EO) steaiyl alcohol, and o yethylenated (21 EO) stearyl alcohol.

Non-limiting examples of polyethylene glycol/polypropylene glycol ethers in particular, include oxyethylenated (5 EO) oxypropylenated (5 PO) lauryl alcohol, oxypropylenated (3 PO) myristyl alcohol, oxyethylenated (20 EO) oxypropylenated (5 PO) cetyl alcohol, oxyethylenated (26 EO) oxypropylenated (26 PO) butyl alcohol, oxyethylenated (26 EO) oxypropylenated (26 PO) butyl alcohol, oxyethylenated (30 EO) oxypropylenated (6 PO) decyltetradecanol, and oxyethylenated (25 EO) oxypropylenated (25 PO) lauryl alcohol.

Non-limiting examples of ethoxylated alkyl or aryl derivatives of polyol include oxyethylenated derivatives of fatty acid esters or of fatty alcohol ethers and of a polyol such as glycerol, sorbitol, glucose orpentaeiythritol. Suitable derivatives of this type include, for example, oxyethylenated (78 EO) glyceryl cocoate, oxyethylenated (120 EO) methylglucose dioleate, oxyethylenated (40 EO) sorbitan septaoleate, oxyethylenated (10 EO) polyglyceryl (2 mol of glycerol) laurate, oxyethylenated (60 EO) glyceryl isostearate, oxyethylenated (20 EO) glyceryl monostearate, and oxyethylenated (200 EO) glyceryl stearate.

Non-limiting examples of suitable oxyalkylenated glyceryl triesters of fatty acids include, for example, oxyethylenated (6 EO) caprylic/capric acid glycerides, and oxyethylenated (50 EO) olive oil.

Particularly preferred for use in the primary adhesion promoter constituent are two or more, yet more preferably at least three different polyalkylene glycols, especially polyethylene glycols at least one of which is a paste or solid at room temperature (20°C), each of which has a minimum (weight average) molecular weight of at least about 500 and has a maximum molecular weight of about 50,000 and further preferably wherein each of the two, preferably three or more different polyalkylene glycols have different (weight average) molecular weights, each between about 500 to about 20,000.

Particularly preferably the primary adhesion promoter constituent includes, or consists of, a plurality o poly(alkylene glycols) having molecular (weight average) molecular weights in the range of from about 500 to about 20,000. Further preferably the primary adhesion promoter constituent includes, or consists of, a plurality of

poly(alkylene glycols) includes two or more, preferably three or more different polyfalkylene glycols) which can be distinguished in having different (weight average) molecular weights wherein the poly(alkylene glycol) having the lowest molecular weight is one having a (weight avg.) molecular weight in the range of from about 500 to about 1000, and is preferably about 600, and where all further poly(alkylene glycols) present have higher molecular weights, preferably have (weight avg.) molecular weights which are preferably at least twice, preferably at least thrice yet more preferably at least 4 or still more preferably at least 5 times the (weight avg.) molecular weight of the poly(alkylene glycol) having the lowest molecular weight present in the primary adhesion promoter constituent. In a further preferred alternative, the mass or weight proportion of the

poly(alkylene glycol) having the lowest molecular weight is greater than that of an other single higher molecular weight poly(alkylene glycol) present in the primary adhesion promoter constituent.

Advantageously in the primary adhesion promoter constituent, the poly(alkylene glycol) having the lowest molecular weight is also liquid at room temperature (20°C), while the remaining poly(alkylene glycol(s)) of higher molecular weights are all pasty solids or solids at room temperature.

Preferred embodiments of the inventive compositions, and preferred embodiments of the primary adhesion promoter constituent and respective weight ratios of each of the separate individual poly(alkylene glycol) present in the primary adhesion promoter constituent are demonstrated with reference to one or more of the Examples.

As noted, the primary adhesion promoter constituent comprises at least 25%wt. of the adhesive lavatory treatment compositions taught herein. Advantageously, and in order of increasing preference the primary adhesion promoter constituent comprises at least 25%wt. of the inventive composition, preferably in order of increasing preference 30%, 32%, 34%, 35%, 37%, 39%, 40%, 42%, 44%, 45%, 46%, 48%, 50%, 52%, 54%, 55%wt. based on the total weight of the inventive composition of which it forms a part.

Concurrently the primary adhesion promoter constituent comprises not more than 90%wt, and in order of increasing preference, not more than 85%wt., 80%w , 78%, 76%. 75%, 74%, 72% and 70% w , based on the total weight of the inventive composition of which it forms a part.

The present inventors have further surprisingly found that via judicious selection of the constituents, particularly the judicious selection of constituents used in the primary adhesion promoter constituent, that very satisfactory adhesive lavatory treatment compositions may be produced which may be dispensed from a suitable dispenser without undue retention within the dispenser, and yet which exhibit good adhesion to dry surfaces, and even under successive exposure to water, e.g, flushing water in a toilet, the adhesive lavatory treatment compositions provide good technical performance characteristics and a very satisfactory surface life. The compositions of the invention may optionally further comprise about 0 - 5%wt. of a co-adhesion promoter constituent, which while being an optional constituent and not necessary in all embodiments of the invention, but in certain embodiments is nonetheless preferably present. Preferred co-adhesion promoters are based on water soluble or water dispersible materials, and are preferably based on water soluble or water dispersible film-forming polymers. Non-limiting examples of such polymers include:

1 ) a olymer having the formula

in which n represents from 20 to 99 and preferably from 40 to 90 mol %, m represents from 1 to 80 and preferably from 5 to 40 mol %; p represents 0 to 50 mol, (n+m+p=100); Ri represents H or C¾; y represents 0 or 1; R₂ represents— CH₂— CHOH— CH₂— or C_xH_2x in which x is 2 to 18; R₃ represents CH₃, C₂H₅ or t-butyl; R4 represents CH₃, C₂¾ or benzyl; X represents CI, Br, I, I/2SO₄, HSO₄ and CH3SO₃; and M is a vinyl or vinylidene monomer copolymerisable with vinyl pyrrolidone other than the monomer identified in [ ]_m;

2) water soluble or water dispersible polyethylene oxide ("PEG");

3) polyvinylpyrrolidone;

4) high molecular weight polyethylene glycol;

5) polyvinylcaprolactam;

6) vinylpynOlidone/vinyl acetate copolymer;

7) vinylpyrrolidone/vinyl caprolactam/ammonium derivative terpolymer, especially where the ammonium derivative is selected from diallylamino alkyl methacryl amides, dialkyl dialkenyl ammonium halides, and a dialkylamino alkyl methacrylate or acrylate;

8) polyvinylalcohol;

9) cationic cellulose polymer;

10) film-forming fatty quaternary ammonium compounds; 1 l) polyol ester;

12) polyacrylate homopolymers and copolymers comprising polyacrylate moieties;

one or more of which may be present in the co-adhesion promoter.

Each of the foregoing water soluble or water dispersible film-forming polymers exhibit a weight average molecular weight of at least 500, preferably of at least 1000 with water soluble or water dispersible film-forming polymers having weight avg. molecular weights of at least 5000 being particularly preferred.

One particularly preferred for use in the co-adhesion promoter constituent are one or more compounds according to the structure:

wherein,

R is a fatty acid moiety, preferably a stearic fatty acid moiety, and

the sum of w + x + y + z is in the range of 50 - 1500, preferably in the range of 70 - 500, more preferably in the range of about 100 - 350 and especially preferably about 150.

A particularly preferred as the co-adhesion promoter constituent is a material presently commercially available under the tradename Crothix OG-CS (ex. Croda, Inc.), described to be an oxyethylenated (150 EO) pentaerythrityl tetrastearate, such as the product sold under the name Crothix.(TM) (ex. Croda, Inc.)

Further particularly preferred co-adhesion promoters include high molecular weight water-soluble poly(ethylene oxide) polymers, which desirably have molecular weights (weight average) in the range from about 100,000 to about 8,000,000. Such high molecular weight water-soluble poly(ethylene oxide) polymers are presently commercially available as Polyox resins (ex. Dow Chem. Co.). In embodiments of the invention, wherein both a primary adhesion promoter and a co-adhesion promoter are concurrently present, preferably the weight ratio of the former to the latter is at least about not more than 10:1, and especially preferably is not more than about 20:1

In certain preferred embodiments, one or more of the foregoing co-adhesion promoters are expressly excluded from the adhesive lavatory treatment compositions.

The inventor has found that the inclusion of one or more of the foregoing polymers as an co-adhesion promoter constituent may advantageously increases the adhesivity of the adhesive lavatory treatment compositions to surface, and thus in certain preferred embodiments at least one of the foregoing co -adhesion promoters is expressly included.

The adhesive lavatory treatment compositions are essentially anhydrous, that is to say that the said compositions comprise less than about 0.01 %wt. water, preferably less than about 0.05%wt. water, as water is not added as a constituent to the compositions and the selection of constituents are based on the absence of water present either as free water or as "bound water" such as may be present in certain inorganic compounds. Alternately the adhesive lavatory treatment compositions, comprise no water as an added constituent to the said compositions. Prior to being contacted with flush water in a lavatory appliance, e.g., water present as a film or laminar of water on a surface of the lavatory appliance or flush water contacting a mass or dose of the adhesive lavatory treatment composition subsequent to being applied to a surface of a lavatory appliance, the sole amount of water which may be present may be that absorbed from the ambient atmosphere, which typically is less than about 0.01%wt. water, preferably less than about 0.05%wt. water, and yet more preferably is less than about 0.025%wt. water.

The present inventors have surprisingly found that the adhesive lavatory treatment compositions exhibit good adhesivity to sloped or inclined hard surfaces, and may be very satisfactorily applied to dry hard surfaces, particularly to dry glazed or unglazed ceramic surfaces are may be found in many lavatory appliances, particularly toilet bowl interior surfaces, and in particular the interior inner sidewalls of toilet bowls. The adhesive lavatory treatment compositions may also be applied to such surfaces when they are wet or wetted with water, but wetted surfaces or the presence of any added water to the adhesive lavatory treatment compositions is not required in order to establish adhesion to such surfaces. The adhered adhesive lavatory treatment compositions of the invention also retain good adhesivity through many flush cycles of the lavatory appliance to which they have been applied, and slowly erode over a series of flush cycles wherein one or more constituents of the adhesive lavatory treatment compositions are eluted to the flush water to form a lavatory treatment composition which is used to treat the lavatory appliance. The adhesive lavatory treatment compositions advantageously also release a visible foam which may be seen by a consumer who typically equates the presence of foam in the toilet bowl with a cleaning benefit.

As noted, the adhesive lavatory treatment compositions may further comprise one or more further optional constituents which may impart a further aesthetic or technical benefit to the said adhesive lavatory treatment compositions. When present, such further optional constituents are generally present in a cumulative amount of less than about 25%wt. based on the total weight of the adhesive lavatory treatment compositions wherein one or more such further optional constituents may be present. By way of non- limiting example such further optional constituents include one or more of: coloring agents, fragrances and fragrance solubilizers, viscosity modifying agents, thickeners, bleaches, bleach releasing compounds, oxidizing agents, germicidal agents, further surfactants in addition to those previously described as being essential to the adhesive lavatory treatment compositions, pH adjusting agents and pH buffers including organic and inorganic salts as well as organic and inorganic acids, builders, chelating agents, opacifying agents, titanium dioxide, inert inorganic or organic fillers, visually discernible additive materials, hydrotropes, enzymes as well as other biologically active constituents, anti-oxidants, preservatives, and anti-corrosion agents, as well as other optional constituents known to the skilled artisan.. When one or more of the optional constituents is added, i.e., fragrance and/or coloring agents, the esthetic and consumer appeal of the product is often favorably improved. The use and selection of these optional constituents should be based on imparting a desired additional aesthetic or technical benefit, as well as to ensure compatibility with the further constituents present in the inventive adhesive lavatory treatment compositions, especially such that the desirable adhesive properties of the adhesive lavatory treatment compositions are not deleteriously diminished. Optionally the inventive compositions may comprise a germicide constituent (other than cationic germicidally active quaternary ammonium halide surfactants noted above) which has germicidal or antimicrobial efficacy against at least one of gram- positive or gram-negative pathogens, e.g., bacteria or other microorganisms. Such may be based, for example, on one or more non-cationic antimicrobial compounds or constituents, e.g., halophenols such 3-trifluoromethyl-4,4'-dichlorocarbanilide, 3,3',4- trichlorocarbanilide, as well as 2,4-dichloro-3,5-m-xylenol ("DCMX"). The phenol based non-cationic antimicrobials are preferred, of which parachlorometacresol

("PCMC") and especially parachlorometaxylenol ("PCMX").

Alternately such may be based, for example, on one or more phenol derivatives such as those based on 2-hydroxydiphenyl compounds, including Triclosan® (ex. Ciba), those based on 2,2'-hydroxy-5,5'-dibromo-diphenyl ethers, such as one or more of chlorophenols (o-, m-, p-), 2,4-dichIorophenol, p-nitrophenol, picric acid, xylenol, p- chloro-m-xylenol, cresols (o-, m-, p-), p-chloro-m-cresol, pyrocatechol, resorcinol, 4-n- hexylresorcinol, pyrogallol, phloroglucin, carvacrol, thymol, p-chlorothymol, o- phenylphenol, o-benzylphenol, p-chloro-o-benzylphenol, phenol, 4-ethylphenol, and 4- phenolsulfonic acid, as well as further diphenol compounds such as hexachlorophene, tetrachlorophene, dichlorophene, 2,3-dihydroxy-5,5'-dichlorodiphenyl sulfide, 2,2'- dihydroxy-S^S^-tetrachlorodiphenyl sulfide, 2,2'-dihydroxy-3,5',5,5', 6,6'- hexachlorodiphenyl sulfide, and 3,3'-dibromo-5,5'-dichloro-2,2'- dihydroxydiphenyl amine, and especially "Triclocarban", 3,4,4'-trichlorocarbanilide as well as derivatives thererof.

The optional germicide constituent may also be based on one or more acids, including organic acids such as salicylic and citric acid, and/or inorganic acid such as hydrochloric acid when present in effective amounts in order to sufficiently acidify the treatment composition formed from the inventive compositions.

Optionally the inventive compositions may comprise bleaches and/or bleach releasing compounds. Examples of such bleaches and/or bleach releasing compounds include those selected from the group of the alkali metal and alkaline earth salts of hypohalite, haloamines, haloimines, haloimides and haloamides. All of these are believed to produce hypohalous bleaching species in situ. Hypochlorite and compounds producing hypochlorite in aqueous solution are preferred, although hypobromite is also suitable. Representative hypochlorite-producing compounnds include sodium, potassium, lithium and calcium hypochlorite, chlorinated trisodium phosphate dodecahydrate, potassium and sodium dichloroisocyanurate and trichlorocyanuric acid. Organic bleach sources suitable for use include heterocyclic N-bromo and N-chloro imides such as trichlorocyanuric and tribromocyanuric acid, dibromo- and dichlorocyanuric acid, and potassium and sodium salts thereof, N-brominated and N-chlorinated succinimide, malonimide, phthalimide and naphthalimide. Also suitable are hydantoins, such as dibromo- and dichloro

dimethylhydantoin, chlorobromo dimethyl hydantoin, N-chloro sulfamide (haloamide) and chloramine (haloamine). Particularly preferred is sodium hypochlorite having the chemical formula NaOCl

Optionally an oxidizing constituent or agent may be present in the inventive compositions. Examples of such an oxidizing agent include peroxyhydrates or other agent which releases hydrogen peroxide in aqueous solution. Such materials are per se, known to the art. Peroxyhydrates are to be understood as including hydrogen peroxide as well as any material or compound which in an aqueous composition yields hydrogen peroxide. Non-limiting examples of such materials and compounds include: alkali metal peroxides including sodium peroxide and potassium peroxide, alkali perborate monohydrates, alkali metal perborate tetrahydrates, alkali metal persulfate, alkali metal percarbonates, alkali metal peroxyhydrate, alkali metal peroxydihydrates, and alkali metal carbonates especially where such alkali metals are sodium or potassium. Further useful are various peroxydihydrate, and organic peroxyhydrates such as urea peroxide. Desirably, when present, the oxidizing agent is hydrogen peroxide.

When an oxidizing agent is present, minor amounts ( < 1 %wt.) o f one or more known art hydrogen peroxide stabilizers such as one or more organic phosphonates, stannates, pyrophosphates, as well as citric acid, may also be present.

Optionally the inventive composition may include visibly discernible materials which may, for example, be particles or particulates which are visibly discernible to a consumer, particularly by a consumer having normal "20/20" vision, visually inspecting a mass or dose of the adhesive lavatory treatment compositions applied to a hard surface. Non-limiting examples of such visibly discernible materials include materials which provide a visual effect of suspended inclusions within the mass of an adhesive lavatory treatment compositions which may be advantageous from a consumer standpoint. Such visibly discernible materials may for example be particulates of mica, colored beads such as glass beads or beads, comminuted particles or spheres formed from uncolored or colored synthetic polymers, visible light reflective particles (commonly referred to as "glitter") which are typically formed of comminuted metallized or reflective polymer particles, alginate beads such as those described in PCT/US95/08313, US Patent 7196046, US Patent 7291586 B2, as well as other visibly discernible materials known to the art which would provide a similar function. Preferably such visibly discernible materials have a maximum dimension in the range of from about 100 to about 1000 μιη.

Optionally the inventive compositions may include one or more inert inorganic or inert organic fillers compounds or materials which are preferably insoluble in water or in organic solvents. Non-limiting examples of such inert fillers include powders such as silicates, chalk, talc, kaolin, chemically modified magnesium aluminum silicate, hydrated aluminum silicate, fumed silica, and mixtures thereof

Optionally the inventive compositions may include one or more constituents which function as viscosity modifying agents or thickeners. Non-limiting examples of such materials include polysaccharide polymers especially those selected from cellulose, alkyl celluloses, alkoxy celluloses, hydroxy alkyl celluloses, alkyl hydroxy alkyl celluloses, carboxy alkyl celluloses, carboxy alkyl hydroxy alkyl celluloses, naturally occurring polysaccharide polymers such as xanthan gum, guar gum, locust bean gum, tragacanth gum, or derivatives thereof Further constituents which function as viscosity modifying agents or thickeners include polycarboxylate polymers, polyacrylamides, clays, and mixtures thereof.

Non-limiting examples of useful cellulose derivatives include methyl cellulose ethyl cellulose, hydroxymethyl cellulose hydroxy ethyl cellulose, hydroxypropyl cellulose, carboxy methyl cellulose, carboxy methyl hydroxyethyl cellulose,

hydroxypropyl cellulose, hydroxy propyl methyl cellulose, ethylhydroxymethyl cellulose and ethyl hydroxy ethyl cellulose.

Non-limiting examples of useful polycarboxylate polymers are those have a molecular weight from about 500,000 to about 4,000,000, preferably from about 1 ,000,000 to about 4,000,000, with, preferably, from about 0.5% to about 4%

crosslinking. Preferred polycarboxylate polymers include polyacrylate polymers including those sold under trade names Carbopol®, Acrysol® ICS-1 and Sokalan®. The preferred polymers are polyacrylates. Other monomers besides acrylic acid can be used to form these polymers including such monomers as ethylene and propylene which act as diluents, and maleic anhydride which acts as a source of additional carboxylic groups.

Non-limiting examples of further useful polycarboxylic acid polymer

compositions which can be employed include, for example, crosslinked copolymers of acrylates, (meth)acrylic acid, maleic anhydride, and various combinations thereof.

Non-limiting examples of useful clay thickeners include colloid-forming clays, for example, such as smectite and/or attapulgite types. The clay materials can be described as expandable layered clays, i.e., alumino silicates and magnesium silicates. The term "expandable" as used to describe the instant clays relates to the ability of the layered clay structure to be swollen, or expanded, on contact with water. The expandable clays used herein are those materials classified geologically as smectites (or

montmorillonite) and attapulgites (or olygorskites). Commercially available clays include, for example, montmorillonite, bentonite, volchonskoite, nontronite, beidellite, hectorite, saponite, sauconite and vermiculite. The clays herein are available under various trade names such as Gelwhite GP, Gelwhite H, Mineral Colloid BP, and Laponite from Southern Clay Products, Inc., Texas; and Van Gel O from R. T. Vanderbilt.

Further constituents which may be optionally included include one or more of: inorganic filler materials, such as one or more of silica, fumed silica, silica dioxide, carbon black, comminuted polymer beads or particulates, sodium silicate. Further materials based on rosins, tall oil and/or teipene compounds may also be included, e.g., polyterpenic resins (e.g., Dercolyte LTG, ex. DRT), or rosin esters, such as diethylene glycol rosin esters (e.g., Dertoline DEG 2, ex. DRT); certain of such may be useful in the organic solvent constituent. Exemplary chelating agents include alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and

polyhydroxysulfonates, as well as tetra sodium salt of glutamic acid-Ν,Ν- diacetic acid, as well as methyl-glycine-diacetic acid. Nonlimiting examples of commercially available chelating agents include those marketed under the "Dissolvine" trademark (ex. AkzoNobel) including Dissolvine GL-PD-S, and Dissolvine E-CA- 10 materials. Further useful as an optional constituent are butane homopolymers, e.g., polyisobutene, such as may be commercially obtained as TPC 1350 from Texas Petro Chemicals Co. Further useful as an optional constituent is an emulsifying agent, preferably sucrose acetate isobutyrate such as is commercially available as Eastman SAIB-100 (ex. Eastman Chemical Co.)

Other optional constituents, although not specifically elucidated above, may also be considered useful for inclusion in the inventive compositions particularly wherein such impart a further aesthetic or technical benefit to the said adhesive lavatoiy treatment compositions.

The compositions of the invention may be formed by first gently heating one or more of the constituents, such as the organic solvent constituent to about 100 - 120°C and thereafter under stirring conditions adding thereto the primary adhesion promoter constituent. Mixing is continued for approximately 30 minutes to ensure the formation of a homogenous mixture, and thereafter the heat sources is removed or turned off, and the temperature of the mixture is monitored. Thereafter, under constant mixing conditions, after the temperature of the mixture has been reduced to approximately 80°C, are thereafter added the surfactants, and mixing continues until the mixture is homogenous. Subsequently the co-adhesion promoter is added and mixing continues. Thereafter, when the temperature of the mixture has been reduced to about 40°C, under high speed mixing are next added the co-adhesion promoters (when present), and then the remaining constituents, and mixing continues under high speed until the mixture is homogenous, after which mixing ceases and the composition is allowed to reduce its temperature to room temperature (approx. 20 - 22°C). Thereafter the composition may be removed from the mixing vessel and used.

In one aspect of the invention, the adhesive lavatory treatment compositions are formed as described above, and while still in a viscous but fluid state above room temperature, aliquots of the composition are poured into suitable dispenser, such as described in copending patent applications GB patent application 1007066.2, or GB patent application 1007064.7, filed 28.Apr.2010, within which they are allowed to cool to room temperature. The compositions may thereafter be dispensed directly from the dispensers and onto a surface.

The inventors have surprisingly found however that the appearance and overall adhesive properties of the compositions are improved if they are allowed to cool to room temperature (approx. 20 - 22°C), or cooler, and are subsequently mixed or mechanically agitated, and only thereafter are either directly applied to a hard surface, or alternately are supplied to a suitable dispenser, especially as disclosed in the foregoing from which the adhesive lavatory treatment composition is dispensed, preferably by extrusion through a part of the dispenser and onto a surface. Optionally following the initial cooling to room temperature, or cooler, and preferably subsequent to or concurrent to mixing or mechanical agitation, the composition may be heated to lower the viscosity thereof and to improve its fluidity to facilitate delivery into a suitable dispenser. While not wishing to be bound by the following, the inventors hypothesize that when the initial cooling of the composition occurred in a bulk mass or bulk volume, that the cooling rate of the composition was retarded due to poor thermal transmissivity of the mass of the cooling adhesive lavatory treatment composition, and this in turn was suspected to reduce the physical homogeneity of the cooling composition leading to different internal regions or zones of cooled composition which might have slightly different chemical compositions in these different zones. This phenomenon was observed to diminish when the cooled adhesive lavatory treatment compositions were subsequently mechanically stirred, mixed or agitated to physically mix and improve the homogeneity of the said compositions.

It is also believed by the inventors that the suspected reduced physical homogeneity of the cooling composition leading to different internal regions or zones of cooled composition which might have slightly different chemical compositions in these different zones could be reduced wherein the heated, formed adhesive lavatory treatment composition were cooled on a flat plate, or in a laminar form such as on the periphery of a drum or other surface which would reduce the bulk thickness of the cooling physical homogeneity of the cooling composition leading to different internal regions or zones of cooled composition which might have slightly different chemical compositions in these different zones and minimize internal compositional discontinuities as described above. Such may also obviate the need or benefits of subsequent stining, mixing or physical agitation.

Preferred adhesive lavatory treatment compositions of the invention are viscous or pasty, and may be characterized in having a viscosity in the range of from about 150,000 cP to about 7,000,000 cP, but preferably from about 200,000 to about 5,000,000. The viscosity may be determined utilizing conventional analytical instruments.

The compositions of the invention may be applied directly to hard surfaces, which may be vertical, or sloped, and may be applied to and retained thereupon even on dry surfaces. As previously noted, especially preferred hard surfaces include non-wetted or dry surfaces of lavatory appliances, particularly the interior surface of a toilet bowl. Once applied, the compositions may be flushed away after a plurality of flushing operations, preferably following a relatively large number of flushing operations. While it is naturally understood that the operating parameters of lavatory devices, e.g., toilets, vary considerably and that the range of compositions which are taught herein are also variable, preferably, once applied a mass ( preferably between about 2 and about 10 grams, more preferably from about 3 to about 7 grams, and covering a surface area of approximately about 1 to about 10 cm²) of the inventive composition are retained in the hard surface for at least 5, and in order of increasing preference, at least 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75 and 80 flushes, or until the mass of the of the adhesive lavatory treatment compositions is eroded by the flushing water of the lavatory device.

The compositions of the invention may be applied either directly by a consumer, but are more conveniently applied utilizing a dispensing means which contains a quantity of an the adhesive lavatory treatment composition as taught herein. For example, a larger quantity of an the adhesive lavatory treatment compositions may be provided in a dispenser such as compressible tube, or bottle, compressible piston and syringe type dispenser, compressible bag or blister-type formed package which is compressed by a consumer to expel and dispense a quantity of the adhesive lavatory treatment composition onto a hard surface. The amount dispensed per dispensing operation may be variable, or may be predetermined so that an approximately uniform mass/quantity of the adhesive lavatory treatment composition may be applied as a dose to a hard surface. The adhesive lavatory treatment compositions may be supplied in a suitable dispenser which dispenses a single dose of the compositions during an application step or application operation. Such dispensing means may be, for example, prefilled cartridges such as blisters, dispensing devices such as may comprise a plurality of cartridges each of which contains a single unit dose, which is expelled from the device, piston containing cylindrical dispensers which may include means to limit the travel of the piston through the bore of the cylindrical dispenser so that upon displacement of the piston, a dose of the adhesive lavatory treatment composition is expelled. Also suitable dispensing means are a pouch which contains in its interior a mass of the adhesive lavatory treatment composition; in application the pouch may be opened at one end thereof and the adhesive lavatory treatment composition squeezed out onto a hard surface, or one part of the pouch may be peeled away, e.g., a film, and thereafter the exposed adhesive lavatory treatment composition may be applied to a hard surface by a consumer, and thereafter the remaining part of the pouch may be withdrawn and discarded by a consumer. Certain particularly preferred dispensing means include those disclosed in copending patent applications GB patent application 1007066.2, or GB patent application 1007064.7, filed 28.Apr.2010, the contents of which are herein incorporated by reference, or may be supplied in a suitable dispenser which dispenses a plurality of single doses. Other dispensing means which provide a similar function as described above and herein may also be used and are considered suitable as dispensing means for the adhesive lavatory treatment compositions taught herein.

An example of a preferred dispensing means or dispensing device useful for applying a mass of an adhesive lavatory treatment composition, here a single use "dose" thereof, is described with reference to Figures 2A1, 2B1, and 2C1, as well as on Figures 2A2, 2B2 and 2C2. Prior to discussing these figures it is to be understood is that said figures are presented as "paired" representations, namely Fig. 2A1 depicts a perspective view of the applicator 10 in first configuration and Fig. 2A2 illustrates the same applicator in a perspective view but in a second configuration. Fig. 2B 1 depicts a cross- sectional view of the applicator 10 from a side thereof in first configuration and Fig. 2B2 illustrates the same applicator in a cross-sectional view in a second configuration. Fig. 2C1 depicts a cross-sectional view of the applicator 10 from an end thereof in a first configuration and Fig. 2C2 illustrates in a cross-sectional view of the same applicator in a second configuration. These respective views illustrate the relative positions of the piston part 40, piston plate 42, perforated compression plate 27 intermediate the first or upper cavity 22 and the second or lower cavity 24, base section 20, and of the mass of an adhesive lavatory treatment composition 70, here provided as a single use "dose" thereof within the applicator 10 and with respect to the surface 90, in Figs. 2A1, 2B1 and 2C1, in an initial state prior to any movement of the piston part 40 within the base section 40, then in Figs. 2A2, 2B2 and 2C2 in the final state and subsequent to maximum movement of the piston part 40 within the base section 20, wherein the stop means 50 are engaged with parts of the base section 20, here corresponding detents 53 in parts of the base section 20 which inhibits or denies retraction of the piston part 40 form the base section 20, and which also inhibits or denies further inward movement of the piston part 40 into the base section 20, such that the bottom face 49 of the piston plate 42 is in contact with, and especially preferably in interfacial contact with the perforated compression plate 27. The movement of the piston part 40 in relation to the base section 20 from the first configuration to the second configuration as illustrated also ensures that the adhesive lavatory treatment composition 70 is compressed between the piston plate 42 and the perforated compression plate 27, which forces or extrudes the said adhesive lavatory treatment composition 70 contained within the volume of the first or upper cavity 22 through the orifice 21 such that most or all of the adhesive lavatory treatment composition 70 is extruded through the orifice 21 and preferably onto a surface 90 to which the adhesive lavatory treatment composition 70 may be adhered. This

compression imparts shear forces in the adhesive lavatory treatment composition 70 as it passes through the orifice 21, and concurrently ensures good interfacial contact with the surface 90. When the parts of the applicator are appropriately configured, specifically the shape and/or contour of the piston plate 42 and the perforated compression plate 27, then the maximum delivery of the mass or dose of the adhesive lavatory treatment

composition 70 can be expelled out from the volume of the first or upper cavity 22 and onto the surface 90. Further preferably, the volume of the first or upper cavity 22 is also less than the volume of the second or lower cavity 24, such when the piston art 40 is at its maximum displacement within the base section 20, as depicted on Figs. 4B2 and 4B3, ideally none of the compressed and laterally deformed mass of the adhesive lavatory treatment composition 70 comes into contact with the interior 28 of the second or lower cavity 24. Such minimizes the likelihood of undesired adhesion between any other part of the applicator 10 other than the piston part 40 exposed through the orifice 21. Such minimizes the likelihood that the applied mass of the adhesive lavatory treatment composition 70 will be inadvertently removed when the applicator 10 is withdrawn.

Figures 3 A, 3B, 3C and 3D illustrates a further example of a preferred dispensing means or dispensing device 10 useful for applying a mass of an adhesive lavatory treatment composition, here a single use "dose" thereof which is similar in many respects to the embodiment of Figures 2A1, 2B1, 2C1, 2A2, 2B2 and 2C2. Figure 3A presents a perspective view of the dispensing device 10, Fig. 3B presents a front plan view of the dispensing device 10, Fig. 3C presents a side plan view of the dispensing device 10 and Fig. 3D presents a bottom plan view of the dispensing device 10. In these figures is illustrated a piston part 40, piston plate 42, a perforated compression plate 27, a base section 20 adapted to contain and deliver a single use "dose" thereof within the applicator 10 and with respect to a surface. Similarly to that described in the embodiment of Figures 2A1 , 2B 1 , 2C 1 , 2A2, 2B2 and 2C2, in the present embodiment the movement of the piston part 40 in relation to the base section 20 from a first configuration to a second configuration ensures that the adhesive lavatory treatment composition is compressed between the piston plate 42 and the perforated compression plate 27, which forces or extrudes the said adhesive lavatory treatment composition 70 contained within the volume of the first or upper cavity through the orifice 21 such that most or all of the adhesive lavatory treatment composition is extruded through the orifice 21 and preferably onto a surface 90 to which the adhesive lavatory treatment composition (not shown) may be adhered. This compression imparts shear forces in the adhesive lavatory treatment composition as it passes through the orifice 21, and concurrently ensures good interfacial contact with the surface 90. When the parts of the applicator are appropriately configured, specifically the shape and/or contour of the piston plate 42 and the perforated compression plate 27, then the maximum delivery of the mass or dose of the adhesive lavatory treatment composition can be expelled out from the volume of the first or upper cavity and onto the surface 90. Further preferably, the base 20 is configured such that when the piston part 40 is moved to its maximum displacement within the base section 20, ideally none of the compressed and laterally deformed mass of the adhesive lavatory treatment composition 70 comes into contact with the interior of the second or lower cavity 24. Such minimizes the likelihood of undesired adhesion between any other part ofthe applicator 10 other than the piston part 40 exposed through the orifice 21. Such also minimizes the likelihood that the applied mass of the adhesive lavatory treatment composition 70 will be inadvertently removed when the applicator 10 is withdrawn.

Figures 4A, 4B, 4C and 4D illustrate a method of applying a unit dose of an adhesive lavatory treatment composition using an applicator according to Figs. 3A, 3B, 3 C and 3D to the inner sidewall of a toilet bowl. As is visible thereon, in Fig. 4A an applicator 10 generally similar to that described with reference to Figs. 3 A, 3B, 3C and 3D is manually grasped by its grip element 44 and with the user peels away a removable cover film 80 with the other hand from the base section 20 thereby exposing a unit dose of a mass ofthe adhesive lavatory treatment composition 70 with the interior of the base section 20. The removable cover film 80 is discarded. In the next step depicted on Fig. 4B, the user grasping the grip element places the base section 20 against an inner sidewall 88 of a toilet bowl, and pushes the grip element 44 in the direction of arrow "A", and towards the sidewall which dispenses the mass of the adhesive lavatory treatment composition 70 from the applicator 10 and onto the sidewall 88. In the next step depicted on Fig. 4C, after the grip element 44 has been frilly compressed and the mass ofthe adhesive lavatory treatment composition 70 has been adhered to the sidewall 88 as shown, the user has pulled the applicator 10 away from the deposited and adhered mass 70 and in the direction of arrow "B" and away from the sidewall. In the next (optional) step, the spent applicator 10 is properly disposed of, e.g. as recyclable plastic materials. While not illustrated it is to be understood that the above method can also be practiced with a two-part applicator of the invention, in which process the handle 45 would be retained, and a spent base part 20 would be properly disposed, but the handle 45 retained for further reuse.

Applicators useful with the adhesive lavatory treatment compositions of the invention may be manufactured or formed from any suitable material of construction. Advantageously, applicators are manufactured, such as by injection molding, from a suitable synthetic polymer. Nonlimiting examples of suitable synthetic polymer materials include, but are not limited to polyamides (e.g., nylons), polyolefins (e.g., polypropylene, polyethylene) as well as polyalkyleneterephalates (e.g., polyethylene terephthalate, polybutylene terephthalate), polystyrenes, polysulfones, polycarbonates as well as copolymers formed from monomers of one or more of the foregoing synthetic polymers. Other naturally occurring or synthetic but may also be used although not specifically described herein, it only being required that the selected polymer or copolymer be fabricable into applicators as described herein. Other formable materials, e.g., metals, paper such as coated papers may also be used in the manufacture of all or parts of the applicators taught herein. After being manufactured and when necessary, assembled, a quantity an adhesive lavatory treatment composition may be provided to part of said applicator, where it may be retained until it is subsequently dispensed from the applicator to a surface by a consumer.

Any of the parts, or surfaces of an applicator 10 may be formed of a release material, or may have applied thereto, a release material, e.g., a material which has poorer interfacial adhesivity with the treatment composition 70. Such a release material may be provided as a coating, e.g. to one or more parts of the applicator 10, e.g., to the piston plate 42 and/or first or upper cavity 22 and a second or lower cavity 24, or such a release material may also be provided as a further element or part of the applicator 10, e.g. a plate which may be fitted or positioned intermediate the piston plate 42 and the mass of the composition 42, or a sheet, film or cup which may be adhered to or fitted to one or more parts of the applicator 10. Such a release material may be present in the applicator 10 prior to it being supplied with the treatment composition 70.

As discussed with reference to Fig. 4A, the applicator of the invention may further include a cover film or sheet of barrier material which advantageously spans the open base of the base section 20, and preferably is removably adhered to the base face 26. After manufacture of the applicator containing a mass of the adhesive lavatory treatment composition, such a cover film or sheet of barrier material may be applied to the applicator 10, such as across the open end of the base section 20 or lower cavity 24, e.g., may be applied to the base face 26. Such a cover film or sheet of barrier material may be of any suitable material, e.g., a synthetic polymer material, a metal or metallic foil or film, a metallized polymer film, multilayered materials, e.g., comprising at least two polymer layers and/or at least one polymer layer and at least one further layer such as a paper, cardboard, foil, metallic film and the like. The cover film or sheet of barrier material may be applied to the applicator using a suitable adhesive. Additionally or alternately the cover film or sheet of barrier material may be a rigid article, such as a cover or cap which may be fitted onto or adhered onto the applicator and removed prior to delivery of the adhesive lavatory treatment composition from the applicator.

Each form of dispensing means provides specific advantages. Dispensers such as compressible tubes, or compressible bottles and flasks may permit for the dispensing of variable amounts of the adhesive lavatory treatment compositions which may be desired from a consumer standpoint, so that the amounts delivered on each application are not limited to a specific dose. However dispensers which supply an approximately uniform mass and/or quantity of the adhesive lavatory treatment composition on each dispensing operation may be advantageous as providing a consistent amount which may be preferred in certain applications or by consumers.

Compositions of adhesive lavatory treatment compositions according to the invention are particularly well adapted for use with a lavatory appliance in order to provide a cleaning and/or fragrancing and/or sanitizing and/or other technical benefit thereto. In use, a quantity of an adhesive lavatory treatment composition is applied directly to a part of a lavatory appliance, advantageously in a part thereof wherein the adhered adhesive lavatory treatment composition is in the path of flowing water, e.g., flush water, which impinges upon the adhered adhesive lavatory treatment compositions and slowly erodes the same, and thereby forming a lavatory treatment liquid which comprises the water which entrains one or more of the constituents of the adhesive lavatory treatment compositions which has been released by the water. Depending upon the specific constituents used to form the adhesive lavatory treatment compositions, various technical benefits may be provided by the thus formed lavatory treatment liquid. Thus, an aspect of the invention provides a method of for treating a lavatory appliance comprising the steps of: applying an adhesive lavatory treatment composition directly to a part ofa lavatory appliance wherein the adhered adhesive lavatory treatment composition is in the path of flowing water, e.g., flush water, which impinges upon the adhered adhesive lavatory treatment compositions and slowly erodes the same, and, operating the lavatory appliance to dispense a flow of water which impinges on the adhesive lavatory treatment composition is in the path of flowing water thereby forming a lavatory treatment liquid which treats the lavatory appliance.

Examples:

Compositions of adhesive lavatory treatment compositions according to the invention were produced, and are identified on Table 1. These example compositions were formed generally in accordance with the following steps.

To a mixing vessel equipped with a motorized stirrer and with a hotplate or suitable heating mantle was first added the organic solvent constituent, to which was added the primary adhesion promoter constituent. Next, the motorized stirrer was activated, and the contents of the mixing vessel was stirred throughout the balance of the process, and the contents of the vessel was heated to approximately 120°C. The mixture of within the vessel were stirred until the primary adhesion promoter was fully melted, and the contents of the vessel were homogenous. Thereafter, the heat was disengaged, and mixing was continued until the composition was homogenous. The heat was removed, and under stirring the contents and the mixing vessel was allowed to cool under ambient room temperature (20 - 22°C) conditions, until the temperature of the vessel contents was about 80°C. Thereafter under stirring conditions were added the surfactants, and these were mixed in until the composition was again homogenous. Then the speed of the agitator of the mixer was increased to a high speed, and then were added the co- adhesion promoters, and mixing continued until the composition was again homogenous, and the temperature was allowed to further decrease. When the temperature of the mixing composition was about 40 - 45 °C, the remaining constituents were added to the mixing vessel, and mixing continued until the composition was again homogenous, after which the motorized stirrer was removed from the mixing vessel and the composition was allowed to cool under ambient room temperature conditions to room temperature, after which the composition was withdrawn and used.

The identity of the constituents of Table 1 are disclosed on the following Table 2.

Samples of the compositions of the invention were very viscous or pasty and are self-supporting, viz., and did not sag or run under their own weight.

Individual samples each weighing 3- 4 grams of each of the formulations of Table 1 were prepared as described above wherein the constituents were heated to 50°C, and supplied to the interior of a single-use extrusion type applicator as disclosed in copending GB Patent Application 1007066.2, or GB patent application 1007064.7, or as described with reference to the dispenser disclosed in Figs. 3A, 3B, 3C and 3D and thereafter were allowed to cool within the interior of the said applicator for at least 1 hour at room temperature. The samples were thereafter we applied to the interior curved surface of a toilet bowl (Type: Jacob Delafon) by operating the applicator to extnide the mass which had been immediately prior been cleaned and dried using a hand operated heated blower in order to ensure that the surface to which the sample composition was applied was anhydrous. The samples were applied at a point approximately 5 - 7 cm. below the rim of the toilet bowl. Thereafter the flushing of the toilet was controlled automatically to provide one of the recited test conditions. During the tests, the condition of the applied samples were visually evaluated and inspected periodically. The performance of the applied sample compositions were evaluated according to the following three tests:

"Accelerated Lifespan Test" which test was performed by automatically controlling the flushing operation of the toilet bowl such that, after application of the sample, the toilet was caused to flush at 60 second intervals, and was flushed at least 84 times. This test evaluated the performance of the samples without permitting for any significant period of time between flushes and for drying of the applied sample. The number of flushes for which the sample was retained on the inner sidewall of the toilet bowl or for which the sample still provided visible foaming in the bottom (sump) of the toilet bowl are reported on the foregoing tables.

"7 Day Lifespan Test" which test was performed by automatically controlling the flushing operation of the toilet bowl such that, after application of the sample, the toilet was caused to flush at 120 minute intervals, 12 times daily, and this flushing pattern was continued for 7 days. The number of flushes for which the sample was retained on the inner sidewall of the toilet bowl or for which the sample still provided visible foaming in the bottom (sump) of the toilet bowl are reported on the foregoing tables.

"Foaming Test" which test was performed by visually observing the coverage of the foam present in the bottom of the toilet bowl following every 10 flushes of the 7 Day Lifespan Test, and ranking the coverage of the surface of the water in the sump relative to the rankings presented on Fig. 1. The percentage of coverage is reported on the foregoing tables.

The sample formulations of Table 1A demonstrate especially preferred examples of the inventive compositions. The sample formulations of Table IB demonstrate satisfactory, but less preferred examples of the inventive compositions. The sample formulations of Table 1 C demonstrate examples which are considered inferior to those of Tables 1 A and lB,and are amongst least preferred embodiments. As is evident from the above, preferred example compositions exhibited adhesivity and a satisfactory service life even under the hard conditions to which the samples were exposed.

While the invention is susceptible of various modifications and alternative forms, it is to be understood that specific embodiments thereof have been shown by way of example in the drawings which are not intended to limit the invention to the particular forms disclosed; on the contrary the intention is to cover all modifications, equivalents and alternatives falling within the scope and spirit of the invention as expressed in the appended claims.

Claims

Claims:

An adhesive lavatory treatment compositions which are essentially anhydrous (comprise less than about 0.01%wt. water, preferably less than about 0.05% water, alternately and/or more preferably, comprise no water as an added constituent to the said compositions) and which comprise:

about 1 - 25%wt, preferably about 5 - 25%wt. of an organic solvent constituent, which is liquid at room temperature (20°C),

about 5 - 50%wt., preferably about 15 - 30%wt. of at least one surfactant; at least about 25%wt, preferably at least about 30%wt., yet more preferably at least about 40%wt. of a primary adhesion promoter constituent based on one or more oxyalkylenated compounds which includes two or more different oxyalkylenated compounds at least one of which is pasty or is solid at room temperature (20°C) and which preferably have different molecular weights, and preferably each having a minimum molecular weight of about 500;

0 - 5%wt. of at least one co-adhesion promoter;

wherein in use, the said adhesive lavatory treatment compositions maybe applied and adhered to a dry ceramic surface, especially the interior sidewall in a toilet bowl or other lavatory appliance, and wherein the said adhesive lavatory treatment compositions is retained adhered to the said surface following a plurality of flushes of water impinging upon the adhered adhesive lavatory treatment compositions.

An adhesive lavatory treatment composition according to claim 1, wherein:

the at least one alkanolamide based nonionic surfactant is selected from fatty monoalkanol amides and fatty dialkanolamides. An adhesive lavatory treatment composition according to any preceding claim, which further comprises a co-adhesion promoter constituent.

An adhesive lavatory treatment composition according to claim 3, containing one or more compounds according to the structure:

wherein,

R is a fatty acid moiety, preferably a stearic fatty acid moiety, and

the sum ofw + x + y + z is in the range of 50 - 1500, preferably in the range of 70 - 500, more preferably in the range of about 100 - 350 and especially preferably about 150, as a co-adhesion promoter constituent

An adhesive lavatory treatment composition according to claim 3, containing one or more high molecular weight water-soluble poly(ethylene oxide) polymers, having molecular weights (weight average) in the range from about 100,000 to about 8,000,000 as a co-adhesion promoter constituent.

An adhesive lavatory treatment composition according to any preceding claim, wherein the primary adhesion promoter constituent includes three or more oxyalkylenated compounds which includes three or more different oxyalkylenated compounds at least one of which is pasty or is solid at room temperature (20°C) and wherein each of the three or more oxyalkylenated compounds have different molecular weights, and each of the three or more oxyalkylenated compounds has a minimum (weight average) molecular weight of about 500. An adhesive lavatory treatment composition according to any preceding claim, wherein the primary adhesion promoter constituent includes, or consists of, a plurality of poly(alkylene glycols) includes two or more, preferably three or more different poly(aIkylene glycols) which can be distinguished in having different (weight average) molecular weights wherein the poly(alkylene glycol) having the lowest molecular weight is one having a (weight avg.) molecular weight in the range of fi-om about 500 to about 1000, and is preferably about 600, and where all further poly(alkylene glycols) present have higher molecular weights, preferably have (weight avg.) molecular weights which are preferably at least twice, preferably at least thrice yet more preferably at least 4 or still more preferably at least 5 times the (weight avg.) molecular weight of the poly(alkylene glycol) having the lowest molecular weight present in the primary adhesion promoter constituent.

An adhesive lavatory treatment composition according to any preceding claim, wherein the primary adhesion promoter constituent includes, or consists of, a plurality of poly(alkylene glycols) includes two or more, preferably three or more different poly(alkylene glycols) which can be distinguished in having different (weight average) molecular weights wherein the mass or weight proportion of the poly(a!kylene glycol) having the lowest molecular weight is greater than that of an other single higher molecular weight poly(alkylene glycol) present in the primary adhesion promoter constituent.

An adhesive lavatory treatment composition according to any preceding claim, substantially as described with reference to the Examples.

A method treating a lavatory appliance comprising the steps of:

applying an adhesive lavatory treatment composition according to any preceding claim directly to a part of a lavatory appliance wherein the adhered adhesive lavatory treatment composition is in the path of flowing water, e.g., flush water, which impinges upon the adhered adhesive lavatory treatment

compositions and slowly erodes the same, and,

operating the lavatory appliance to dispense a flow of water which impinges on the adhesive lavatory ti-eatment composition is in the path of flowing water thereby forming a lavatory treatment liquid which treats the lavatory appliance.