WO2012042251A1 - Compositions adhésives de traitement des wc - Google Patents

Compositions adhésives de traitement des wc Download PDF

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Publication number
WO2012042251A1
WO2012042251A1 PCT/GB2011/051818 GB2011051818W WO2012042251A1 WO 2012042251 A1 WO2012042251 A1 WO 2012042251A1 GB 2011051818 W GB2011051818 W GB 2011051818W WO 2012042251 A1 WO2012042251 A1 WO 2012042251A1
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WO
WIPO (PCT)
Prior art keywords
lavatory treatment
adhesive lavatory
adhesive
water
compositions
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PCT/GB2011/051818
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English (en)
Inventor
Lydia Nycz
Diane Joyce Burt
Original Assignee
Reckitt Benckiser Llc
Reckitt & Colman (Overseas) Limited
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Publication of WO2012042251A1 publication Critical patent/WO2012042251A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0056—Lavatory cleansing blocks
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/523—Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43—Solvents

Definitions

  • 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.
  • 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.
  • 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.
  • 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.
  • the example compositions disclosed therein comprise 3 - 60%wt. of water as a necessary constituent.
  • 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.
  • 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.
  • 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:
  • At least one surfactant which preferably is an alkanolamide based nonionic surfactant
  • 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;
  • 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.
  • 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.
  • 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.
  • 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.
  • organic solvent constituent may be single organic solvent, or may be a mixture of blend of two or more organic solvents.
  • 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
  • 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.
  • R a is an alkoxy of 1 to 20 carbon atoms, or aryloxy of at least 6 carbon atoms
  • Rb is an ether condensate of propylene glycol and/or ethylene glycol having from one to ten glycol monomer units.
  • 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.
  • 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
  • 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):
  • 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
  • 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.
  • 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.
  • the latter include paraffinic hydrocarbons including both linear and branched paraffinic hydrocarbons; the former are commercially available as NORPAR solvents (ex. ExxonMo
  • the organic solvent constituent is a single organic solvent, and preferably is a glycol ether, and other organic solvents are excluded.
  • 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.
  • 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.
  • 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
  • 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:
  • 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;
  • R 2 represents a -CH 2 - or -CH 2 C33 ⁇ 4-, and m is an integer from 1 to 3, but is preferably 1.
  • 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 ⁇ , 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
  • 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.
  • 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.
  • 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.
  • compositions may optionally but in certain cases preferably also include one or more further additional surfactants.
  • additional surfactants 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.
  • 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.
  • 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.
  • nonionic surfactants include primary and secondary linear and branched alcohol ethoxylates, such as those based on C 6 -Ci 8 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(CH 2 CH 2 0) n H wherein R is a mixture of linear, even carbon-number hydrocarbon chains ranging from Ci 2 H 25 to Ci6H 33 and n represents the number of repeating units and is a number of from 1 to about 12.
  • nonionic surfactants include secondary Ci 2 -Ci 5 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
  • nonionic surfactants include C 8 -Ci 6 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:
  • usefiil nonionic surfactants include C 6 -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.
  • alkyl glycoside surfactants including those which may be represented by formula I below:
  • 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.
  • x is a number having an average value from about 1 to 5 (preferably from 1.1 to 2); Z is 0 2 M
  • R 2 is (CH 2 )C0 2 M' or
  • CE CHCO2M 1 (with the proviso that Z can he 0 2 M ] only if Z is in place of a primary hydroxyl group in which the primary hydro xyl-bearing
  • b is a number of from 0 to 3 +l preferably an average of from 0.5 to 2 per glycosal group;
  • p 1 to 10
  • M 1 is H + or an organic or inorganic cation, such as, for example, an alkali metal, ammonium, mono ethanol amine, or calcium.
  • 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, APGTM 325 CS GLYCOSIDE which is described as being a 50% C9-C1 1 alkyl polyglycoside, also commonly referred to as D-glucopyranoside, (commercially available from Henkel Corp, Ambler PA) and GLUCOPONTM 625 CS which is described as being a 50% Ci 0 -C 16 alkyl polyglycoside, also commonly referred to as a D-glucopyranoside.
  • APGTM 325 CS GLYCOSIDE which is described as being a 50% C9-C1 1 alkyl polyglycoside, also commonly referred to as D-glucopyranoside, (commercially available from Henkel Corp, Ambler PA)
  • GLUCOPONTM 625 CS which is described as being a 50% Ci 0 -C 16 alkyl polyglycoside, also commonly referred to as a D-glucopyranoside.
  • nonionic surfactants are alkoxy block
  • Polymeric alkylene oxide block copolymers include nonionic surfactants in which the major portion of the molecule is made up of block polymeric C 2 -C 4 alkylene oxides.
  • 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-C 7 ) 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.
  • alkyl di(Ci-C 7 ) 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.
  • 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;
  • 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.
  • alkyl di(Ci-C 2 ) amine oxides in which the alkyl group has about 10-14, and preferably has 12 carbon atoms, which are preferably saturated.
  • 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
  • sulfosuccinates (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.
  • anionic surfactants include water soluble salts or acids of the formula (ROS0 3 ) x M or (RS0 3 ) x M wherein R is preferably a C 6 -C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a Cio-C 20 alkyl component, more preferably a Ci 2 -C 18 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.
  • R is preferably a C 6 -C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a Cio-C 20 alkyl component, more preferably a Ci 2 -C 18 alkyl or hydroxyalkyl
  • M is H or a mono-, di- or tri-valent cation, 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.
  • alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like
  • 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.
  • 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, C 6 -C 2 o linear alkylbenzenesulfonates, C 6 -C 22 primary or secondary alkanesulfonates, C 6 -C 2 4 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, C 6 -C 2 4 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)
  • 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.
  • carboxylates such as alkyl carboxylates which include those which may be represented by the general formula:
  • 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,
  • 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[, R 2 , R 3 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, R 2 , R 3 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.
  • alkylbetaines particularly those which may be represented by the following structural formula:
  • 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.
  • exemplary useful amphoteric surfactants include amidoalkylbetaines, such as amidopropylbetaines which may be represented by the following structural formula:
  • 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.
  • the cumulative amount of further surfactant compounds may form up to about 50%wt. of the present inventive compositions.
  • 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.
  • 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.
  • 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.
  • 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).
  • oxyalkylenated compound(s) typically comprise ethylene oxide groups (“EO") (oxyetnylenated compounds), or propylene oxide groups (“PO”) (oxypropylenated compounds) or both (“EO/PO”)
  • 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.
  • 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)
  • 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).
  • polypropylene glycol esters include condensates of polyethylene glycol and/or polypropylene glycol with one or more fatty acids. These compounds typically have the formula:
  • 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,
  • 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:
  • 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.
  • 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 (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.
  • 5 EO oxyethylenated EO
  • 5 PO oxypropylenated
  • 3 PO myristyl 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.
  • 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.
  • 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.
  • 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.
  • the primary adhesion promoter constituent comprises at least 25%wt. of the adhesive lavatory treatment compositions taught herein.
  • 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.
  • 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:
  • 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 %
  • Ri represents H or C3 ⁇ 4
  • y represents 0 or 1
  • R 2 represents— CH 2 — CHOH— CH 2 — or C x H 2x in which x is 2 to 18
  • R 3 represents CH 3 , C 2 H 5 or t-butyl
  • R4 represents CH 3 , C 2 3 ⁇ 4 or benzyl
  • X represents CI, Br, I, I/2SO 4 , HSO 4 and CH3SO 3
  • M is a vinyl or vinylidene monomer copolymerisable with vinyl pyrrolidone other than the monomer identified in [ ] m ;
  • 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;
  • 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:
  • R is a fatty acid moiety, preferably a stearic fatty acid moiety
  • 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.)
  • 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.).
  • 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
  • one or more of the foregoing co-adhesion promoters are expressly excluded from the adhesive lavatory treatment compositions.
  • 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.
  • 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 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.
  • 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.
  • 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.
  • 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..
  • 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.
  • 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.
  • a germicide constituent other than cationic germicidally active quaternary ammonium halide surfactants noted above
  • 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").
  • PCMC parachlorometaxylenol
  • PCMX parachlorometaxylenol
  • 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
  • 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.
  • organic acids such as salicylic and citric acid
  • inorganic acid such as hydrochloric acid
  • inventive compositions may comprise bleaches and/or bleach releasing compounds.
  • 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
  • sodium hypochlorite having the chemical formula NaOCl
  • an oxidizing constituent or agent may be present in the inventive compositions.
  • 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.
  • the oxidizing agent is hydrogen peroxide.
  • oxidizing agent 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.
  • 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.
  • 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.
  • 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.
  • comminuted particles or spheres formed from uncolored or colored synthetic polymers such as “glitter”
  • visible light reflective particles commonly referred to as "glitter”
  • alginate beads such as those described in PCT/US95/08313, US Patent 7196046, US Patent 7291586 B2
  • such visibly discernible materials have a maximum dimension in the range of from about 100 to about 1000 ⁇ .
  • 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.
  • inert fillers include powders such as silicates, chalk, talc, kaolin, chemically modified magnesium aluminum silicate, hydrated aluminum silicate, fumed silica, and mixtures thereof
  • 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%
  • 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.
  • 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.
  • 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.
  • 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- ⁇ , ⁇ - diacetic acid, as well as methyl-glycine-diacetic acid.
  • chelating agents include those marketed under the "Dissolvine" trademark (ex. AkzoNobel) including Dissolvine GL-PD-S, and Dissolvine E-CA- 10 materials.
  • butane homopolymers e.g., polyisobutene, such as may be commercially obtained as TPC 1350 from Texas Petro Chemicals Co.
  • an emulsifying agent preferably sucrose acetate isobutyrate such as is commercially available as Eastman SAIB-100 (ex. Eastman Chemical Co.)
  • 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.
  • the constituents such as the organic solvent constituent
  • 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.
  • 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.
  • the composition may be heated to lower the viscosity thereof and to improve its fluidity to facilitate delivery into a suitable dispenser.
  • 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.
  • 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.
  • 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.
  • especially preferred hard surfaces include non-wetted or dry surfaces of lavatory appliances, particularly the interior surface of a toilet bowl.
  • the compositions may be flushed away after a plurality of flushing operations, preferably following a relatively large number of flushing operations.
  • lavatory devices e.g., toilets
  • 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 cm 2 ) 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.
  • 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.
  • a dispensing means which contains a quantity of an the adhesive lavatory treatment composition as taught herein.
  • 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.
  • 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.
  • 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.
  • FIG. 2A1 depicts a perspective view of the applicator 10 in first configuration
  • 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
  • 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.
  • 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.
  • 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
  • Fig. 3C presents a side plan view of the dispensing device 10
  • Fig. 3D presents a bottom plan view of the dispensing device 10.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • the spent applicator 10 is properly disposed of, e.g.
  • Applicators useful with the adhesive lavatory treatment compositions of the invention may be manufactured or formed from any suitable material of construction.
  • applicators are manufactured, such as by injection molding, from a suitable synthetic polymer.
  • 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.
  • polyamides e.g., nylons
  • polyolefins e.g., polypropylene, polyethylene
  • polyalkyleneterephalates e.g., polyethylene terephthalate, polybutylene terephthalate
  • polystyrenes e.g., poly
  • 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.
  • 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.
  • a release material may be present in the applicator 10 prior to it being supplied with the treatment composition 70.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • an adhesive lavatory treatment composition 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
  • operating the lavatory appliance to dispense a flow of water which impinges on the adhesive lavatory treatment composition is
  • 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.
  • 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.
  • 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:
  • 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.
  • preferred example compositions exhibited adhesivity and a satisfactory service life even under the hard conditions to which the samples were exposed.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

La présente invention concerne des compositions adhésives de traitement des WC qui sont essentiellement anhydres (qui comprennent moins d'environ 0,01 % en poids d'eau, de préférence moins d'environ 0,05 % d'eau, en variante et/ou de préférence, qui ne comprennent pas d'eau en tant que constituant ajouté auxdites compositions) et qui comprennent : environ 1 à 25 % en poids, de préférence environ 5 à 25 % en poids d'un constituant solvant organique, environ 5 à 50 % en poids d'au moins un tensioactif, de préférence un tensioactif non ionique à base alcanolamide; au moins environ 25 % en poids d'un constituant promoteur d'adhésion primaire à base d'un ou plusieurs composés oxyalkylénés qui comprennent deux composés oxyalkylénés différents ou plus, 0 à 5 % en poids d'au moins un co-promoteur d'adhésion; éventuellement un ou plusieurs autres constituants facultatifs qui peuvent conférer un avantage esthétique ou technique supplémentaire auxdites compositions adhésives de traitement des WC. Lesdites compositions adhésives de traitement des WC peuvent, durant l'utilisation, être appliquées et collées sur une surface en céramique sèche, notamment à la paroi latérale intérieure d'une cuvette de WC ou d'un autre appareil sanitaire de WC, et lesdites compositions adhésives de traitement des WC restant collées sur ladite surface après avoir été exposées à une pluralité de rinçages par la chasse d'eau.
PCT/GB2011/051818 2010-10-01 2011-09-26 Compositions adhésives de traitement des wc WO2012042251A1 (fr)

Applications Claiming Priority (2)

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GB1016491.1 2010-10-01
GBGB1016491.1A GB201016491D0 (en) 2010-10-01 2010-10-01 Adhesive lavatory treatment compositions

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015114306A1 (fr) * 2014-01-30 2015-08-06 Reckitt Benckiser (Brands) Limited Composition de traitement de toilettes adhésive et article de distribution
KR20180120426A (ko) 2017-04-27 2018-11-06 주식회사 엘지생활건강 고부착성 욕실 세정용 조성물
US20220282181A1 (en) * 2021-03-04 2022-09-08 The Procter & Gamble Company Hard surface cleaning composition comprising polyalkylene glycol

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EP1978080A1 (fr) 2007-03-29 2008-10-08 Bolton Manitoba SpA Composition hygiénisante adhésive pour le nettoyage et/ou la désinfection et/ou parfumer des installations sanitaires
WO2009106220A1 (fr) * 2008-02-29 2009-09-03 Buck-Chemie Gmbh Agent collant pour l'application sur un objet sanitaire
US9508313B2 (en) 2007-11-15 2016-11-29 Sony Corporation Display device, program information display method in display device, receiving device, and signal transmission method in receiving device

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Publication number Priority date Publication date Assignee Title
GB1007066A (en) 1962-12-22 1965-10-13 Le Bouchon Rapid Improvements in or relating to metallic capsule, notably for bottles
GB1007064A (en) 1963-09-24 1965-10-13 Austin Motor Co Ltd Thermal regenerators
GB1082179A (en) 1965-07-19 1967-09-06 Citrique Belge Nv Unsaturated carboxylic salt materials and derivatives thereof
US3929678A (en) 1974-08-01 1975-12-30 Procter & Gamble Detergent composition having enhanced particulate soil removal performance
EP0154421A1 (fr) * 1984-02-09 1985-09-11 Creative Products Resource Associates Ltd. Produit pour le lavage de la vaisselle en machine
EP0369992A2 (fr) * 1986-06-20 1990-05-23 Kiwi Brands Inc Agent de nettoyage pour cuvette de toilettes
US6667286B1 (en) 1998-06-12 2003-12-23 Buck-Chemie Gmbh Adhesive sanitary agent
US7196046B2 (en) 2001-08-31 2007-03-27 Reckitt Benckiser Inc. Hard surface cleaner comprising a suspension of alginate beads
US7291586B2 (en) 2003-02-22 2007-11-06 Reckitt Benckiser Inc. Hard surface cleaning compositions comprising suspended alginate inclusions
DE102004056554A1 (de) * 2004-11-23 2006-05-24 Buck-Chemie Gmbh Haftendes Sanitärreinigungs- und Beduftungsmittel
EP1978080A1 (fr) 2007-03-29 2008-10-08 Bolton Manitoba SpA Composition hygiénisante adhésive pour le nettoyage et/ou la désinfection et/ou parfumer des installations sanitaires
US9508313B2 (en) 2007-11-15 2016-11-29 Sony Corporation Display device, program information display method in display device, receiving device, and signal transmission method in receiving device
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Publication number Priority date Publication date Assignee Title
WO2015114306A1 (fr) * 2014-01-30 2015-08-06 Reckitt Benckiser (Brands) Limited Composition de traitement de toilettes adhésive et article de distribution
AU2015212604B2 (en) * 2014-01-30 2019-05-02 Reckitt Benckiser (Brands) Limited Adhesive lavatory treatment composition and dispensing article
AU2015212604B9 (en) * 2014-01-30 2019-05-30 Reckitt Benckiser (Brands) Limited Adhesive lavatory treatment composition and dispensing article
KR20180120426A (ko) 2017-04-27 2018-11-06 주식회사 엘지생활건강 고부착성 욕실 세정용 조성물
US20220282181A1 (en) * 2021-03-04 2022-09-08 The Procter & Gamble Company Hard surface cleaning composition comprising polyalkylene glycol

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