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EP2207870A2 - Compositions de bloc de traitement de toilettes ayant une substantivité de moussage avantageuse et une durée de vie améliorée - Google Patents

Compositions de bloc de traitement de toilettes ayant une substantivité de moussage avantageuse et une durée de vie améliorée

Info

Publication number
EP2207870A2
EP2207870A2 EP08806319A EP08806319A EP2207870A2 EP 2207870 A2 EP2207870 A2 EP 2207870A2 EP 08806319 A EP08806319 A EP 08806319A EP 08806319 A EP08806319 A EP 08806319A EP 2207870 A2 EP2207870 A2 EP 2207870A2
Authority
EP
European Patent Office
Prior art keywords
blocks
lavatory
treatment
water
lavatory treatment
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP08806319A
Other languages
German (de)
English (en)
Inventor
Robert Zhong Lu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Reckitt Benckiser LLC
Original Assignee
Reckitt Benckiser LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Reckitt Benckiser LLC filed Critical Reckitt Benckiser LLC
Publication of EP2207870A2 publication Critical patent/EP2207870A2/fr
Withdrawn legal-status Critical Current

Links

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
    • 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
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0094—High foaming compositions
    • 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2065—Polyhydric alcohols

Definitions

  • the present invention relates to improved solid treatment block compositions useful for providing an active treatment composition to a sanitary appliance, e.g., a toilet or urinal.
  • Solid treatment blocks have found widespread use in the cleaning and/or disinfecting treatment of sanitary appliances as, once installed they require little or no user intervention during their effective service life. Such solid treatment block compositions are considered to operate in an automatic fashion and their effective functioning is dependent in great part upon their composition, their dissolution characteristics when contacted with water and their placement within the sanitary appliance which they are used to treat. Typically such solid treatment block compositions are used in either one of two modes, either as an "ITC” or "in the cistern” mode, or as an "ITB" or “in the bowl” mode.
  • the solid treatment block composition is placed in water supply tank, also known as the cistern or toilet tank wherein it is expected to dissolve over a period of time and thus deliver active cleaning and/or disinfecting constituents to the water present in the cistern which is periodically used to flush the toilet bowl or other sanitary appliance, e.g., a urinal.
  • a solid treatment block composition may be supplied to the interior of the cistern as a tablet or other self supporting shape, or alternately the solid treatment block composition may be provided in a container or cage, or as part of a dispensing device, from which the active cleaning and/or disinfecting constituents are delivered to the water present in the cistern.
  • the solid treatment block composition is placed within the bowl, typically supported by a device, cage, or even a simple bent wire such that the active cleaning and/or disinfecting constituents are contacted with water flushed into the sanitary appliance, especially the bowl of a toilet, or the interior of a urinal.
  • a part of the solid treatment block composition is dissolved with each flush of water passing though the device such that an amount of active cleaning and/or disinfecting constituents are dispensed to the toilet bowl, urinal, etc.
  • the art is replete with many forms of solid treatment block compositions which find use either as ITB or ITC type compositions.
  • solid treatment block compositions include those described in the following: US Patent 4246129; US Patent 4269723; US Patent 4043931; US Patent 4460490; US Patent 4722802; US Patent 4820449; US Patent 5342550; US Patent 5562850; US Patent 5711920; US Patent5759974; US Patent 5939372; US Patent 6001789 as well as US Patent 6294510.
  • Each of these patents disclosed solid treatment block compositions which provide specific technical benefits, or overcome specific technical shortcomings which were hithero known to the art until the time of the respective invention.
  • various processing shortcomings are known from the manufacture of such blocks, or from the dissolution characteristics of such blocks as are described in these patents or which are otherwise known to the relevant ait.
  • a primary shortcoming resides in the fact that the foam formation characteristics of such devices including conventional lavatory treatment blocks are poor. Frequently little or no foam is retained in the sanitary appliance, e.g., a toilet bowl at the conclusion of a flush cycle for any appreciable period of time. Such foam, if formed, rarely covers the surface of the water present in the bottom of a toilet bowl for any satisfactory length of time, and such foam frequently rather quickly breaks down or dissipates. When such foam is formed it generally not particularly voluminous and/or particularly substantive and may appeal" thin, and also frequently rather quickly breaks down or dissipates. Thus, prior art compositions suffer these and other technical shortcomings which the present invention addresses.
  • the present invention in its various aspects, provides lavatory treatment blocks which are used to deliver a treatment composition to a sanitary appliance, particularly to a toilet, which treatment composition contains one or more chemical constituents e.g., coloring agents, cleaning agents, disinfecting agents, anti-lime scale agents which blocks are used to provide a cleaning composition and/or a sanitizing composition and/or disinfecting compsition to a sanitary appliance, e.g. a toilet bowl.
  • the lavatory treatment blocks can be used either as an ITC type device, or an ITB type device for a sanitary appliance such as a urinal, toilet tank or toilet bowl, or can be used independently in the form of a block, tablet or cake and not necessarily as a part of an ETC or ITB device.
  • the device according to the invention is used as an ITB type device, hi certain alternate preferred embodiments the device according to the invention is used as an ITC type device.
  • the lavatory treatment blocks provide improved foaming benefits, which may be manifested by improved foaming and/or improved substantivity of foam formed with the use of the improved lavatory treatment blocks taught herein.
  • lavatory treatment blocks with improved foaming benefits wherein the said blocks contain a foam improving amount of glycerine.
  • lavatory treatment blocks with improved foaming benefits wherein the said blocks contain a foam improving amount of a surfactant constituent which comprises glycerine.
  • lavatory treatment blocks with improved foaming benefits wherein the said blocks contain a foam improving amount of a surfactant constituent which comprises, in combination, a fatty amide, such as cocoamide diethanolamide with glycerine.
  • a surfactant constituent which comprises, in combination, a fatty amide, such as cocoamide diethanolamide with glycerine.
  • a lavatory dispensing device preferably which may be an ITB device or an ITC device, comprising one or more lavatory treatment blocks according to the first, second or third aspects of the invention which are adapted for use with a sanitary appliance, preferably a toilet.
  • a lavatory dispensing device comprising one or more lavatory treatment blocks according to the first, second or third aspects of the invention which are adapted for use with a sanitary appliance, preferably a toilet, wherein the said blocks provide an improved foaming benefit.
  • a process for delivering a treatment composition to a sanitary appliance comprises: providing one or more lavatory treatment blocks according to the first, second or third aspects recited above, and, periodically flushing water about the exterior of the said blocks to elute at least one chemical constituent to form a treatment composition with said water which treatment composition is used to treat apart of the sanitary appliance.
  • a process for delivering a treatment composition to a toilet bowl comprises: providing one or more lavatory treatment blocks according to the first, second or third aspects recited above, and, periodically flushing water about the exterior of the said blocks to elute at least one chemical constituent to form a treatment composition with said water which treatment composition is used to treat a part of the sanitary appliance.
  • a process for delivering a treatment composition to a sanitary appliance comprises: providing one or more lavatory treatment blocks according to the first, second or third aspects recited above within the said cistern or tank, and, continuously immersing or periodically immersing at least a part of the blocks in the water within the cistern or tank so to elute at least one chemical constituent from each of the lavatory treatment blocks to form a treatment composition with the water which is used to treat a part of the sanitary appliance.
  • a process for delivering a treatment composition to a to the interior of a toilet bowl comprises: providing one or more lavatory treatment blocks according to the first, second or third aspects recited above, preferably via use of an ITB device, suspending said block from a part of the toilet bowl, preferably from a part of the rim thereof, such that at least one chemical constituent of the block is used to form a treatment composition therefrom which is used to treat the interior of the toilet bowl when the treatment composition formed is used to flush the toilet bowl.
  • a vendible article one or more lavatory treatment blocks according to the first, second or third aspects recited above for use with a sanitary appliance, particularly a toilet.
  • a lavatory dispensing device comprising one or more lavatory treatment blocks according to the first, second or third aspects recited above for use with a sanitary appliance, particularly a toilet.
  • the lavatory treatment blocks of the invention provide an improved foaming benefit.
  • Such may be provided, for example by including glycerine as an essential constituent in order to improve the foaming characteristics of the blocks.
  • Glycerine may be provided as a separate or discrete constituent which used to form a block composition, or it may be provided as part of a surfactant constituent or composition which comprises glycerine, such as a commercially available surfactant preparation which in addition to at least one surfactant such as a fatty amide, such as coco amide diethanolamide, also includes glycerine.
  • the lavatory treatment blocks may additionally include one or more further chemical constituents such that when the block is immersed, rinsed or washed with water, said chemical constituents are eluted or dissolved into said water and forms a treatment composition which is useful in treating a sanitary appliance, and particularly a toilet tank or cistern or a toilet bowl.
  • a treatment composition formed from the blocks may provide a cleaning and/or sanitizing and/or disinfecting benefit to the toilet or other sanitary appliance being treated with the blocks of the invention.
  • the lavatory treatment blocks may include any known art cleaning agents or cleaning constituents known to those of ordinary skill in the relevant art, and without limitation include one or more detersive surfactants selected from anionic, cationic, nonionic as well as amphoteric or zwitterionic surfactants. Certain detersive surfactants may also provide a dual role in providing detergency as well as a disinfecting effect, viz, certain cationic surfactants, which are described hereinafter as a disinfecting agent. These one or more cleaning agents or cleaning constituents may be used with or without other constituents being present in the lavatory treatment blocks of the invention.
  • the lavatory treatment blocks of the invention desirably comprises a surfactant constituent which may be one or more detersive surfactants.
  • exemplary useful surfactants include anionic, nonionic, cationic, amphoteric, and zwitterionic surfactants, particularly those whose melting points are sufficiently high, above about 110 0 F., preferably above 125°F., to permit processing according to known art techniques.
  • small amounts of low melting point surfactants and even liquid surfactants may be used in providing the surfactant constituent.
  • Exemplary useful anionic surfactants which may be used in the treatment block compositions of the invention can be broadly described as the water-soluble salts, particularly the alkali metal salts, of organic sulfuric acid reaction products having in their molecular structure an alkyl or alkaryl radical containing from about 8 to about 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals.
  • alkyl is the alkyl portion of higher acyl radicals.
  • anionic surfactants which can be employed in practicing the present invention are the sodium or potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C 8 -Cis carbon atoms) produced by reducing the glycerides of tallow or coconut oil; sodium or potassium alkyl benzene sulfonates, in which the alkyl group contains from about 9 to about 15 carbon atoms, (the alkyl radical can be a straight or branched aliphatic chain); paraffin sulfonate surfactants having the general formula RSO 3 M, wherein R is a primary or secondary alkyl group containing from about 8 to about 22 carbon atoms (preferably 10 to 18 carbon atoms) and M is an alkali metal, e.g., sodium, lithium or potassium; sodium alkyl glyceryl ether sulfonates, especially those ether
  • a preferred class of anionic surfactants are linear alkyl benzene sulfonate surfactant wherein the alkyl portion contains 8 to 16 carbon atoms, and most preferably about 11 to 13 carbon atoms.
  • the solid block compositions necessarily include an anionic surfactant.
  • a further preferred class of anionic surfactants are alpha olefin sulfonates, as well as salts thereof, e.g., alkali metal salts.
  • Preferred are C 8 through C 22 alpha olefin sulfonates, particularly Ci 2 through C 18 , and especially Ci 4 , and Ci 6 alpha olefin sulfonates as well as blends of two or more thereof.
  • the solid block compositions necessarily include an alpha olefin sulfonate anionic surfactant.
  • a yet further preferred class of anionic surfactants are linear alkyl benzene sulfonate surfactant wherein the alkyl portion contains 8 to 16 carbon atoms, and most preferably about 11 to 13 carbon atoms.
  • the solid block compositions necessarily include an anionic surfactant, especially linear alkyl benzene sulfonates containing 11, 12 or 13 carbon atoms, as well as salt forms thereof.
  • the most preferred anionic surfactants are sodium alkylaryl sulfonates sold commercially by Albright & Wilson Warley, England under the trademarks NANSA, and UFARYL sold by Unger Fabrikker, Fredistad, Norway, either individually or in combination.
  • the detersive surfactant constituent of the solid block compositions of the invention may include one or more nonionic surfactants.
  • any hydrophobic compound having a carboxy, hydroxy, amido, or amino group with a free hydrogen attached to the nitrogen can be condensed with an alkylene oxide, especially ethylene oxide or with the polyhydration product thereof, a polyalkylene glycol, especially polyethylene glycol, to form a water soluble or water dispersible nonionic surfactant compound.
  • the length of the polyethenoxy hydrophobic and hydrophilic elements may various.
  • nonionic compounds include the polyoxyethylene ethers of alkyl aromatic hydroxy compounds, e.g., alkylated polyoxyethylene phenols, polyoxyethylene ethers of long chain aliphatic alcohols, the polyoxyethylene ethers of hydrophobic propylene oxide polymers, and the higher alkyl amine oxides.
  • One class of useful nonionic surfactants include polyalkylene oxide condensates of alkyl phenols.
  • These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration with an alkylene oxide, especially an ethylene oxide, the ethylene oxide being present in an amount equal to 5 to 25 moles of ethylene oxide per mole of alkyl phenol.
  • the alkyl substituent in such compounds can be derived, for example, from polymerized propylene, diisobutylene and the like.
  • Examples of compounds of this type include nonyl phenol condensed with about 9.5 moles of ethylene oxide per mole of nonyl phenol; dodecylphenol condensed with about 12 moles of ethylene oxide per mole of phenol; dinonyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol and diisooctyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol.
  • a further class of useful nonionic surfactants include the condensation products of aliphatic alcohols with from about 1 to about 60 moles of an alkylene oxide, especially an ethylene oxide.
  • the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms.
  • Examples of such ethoxylated alcohols include the condensation product of myristyl alcohol condensed with about 10 moles of ethylene oxide per mole of alcohol and the condensation product of about 9 moles of ethylene oxide with coconut alcohol (a mixture of fatty alcohols with alkyl chains varying in length from about 10 to 14 carbon atoms).
  • C 6 -C 11 straight-chain alcohols which are ethoxylated with from about 3 to about 6 moles of ethylene oxide.
  • Their derivation is well known in the art.
  • Examples include Alfonic® 810-4.5, which is described in product literature from Sasol as a Cg-C 10 straight-chain alcohol having an average molecular weight of 356, an ethylene oxide content of about 4.85 moles (about 60 wt.%), and an HLB of about 12;
  • Alfonic® 810-2 which is described in product literature as a C 8 -C I0 straight-chain alcohols having an average molecular weight of 242, an ethylene oxide content of about 2.1 moles (about 40 wt.%), and an HLB of about 12;
  • Alfonic® 610-3.5 which is described in product literature as having an average molecular weight of 276, an ethylene oxide content of about 3.1 moles (about 50 wt.%), and an HLB of 10.
  • alcohol ethoxylates are Ci 0 oxo-alcohol ethoxylates available from BASF under the Lutensol® ON tradename. They are available in grades containing from about 3 to about 11 moles of ethylene oxide (available under the names Lutensol® ON 30; Lutensol® ON 50; Lutensol® ON 60; Lutensol® ON 65; Lutensol® ON 66; Lutensol® ON 70; Lutensol® ON 80; and Lutensol®ON 110).
  • ethoxylated alcohols include the Neodol® 91 series non-ionic surfactants available from Shell Chemical Company which are described as Cg-C 11 ethoxylated alcohols.
  • Neodol® 91 series non-ionic surfactants of interest include Neodol® 91-2.5, Neodol® 91-6, and Neodol® 91-8.
  • Neodol® 91-2.5 has been described as having about 2.5 ethoxy groups per molecule;
  • Neodol 91-6 has been described as having about 6 ethoxy groups per molecule;
  • Neodol 91-8 has been described as having about 8 ethoxy groups per molecule.
  • Further examples of ethoxylated alcohols include the Rhodasurf® DA series non-ionic surfactants available from Rhodia which are described to be branched isodecyl alcohol ethoxylates.
  • Rhodasurf® DA-530 has been described as having 4 moles of ethoxylation and an HLB of 10.5; Rhodasurf® DA-630 has been described as having 6 moles of ethoxylation with an HLB of 12.5; and Rhodasurf® DA-639 is a 90% solution of DA- 630.
  • ethoxylated alcohols include those from Tomah Products (Milton, WI) under the Tomadol® tradename with the formula RO(CH 2 CH 2 O) n H where R is the primary linear alcohol and n is the total number of moles of ethylene oxide.
  • the ethoxylated alcohol series from Tomah include 91-2.5; 91-6; 91-8 - where R is linear CyCio/Cn and n is 2.5, 6, or 8; 1-3; 1-5; 1-7; 1-73B; 1-9; where R is linear C n and n is 3, 5, 7 or 9; 23-1; 23-3; 23-5; 23-6.5 - where R is linear C 12 /C 13 and n is 1, 3, 5, or 6.5; 25-3; 25-7; 25-9; 25-12 - where R is linear Q2/C1 3 /C 14 / Ci 5 and n is 3, 7, 9, or 12; and 45-7; 45- 13 - where R is linear C 14 / C 15 and n is 7 or 13.
  • a further class of useful 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 moles of ethoxylation per mol of alcohol. These examples include the Genapol® UD (ex.
  • Genapol® UD 030 Cn-oxo-alcohol polyglycol ether with 3 EO
  • Genapol® UD 050 C ⁇ -oxo-alcohol polyglycol ether with 5 EO
  • Genapol® UD 070 Cn- oxo-alcohol polyglycol ether with 7 EO
  • Genapol® UD 080 C ⁇ -oxo-alcohol polyglycol ether with 8 EO
  • Genapol® UD 088 C ⁇ -oxo-alcohol polyglycol ether with 8 EO
  • Genapol® UD 110 C ⁇ -oxo-alcohol polyglycol ether with 11 EO.
  • Exemplary useful nonionic surfactants include the condensation products of a secondary aliphatic alcohols containing 8 to 18 carbon atoms in a straight or branched chain configuration condensed with 5 to 30 moles of ethylene oxide.
  • Examples of commercially available nonionic detergents of the foregoing type are those presently commercially available under the trade name of Tergitol® such as Tergitol 15-S-12 which is described as being C 11 - C 1S secondary alkanol condensed with 9 ethylene oxide units, or Tergitol 15-S-9 which is described as being Cn -C1 5 secondary alkanol condensed with 12 ethylene oxide units per molecule.
  • a further class of useful nonionic surfactants include those surfactants having a formula:
  • R is amixture of linear, even carbon-number hydrocarbon chains ranging from C 12 H 25 to C 16 H 33 and n represents the number of ethoxy repeating units and is a number of from about 1 to about 12.
  • Surfactants of this formula are presently marketed under the Genapol® tradename (ex. Clariant), which surfactants include the "26-L” series of the general formula RO(CH 2 CH 2 O) n H wherein R is a mixture of linear, even carbon-number hydrocarbon chains ranging from C 12 H 25 to C 16 H 33 and n represents the number of repeating units and is a number of from 1 to about 12, such as 26-L-l, 26-L-1.6, 26-L-2, 26-L-3, 26-L-5, 26- L-45, 26-L-50, 26-L-60, 26-L-60N, 26-L-75, 26-L-80, 26-L-98N, and the 24-L series, derived from synthetic sources and typically contain about 55% C 12 and 45% Q 4 alcohols, such as 24-L-3, 24-L-45, 24-L-50, 24-L-60, 24-L-60N, 24-L-75, 24-L-92, and 24-L-98N, all sold under the Genapol® tradename.
  • non-ionic surfactants which may be used in the inventive compositions include those presently marketed under the trade name Pluronics® (ex. BASF).
  • the compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol.
  • the molecular weight of the hydrophobic portion of the molecule is of the order of 950 to 4,000 and preferably 200 to 2,500.
  • the addition of polyoxyethylene radicals of the hydrophobic portion tends to increase the solubility of the molecule as a whole so as to make the surfactant water-soluble.
  • the molecular weight of the block polymers varies from 1,000 to 15,000 and the polyethylene oxide content may comprise 20% to 80% by weight.
  • these surfactants are in liquid form and particularly satisfactory surfactants are available as those marketed as Pluronics® L62 and Pluronics® L64.
  • nonionic surfactants which may be included in the inventive compositions include alkoxylated alkanolamides, preferably C 8 -C 24 alkyl di(C 2 -C 3 alkanol amides), as represented by the following formula: R 5 -CO-NH-R 6 -OH wherein R 5 is a branched or straight chain C 8 -C 24 alkyl radical, preferably a Ci 0 -C 16 alkyl radical and more preferably a C 12 -C 14 alkyl radical, and R 6 is a C 1 -C 4 alkyl radical, preferably an ethyl radical.
  • the detersive surfactant constituent necessarily comprises a nonionic surfactant based on a linear primary alcohol ethoxylate particularly wherein the alkyl portion is a C 8 to Ci 6 , but particularly a C 9 to Cu alkyl group, and having an average of between about 6 to about 8 moles of ethoxylation.
  • nonionic surfactants include those in which the major portion of the molecule is made up of block polymeric C 2 -C 4 alkylene oxides, with alkylene oxide blocks containing C 3 to C 4 alkylene oxides.
  • Such nonionic surfactants while preferably built up from an alkylene oxide chain starting group, can have as a starting nucleus almost any active hydrogen containing group including, without limitation, amides, phenols, and secondary alcohols.
  • One group of nonionic surfactants containing the characteristic alkylene oxide blocks are those which may be generally represented by the formula (A):
  • PO represents propylene oxide
  • y equals at least 15
  • (EO) x+Z equals 20 to 50% of the total weight of said compounds, and, the total molecular weight is preferably in the range of about 2000 to 15,000.
  • Another group of nonionic surfactants appropriate for use in the new compositions can be represented by the formula (B):
  • nonionic surfactants which in general are encompassed by Formula B include butoxy derivatives of propylene oxide/ethylene oxide block polymers having molecular weights within the range of about 2000-5000.
  • nonionic surfactants containing polymeric butoxy (BO) groups can be represented by formula (C) as follows:
  • nonionic block copolymer surfactants which also include polymeric butoxy groups are those which may be represented by the following formula (D):
  • n is about 15, x is about 15 and y is about 15.
  • Still further useful nonionic block copolymer surfactants include ethoxylated derivatives of propoxylated ethylene diamine, which may be represented by the following formula: where (EO) represents ethoxy, (PO) represents propoxy, the amount of (PO) x is such as to provide a molecular weight prior to ethoxylation of about 300 to 7500, and the amount of (EO) y is such as to provide about 20% to 90% of the total weight of said compound.
  • nonionic surfactants include nonionic amine oxide constituent.
  • exemplary amine oxides include:
  • Alkyl di (lower alkyl) amine oxides in which the alkyl group has about 10- 20, and preferably 12-16 carbon atoms, and can be straight or branched chain, saturated or unsaturated.
  • the lower alkyl groups include between 1 and 7 carbon atoms. Examples 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;
  • Examples are bis(2 -hydro xyethyl) cocoamine oxide, bis(2- hydroxyethyl) 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.
  • the amine oxide constituent is an alkyl di (lower alkyl) amine oxide as denoted above and which may be represented by the following structure: wherein each:
  • R 1 is a straight chained C 1 -C 4 alkyl group, preferably both R 1 are methyl groups; and, R 2 is a straight chained C 8 -Ci 8 alkyl group, preferably is Ci 0 -C 14 alkyl group, most preferably is a C 12 alkyl group.
  • Each of the alkyl groups may be linear or branched, but most preferably are linear.
  • the amine oxide constituent is lauryl dimethyl amine oxide.
  • Technical grade mixtures of two or more amine oxides may be used, wherein amine oxides of varying chains of the R 2 group are present.
  • the amine oxides used in the present invention include R 2 groups which comprise at least 50%wt, preferably at least 60%wt. of Ci 2 alkyl groups and at least 25%wt. of Ci 4 alkyl groups, with not more than 15%wt. of Ci 6 , Ci 8 or higher alkyl groups as the R 2 group.
  • Still further exemplary useful nonionic surfactants which may be used include certain alkanolamides including monoethanolamides and diethanolamides, particularly fatty monoalkanolamides and fatty dialkanolamides.
  • a cationic surfactant may be incorporated as a germicide or as a detersive surfactant in the solid block composition of the present invention, particularly wherein a bleach constituent is absent from the solid block composition.
  • Cationic surfactants are per se, well known, and exemplary useful cationic surfactants may be one or more of those described for example in McCutcheon 's Functional Materials, Vol.2, 1998; Kirk- Othmer, Encyclopedia of Chemical Technology, 4th Ed., Vol. 23, pp. 481-541 (1997), the contents of which are herein incorporated by reference. These are also described in the respective product specifications and literature available from the suppliers of these cationic surfactants.
  • cationic surfactant compositions useful in the practice of the instant invention are those which provide a germicidal effect to the concentrate compositions, and especially preferred are quaternary ammonium compounds and salts thereof, which may be characterized by the general structural formula:
  • Ri, R 2 , R 3 and R 4 is a alkyl, aryl or alkylaryl substituent of from 6 to 26 carbon atoms, and the entire cation portion of the molecule has a molecular weight of at least 165.
  • the alkyl substituents maybe 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 R 1 , R 2 , R 3 and R 4 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 quaternary ammonium salts within the above description include the alkyl ammonium halides such as cetyl trimethyl ammonium bromide, alkyl aryl ammonium halides such as octadecyl dimethyl benzyl ammonium bromide, N-alkyl pyridinium halides such as N-cetyl pyridinium bromide, and the like.
  • quaternary ammonium salts include those in which the molecule contains either amide, ether or ester linkages such as octyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride, N-(laurylcocoaminoformylmethyl)-pyridinium chloride, and the like.
  • Preferred quaternary ammonium compounds which act as germicides and which are found useful in the practice of the present invention include those which have the structural formula:
  • R 2 and R 3 are the same or different Cs-C 12 alkyl, or R 2 is Ci 2-16 alkyl, C 8 . isalkylethoxy, Cs -18 alkylphenolethoxy and R 3 is benzyl, and X is a halide, for example chloride, bromide or iodide, or is a methosulfate anion.
  • the alkyl groups recited in R 2 and R 3 may be straight-chained or branched, but are preferably substantially linear.
  • Particularly useful quaternary germicides include compositions which include a single quaternary compound, as well as mixtures of two or more different quaternary compounds.
  • Such useful quaternary compounds are available under the BARD AC®, BARQUAT®, HYAMINE®, LONZABAC®, and ONYXIDE® trademarks, which are more fully described in, for example, McCutcheon's Functional Materials (Vol. 2), North American Edition, 1998, as well as the respective product literature from the suppliers identified below.
  • BARD AC® 205M is described to be a liquid containing alkyl dimethyl benzyl ammonium chloride, octyl decyl dimethyl ammonium chloride; didecyl dimethyl ammonium chloride, and dioctyl dimethyl ammonium chloride (50% active) (also available as 80% active (BARDAC® 208M)); described generally in McCutcheon 's as a combination of alkyl dimethyl benzyl ammonium chloride and dialkyl dimethyl ammonium chloride); BARDAC® 2050 is described to be a combination of octyl decyl dimethyl ammonium chloride/didecyl dimethyl ammonium chloride, and dioctyl dimethyl ammonium chloride (50% active) (also available as 80% active (BARDAC® 2080)); BARDAC ® 2250 is described to be didecyl dimethyl ammonium chloride (50% active); BARDAC® LF (
  • HYAMINE® 1622 described as diisobutyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride (50% solution); HYAMINE® 3500 (50% actives), described as alkyl dimethyl benzyl ammonium chloride (also available as 80% active (HYAMINE® 3500-80)); and HYMAINE® 2389 described as being based on methyldodecylbenzyl ammonium chloride and/or methyldodecylxylene-bis-triniethyl ammonium chloride.
  • B ARD AC®, BARQUAT® and HYAMINE® are presently commercially available from Lonza, Inc., Fairlawn, New Jersey).
  • BTC® 50 NF (or BTC® 65 NF) is described to be alkyl dimethyl benzyl ammonium chloride (50% active); BTC® 99 is described as didecyl dimethyl ammonium chloride (50% acive); BTC® 776 is described to be myrisalkonium chloride (50% active); BTC® 818 is described as being octyl decyl dimethyl ammonium chloride, didecyl dimethyl ammonium chloride, and dioctyl dimethyl ammonium chloride (50% active) (available also as 80% active (BTC® 818-80%)); BTC® 824 and BTC® 835 are each described as being of alkyl dimethyl benzyl ammonium chloride (each 50% active); BTC® 885 is described as a combination of BTC® 835 and BTC® 818 (50% active) (available also as 80% active (BTC® 888)); BTC® 1010 is described as didecyl dimethyl ammoni
  • polymeric quaternary ammonium salts based on these monomelic structures are also considered desirable for the present invention.
  • POLYQUAT® described as being a 2-butenyldimethyl ammonium chloride polymer.
  • Preferred quaternary germicides used in the solid block compositions are those which are supplied in a solid or powdered form, as such greatly facilitates the manufacture of the solid block compositions.
  • the germicidal cationic surfactant(s) are present in amounts so to dispense at least about 200 parts per million (ppm) in the water flushed into the sanitary appliance, e.g., toilet bowl, or into the water retained in the sanitary appliance at the conclusion of the flush cycle.
  • amphoteric and zwitterionic surfactants which provide a detersive effect.
  • exemplary useful amphoteric surfactants include 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.
  • Further exemplary useful amphoteric surfactants include amidoalkylbetaines, such as amidopropylbetaines which may be represented by the following structural formula:
  • preferred detersive surfactants are those which exhibit a melting points above about 110°F., preferably above 125°F., in order to permit convenient processing according to known art techniques. Nonetheless small amounts of low melting point surfactants, i.e., those exhibiting melting points below about 110°F and even liquid surfactants may be used in providing the surfactant constituent of the solid block composition.
  • the amounts of the constituents present in a particular solid block of the device may vary as well depending upon the final intended use of the treatment block.
  • the detersive surfactant constituent may be present in any effective amount and generally comprises up to about 90%wt. of the total weight of a solid block composition, and the resultant treatment block formed therefrom.
  • the detersive surfactant constituent comprises about 20 - 90%wt, more preferably 35-80%wt. of a solid block composition, and when used as an ITB block the detersive surfactant constituent most preferably comprises about 50 - 75%wt.
  • the detersive surfactant constituent may be present in any effective amount and generally comprises up to about 60%wt. of the total weight of a solid block composition, and the resultant treatment block formed therefrom.
  • the detersive surfactant constituent comprises about 10 - 55 %wt., more preferably 20-50%wt. of a solid block composition, and the resultant treatment block formed therefrom.
  • the lavatory treatment blocks of the invention necessarily comprise at least one surfactant, preferably at least one anionic surfactant.
  • exemplary chemical constituents may be one or more sanitizing agents or germicides which may be present with our without other constituents being present in the lavatory treatment blocks of the present invention.
  • the sanitizing agent can be any sanitizing composition known to those of ordinary skill in the relevant art, and without limitation exemplary sanitizing compositions include materials containing alkyl halohydantoins, alkali metal haloisocyanurates, bleach, essential oils, non-quaternary ammonium based germicidal compounds as well as quaternary ammonium germicidal compounds.
  • the blocks may also include a bleach constituent.
  • the bleach constituent is relatively inert in the dry state but, which on contact with water, releases oxygen, hypohalite or a halogen especially chlorine.
  • X 1 and X 2 are independently hydrogen, chlorine or bromine; and, R 1 and R 2 are independently alkyl groups having from 1 to 6 carbon atoms.
  • halohydantoins include, for example, N,N'-dichloro-dimethyl-hydantoin, N- bromo-N-chloro-dimethyl-hydantoin, N,N'-dibromo ⁇ dimethyl-hydantoin, 1 ,4-dichloro, 5,5-dialkyl substituted hydantoin, wherein each alkyl group independently has 1 to 6 carbon atoms, N-monohalogenated hydantoins such as chlorodimethylhydantoin (MCDMH) and N-bromo-dimethylhydantoin (MBDMH); dihalogenated hydantoins such as dichlorodimethylhydantoin (DCDMH), dibromodimethylhydantoin (DBDMH), and 1- bromo-3-chloro-5,5,-dimethylhydantoin (BCDMH); and halogenated methylethylh
  • Suitable organic hypohalite liberating bleaching agents include halogenated melamines such as tribromomelamine and trichloromelamine.
  • Suitable inorganic hypohalite-releasing bleaching agents include lithium and calcium hypochlorites and hypobromites.
  • the various chlorine, bromine or hypohalite liberating agents may, if desired, be provided in the form of stable, solid complexes or hydrates, such as sodium p-toluene sulfobromamine trihydrate; sodium benzene sulfochloramine dihydrate; calcium hypobromite tetrahydrate; and calcium hypochlorite tetrahydrate.
  • Brominated and chlorinated trisodium phosphates formed by the reaction of the corresponding sodium hypohalite solution with trisodium orthophosphate (and water, as necessary) likewise comprise useful inorganic bleaching agents for incorporation into the solid lavatory treatment blocks formed therefrom.
  • the bleach constituent is a hypohalite liberating compound and more preferably is a hypohalite liberating compound in the form of a solid complex or hydrate thereof.
  • Particularly preferred are chloroisocynanuric acids and alkali metal salts thereof, preferably potassium, and especially sodium salts thereof.
  • Examples of such compounds include trichloroisocyananuric acid, dichloroisocyanuric acid, sodium dichloroisocyanurate, potassium dichloroisocyanurate, and trichloro- potassium dichloroisocynanurate complex.
  • the most preferred chlorine bleach material is sodium dichloroisocyanurate; the dihydrate of this material being particularly preferred.
  • the bleach constituent may be present in any effective amount and may comprise up to about 90%wt, preferably at least about 0.1 - 60% wt of the solid block composition. More preferably, when present, the bleach constituent comprises about 0.5 - 50%wt, more preferably at least l-40%wt. of the solid block composition.
  • Other germicidally effective agents useful as sanitizing agents include sodium dichloroisocyanurate (DCCNa) and sodium dibromoisocyanurate.
  • non-quaternary ammonium based sanitizing agents include pyrithiones, dimethyldimethylol hydantoin, methylchloroisothiazolinone/methylisothiazolinone sodium sulfite, sodium bisulfite, imidazolidinyl urea, diazolidinyl urea, benzyl alcohol, 2- bromo-2-nitropropane-l,3-diol, formalin (formaldehyde), iodopropenyl butylcarbamate, chloroacetamide, methanamine, methyldibromonitrile glutaronitrile, glutaraldehyde, 5- bromo-5-nitro-l,3-dioxane, phenethyl alcohol, o-phenylphenol/sodium o-phenylphenol, sodium hydroxymethylglycinate, polymethoxy bicyclic oxazolidine, dimethoxan
  • the non-cationic antimicrobial agent is a mono- and poly-alkyl and aromatic halophenol selected from the group p-chlorophenol, methyl p-chlorophenol, ethyl p-chlorophenol, n-propyl p-chlorophenol, n-butyl p- chlorophenol, n-amyl p-chlorophenol, sec-amyl p-chlorophenol, n-hexyl p-chlorophenol, cyclohexyl p-chlorophenol, n-heptyl p-chlorophenol, n-octyl p-chlorophenol, o- chlorophenol, methyl o-chlorophenol, ethyl o-chlorophenol, n-propyl o-chlorophenol, n- butyl o-chlorophenol, n-amyl o-chlorophenol, tert
  • Quaternary ammonium based sanitizing agents include any cationic surfactant which is known or may be found to provide a broad antibacterial or sanitizing function; these have been described above with reference to detersive surfactants.
  • the solid block compositions of the invention may also comprise a coloring agent which imparts either a color to the lavatory treatment blocks, to the water in which it comes into contact, but especially which imparts color to the water contained within the sanitary appliance.
  • the sanitary appliance is a toilet
  • the coloring agent imparts a color to the water contained within the cistern, or within the toilet bowl particularly following the flush cycle of a toilet, or may impart a color in both locations.
  • coloring agents have great consumer appeal, and indeed any known art coloring agent may be provided in any effective amount in order to impart a coloring effect.
  • Colorants especially dyes, are preferred when formulated as dry powders to enable direct incorporation into lavatory treatment blocks of the invention, however, liquid colorants may be employed in conjunction with suitable carriers.
  • Useful colorants include any materials which may provide a desired coloring effect.
  • Exemplarly useful coloring agents include dyes, e.g., Alizarine Light Blue B (CI. 63010), Carta Blue VP (C.I. 24401), Acid Green 2G (CI. 42085), Astragon Green D (CI. 42040) Supranol Cyanine 7B (CI. 42675), Maxilon Blue 3RL (CI.
  • the colorant e.g., dye
  • the colorant should be selected so to ensure the compatibility of the colorant with the bleach constituent, or so that its color persists despite the presence in the toilet bowl of a concentration of hypochlorite which is effective to maintain sanitary conditions.
  • a solid block composition which includes a bleach constituent do not comprise any colorants. Desirably the colorants, when present, do not exceed 15%wt.
  • the solid block compositions may include a fragrance or other air treatment constituent.
  • the fragrance may be any composition which is known to the art to provide a perceptible fragrancing benefit, any may be based on naturally occurring materials such as one or more essential oils, or may be based on synthetically produced compounds as well.
  • essential oils examples include pine oil, Anetlhole 20/21 natural, Aniseed oil china star, Aniseed oil globe brand, Balsam (Perui), Basil oil (India), Black pepper oil, Black pepper oleoresin 40/20, Bois de Rose (Brazil) FOB, Bomneol Flakes (China), Camphor oil, White, Camphor powder synthetic technical, Canaga oil (Java), Cardamom oil, Cassia oil (China), Cedarwood oil (China) BP, Cinnamon bark oil, Cinnamon leaf oil, Citronella oil, Clove bud oil, Clove leaf, Coriander (Russia), Counmarin 69 0 C.
  • fragrance agent which fragrance agent which may be a substance or mixture of various substances including those which are naturally derived (i.e., obtained by extraction of flower, herb, blossom or plant), those which are artificially derived or produced (i.e., mixture of natural oils and/or oil constituents), and those which are synthetically produced substances (odiferous substances).
  • fragrance agents are complex mixtures or blends various organic compounds including, but not limited to, certain alcohols, aldehydes, ethers, alamatic compounds and varying amounts of essential oils such as from about 0 to about 25% by weight, usually from about 0.05 to about 12% by weight, the essential oils themselves being volatile odiferous compounds and also functioning to aid in the dissolution of the other components of the fragrance agent.
  • essential oils such as from about 0 to about 25% by weight, usually from about 0.05 to about 12% by weight, the essential oils themselves being volatile odiferous compounds and also functioning to aid in the dissolution of the other components of the fragrance agent.
  • the precise composition of the fragrance agent desirably emanates a pleasing fragrance, but the nature of the fragrance agent is not critical to the success of the invention.
  • the solid block compositions may comprise an air treatment constituent.
  • an air treatment constituent may be any other material which is useful in providing treatment of ambient air, such as a sanitizing agents . e.g., one or more glycols or alcohols, or materials which are intended to counteract, neutralize, or mask odors in the absence of, or in conjunction with, the fragrance composition of the present invention.
  • the air treatment constituent may be one or more materials which provide and effective insecticide repelling or insecticidal benefit; such would be particularly useful in climates or environments where insects present a nuisance or health hazard.
  • the solid block compositions of the invention may comprise an anti-limescale agent, which can be generally classified as a cleaning agent in that it provides a cleaning effect to treated lavatory device surfaces.
  • the anti- limescale agent can virtually any known anti-limescale agent compositions known to those of ordinary skill in the relevant art.
  • compositions containing anionic and/or nonionic surfactants together with typical anti-limescale agents for example, amidosulfonic acid, bisulfate salts, organic acids, organic phosphoric salts, alkali metal polyphosphates, and the like.
  • anti-limescale agent compositions can be found in, for example, United States Patent Nos.
  • anti- limescale agents include organic acids (for example, citric acid, lactic acid, adipic acid, oxalic acid and the like), organic phosphoric salts, alkali metal polyphosphates, sulfonic, and sulfamic acids and their salts, bisulfate salts, EDTA, phosphonates, and the like.
  • organic acids for example, citric acid, lactic acid, adipic acid, oxalic acid and the like
  • organic phosphoric salts for example, alkali metal polyphosphates, sulfonic, and sulfamic acids and their salts, bisulfate salts, EDTA, phosphonates, and the like.
  • the solid block compositions may comprise stain inhibiting materials.
  • the solid block composition of the invention may, for example, include an effective amount of a manganese stain inhibiting agent which is advantageously included wherein the sanitary appliance is supplied by a water source having an appreciable or high amount of manganese.
  • a water source having an appreciable or high amount of manganese.
  • Such water containing a high manganese content are known to frequently deposit unsightly stains on surfaces of sanitary appliances, especially when the solid block composition also contains a bleach source which provides a hypochlorite.
  • the solid block composition of the present invention may comprise a manganese stain inhibiting agent, such as a partially hydrolyzed polyacrylamide having a molecular weight of about 2000 to about 10,000, a polyacrylate with a molecular weight of about 2000 to about 10,000, and/or copolymers of ethylene and maleic acid anhydride with a molecular weight of from about 20,000 to about 100,000.
  • a manganese stain inhibiting agent such as a partially hydrolyzed polyacrylamide having a molecular weight of about 2000 to about 10,000, a polyacrylate with a molecular weight of about 2000 to about 10,000, and/or copolymers of ethylene and maleic acid anhydride with a molecular weight of from about 20,000 to about 100,000.
  • the satin inhibiting materials may comprise to about 10%wt. of the weight of the solid block composition.
  • the solid block compositions of the invention may include one or more preservatives.
  • Such preservatives are primarily included to reduce the growth of undesired microorganisms within the lavatory treatment blocks formed from the solid block composition during storage prior to use or while used, although it is expected that the such a preservative may impart a beneficial antimicrobial effect to the water in the sanitary appliance to which the treatment block is provided.
  • Exemplary useful preservatives include compositions which include parabens, including methyl parabens and ethyl parabens, glutaraldehyde, formaldehyde, 2-bromo-2-nitropropoane-l,3-diol, 5- chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazoline-3-one, and mixtures thereof.
  • One exemplary composition is a combination 5-chloro-2-methyl-4-isothiazolin- 3-one and 2-methyl-4-isothiazolin-3-one where the amount of either component may be present in the mixture anywhere from 0.001 to 99.99 weight percent, based on the total amount of the preservative.
  • the most preferred preservative are those commercially available preservative comprising a mixture of 5-chloro-2- methyl-4-isothiazolin-3 -one and 2-methyl-4-isothiazolin-3 -one marketed under the trademark KATHON® CG/ICP as a preservative composition presently commercially available from Rohm and Haas (Philadelphia, PA).
  • preservative compositions include KATHON® CG/ICP II, a further preservative composition presently commercially available from Rohm and Haas (Philadelphia, PA), PROXEL® which is presently commercially available from Zeneca Biocides (Wilmington, DE),
  • SUTTOCIDE® A which is presently commercially available from Sutton Laboratories (Chatam, NJ) as well as TEXTAMER® 38AD which is presently commercially available from Calgon Corp. (Pittsburgh, PA).
  • the optional preservative constituent should not exceed about 5%wt. of the solid block composition, although generally lesser amounts are usually effective.
  • the inventive solid block compositions may include a binder constituent.
  • the binder may function in part controlling the rate of dissolution of the tablet.
  • the binder constituent may be a clay, but preferably is a water-soluble or water-dispersible gel- forming organic polymer.
  • gel-forming as applied to this polymer is intended to indicate that on dissolution or dispersion in water it first forms a gel which, upon dilution with further water, is dissolved or dispersed to form a free-flowing liquid.
  • the organic polymer serves essentially as binder for the tablets produced in accordance with the invention although, as will be appreciated, certain of the polymers envisaged for use in accordance with the invention also have surface active properties and thereby serve not only as binders but also enhance the cleansing ability of the tablets of the invention. Further certain organic polymers, such as substituted celluloses, also serve as soil antiredeposition agents.
  • a wide variety of water-soluble organic polymers are suitable for use in the solid block composition of the present invention. Such polymers may be wholly synthetic or may be semi-synthetic organic polymers derived from natural materials.
  • organic polymers for use in accordance with the invention are chemically modified celluloses such as ethyl cellulose, methyl cellulose, sodium carboxymethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl hydro xyethyl cellulose, and hydroxyethyl cellulose.
  • Another class of organic polymers which may be used include naturally derived or manufactured (fermented) polymeric materials such as alginates and carageenan. Also, water-soluble starches and gelatin maybe used as the optional binder constituent.
  • the cellulose based binders are a preferred class of binders for use in the solid block composition and may possess the property of inverse solubility that is their solubility decreases with increasing temperature, thereby rendering the tablets of the invention suitable for use in locations having a relatively high ambient temperature.
  • the optional binder constituent may also be one or more synthetic polymers e.g, polyvinyl alcohols; water-soluble partially hydrolyzed polyvinyl acetates; polyacrylonitroses; polyvinyl pyrrolidones; water-soluble polymers of ethylenically unsaturated carboxylic acids, such as acrylic acid and methacrylic acid, and salts thereof; base-hydrolysed starch-polyacrylonitrile copolymers; polyacrylamides; ethylene oxide polymers and copolymers; as well as carboxypolymethylenes.
  • synthetic polymers e.g, polyvinyl alcohols; water-soluble partially hydrolyzed polyvinyl acetates; polyacrylonitcludes; polyacryloniters; polyvinyl pyrrolidones; water-soluble polymers of ethylenically unsaturated carboxylic acids, such as acrylic acid and methacrylic acid, and salts thereof; base-hydrolysed starch-polyacryl
  • the total binder content may comprise up to 75%wt. of the solid block composition, but preferably is from 0.5 to 70% by weight, preferably from 1 to 65% by weight, more preferably from 5 to 60% by weight.
  • the solid block composition may optionally include one or more dissolution control agents.
  • Such dissolution control agent are materials which provide a degree of hydrophobicity to the treatment block formed from the solid block composition whose presence in the treatment block contributes to the slow uniform dissolution of the treatment block when contacted with water, and simultaneously the controlled release of the active constituents of the solid block composition.
  • the dissolution control agents are mono- or di-alkanol amides derived from C 8 -C 16 fatty acids, especially Ci 2 -C 14 fatty acids having a C 2 -C 6 monoamine or diamine moiety.
  • the dissolution control agent may be included in any effective amount, but desirably the dissolution control agent is present in an amount not to exceed about 600% wt. of the solid block composition, although generally lesser amounts are usually effective.
  • the dissolution control agent is present to about 12%wt., more preferably is present from 0.1 - 10%wt. and most preferably is present from about 3 - 8%wt.
  • the dissolution control agent is present to about 50%wt, more preferably is present from 1 - 50%wt. and most preferably is present from about 10 - 40%wt. of the solid block compositions, as well as in the lavatory treatment blocks formed therefrom.
  • the solid block compositions may optionally include one or more water- softening agents or one or more chelating agents, for example inorganic water-softening agents such as sodium hexametaphosphate or other alkali metal polyphosphates or organic water-softening agents such as ethylenediaminetetraacetic acid and nitrilotriacetic acid and alkali metal salts thereof.
  • water-softening agents or chelating agents should not exceed about 20%wt. of the solid block composition, although generally lesser amounts are usually effective.
  • the solid block composition may optionally include one or more solid water- soluble acids or acid-release agents such as sulphamic acid, citric acid or sodium hydrogen sulphate. When present, such solid water-soluble acids or acid-release agents should not exceed about 20%wt. of the solid block composition, although generally lesser amounts are usually effective.
  • the solid block compositions may include diluent materials may be included to provide additional bulk of the product solid block composition and may enhance leaching out of the surfactant constituent when the solid block composition is placed in water.
  • Exemplary diluent materials include any soluble inorganic alkali, alkaline earth metal salt or hydrate thereof, for example, chlorides such as sodium chloride, magnesium chloride and the like, carbonates and bicarbonates such as sodium carbonate, sodium bicarbonate and the like, sulfates such as magnesium sulfate, copper sulfate, sodium sulfate, zinc sulfate and the like, borax, borates such as sodium borate and the like, as well as others known to the art but not particularly recited herein.
  • Exemplary organic diluents include, inter alia, urea, as well as water soluble high molecular weight polyethylene glycol and polypropylene glycol. When present, such diluent materials should not exceed about 80%wt. of the solid block composition, although generally lesser amounts are usually effective.
  • the solid block composition and lavatory treatment blocks formed therefrom may include one or more fillers.
  • Such fillers are typically particulate solid water- insoluble materials which may be based on inorganic materials such as talc or silica, particulate organic polymeric materials such as finely comminuted water insoluble synthetic polymers. When present, such fillers should not exceed about 30%wt. of the solid block composition, although generally lesser amounts are usually effective.
  • the solid block of the invention includes silica. Silica has been observed to aid in the controlling the rate of dissolution of the lavatory treatment blocks of the invention.
  • the solid block composition and lavatory treatment blocks formed therefrom may include one or more further processing aids.
  • the solid block composition may also include other binding and/or plasticizing ingredients serving to assist in the manufacture thereof, for example, polypropylene glycol having a molecular weight from about 300 to about 10,000 in an amount up to about 20% by weight, preferably about 4% to about 15% by weight of the mixture may be used.
  • the polypropylene glycol reduces the melt viscosity, acts as a demolding agent and also acts to plasticize the block when the composition is prepared by a casting process.
  • suitable plasticizers such as pine oil fractions, d-limonene, dipentene and the ethylene oxide-propylene oxide block copolymers may be utilized.
  • Other useful processing aids include tabletting lubricants such as metallic stearates, stearic acid, paraffin oils or waxes or sodium borate which facilitate in the formation of the lavatory treatment blocks in a tabletting press or die.
  • R 1 and R 2 can independently be C 1 -C 6 alkyl which may optionally substituted,
  • Y is (CH 2 ) X , wherein x is 0-10, but is preferably 1-8, and while Y may be a linear alkyl or phenyl moiety, desirably Y includes one or more oxygen atoms and/or is a branched moiety.
  • Exemplary diester constituents include the following diester compounds according to the foregoing structure: dimethyl oxalate, diethyl oxalate, diethyl oxalate, dipropyl oxalate, dibutyl oxalate, d ⁇ sobutyl oxalate, dimethyl succinate, diethyl succinate, diethylhexyl succinate, dimethyl glutarate, diisostearyl glutarate, dimethyl adipate, diethyl adipate, diisopropyl adipate, dipropyl adipate, dibutyl adipate, diisobutyl adipate, dihexyladipate, di-Ci2-i5-alkyl adipate, dicapryl adipate, dicetyl adipate, diisodecyl adipate, diisocetyl adipate, diisononyl adipate, dih
  • Preferred diester constituents include those wherein Y is -(CH 2 ) X - wherein x has a value of from 0 — 6, preferably a value of 0 - 5 , more preferably a value of from 1 -4, while R 1 and R 2 are C 1 -C 6 alkyl groups which may be straight chained alkyl but preferably are branched, e.g, iso- and tert-moieties.
  • Particularly preferred diester compounds are those in which the compounds terminate in ester groups.
  • a further advantageously utilized processing aid is a hydrocarbon solvent constituent.
  • the hydrocarbon solvents are immiscible in water, may be linear or branched, saturated or unsaturated hydrocarbons having from about 6 to about 24 carbon atoms, preferably comprising from about 12 to about 16 carbon atoms. Saturated hydrocarbons are preferred, as are branched hydrocarbons. Such hydrocarbon solvents are typically available as technical grade mixtures of two or more specific solvent compounds, and are often petroleum distillates. Nonlimiting examples of some suitable linear hydrocarbons include decane, dodecane, decene, tridecene, and combinations thereof. Mineral oil is one particularly preferred form of a useful hydrocarbon solvent. Further preferred hydrocarbon solvents include paraffinic hydrocarbons including both linear and branched paraffinic hydrocarbons.
  • NORPAR solvents Ex. ExxonMobil Corp.
  • ISOPAR solvents Ex. ExxonMobil Corp.
  • Mixtures of branched hydrocarbons especially as isoparaffins form a further particularly preferred form of a useful hydrocarbon solvent of the invention.
  • Particularly useful technical grade mixtures of isoparaffins include mixtures of isoparaffinic organic solvents having a relatively narrow boiling range.
  • isoparaffinic organic solvents examples include ISOPAR C described to be primarily a mixture Of C 7 -C 8 isoparaffins, ISOPAR E described to be primarily a mixture of C 8 -C 9 isoparaffins, ISOPAR G described to be primarily a mixture of Ci 0 -Cn isoparaffins, ISOPAR H described to be primarily a mixture of Cn-Ci 2 isoparaffins, ISOPAR J, ISOPAR K described to be primarily a mixture of Cn-Ci 2 isoparaffins, ISOPAR L described to be primarily a mixture OfC 11 -Ci 3 isoparaffins, ISOPAR M described to be primarily a mixture OfCi 3 -Ci 4 isoparaffins, ISOPAR P and ISOPAR V described to be primarily a mixture OfCi 2 -C 20 isoparaffins.
  • ISOPAR C described to be primarily a mixture Of C 7 -C 8 isoparaffins
  • Such further processing aids are typically included in amounts of up to about 30% by weight, preferably to 20%wt. of the solid block composition, although generally lesser amounts are usually effective.
  • one or more of the foregoing constituents may be provided as an encapsulated, particularly a microencapsulated material. That is to say, quantities of one or more constituents are provided covered or encapsulated in an encapsulating material.
  • Methods suitable for such an encapsulation include the customary methods and also the encapsulation of the granules by a melt consisting e.g. of a water- soluble wax, coacervation, complex coacervation and surface polymerization.
  • Non- limiting examples of useful encapsulating materials include e.g. water-soluble, water- dispersible or water-emulsifiable polymers and waxes.
  • reactive chemical constituents particularly the fragrance composition when present, may be provided in an encapsulated form so to ensure that they do not prematurely degrade during processing of the constituents used to form the solid block composition and that they are retained with minimal degradation in the solid block composition prior to their use.
  • the use of water soluble encapsulating material is preferred as such will release the one or more chemical constituents when the solid block composition is contacted with water supplied either in the cistern or in the toilet bowl.
  • the lavatory treatment blocks exhibit a density greater than that of water which ensures that they will sink when suspended in a body of water, e.g., the water present within a cistern.
  • the lavatory treatment blocks formed from the solid block composition exhibit a density in excess of about 1 g/cc of water, preferably a density in excess of about 1.5 g/cc of water and most preferably a density of at least about 2 g/cc of water.
  • the mass of the lavatory treatment blocks may vary, and amount of up to an including 500 grams may be practiced, generally the mass of the solid block compositions do not exceed about 150 grams.
  • the mass of the lavatory treatment blocks is between about 20 and 100 grams. It is appreciated that lavatory treatment blocks having great mass should provide a longer useful service life of the lavatory treatment blocks, with the converse being equally true.
  • the lavatory treatment blocks according to the present invention may also be provided with a coating of a water-soluble film, such as polyvinyl acetate following the formation of the lavatory treatment blocks from the recited solid block composition.
  • a water-soluble film such as polyvinyl acetate
  • Such may be desired for improved handling, however such is often unnecessary as preferred embodiments of the blocks exhibit a lower likelihood of sticking to one another following manufacture than many prior art treatment block compositions.
  • the lavatory treatment blocks maybe formed of a single chemical composition, or may formed of two (or more) different chemical compositions which may be provided as separate regions of a solid block, such as a first layer of a solid block consisting of a first chemical composition, alongside a second layer of a the solid block consisting of a second chemical composition which is different than the first chemical composition.
  • the block may also be formed of two or more separate blocks which are simply layered or otherwise assembled, without or without the use of an adhesive. Further layers of still further different chemical compositions may also be present.
  • Such solid blocks formed having two or more discrete layers or regions of, respectively, two or more different chemical compositions may be referred to as composite blocks.
  • any form of the lavatory treatment blocks may also be provided with a coating film or coating layer, such as a water soluble film which is used to overwrap the chemical composition provided in the device which film provides a vapor barrier when dry, but which dissolves when contacted with water.
  • a coating film or coating layer such as a water soluble film which is used to overwrap the chemical composition provided in the device which film provides a vapor barrier when dry, but which dissolves when contacted with water.
  • the lavatory treatment blocks may be oversprayed or dipped into a bath of a water soluble film forming constituent, and thereafter removed and thus allowing the water soluble film forming constituent to dry and form a coating layer on the solid block.
  • Exemplary materials which may be used to provide such a coating on some or all of the surfaces of the solid block compositions include one or more of the following: Rhodasurf TB-970 described by its supplier to be a tridecyl alcohol having a degree of ethoxylation of approximately 100 having an HLB ofl9, and exhibiting a melting point in the range of 52-55 0 C; Antarox F-108 which is desciibed to be an EO-PO block copolymer having a degree of ethoxylation of approximately 80% and having a melting point in the range of 54-6O 0 C; further materials including those identified as Pluriol Z8000, and Pluriol E8000 which are believed to be optionally substituted, high molecular weight polyethylene glycols (“PEG”) having a sufficiently high molecular weight such that they have a melting point of at least 25°C, preferably a melting point of at least about 30 0 C may also be used.
  • Rhodasurf TB-970 described by its supplier to be
  • water soluble materials desirably those which have a melting point in the range of about 30 - 70°C, and which may be used to provide a water soluble or water dispersible coating on the lavatory treatment blocks are also contemplated to be useful, especially synthetic or naturally occurring waxy materials, and high molecular weight polyalkylene glycols, especially polyethylene glycols.
  • Certain of these coating materials may be surfactants. Generally such materials may be provided as a dispersion in water, an organic solvent or in an aqueous/organic solvent, but preferably are used as supplied from their respective supplier and are heated to at least their melting points in order to form a liquid bath.
  • the lavatory treatment blocks affixed to the plate of a hanger are then conveniently dipped into the said bath, thereby providing a coating layer to the lavatory treatment blocks.
  • the coating materials may be sprayed, brushed on or padded onto at least part of the surfaces of the previously formed lavatory treatment blocks.
  • the application of a water soluble film or coating is preferred in certain embodiments of the invention as the surface film may facilitate the handling of the blocks during packaging and storage prior to use of the lavatory treatment blocks. Further, the application of a water soluble film or coating is preferred as certain water soluble film former compositions may impart a desirable surface gloss to the lavatory blocks.
  • glycerine forms from 0.001%wt. to about 5 %wt., preferably from 0.005%wt. of the total mass of a lavatory treatment block composition. While not wishing to be bound by the following theory, the inclusion of glycerine is believed to impart improved substantivity to the foam formed from the lavatory treatment blocks when contacted with water, which often provides for a more dense foam, and frequently also provides for a greater initial volume of foam formed with each flush of the lavatory appliance as compared with like compositions wherein the glycerine is however omitted.
  • Such foam formed from a lavatory treatment block containing glycerine has also been observed to have a longer lifespan prior to breakdown.
  • Such benefits of increased foam production and/or increased foam volume and/or improved foam lifespan are particularly advantageous from a technical viewpoint as well as from a consumer viewpoint, as providing for improved cleaning of sanitary appliance surfaces above the water line present in the sanitary appliance.
  • the present inventors have also unexpectedly discovered that the inclusion of glycerine in the lavatory block compositions provides improved foaming benefits, but at the same time reduces the rate of erosion of the lavatory treatment blocks, hence improving their lifespan and useful service life.
  • glycerine in the lavatory block compositions provides improved foaming benefits, but at the same time reduces the rate of erosion of the lavatory treatment blocks, hence improving their lifespan and useful service life.
  • Glycerine as an essential constituent of the lavatory treatment blocks of the invention.
  • glycerine is to be understood to encompass glycerol, and is to be understood to encompass C 3 -C 8 alkanols (preferably C 3 - C 6 alkanols) comprising a plurality of hydroxyl groups within the molecule, preferably including a hydroxyl group on each carbon atom present in the molecule.
  • C 3 -C 8 alkanols preferably C 3 - C 6 alkanols
  • glycerine which may also be referred to as 1, 2, 3 -propanediol is particularly preferred.
  • the glycerine may be provided as a separate or discrete constituent which used to form a treatment block composition, or it may be provided as part of a surfactant constituent or composition which comprises glycerine, such as a commercially available surfactant preparation.
  • the glycerine may be present in any effective amount, but in order of increasing preference is present in amounts of: .001, 0.01, 0.025, 0.05, 0.075, 0.1, 0.2, 0.25, 0.5, 0.75, 1, 1.2, 1.4, 1.6, 1.8, 2, 2.2, 2.4, 2.5, 3, 3.5, 4, 4.5 to about 5%wt, based of the total mass of a lavatory treatment block composition of which the glycerine forms apart.
  • the glycerine may be provided as a part of or a component of a commercially preparation, such as a commercially available surfactant preparation.
  • a commercially available surfactant preparation is one which includes a fatty acid alkanolamides that are derived from alkanol amines, such as the diethanolamide of coconut fatty acids (cocomide diethanolamide) and mixtures thereof which also include glycerine.
  • One such commercially available material is Ninol® 40-CO (ex. Stepan Co.) which comprises at least 85%wt. of a coco fatty acid alkanolamide derived from diethanolamide and which also comprises about 8%wt. of 1, 2, 3-propanetriol (glycerine).
  • the lavatory treatment blocks are those which comprise at least one surfactant, preferably at least one anionic or nonionic surfactant.
  • compositions which can be used to form the lavatory treatment blocks of the present invention are shown in the following table below; the amounts indicates are in %wt. of the "as supplied" constituent used to form an example block compositions, labeled A through F.
  • compositions indicated on the next table having the general ranges as follows:
  • additive constituents including but not limited to further surfactants, fillers, binders, fragrances, processing aids such as lubricants and tabletting aids, bleaches, sanitizing compositions and the like.
  • compositions which include a bleach constituent which find use as lavatory treatment blocks of the present invention include those recited on the following tables, and labeled as G through N:
  • compositions which include d ⁇ sopropyl adipates which find use as lavatory treatment blocks of the present invention include those recited on the following tables, and labeled as P through W:
  • compositions which include paraffinic hydrocarbon solvents or mineral oil which find use as lavatory treatment blocks of the present invention include those recited on the following tables, and labeled as AA through AK:
  • lavatory treatment blocks and their compositions include those which are recited on Table 1.
  • the manufacture of the lavatory treatment blocks of the invention contemplates mixing the constituents of the block composition into a generally homogenous mass such as by noodling, as well as by plodding, but preferably by extruding, and thereafter forming a "preform" from a measured quantity of the homogenous mass.
  • a generally homogenous mass such as by noodling, as well as by plodding, but preferably by extruding, and thereafter forming a "preform" from a measured quantity of the homogenous mass.
  • all of the solid ingredients are mixed in any suitable blending equipment followed by the addition of liquid ingredients under blending conditions.
  • ITB and ITC devices include those described in one or more of: PCT/GB2005/002831, published as WO2006/013321; US Patent D541902, US 20050014668 Al; US Patent D514661; US Patent D501532; US Patent D508106; EP1797251 the contents of which are incoiporated herein by reference.
  • the lavatory treatment blocks may also be useful in so called “cageless" lavatory dispensing devices, such as disclosed in US Patent D548304, US Patent D547418 and in one or more of WO2007107769, WO2007/107750, WO2007107755, EP 1797251 the contents of which are incorporated herein by reference.
  • the lavatory treatment blocks may be used as formed or shaped, and thus wholly independently from any device, hanger, cage or holder.
  • the service life of the lavatory treatment blocks of the devices of the invention should be from about 5 to about 30 days, based on 6 flushes per day.
  • the service life of the lavatory treatment blocks is measured when the devices of the invention are installed on the rim of a toilet bowl such that the said block is positioned adjacent to the sloping interior sidewall of the toilet bowl and is subjected to between 6 - 12 flushes per day.
  • the temperature of the water which is flushed is in the range of 16 - 24 0 C.
  • the length of life of the plurality of lavatory treatment blocks will of course depend on a variety of factors including their individual formulation, their relative position to the sidewall of the lavatory appliance, their geometries, the water temperature, tank size, the number of flushes over the period of use and the volume of the water which contacts the lavatory treatment blocks.
  • lavatory treatment blocks were formed in order to evaluate their performance characteristics, including foaming characteristics and block lifespan characteristics against a similar comparative lavatory treatment block which excluded the surfactant preparation which comprised 8%wt. of glycerine.
  • the identity of the constituents used to form the lavatory treatment blocks are identified more specifically on the following Table 2.
  • the individual constituents were used "as supplied” from their respective suppliers and may constitute less than 100%wt, or 100%wt. of the named compound, as indicated in Tables 1 and 2.
  • an ITB device 10 including a body 12 which includes an integral cage adapted to receive and retain in its interior a treatment block composition according to the invention.
  • the body 12 containing a treatment block composition may be suspended via a hook 14, from the rim of a toilet bowl such that the body 12 is positioned beneath the rim and within the path of flush water released by a sanitary appliance, e.g., a toilet bowl Flush water enters and exits into the interior of the body 12 via one or more passages 16 wherein it contacts the treatment block and forms a treatment composition by dissolving a part thereof.
  • a sanitary appliance e.g., a toilet bowl
  • Flush water enters and exits into the interior of the body 12 via one or more passages 16 wherein it contacts the treatment block and forms a treatment composition by dissolving a part thereof.
  • Samples of each solid treatment block compositions indicated on Table 1 in such a lavatory dispensing device were separately supplied to one or more of three toilets, a "Remo” model toilet bowl, (ex. Shires Co., Ireland), and/or an “Alto” model toilet bowl (ex. Ideal Standard Co, UK), and/or a "Jacob Delafon” toilet bowl (ex. Delafon, France).
  • the placement of the ITB device varied but once positioned prior to the test was not moved until the test was concluded. The test was performed over a number of successive days, and all testing was performed at approximately room temperature (19 - 22°C).
  • Each of the toilets was periodically and automatically flushed by a machine-controlled device which operated the toilets to flush 24 times daily at intervals of approximately 30 minutes between flushes.
  • This flushing protocol was considered to be particularly harsh, and simulated exceptionally heavy usage far in excess of what is normally expected in a domestic household environment.
  • the loss of the mass of the solid treatment block compositions were evaluated at regular intervals. The results of the test are indicated on the following Tables 3A, 3B and 3C.
  • the block compositions according to the examples (El, E2) described on Table 1 exhibited a good service life and furthermore, while not disclosed in the table, provided superior foaming as compared to the solid block composition according to the comparative example (Cl). This was particularly surprising as the improved foaming benefit was provided by block composition which apparently underwent less dissolution per flush of the toilet bowl. It is further generally surprising that the blocks according to the invention, viz. according to El and E2 exhibited a good service life notwithstanding the frequency of daily flushings, which provided at most about 30 minutes of time for the solid block composition to dry before being contacted with water from the next flush cycle.
  • test ITBs containing a block composition may have undergone greater dissolution of a solid block composition primarily caused by a greater volume of water exiting the rim of a toilet bowl at a specific location thereof.

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  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)

Abstract

L'invention porte sur des blocs de traitement de toilettes qui offrent l'avantage d'un moussage amélioré et une substantivité de moussage améliorée. Les blocs de traitement de toilettes peuvent être utilisés avec ou sans dispositif de traitement de toilettes, tel que dans le type à bol, ou dans un dispositif de type à citerne. Des modes de réalisation préférés des blocs de traitement de toilettes permettent à un appareil sanitaire qui est traité à l'aide desdits blocs de bénéficier d'un nettoyage et/ou d'un assainissement avantageux et/ou d'une désinfection avantageuse.
EP08806319A 2007-10-09 2008-09-18 Compositions de bloc de traitement de toilettes ayant une substantivité de moussage avantageuse et une durée de vie améliorée Withdrawn EP2207870A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB0719712.2A GB0719712D0 (en) 2007-10-09 2007-10-09 Lavatory treatment block compositions with substantive foaming benefits and improved lifespan
PCT/GB2008/003164 WO2009047475A2 (fr) 2007-10-09 2008-09-18 Compositions de bloc de traitement de toilettes ayant une substantivité de moussage avantageuse et une durée de vie améliorée

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EP2207870A2 true EP2207870A2 (fr) 2010-07-21

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US (1) US20100299818A1 (fr)
EP (1) EP2207870A2 (fr)
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WO2009047475A3 (fr) 2009-06-11
WO2009047475A2 (fr) 2009-04-16
US20100299818A1 (en) 2010-12-02
GB0719712D0 (en) 2007-11-21

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