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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
  • C11D3/3738—Alkoxylated silicones
• • 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
  • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
  • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
• • 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
  • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
  • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
• • 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
  • C11D3/2075—Carboxylic acids-salts thereof
  • C11D3/2082—Polycarboxylic acids-salts thereof
• • 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
  • C11D3/22—Carbohydrates or derivatives thereof
  • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
• • 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
  • C11D3/26—Organic compounds containing nitrogen
  • C11D3/33—Amino carboxylic acids
• • 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
  • C11D3/36—Organic compounds containing phosphorus
  • C11D3/361—Phosphonates, phosphinates or phosphonites
• • E—FIXED CONSTRUCTIONS
  • E03—WATER SUPPLY; SEWERAGE
  • E03D—WATER-CLOSETS OR URINALS WITH FLUSHING DEVICES; FLUSHING VALVES THEREFOR
  • E03D9/00—Sanitary or other accessories for lavatories ; Devices for cleaning or disinfecting the toilet room or the toilet bowl; Devices for eliminating smells
  • E03D9/02—Devices adding a disinfecting, deodorising, or cleaning agent to the water while flushing
  • E03D9/03—Devices adding a disinfecting, deodorising, or cleaning agent to the water while flushing consisting of a separate container with an outlet through which the agent is introduced into the flushing water, e.g. by suction ; Devices for agents in direct contact with flushing water
  • E03D9/032—Devices connected to or dispensing into the bowl

Definitions

• the present invention relates to lavatory bowl rim-blocks.
• rim-blocks are devices that dispense liquid or solid compositions directly into a lavatory bowl from under the rim of said bowl.
• Such rim-blocks are usually attached by various means, such as hooks and the like, to the rim of the lavatory bowl. Every time a toilet equipped with a rim-block is flushed, an amount of composition is dispensed into the lavatory bowl.
• Liquid and solid rim-blocks are already known in the art.
• the present invention relates to so-called liquid rim-blocks, this means the composition to be released into the lavatory bowl are in liquid form.
• liquid rim-blocks examples include a liquid rim-block device having a suspension means and at least two compartments for active substances (WO 02/40792), or a lavatory cleaning system comprising a dispenser for dispensing a liquid composition from under the rim of a lavatory bowl, wherein the composition has a viscosity of greater than 2500 mPa s (WO 02/04951).
• WO 02/40792 a liquid rim-block device having a suspension means and at least two compartments for active substances
• a lavatory cleaning system comprising a dispenser for dispensing a liquid composition from under the rim of a lavatory bowl, wherein the composition has a viscosity of greater than 2500 mPa s (WO 02/04951).
• Other similar systems are described in EP 775741 or WO 01/94520.
• the active composition of a lavatory bowl rim-block is only dispensed upon flushing of the lavatory bowl. Once, the lavatory bowl is flushed, the active composition should be retained in the lavatory rim-block until the next flushing operation.
• existing lavatory bowl rim-blocks tend to leak the active compositions in-between the flushing of the lavatory bowls. This leakage leads to an increased consumption of the active composition as well as to unsightly staining of the lavatory bowl.
• a lavatory bowl rim-block comprising at least one liquid composition, wherein leakage upon use (i.e., while suspended from a lavatory bowl) is reduced or even prevented, whilst maintaining the delivery performance upon flushing of the lavatory bowl (i.e., good product release upon flushing).
• leakage it is meant herein, unwanted delivery of said at least one liquid composition in-between flushing of the lavatory bowl.
• the lavatory bowl rim-blocks as described herein may be used to clean surfaces made of a variety of materials like glazed and non-glazed ceramic tiles, enamel, stainless steel, Inox®, Formica®, vinyl, no-wax vinyl, linoleum, melamine, glass, plastics and plastif ⁇ ed wood.
• compositions according to the present invention have the ability to provide long lasting shine to the surface they have cleaned.
• the present invention encompasses a lavatory bowl rim-block comprising : at least one liquid composition; and a dispenser, said dispenser comprising at least one container and a dispensing means connected to said container(s) for dispensing said liquid composition onto a lavatory bowl surface; wherein said liquid composition comprises gellan gum.
• the lavatory bowl rim-block herein is used to clean the surface or at least parts thereof of a lavatory bowl, such as a toilet bowl, urinals and the like.
• the lavatory bowl rim-block herein is used to clean the surface or at least parts thereof of the inside portion of a lavatory bowl, such as a toilet bowl, urinals and the like.
• the lavatory bowl rim-block herein is used to clean at least parts of the inside portion of a toilet bowl or a urinal, preferably a toilet bowl.
• the lavatory bowl rim-block herein may be used to clean lavatory bowl surfaces made of different materials like ceramic, enamel, vinyl, no-wax vinyl, linoleum, melamine, glass, Inox®, Formica®, any plastics, plastif ⁇ ed wood, metal or any painted or varnished or sealed surface and the like.
• the lavatory bowl rim-block herein comprises : at least one liquid composition; and a dispenser, said dispenser comprising at least one container and a dispensing means connected to at least one of said container(s) for dispensing a liquid composition onto a lavatory bowl surface.
• the lavatory bowl rim-block herein dispenses a single liquid composition or a combination of liquid compositions onto a lavatory bowl surface.
• the lavatory bowl rim-block herein dispenses at least one liquid composition from the rim portion of a lavatory bowl onto the lavatory bowl surface.
• the lavatory bowl rim-block herein is preferably designed such that a sufficient amount of the liquid composition herein is transferred to the lavatory bowl upon flushing of the lavatory bowl with water.
• the lavatory bowl rim-block herein is a toilet rim-block.
• the dispenser The lavatory bowl rim-block of the present invention is preferably made of two main parts : a) at least one liquid composition; and b) a dispenser.
• Said dispenser of the lavatory bowl rim-block comprises at least one container and a dispensing means connected to at least one of said container(s) for dispensing a liquid composition (or a combination of liquid compositions) onto a lavatory bowl surface.
• the at least one liquid composition is contained in the at least one container of the dispenser.
• the container herein may by any suitable container to hold a liquid composition.
• suitable containers herein include, but are not limited to bottles, jars, pouches, boxes, sachets and the like.
• said container has at least one opening.
• the container is preferably made by blow molding of thermoplastic material, more preferably a material selected from group consisting of Polyethylene Terephthalate (PET), Polyethylene Terephthalate-G (PETG), Polyvinyl Chloride (PVC), Polypropylene (PP), Polystyrene (PS), High Impact Polystyrene (HIPS), Polyvinylidene Chloride (PVDC), and mixtures thereof.
• PET Polyethylene Terephthalate
• PET Polyethylene Terephthalate-G
• PVC Polyvinyl Chloride
• PP Polypropylene
• PS Polystyrene
• HIPS High Impact Polystyrene
• PVDC Polyvinylidene Chloride
• the container of the lavatory bowl rim-block is refillable and/or replaceable. Indeed, the container as a whole may be replaced once it is empty (replaceable) or the composition may be refilled into the existing container. The container may be refilled through an aperture in the container with the composition provided in a separate container, such as a bottle.
• the dispensing means herein may by any suitable means to dispense the liquid composition herein onto a lavatory bowl surface.
• the lavatory bowl rim-block may comprise one or a multitude of dispensing means. Suitable means to dispense at least one liquid composition onto a lavatory surface are apertures, spray heads, trays, pads with or without capillary channels, plates with or without capillary channels, blotter type dispensing means such as described in EP 775 741, and the like.
• the dispensing means herein comes into contact with water used to flush said lavatory bowl.
• the water used to flush said lavatory bowl mixes with at least one liquid composition of the lavatory bowl rim-block herein and thereby delivers the composition(s) onto the lavatory bowl surface.
• the dispensing means herein is connected to at least one of said container(s) by any suitable means, such as pipes, tubes, and the like, and may further contain valves, mixing chambers, shutters, and the like.
• the dispenser as described above may comprise other elements such as : an attachment means; a supporting structure, holding the different elements of the dispenser together; blinds, used for aesthetics or to regulated water flow; wings, used to regulated water flow; etc.
• the lavatory bowl rim-block preferably said dispenser, additionally comprises an attachment means.
• Said attachment means is used to connect the lavatory bowl rim- block, preferably the dispenser, to said lavatory bowl and hold it in place over its lifetime.
• Suitable attachment means are selected from the group consisting of : hooks, a suction cup or a set thereof, an adhesive, and mixtures thereof.
• said attachment means attaches the dispenser to the rim or suspends the dispenser from said rim.
• said attachment means is a hook to suspend the dispenser from the rim of a lavatory bowl.
• the dispenser herein additionally comprises an attachment means. More preferably, the dispenser herein additionally comprises an attachment means and a supporting structure.
• the lavatory bowl rim-block comprises one container
• the lavatory bowl rim-block comprises one liquid composition comprising all the essential ingredients of said composition ("single compartment liquid rim- block" or “single compartment dispenser”).
• the lavatory bowl rim-block comprises more than one container, preferably two to four, more preferable two to three, most preferably two containers
• the essential ingredients of the liquid composition(s) (hereinafter "essential ingredients") of the lavatory bowl rim-block may be present together in one and the same liquid composition contained in one of the container or these essential ingredients of the composition(s) of the lavatory bowl rim-block, may be in separate compositions contained in different containers, wherein preferably one of said separate compositions is a liquid composition and the other composition(s) are liquid, fluid gel, gel or solid compositions more preferably the other composition(s) are liquid compositions.
• compositions containing the essential ingredients are dispensed as a combination of compositions.
• “combination of compositions” it is meant that the various compositions comprising the essential ingredients are mixed or at least combined : prior to being dispensed, e.g., in a mixing chamber, if any, or the dispensing means; during the dispensing, e.g., on the dispensing means; or after being dispensed, on the lavatory surface itself (this means in the flushed water).
• at least the containers containing essential ingredients are connected to the dispensing means or a multitude thereof in way that the compositions containing the essential ingredients are dispensed onto said lavatory bowl surface.
• the lavatory bowl rim-block comprises at least one solid and/or gel composition(s)
• the container(s) not comprising essential ingredients are not necessarily used to dispense compositions onto said lavatory bowl surface, however it is in the scope of the present invention that such a container(s) also dispense compositions onto the lavatory bowl surface.
• a container(s) may contain compositions, such as perfumes and the like, that are dispensed into the air.
• such containers may contain liquid and/or solid compositions.
• Suitable dispensers for use in the lavatory bowl rim-block as described herein are for example described in WO 01/44591, WO 99/66140, GB 2345494, WO 99/15375, WO 00/49238, GB 2358028, WO 95/38637, WO 01/77451, WO 00/42261, WO 01/06067, EP 538957, US 6,230,334, EP 1046756 and WO 01/02653.
• At least one of the compositions of the lavatory bowl rim-block as described herein is formulated as liquid composition(s).
• the tenn liquid composition encompasses aqueous, thickened, fluid gel, gel and pasteous composition.
• the composition herein is a thickened composition.
• the thickened composition herein may be in the form of a fluid gel, gel or a pasteous composition. If more than one composition is present in the lavatory bowl rim-block herein, said compositions may have different rheologies and/or pH. Indeed, preferably one of said separate compositions is a liquid composition and the other composition(s) are liquid, fluid gel, gel or solid compositions more preferably the other composition(s) are liquid compositions.
• the thickened composition herein is a fluid gel.
• a fluid gel it is meant herein a weak gel structure that exhibits an apparent yield stress, this means that a finite stress must be exceeded before the system will flow.
• these fluid gel properties preferably provided by the gellan gum present in the composition, contribute to the reduction or prevention of leakage and helps maintain the excellent product release from the dispenser.
• the stress exerted by the action of gravity on the composition present in the container of the lavatory rim-block herein is less than the yield stress, leakage of the composition is reduced or even prevented, due to the fact that the composition does not flow.
• the flush-water Upon flushing of the lavatory bowl equipped with a lavatory rim-block according to the present invention, the flush-water enters through the dispensing means into the dispenser and exert sufficient yield stress onto the composition to release said composition from the container (i.e., the composition flows).
• fluid gels are also highly pseudoplastic, which means low viscosity at higher levels of shear.
• the pseudoplastic properties of the composition herein contribute to maintain excellent product release from the dispenser.
• the fluid gel makes compositions very good for suspending particulate matter. It is the weak gel structure that gives gellan gum fluid-gels excellent prevention of leakage as well as suspending ability. It is possible to quantify this structure using Dynamic Mechanical Spectroscopy. This method gently oscillates the sample and from the response measures the degree of structure (storage modulus G' in Pa).
• the preferred thickened composition of the present invention has a viscosity from 100 to 50000 cps at 50 sec "1 and a viscosity of from 5000 to 50000 at 0.01 sec "1 , more preferably of from 100 to 1000 cps at 50 sec "1 , and still more preferably of from 100 to 600 cps at 50 sec "1 and a viscosity of 6000-30000 cps at 0.01 sec "1 at 20°C when measured with a Carri-Med Rheometer model CSL 2 100® (Supplied by TA Instruments) with a 4 cm conic spindle in stainless steal (linear increment from 0.01 to 100 sec "1 in max. 8 minutes).
• composition herein is done by performing a creep test, wherein yield stress (at 0.05 Pa) is applied to a sample and deformation or strain on the sample is measured.
• yield stress at 0.05 Pa
• Preferred thickened composition of the present invention has a viscosity after 10 min of creep of more than 20000 cps.
• the preferred liquid composition herein comprises water in an amount of from 0.01% to 90%, even more preferably of from 2% to 70% and most preferably 5% to 60% by weight of the total composition.
• the liquid composition herein is substantially free of water, preferably free of water.
• substantially free of water it is meant that no water as such is added to the liquid composition(s).
• said liquid composition(s) may comprise traces of water added into the composition(s) through the raw-materials used to produce the liquid composition(s).
• the level of water added into the composition(s) through the raw-materials used to produce the liquid composition(s) is preferably below 10%, more preferably below 5%, even more preferably below 3% by weight of the total composition.
• the pH of the liquid composition according to the present invention may typically be from 0 to 14.
• the pH of the liquid composition herein is at least, with increasing preference in the order given, 2, 3, 4, 5, or 5.9.
• the pH of the liquid composition herein, as is measured at 25 °C preferably is no more than, with increasing preference in the order given, 14, 13, 12, 11, 10, 9, 8, 7 or 6.1.
• the compositions herein may further comprise an acid or base to adjust pH as appropriate.
• Acidity may further contribute to formulate the composition herein that exhibits good limescale removing performance whilst exhibiting also good disinfecting properties.
• Suitable acids herein may be organic and/or inorganic acids.
• Particularly suitable organic acids to be used herein are aryl and/or alkyl sulfonate, such as methane sulphonic acids, citric acid, succinic acid, sulphamic acid, maleic acid and the like.
• Particularly suitable inorganic acids are sulfuric, phosphoric, nitric acids and the like.
• a typical level of acid, when present, is of from 0.0001% to 15%, preferably from 0.001% to 10% and more preferably from 0.01% to 7% by weight of the total composition.
• Suitable bases for use herein are the caustic alkalis, such as sodium hydroxide, potassium hydroxide and/or lithium hydroxide, and/or the alkali metal oxides such, as sodium and/or potassium oxide or mixtures thereof.
• a preferred base is a caustic alkali, more preferably sodium hydroxide and/or potassium hydroxide.
• Suitable bases include ammonia, ammonium carbonate and hydrogen carbonate.
• Typical levels of a base when present, are of from 0.001% to 5% by weight, preferably from 0.01% to 3% and more preferably from 0.1% to 2% by weight of the composition.
• the liquid composition herein comprises gellan gum as an essential ingredient.
• Gellan gum is a polysaccharide manufactured by microbial fermentation of the Sphingomonas Elodea Microorganism and has a mol. wt. of between 400 '000 and 1 '000 '000. Gellan gum is used to preferably form a fluid gel structure of the liquid composition according to the present invention.
• the liquid composition herein may comprise from 0.001% to 1%, preferably from 0.005% to 0.5%, more preferably from 0.001% to 0.2% by weight of the total composition of gellan gum.
• Gellan gum is for example commercially available under the trade name Kelcogel from CPKelco.
• the gellan gum herein is a low acyl gellan gum, preferably the acyl content of the gellan gum herein is below 5%, more preferably below 3%, still more preferably below 2%, yet still more preferably below 1.5% and most preferably below 1%.
• gellan gum prevents leaking of the liquid composition from the dispenser onto the lavatory bowl surface. This leakage would be observable by consumers during the in-between flushes intervals due to the coloring, if any, of the liquid composition. Gellan gum prevents leakage on the lavatory bowl without negatively affecting product release from the dispenser by providing a yield value on the fluid (e.g., the fluid behaves as a solid at very low stresses). This may be due to the fluid gel properties (as discussed herein above), of gellan gum- containing compositions.
• the present invention encompasses a process of cleaning a lavatory bowl surface with a lavatory bowl rim-block according to the present invention, wherein said process comprises the step of applying a liquid composition (or a combination of liquid compositions) onto a lavatory bowl surface.
• said application of a liquid composition (or a combination of liquid compositions) onto a lavatory bowl surface is done upon flushing said lavatory bowl surface with water.
• liquid composition is applied onto said lavatory bowl surface in diluted form.
• composition in its diluted form it is meant herein that said composition may be diluted with water up to 120.000x dilution level, preferably between 50.000x to 80.000x, more preferably lO.OOOx to 60.000x, even more preferably lO.OOOx to 55.000x, and most preferably 20.000x to 50.000x dilution level. Said dilution occurs upon application of the liquid composition herein or the combination of the liquid compositions herein to said surface.
• concentrations and levels (in %) of the different compounds present in the composition herein are given prior to any dilution of said composition upon dispensing of the composition.
• present invention encompasses the manufacture of a composition for use in one of the processes as described herein above.
• the liquid composition according to the present invention may further comprise a chelant as an optional but highly preferred ingredient.
• Chelants are preferred optional ingredients of the present invention, as it has been found that the presence of a chelant herein significantly reduces the mineral deposition on the lavatory bowl surface by chelating ions of the mineral deposition.
• Suitable chelants may be any of those known to those skilled in the art, such as the ones selected from the group comprising phosphonate chelants, amino carboxylate chelants, other carboxylate chelants, polyfunctionally-substituted aromatic chelants, ethylenediamine N,N'- disuccinic acids, or mixtures thereof.
• Suitable phosphonate chelants to be used herein may include ethane 1-hydroxy diphosphonates (HEDP) or salts thereof, alkylene poly (alkylene phosphonate), as well as amino phosphonate compounds, including amino aminotri(methylene phosphonic acid) (ATMP), nitrilo trimethylene phosphonates (NTP), ethylene diamine tetra methylene phosphonates, and diethylene triamine penta methylene phosphonates (DTPMP).
• the phosphonate compounds may be present either in their acid form or as salts of different cations on some or all of their acid functionalities.
• Preferred phosphonate chelants to be used herein are diethylene triamine penta methylene phosphonate (DTPMP) and ethane 1-hydroxy diphosphonate (HEDP).
• DTPMP diethylene triamine penta methylene phosphonate
• HEDP ethane 1-hydroxy diphosphonate
• Such phosphonate chelants are commercially available from Monsanto under the trade name DEQUEST®-
• the chelant herein is a phosphonate chelant or a mixture thereof. More preferably, the chelant herein is selected from the group consisting of ethane 1-hydroxy diphosphonates (HEDP) or salts thereof, alkylene poly (alkylene phosphonate), as well as amino phosphonate compounds, including amino aminotri(methylene phosphonic acid) (ATMP), nitrilo trimethylene phosphonates (NTP), ethylene diamine tetra methylene phosphonates, and diethylene triamine penta methylene phosphonates (DTPMP) and mixtures thereof. Most preferably, the chelant herein is ethane 1-hydroxy diphosphonate (HEDP) or a salt thereof.
• HEDP ethane 1-hydroxy diphosphonate
• ATMP amino aminotri(methylene phosphonic acid)
• NTPMP nitrilo trimethylene phosphonates
• DTPMP diethylene triamine penta methylene phosphonates
• Polyfunctionally-substituted aromatic chelants may also be useful in the compositions herein. See U.S. patent 3,812,044, issued May 21, 1974, to Connor et al.
• Preferred chelants of this type in acid form are dihydroxydisulfobenzenes such as 1 ,2-dihydroxy -3,5-disulfobenzene.
• a preferred biodegradable chelant for use herein is ethylene diamine N,N'- disuccinic acid, or alkali metal, or alkaline earth, ammonium or substitutes ammonium salts thereof or mixtures thereof.
• Ethylenediamine N,N'- disuccinic acids especially the (S,S) isomer, have been extensively described in US patent 4, 704, 233, November 3, 1987, to Hartman and Perkins.
• Ethylenediamine N,N'- disuccinic acid is, for instance, commercially available under the tradename ssEDDS® from Palmer Research Laboratories.
• Suitable amino carboxylates to be used herein as chelants include ethylene diamine tetra acetates, diethylene triamine pentaacetates, diethylene triamine pentaacetate (DTPA),N- hydroxyethylethylenediamine triacetates, nitrilotri-acetates, ethylenediamine tetrapropionates, triethylenetetraaminehexa-acetates, ethanol-diglycines, propylene diamine tetracetic acid (PDTA) and methyl glycine di-acetic acid (MGDA), both in their acid form, or in their alkali metal, ammonium, and substituted ammonium salt forms.
• PDTA propylene diamine tetracetic acid
• MGDA methyl glycine di-acetic acid
• Particularly suitable amino carboxylates to be used herein are diethylene triamine penta acetic acid, propylene diamine tetracetic acid (PDTA) which is, for instance, commercially available from BASF under the trade name Trilon FS® and methyl glycine di-acetic acid (MGDA).
• PDTA propylene diamine tetracetic acid
• MGDA methyl glycine di-acetic acid
• carboxylate chelants to be used herein include salicylic acid, aspartic acid, glutamic acid, glycine, malonic acid or mixtures thereof.
• Another chelant for use herein is of the formula:
• R1 , R2, R3, and R4 are independently selected from the group consisting of -H, alkyl, alkoxy, aryl, aryloxy, -Cl, -Br, -NO2, -C(0)R', and -SO2R"; wherein R' is selected from the group consisting of -H, -OH, alkyl, alkoxy, aryl, and aryloxy; R" is selected from the group consisting of alkyl, alkoxy, aryl, and aryloxy; and R5, Rg, R7, and Rg are independently selected from the group consisting of -H and alkyl.
• the composition herein may comprise up to about 5%, preferably from about 0.1% to about 3% by weight and more preferably from about 0.5%% to about 2% by weight of the total composition of a chelant.
• the liquid composition according to the present invention may further comprise a silicone polymer as an optional but highly preferred ingredient.
• Silicon polymers are preferred optional ingredients herein as they deposit onto the surfaces cleaned with a composition according to the present invention. Thereby, soil adherence, limescale and/or mineral encrustation build-up, is prevented. Indeed, it has been found, that the optional silicone polymers herein, deposit onto the lavatory bowl surface, which is thereby rendered less prone the adherence and/or the build-up of limescale and mineral encrustation, etc. ("mineral deposition").
• composition herein may comprise up to 50%, more preferably of from 0.01% to 30%, even more preferably of from 0.01% to 20%, and most preferably of from 0.01% to 10%, by weight of the total composition of said silicone polymer.
• Suitable silicone polymers are selected from the group consisting of silicone glycol polymers and mixtures thereof.
• the silicone polymer herein is a silicone glycol polymer.
• the silicone glycol polymer can be either linear or grafted.
• said silicone glycol polymer is according to the following formulae :
• each Ri independently is H or a hydrocarbon radical; R 2 is a group bearing a polyether functional group; n is an integer of from 0 to 500; and for the grafted structure m is an integer of from 1 to 300, and preferably with n+m more than 1.
• each Ri independently is H or a hydrocarbon chain comprising from 1 to 16, more preferably a hydrocarbon chain comprising from 1 to 12 carbon atoms, and even more preferably Ri is a CHrgroup. Ri can also contain NH 2 groups and/or quaternary ammoniums.
• n is an integer of from 0 to 100, more preferably an integer of from 1 to 100, even more preferably n is an integer of from 1 to 50, and most preferably n is an integer of from 5 to 30.
• n (for the grafted structure) is an integer of from 1 to 80, more preferably m is an integer of from 1 to 30, and even more preferably m is an integer of from 2 to 10.
• n+m is more than 2.
• R 2 is an alkoxylated hydrocarbon chain. More preferably, R 2 is according to the general formulae :
• R 3 is a hydrocarbon chain
• A is an alkoxy group or a mixture thereof
• p is an integer of from 1 to 50
• t is H or a hydrocarbon chain, or -COOH.
• R 3 is a hydrocarbon chain comprising from 1 to 12, more preferably 3 to 10, even more preferably from 3 to 6, and most preferably 3 carbon atoms.
• A is an ethoxy or propoxy or butoxy unit or a mixture thereof, more preferably A is an ethoxy group.
• p is an integer of from 1 to 50, more preferably p is an integer of from 1 to 30, and even more preferably p is an integer of from 5 to 20.
• t is H or a hydrocarbon chain comprising from 1 to 12, more preferably 1 to 6, even more preferably from 3 to 6, and still even preferably 3 carbon atoms, most preferably R 4 is H.
• the silicone glycol polymers suitable herein have an average molecular weight of from 500 to 100,000, preferably from 600 to 50,000, more preferably from 1000 to 40,000, and most preferably from 2,000 to 20,000.
• Suitable, silicone glycol polymers are commercially available from General electric, Dow Corning, and Witco (see Applicant's co-pending European Patent Applications 03 447 099.7 and 03 447 098.9 for an extensive list of trade names of silicone glycol polymers).
• the polymer herein is a Silicones-Polyethers copolymer, commercially available under the trade name SF 1288® from GE Bayer Silicones.
• the liquid composition according to the present invention may comprise, as an optional ingredient but highly preferred ingredient a nonionic surfactant, or mixtures thereof.
• composition herein may comprise up to 70%, preferably of from 1% to 30%, more preferably of from 1% to 20%, and most preferably of from 1% to 10% by weight of the total composition of a nonionic surfactant or mixtures thereof.
• nonionic surfactants in the composition of the present invention allows to provide good cleaning performance.
• the presence of nonionic surfactants in the composition herein may also allow to provide compositions with further improved shine benefit. Indeed, it has been found that the presence of a nonionic surfactant further contributes to the reduction or even prevention of mineral deposits as described herein above.
• Suitable nonionic surfactants to be used herein are alkoxylated fatty alcohol nonionic surfactants that can be readily made by condensation processes that are well known in the art. Indeed, a great variety of such alkoxylated fatty alcohols are commercially available which have very different HLB values.
• the HLB values of such alkoxylated nonionic surfactants depend essentially on the chain length of the fatty alcohol, the nature of the alkoxylation and the degree of alkoxylation. Hydrophilic nonionic surfactants tend to have a high degree of alkoxylation and a short chain fatty alcohol, while hydrophobic surfactants tend to have a low degree of alkoxylation and a long chain fatty alcohol.
• Surfactants catalogues are available which list a number of surfactants including nonionics, together with their respective HLB values.
• preferred alkoxylated alcohols for use herein are nonionic surfactants according to the formula RO(E) e (P) p H where R is a hydrocarbon chain of from 2 to 24 carbon atoms, E is ethylene oxide and P is propylene oxide, and e and p which represent the average degree of, respectively ethoxylation and propoxylation, are of from 0 to 24.
• the hydrophobic moiety of the nonionic compound can be a primary or secondary, straight or branched alcohol having from 8 to 24 carbon atoms.
• Preferred nonionic surfactants for use in the compositions according to the invention are the condensation products of ethylene oxide with alcohols having a straight alkyl chain, having from 6 to 22 carbon atoms, wherein the degree of ethoxylation is from 1 to 15, preferably from 5 to 12.
• Such suitable nonionic surfactants are commercially available from Shell, for instance, under the trade name Dobanol® or from Shell under the trade name Lutensol®. These nonionics are preferced because they have been found to allow the formulation of a stable product without requiring the addition of stabilisers or hydrotropes. When using other nonionics, it may be necessary to add hydrotropes such as cumene sulphonate or solvents such as butyldiglycolether.
• the liquid composition according to the present invention may further comprise a surfactant other than the nonionic surfactant, if any, as described above.
• surfactants may be used in the present invention including anionic, cationic, amphoteric or zwitterionic surfactants. It is also possible to use mixtures of such surfactants without departing from the spirit of the present invention.
• surfactants other than the nonionic surfactants allows to provide good cleaning performance.
• the liquid composition herein may comprise up to 70%, preferably of from 0.1% to 60%, more preferably of from 1% to 50%, and most preferably of from 5% to 40% by weight of the total composition of a surfactant, or mixtures there.
• Suitable amphoteric surfactants to be used in the compositions according to the present invention include amine oxides.
• Preferred long chain amine oxides for use herein are for instance natural blend C 8 -C ⁇ o amine oxides as well as C ⁇ 2 -C ⁇ 6 amine oxides commercially available from Hoechst.
• Preferred short chain amine oxides for use herein are for instance natural blend C 8 -C ⁇ 0 amine oxides available from Hoechst.
• the liquid composition (or combination of liquid compositions) according to the present invention may further comprise an alkyl alkoxylated sulphate surfactant.
• Suitable alkyl alkoxylated sulphate surfactants for use herein are according to the formula RO(A) m S03M wherein : R is a substituted or unsubstituted, linear or branched Cg-C24, preferably a Cg-C20, more preferably a C12-C20 .
• A is an ethoxy or propoxy or butoxy unit
• m is greater than zero, preferably at least 0.1, more preferably between 0.1 and 15, even more preferably between 0.5 and 6, and most preferably between 0.5 and 4
• M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation.
• Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates and alkyl butoxylated sulfates are contemplated herein.
• alkyl alkoxylated sulphate surfactants are alkyl ethoxylated sulfates, i.e., A is an ethoxy group.
• substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium and quaternary ammonium cations, such as tetramethyl-ammonium, dimethyl piperdinium and cations derived from alkanolamines such as ethylamine, diethylamine, triethylamine isopropanolamine, mixtures thereof, and the like.
• Exemplary surfactants are C12- Cig alkyl polyethoxylate (1.0) sulfate (C 12 -C 18 E(1.0)SM), C 12 -C 18 alkyl polyethoxylate (2.25) sulfate (C 12 -C 18 E(2.25)SM), C 12 -C ⁇ g alkyl polyethoxylate (3.0) sulfate (C 12 -C 18 E(3.0)SM), Ci2-C 14 alkyl polyethoxylate (3.0) sulfate (C 12 -C 4E(3.0)SM) and Ci2-C 18 alkyl polyethoxylate (4.0) sulfate (Ci2-C ⁇ gE(4.0)SM), wherein M is conveniently selected from sodium and potassium.
• alkyl ethoxylated sulfate with a degree of ethoxylation of 2.4 or between 2-3.
• Sodium C12/C14 E3 sulphate may be for example commercially available from Albright & Wilson under the name EMPICOL ESC3®.
• alkyl alkoxylated sulphate surfactants When present, alkyl alkoxylated sulphate surfactants contribute to suds stability, and volume and also contribute to product viscosity.
• liquid composition according to the present invention may further comprise a solvent.
• composition herein may comprise up to 30%, preferably of from 0.1% to 30%, more preferably of from 1% to 20%, and most preferably of from 1% to 15% by weight of the total composition of a solvent, or mixtures there.
• Suitable solvents for use herein include ethers and diethers having from 4 to 14 carbon atoms, preferably from 6 to 12 carbon atoms, and more preferably from 8 to 10 carbon atoms, glycols or alkoxylated glycols, glycol ethers and/or derivatives, polyols, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched or linear alcohols, alkoxylated aliphatic branched or linear alcohols, terpenes, and mixtures thereof.
• Suitable glycols for use herein are according to the formula HO-CR1 R2-OH wherein R and R2 are independently H or a C2-C12 saturated or unsaturated aliphatic hydrocarbon chain and/or cyclic.
• Suitable glycols to be used herein are dodecaneglycol, 1 ,2-hexanediol and/or propanediol.
• Suitable alkoxylated glycols for use herein are according to the formula R-(A) n -R ⁇ -OH wherein R is H, OH, a linear saturated or unsaturated alkyl of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 2 to 10, wherein R ⁇ is H or a linear saturated or unsaturated alkyl of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 2 to 10, and A is an alkoxy group preferably ethoxy, methoxy, and/or propoxy and n is from 1 to 5, preferably 1 to 2.
• Suitable alkoxylated glycols to be used herein are methoxy octadecanol and/or ethoxyethoxyethanol.
• Suitable glycol ethers and/or derivatives thereof for use herein include monoglycol ethers and/or derivatives thereof, di-, tri- and poly-glycol ethers and/or derivatives thereof and mixtures thereof.
• Suitable monoglycol ethers and derivatives thereof for use herein include propylene glycol butyl ether, and water-soluble CELLOSOLVE® solvents or mixtures thereof.
• Preferred Cellosolve® solvents include 2-(Hexyloxy)ethanol (i.e., 2-hexyl Cellosolve®), ethylene glycol ethyl ether (i.e., 2-ethyl Cellosolve®), ethylene glycol butyl ether (i.e., 2-butyl Cellosolve®) or mixtures thereof.
• Suitable polyglycol ethers and derivatives thereof for use herein include n- butoxypropoxypropanol (n-BPP), butyl triglycol ether (BTGE), butyl diglycol ether (BDGE), diethylene glycol butyl ether, water-soluble CARBITOL® solvents or mixtures thereof.
• Preferred water-soluble CARBITOL® solvents are compounds of the 2-(2-alkoxy ethoxy)ethanol class, 2-(2-alkoxy ethoxy)propanol class and/or 2-(2-alkoxy ethoxy)butanol class wherein the alkoxy group is derived from ethyl, propyl, butyl and tert-butyl.
• a preferred water-soluble carbitol is 2-(2-butoxyethoxy)ethanol also known as butyl carbitol®.
• Suitable polyols for use herein are aliphatic linear or branched saturated or unsaturated hydrocarbons having from 2 to 12 carbon atoms, preferably 4 to 10, and comprising at least 2 hydroxyl groups, preferably from 2 to 4.
• Suitable polyols herein are diols such as 2-ethyl-l,3- hexanediol, 2,2,4-trimethyl-l,3-pentanediol, methyl-2,4 pentanediol, 1 ,6-hexanediol or mixture thereof.
• Suitable alkoxylated aromatic alcohols for use herein are according to the formula R (A) n -OH wherein R is an alkyl substituted or non-alkyl substituted aryl group of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 2 to 10, wherein A is an alkoxy group preferably butoxy, propoxy and/or ethoxy, and n is an integer of from 1 to 5, preferably 1 to 2.
• Suitable alkoxylated aromatic alcohols are benzoxyethanol and/or benzoxypropanol.
• Suitable aromatic alcohols for use herein are according to the formula R-OH wherein R is an alkyl substituted or non-alkyl substituted aryl group of from 1 to 20 carbon atoms, preferably from 1 to 15 and more preferably from 1 to 10.
• R is an alkyl substituted or non-alkyl substituted aryl group of from 1 to 20 carbon atoms, preferably from 1 to 15 and more preferably from 1 to 10.
• a suitable aromatic alcohol to be used herein is benzyl alcohol.
• Suitable aliphatic linear or branched alcohols for use herein are according to the formula R-OH wherein R is a branched or linear saturated or unsaturated alkyl group of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 2 to 12.
• Particularly suitable aliphatic branched alcohols to be used herein include 2-ethylbutanol and/or 2-methylbutanol.
• Particularly suitable aliphatic linear alcohols to be used herein include decanol, ethanol and/or 1- or 2- propanol.
• Suitable alkoxylated aliphatic linear or branched alcohols for use herein are according to the formula R-(A) n -OH wherein R is a branched or linear saturated or unsaturated alkyl group of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 5 to 12, wherein A is an alkoxy group preferably butoxy, propoxy and/or ethoxy, and n is an integer of from 1 to 5, preferably 1 to 2.
• Suitable alkoxylated aliphatic branched alcohols include 1- methylpropoxyethanol and/or 2-methylbutoxyethanol.
• Suitable alkoxylated aliphatic linear alcohols include ethoxy propanol and/or propoxy propanol.
• Suitable solvents include ter amilic alcohol, terpene solvents and the like.
• Suitable terpenes for use herein are mono-and bicyclic terpenes, especially those of the hydrocarbon class, which include the terpinenes, terpinolenes and pinenes and mixtures thereof. Highly preferred materials of this type are dipentene, alpha-pinene and/or beta-pinene.
• pinene is commercially available from SCM Glidco (Jacksonville) under the name Alpha Pinene P&F®.
• solvents for use herein are ethylene glycol butyl ether, propylene glycol butyl ether, diethylene glycol butyl ether, butoxy propoxy propanol, butyl diglycol ether, benzyl alcohol, butoxypropanol, 2-(2-butoxyethoxy) ethanol, ethanol, methanol, benzyl alcohol, isopropanol, 1 -propanol and mixtures thereof.
• composition herein may comprise a thickener or a thickening system as a highly preferred optional ingredient, in addition to the Gellan gum
• Suitable thickeners herein are selected from the group consisting of organic thickeners, and inorganic thickeners and mixtures thereof.
• the thickener herein when present is an organic thickeners, more preferably a polyacrylate; a gum, which can be derived from marine sources (agar, alginates, carrageenan, furcellaran), terrestrial plants (guar gum, gum Arabic, gum tragacenth, karaya gum, locust bean gum and pectin), animal sources (gelatin), microbial polysaccharides other than Gellan gum (such as dextran, rhamsam gum, welan gum, Xanthan gum); a polysaccharide derivative (carboxymethylcellulose, methylhydroxypropyl cellulose, hydroxy propyl cellulose, hydroxyethyl cellulose, propylene glycol alginate, hydroxy propyl guar and modified starters); or a mixture thereof.
• a gum which can be derived from marine sources (agar, alginates, carrageenan, furcellaran), terrestrial plants (guar gum, gum Arabic, gum tragacenth, karaya gum,
• Suitable thickening systems are selected from the group consisting of a cationic/anionic surfactant system self-thickening systems.
• compositions herein comprise a polyacrylate or a gum or a combination thereof .
• composition herein may comprise from 0.005% to 15%, preferably from 0.01% to 10%, more preferably from 0.02% to 5% by weight of the total composition of a thickener or a thickening system.
• composition herein may comprise, as an optional ingredient, a perfume ingredient.
• the composition herein may comprise from 0.01% to 40%, preferably from 0.01% to 35%, more preferably from 0.1% to 30%, and most preferably from 0.1% to 25% by weight of the total composition of said perfume ingredient.
• compositions according to the present invention may further comprise a variety of other ingredients including dyes, optical brighteners, builders, pigments, solvents, buffering agents, radical scavengers, polymers, stabilizers and the like.
• compositions are made by combining the listed ingredients in the listed proportions (weight % unless otherwise specified). Furthermore, the compositions comprise water and minors up to 100%.
• the following Examples are meant to exemplify compositions according to the present invention but are not necessarily used to limit or otherwise define the scope of the present invention.
• the compositions are present in the container of a lavatory bowl rim-block comprising : at least one container; at least one liquid composition; and a dispensing means connected to at least one of said container(s) for dispensing a single liquid composition or a combination of liquid compositions onto a lavatory bowl surface.
• Kelzan T® is Xanthan Gum and Kelcogel F® is gellan gum, both commercially available from
• Dobanol® 23-3 is a C12-C13 E03 nonionic surfactant
• Dobanol® 91-8 is a C9-C1 1 E08 nonionic surfactant, all commercially available from SHELL.
• Na HEDP is Sodium ethane 1-hydroxy diphosphonate.
• SF 1288® is a Silicones-Polyether copolymer, commercially available from GE Bayer Silicones.
• HLAS is a linear alkylbenzene sulphonic acid anionic surfactant.
• Marlinat 242/90® is an alkyl ethoxylated sulfate commercially available from Sasol.

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