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
  • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/83—Mixtures of non-ionic with anionic compounds
• • 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
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3942—Inorganic per-compounds
• • 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
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
  • C11D1/143—Sulfonic acid esters
• • 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
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
  • C11D1/146—Sulfuric acid esters

Definitions

• the present invention relates to a cleansing and sanitizing composition for sanitary appliances.
• the present invention relates to a cleansing and sanitizing composition in the form of rim- block for sanitary appliances, adapted to be suspended from the rim of the water closet bowl, and as such to be partly and periodically brought into contact with the flush water, or in the form of in-cistern blocks, adapted to be entirely immersed in the flush water stored in a cistern or in a container interlocked with a water close .
• the various ingredients of the composition may be mixed to give a mixture having viscosity and plasticity characteristics that allow "the mixture to be formed into blocks or rim-blocks by extrusion, which is a technique that allows to obtain a high productive capacity together with a reduction in productive costs.
• a halogen-based bleaching agent in particular chlorine obtained from the decomposition of dichloroisocyanurate- based compounds .
• halogen-based bleaching agent involved problems of compatibility between the various ingredients of the composition of the rim-blocks or blocks, both during their producing step and during their use, because of the intrinsic reactivity of the bleaching agent which tends to destabilize itself, on the one hand by reacting with the surfactant included in the composition, and on the other hand by releasing the halogen, causing thereby a reduction in the bleaching activity of the composition.
• a non-oxidizable liquid material selected from liquid ketones, liquid tertiary alcohols, liquid complex esters of glycerol and propylene glycol, triethylene glycol esters of C 8 -C 10 fatty acids and/or succinic acid.
• non-oxidizable liquid material allows, during the rim-block or block producing step, to create a protective film made of said material around the individual grains of bleaching agent, preventing thereby their reactivity.
• cleansing/sanitizing compositions including dichloroisocyanurates do not allow to entirely solve the problem of the compatibility between the ingredients, which leads to a reduction of the cleansing and/or sanitizing power of the composition over the time.
• the technical problem underlying the present invention is therefore that of devising and providing a cleansing and sanitizing compositions which may be conformed by extrusion, has excellent cleansing and scales removing properties and an effective bactericidal activity, and which is capable at the same time of keeping as much as possible constant both its cleansing and sanitizing characteristics over the time, both during the producing step of the finished product and during its subsequent storage, or during the use of the composition.
• a cleansing and sanitizing composition for sanitary appliances comprising:
• the Applicant has in fact found that, thanks to the combination of the aforementioned ingredients and in spite of the use of an oxidizing agent including at least one peroxide bond which is per se strongly unstable in the presence of even minor amounts of moisture and highly reactive in the presence of oxidable substances, such as for instance the surfactants included m the composition, it is possible to ensure both an adequate workability of the mixture obtained starting from said ingredients and an adequate stability of the composition so obtained over the
• an anionic surfactant and preferably an anionic surfactant with a moisture content not higher than 3% by weight, a non ionic surfactant substantially free from water and having a viscosity at 70°C of from 200 to 1000 mPa*s and a suitable pH adjusting agent, it is possible both to obtain a mixture of ingredients having viscosity and plasticity characteristics such as to allow the mixture to be formed m continuous by extrusion, and to achieve the desired stability of the cleansing/sanitizing activity of the final composition over the time.
• the anionic surfactant preferably has a moisture content not higher than 3% by weight and, still more preferably, not higher than 1.5% by weight .
• the anionic surfactant may be selected from the surfactants suitable for use m a rim-block or block for sanitary appliances, and is preferably selected from the group comprising: sodium alkylarylsulfonate, sulfonated sodium paraffins, sodium alkylsulfate, sulfonated ⁇ -olefms, and mixtures thereof.
• surfactants are available on the market and sometimes may include small amounts of inert fillers, such as sodium sulfate or sodium phosphate.
• the anionic surfactant performs the function of cleansing agent and foaming product, whose effects are proportional to the amount of surfactant included in the composition.
• the anionic surfactant may be used in an amount of from 10 to 80% by weight, preferably of from 40 to 60% by weight .
• the Applicant has surprisingly found that by using in the composition at least one non ionic surfactant substantially free from water and having a viscosity at 70°C of from 200 to 1000 mPa*s, it is possible to achieve some important advantages .
• non ionic surfactant substantially free from water it is intended to indicate a surfactant comprising a moisture amount not higher than 0.5% by weight .
• a non ionic surfactant having the aforementioned characteristics it is, in fact, possible to obtain a mixture of ingredients having viscosity, plasticity and mechanical stability characteristics, which are thought to be ascribable to the binding action performed by the same surfactant, such as to allow the mixture to be formed by extrusion.
• non ionic surfactant imparts to the finished product the consistency and hardness required for the use, when the product is either in the form of a water closet rim-block or a in-cistern block for sanitary appliances .
• said non ionic surfactant during the use acts as a booster of the foaming effect, allowing a persistency of the foam generated for several minutes after each flushing.
• the first non ionic surfactant substantially free from water is preferably selected from the group comprising: alkanolamides of C 8 -C 18 saturated and unsaturated fatty acids, ethoxylated fatty alcohols, and mixtures thereof.
• alkanolamides of fatty acids and in particular coco mono- and di-ethanolamide, are preferred.
• the oxidizing agent of the invention is highly reactive and is capable per se of decomposing - generating nascent oxygen by a mechanism known per se - when it gets into contact with water in the use conditions of the sanitary appliances considered herein.
• such oxidizing agent can decompose each time its gets in contact with water having a temperature of from 13° to 20°C, which generally is just the temperature of flush water in sanitary appliances.
• the oxidizing agent is selected from the salts of an alkali metal of a peroxy-acid and, still more preferably, it is potassium monopersulfate .
• Potassium monopersulfate of preferred use is that in the form of a triple salt with potassium bisulfate and potassium sulfate, which is particularly stable in the manufacture and use conditions of the composition.
• a triple salt having ratios between monopersulfate, bisulfate and sulfate of 2:1:1 respectively is available on the market under the trade name of OXONE® (E. DuPont De Nemours & Co. , Inc. ) .
• the composition of the invention comprises an effective amount of at least one pH adjusting agent adapted to maintain the pH of the composition at a value such as to stabilize said oxidizing agent, i.e. values at which the peroxide bond of the oxidizing agent has been found to be stable in the storage and use conditions of the composition.
• the pH adjusting agent is included in an amount of from 0.5 to 3% by weight, more preferably of from 1 to 2% by weight.
• the presence of a pH adjusting agent allows to maintain within the composition pH values such as to substantially make stable the peroxide oxidizing agent in the same composition.
• the pH adjusting agent prevent losses of oxidizing agent when the rim-block or block is not in contact with water, while when the rim-block or block is in contact with water, the outermost layer of the rim-block or block in contact with water reaches a pH value approaching neutrality, so as to destabilize the composition through the release of nascent oxygen.
• the pH adjusting agent may be selected from any compounds adapted to maintain the pH of the composition either in an acid field, i.e. at pH values lower than 7 and preferably lower than 6, or in a basic field, i.e. at pH values higher than 7 and preferably higher than 9.
• the pH adjusting agent is an acid adapted to maintain the composition pH in an acid field and in particular at a pH value lower than 5 and, more preferably lower than 3: in this case, in fact, it is easier to minimize the risk of reaching pH value approaching neutrality and therefore the risk of decomposition of the oxidizing agent, during the various working and/or storing steps of the composition.
• an acid as pH adjusting agent allows to prevent limestone from depositing on the internal walls of the sanitary appliance, and to remove possible existing limestone deposits on the same walls.
• the acid used as pH adjusting agent preferably is an organic or inorganic weak acid.
• Organic or inorganic acids suitable for the purposes of the invention are protic acids selected from weak acids having a first ionization constant (pK at 25°C of from 3 to 5, such as for instance phosphoric, sulfamic, citric, tartaric or malic acids, individually or combined with one another.
• pK at 25°C a first ionization constant
• the pH adjusting agent is an organic -hydroxyacid, such 'as for instance, citric acid, malic acid, and mixtures thereof.
• the pH adjusting agent may instead be selected from any substances that can bring the solution pH into the basic field, such as for instance sodium carbonate.
• the cleansing and sanitizing composition of the invention further comprises 0.2 to 14% by weight, preferably 6 to 12% by weight, of a halogen releasing agent by reacting with the oxidizing agent comprising a metal, halide, preferably of an alkali metal.
• a halogen releasing agent by reacting with the oxidizing agent comprising a metal, halide, preferably of an alkali metal.
• the halogen releasing agent of the oxidizing agent is selected from the group comprising sodium chloride, sodium bromide, and mixtures thereof.
• the halogen releasing agent of preferred use is sodium chloride which, by reacting with potassium monopersulfate, originates, through a mechanism known per se, sodium hypochlorite which, in its turn, allows to increase the antibacterial activity of the composition.
• the cleansing and sanitizing composition further comprises 0.3 to 10% by weight, preferably 2 to 8% by weight, of at least one second non ionic surfactant substantially free from water and having a viscosity at 70°C of from 50 to 500 mPa*s and more preferably of from 100 to 150 mPa*s.
• the addition of such a second non ionic surfactant allows to reduce the working time of the mixture of ingredients with respect to that required in case of a composition having no such second surfactant.
• the latter in fact, advantageously acts as lubricant and diluent and therefore allows to amalgamate the ingredients of the composition in a time markedly shorter than that which may be obtained only with the first non ionic surfactant .
• composition of ' the invention may be manufactured in full compliance with the producing times required by the modern technologies of manufacturing by extrusion which are adopted for large scale production.
• the second non ionic surfactant advantageously allows to chemically and mechanically stabilize the composition and to adjust its use life.
• the second non ionic surfactant is preferably selected from the group comprising polyalkylene glycols, for instance polyethylene glycol or polypropylene glycol, complex liquid esters of glycerol with C 12 -C 18 fatty acids, and mixtures thereof.
• polyethylene glycols having an average molecular weight of from 200 to 6000, and in particular polyethylene glycol 400, are preferred.
• the composition preferably comprises 0.5 to 10% by weight of polyethylene glycol 400, and 0.5 to 10% by weight of coco diethanolamide, and still more preferably, 1 to 7% by weight of polyethylene glycol 400 and 1 to 5% by weight of coco diethanolamide.
• the composition preferably comprises 0.3 to 5% by weight of polyethylene glycol 400 and 5 to 25% by weight of coco monoethanolamide, and still more preferably, 0.5 to 3% by weight of polyethylene glycol 400 and 10 to 20% by weight of coco monoethanolamide .
• the cleansing and sanitizing composition of the invention further comprises 0.003 to 1% by weight of at least one suitable dyestuff adapted to impart to the rim- block or block an homogeneous color, preferably white, for a more pleasant and uniform appearance.
• the composition of the invention may advantageously comprise a greater amount of perfume with respect to the amount allowed in the known composition including dichloroisocyanurates as halogen- based bleaching agents described, for instance, in European Patent EP 0 672 103.
• the perfume is preferably added in an amount of from 0.0002 to 5% by weight, still more preferably of from 2 to 4% by weight for conventional perfumes, and of from 0.001 to 0.005% by weight in case of essences.
• the amount of perfume can easily dose to obtain the effect desired.
• the composition of -the invention may further comprise 0.25 to 3% by weight of at least one suitable solubility control agent, adapted to control the velocity of dissolution of the composition in water.
• such adjusting agent is a carboxymethylcellulose sodium salt. Thanks to its high affinity for water, the carboxymethylcellulose sodium salt is, in fact, advantageously capable of reducing the amount of free moisture within the composition, thus reducing the risk of a premature destabilization of the oxidizing agent.
• the ingredients of the composition in the form of powders and liquids are mixed at a temperature selected in the range of from 30 to 70°C, so as to facilitate the blending of the ingredients (melting, if necessary, those that are solid at room temperature) , and to obtain a mixture having viscosity and plasticity characteristics such as to allow the subsequent forming by extrusion.
• the mixture is drawn through a drawplate maintained at a temperature of about 70 °C and afterward subdivided with a special cutter into rim-blocks or blocks having the shape and size appropriate for the use.
• the drawing operation may be carried out also at a temperature of 70°C, without adversely affecting the chemical -physical characteristics of the same composition.
• the rim-blocks or blocks come out from the drawplate at a temperature of about 50 °C and are allowed to cool at room temperature .
• anionic surfactant sodium alkylaryl sulfonate
• non ionic surfactants coco diethanolamide and polyethylene glycol 400;
• - oxidizing agent potassium monopersulfate , available on the market under the trade name of OXONE® (E. DuPont de Nemours & Co., Inc.);
• dissolution velocity adjusting agent carboxymethylcellulose sodium salt
• composition was subdivided into water closet rim-blocks.
• composition of the mixture is shown in Table I, below.
• Example 2 In accordance with the procedures described in the preceding Example 1, a second mixture was prepared comprising the same ingredients as Example 1, except that the amount of coco diethanolamide was reduced and that of polyethylene glycol was increased.
• composition of the mixture is shown in Table I, below.
• Example 3 In accordance with the procedures described in the preceding Example 1, a third mixture was prepared comprising the same ingredients as Example 1 except for polyethylene glycol 400, and additionally including:
• - inert filler anhydrous sodium sulfate
• composition of the mixture is shown in Table I, below.
• Example 1 a fourth mixture was prepared comprising the same ingredients as Example 1 except for polyethylene glycol 400 and for carboxymethylcellulose sodium salt, and additionally including:
• - inert filler anhydrous sodium sulfate.
• composition of the mixture is shown in Table I, below.
• Example 1 (Invention) In accordance with the procedures described in the preceding Example 1, a fifth mixture was prepared comprising the same ingredients as Example 1, and additionally including perfume.
• the time required to obtain a homogeneous mixture of the ingredients was of about 20 minutes.
• composition of the mixture is shown in Table I, below.
• Example 2 In accordance with the procedures described in the preceding Example 1, a sixth mixture was prepared comprising the same ingredients as Example 1, except that coco monoethanolamide replaced coco diethanolamide.
• coco monoethanolamide was heated to a temperature of about 70 °C to obtain its melting and then was mixed in the liquid state with the other ingredients.
• the time required to obtain a homogeneous mixture of the ingredients was of about 30 minutes.
• Example 2 the mixture was then extruded and drawn, but was subdivided into in-cistern blocks for sanitary appliances.
• composition of the mixture is shown in Table II, below.
• Example 7 a seventh mixture was prepared comprising the same ingredients as Example 6, except that the amounts of sodium alkylarylsulfonate , sodium chloride, carboxymethylcellulose and OXONE® were changed.
• the time required to obtain a homogeneous mixture of the ingredients was of about 30 minutes.
• Example 6 the mixture was then extruded, drawn and subdivided into in-cistern blocks for sanitary appliances.
• composition of the mixture is shown in Table II, below.
• Example 1 In accordance with the procedures described in the preceding Example 1, an eighth mixture was prepared comprising the same ingredients as Example 1, except for sodium chloride.
• the time required to obtain a homogeneous mixture of the ingredients was of about 20 minutes.
• composition of the mixture is shown in Table I, below.
• a water closet rim-block available on the market was selected as comparison composition, including the following ingredients :
• chlorine-based bleaching agents dihydrated dichloroisocyanurate
• - anionic surfactants > 30%.
• a sample of each of the rim-blocks or blocks of Examples 1, 3, 4, 6, 8 and 9 was submitted to a set of tests in order to evaluate the stability of the oxidizing agent thereof over the time, i.e. to evaluate the amount of non- decomposed oxidizing agent that was still present after a given time.
• rim-blocks or blocks just produced were placed within a stove, conventional per se, at the temperature of 42.5°C for a time of about 10 days .
• these samples including those withdrawn from the stove, were evaluated for the stability of the oxidizing agent.
• the solution containing the cleansing and sanitizing product was mechanically stirred until the dissolution of the product was complete.
• the solution obtained was then titrated with sodium thiosulfate 0,1 N until the color disappeared.
• the values of sodium thiosulfate added are indicative of the amount of oxidizing agent still present within the composition.
• sodium thiosulfate are expressed as percent values, i.e. they are referred to the amount of sodium thiosulfate employed for the titration of a solution containing the theoretical amount of oxidizing agent and halogen release agent (if it is present) in 1 g of. rim-block or block.
• compositions of the invention include an amount of oxidizing agent comparable to that of the known comparison composition.
• a sample of each of the rim-blocks of the preceding Examples 2 , 8 and 9 and a sample of a rim-block of standard formulation including:
• each sample separately from the other, was dipped in 1 liter of water containing the selected microorganism, in the case in point Escherichia coli ATCC8739, at the concentration of 10 9 c.f.u. per milliliter.
• the dipping procedure included 10 dipping with 3 sec intervals from one another.
• the controls of microbial surviving in water were performed before dipping, after dipping at zero time and after 10 minutes, by the counting method in agarized medium indicated in the book "La microbiologia nell'self cosmetica", chap. IV, pp. 73-77, UNIPRO 1990.
• compositions of the invention can reduce to a substantial extent the microbial surviving already at zero time with respect to both the standard composition free from antimicrobial agent and the known comparison composition (Example 9) . .
• Example 8 comprises an amount of oxidizing agent theoretically active and capable of exercising its sanitizing power comparable to that of Example 8 (see Table III) , it actually has a substantially null sanitizing power, similar to the one of the standard rim-block, probably because of an insufficient reactivity of the oxidizing agent in the test conditions.

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• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
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• 1999
  • 1999-06-22 EP EP99926755A patent/EP1204735A1/de not_active Ceased
  • 1999-06-22 AU AU43914/99A patent/AU4391499A/en not_active Abandoned
  • 1999-06-22 WO PCT/IT1999/000181 patent/WO2000078911A1/en not_active Ceased

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