Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/04—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
  • 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
• • 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
  • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
  • C11D1/29—Sulfates of polyoxyalkylene ethers
• • 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
  • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
  • C11D3/3905—Bleach activators or bleach catalysts
  • C11D3/3907—Organic compounds
  • C11D3/3917—Nitrogen-containing compounds
  • C11D3/3925—Nitriles; Isocyanates or quarternary ammonium nitriles
• • 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
  • C11D3/3947—Liquid compositions

Definitions

• the invention relates to hard surface cleaning compositions comprising a peroxygen bleach compound and a cationic nitrile.
• the invention particularly relates to liquid hard surface cleaning compositions.
• agents which bleach unsightly stains on substrates such as surfaces or fabric which help removing soil, remove mould stains and kill microorganisms.
• Common agents for this purpose are those which contain active chlorine, the most common being sodium hypochlorite, which is widely used in cleaning compositions.
• hypochlorite A problem which is associated with hypochlorite is its unpleasant odour and, when accidentally mixed with an acidic product, the possibility that toxic amounts of chlorine gas are liberated. Therefore, alternative bleaching agents, particularly peroxygen compounds, such as peroxides and peracids and their salts, are gaining popularity.
• peroxygen compounds such as peroxides and peracids and their salts
• Such agents generally operate by reacting with the peroxygen compound to form an oxidative bleaching species, which subsequently reacts with the substrate to be bleached, cleaned or disinfected.
• EP-A-0 303 520 Typical examples of such compounds are disclosed in EP-A-0 303 520, EP-A-0 458 396 and EP-A-0 464 880 in which the organic groups attached to the positive nitrogen are alkyl groups.
• the positive nitrogen is part of a heterocyclic ring.
• EP-A-0 897 974 the general formula comprises a large group of organic substituents on the positive nitrogen, but N-methylmorpholinium-acetonitrile methosulphate is the only compound actually disclosed.
• cationic nitriles have been disclosed to lead to good bleaching in combination with a peroxygen compound and particularly with hydrogen peroxide or precursors thereof. Without being bound by theory, the bleaching is believed to take place by a reactive peroxy species formed in situ by oxidation of the cationic nitrile by the peroxygen compound.
• Bleach containing hard surface cleaning compositions are often used for bleaching black mould stains which regularly occur in enclosed spaces with a high humidity, such as bathrooms and shower cabins.
• black mould stains are caused by either of two species, i.e. Aspergillus niger or Cladosporium cladosporoides. The latter is most predominat and its stains are the most difficult ones to bleach.
• Aspergillus niger or Cladosporium cladosporoides The latter is most predominat and its stains are the most difficult ones to bleach.
• US 6,046,150 combinations of MMA with hydrogen peroxide have been described to be successful in bleaching A. niger stains when used in pure aqueous solution.
• compositions comprising a cationic nitrile/peroxygen compound bleach system as well as a surfactant, which compositions would be suitable for use against a variety of soils and stains, including black mould stains.
• a hard surface composition which comprise a cationic nitrile/peroxygen compound bleach system and an anionic sulphate or sulphonate surfactant containing an alkyl group having no more than 15 carbon atoms, and little or no surfactant which interferes with the bleaching capability of the bleach system
• a liquid cleaning composition comprising a cationic nitrile/peroxygen compound bleach system and an anionic sulphate or sulphonate surfactant containing an alkyl group having no more than 15 carbon atoms, and little or no surfactant which interferes with the bleaching capability of the bleach system.
• the invention concerns liquid hard surface cleaning compositions characterised in that they comprise:
• the bleach system comprises a cationic nitrile of the type known in art to be useful as bleach activators. Particularly useful are the heterocyclic cationic nitriles described in WO 98/23533, WO 96/40661 and US 6,046,150, more specifically N-methylmorpholinium-acetonitrile salts.
• R 1 is an alkyl group of 3-10 carbon atoms, a phenyl-substituted alkyl group with a total of 7-12 carbon atoms, or a (alkyl-substituted) phenyl group of 6-10 carbon atoms
• R 2 and R 3 are independently methyl or ethyl groups and X ⁇ is a counterion.
• R 1 is an alkyl group it is linear and most preferably has 3-6 carbon atoms. If R 1 is a phenyl-substituted alkyl group it preferably has the structure R 4 -C 6 H 4 -(CH 2 ) n - wherein R 4 is hydrogen, methyl or ethyl, most preferably hydrogen, and n is 1-4. Preferably R 2 and R 3 are methyl.
• the concentration of cationic nitrile in the total, ready-to-use cleaning composition according to the invention is preferably between 1 and 200mmol/l, more preferably 2-100mmol/l, even more preferably 5-50mmol/l.
• the peroxygen bleach compound may be any peroxide or peroxide generating system known in the art such as dihydrocarbon peroxides, diacyl peroxides, hydrocarbon hydroperoxides, organic and inorganic peracids and persalts and in particular hydrogen peroxide.
• Preferred peroxygen bleach compounds are hydrogen peroxide, peracetic acid, PAP and alkali metal or alkaline earth metal monoperoxosulphate salts. Hydrogen peroxide is particularly suitable.
• the amount of peroxygen compound in the total composition is preferably chosen such that the composition will contain 0.1-10% active oxygen, more preferably 0.5-5%, most preferably 1-3%.
• the molar ratio between peroxygen compound and cationic nitrile is preferably between 100:1 and 1:5, more preferably between 50:1 and 1:1, most preferably above 3:1, or even 10:1.
• the cleaning compositions according to the invention comprise a sulphate or sulphonate anionic surfactant containing an alkyl group of at most 15 carbon atoms.
• Suitable surfactants are the alkali or alkaline earth metal or ammonium alkylbenzene sulphonates, alkyl sulphates and ethoxylated alkyl sulphates in which the alkyl group has at most 15 carbon atoms, more preferably at most 13 carbon atoms, most preferably 6-12 carbon atoms.
• the alkyl group may be linear (primary or depoty) or branched.
• the amount of sulphate or sulphonate anionic surfactant with alkyl ⁇ C15 is preferably 0.1-10% of the total composition, more preferably 0.2-5%, most preferably at most 2% or even 1%.
• the sulphate/sulphonate anionic surfactant defined above is preferably at least 80% of the total surfactant content of the total composition, more preferably at least 90% or even 99%.
• Various surfactants have been found to interfere with the bleaching ability of cationic nitrile/peroxygen compound bleach systems. Therefore, the amount of such surfactants, if present at all, is preferably less than 0.1% of the composition, more preferably less than 0.05%, even more preferably they should be totally absent.
• Nonionic and cationic surfactants are particularly detrimental to the bleaching ability of cationic nitrile/peroxygen compound bleach systems.
• composition according to the present invention is characterised in that it comprises:
• the third essential component for a liquid cleaning composition according to the invention is a solvent for the surfactant and the bleach system.
• This solvent may be water or an organic solvent or a combination thereof. Preferably at least 50% of the total solvent is water, more preferably at least 70%.
• Preferred organic solvents, if present, are those, which are miscible with water in the amount used. Suitable solvents are those which are well known for use in hard surface cleaning and include e.g. C1-C6 aliphatic alcohols, ethylene and propylene mono- and diglycols and mixed ethylene/propylene glycols and the C1-C6 aliphatic monoethers thereof.
• Suitable examples of such solvents are di-ethylene glycol mono-butyl ether, monoethylene glycol mono-butyl ether, propylene glycol butyl ether, isopropanol, ethanol, butanol and mixtures thereof.
• the level of organic solvent in cleaning compositions is 1-10%, preferably 1-5%.
• compositions according to the invention are suitable for a wide variety of hard surfaces cleaning and bleaching purposes. They are particularly suitable for cleaning bathrooms and similar spaces where black mould stains may a problem. For efficient cleaning the compositions preferably have a pH between 6 and 10, more preferably 7-9. For bathroom cleaning a pH between 7.5 and 8.5 is particularly suitable.
• compositions according to the invention preferably also contain a sequestering agent to bind transition metal ions, which could otherwise destabilise the peroxygen compound.
• Suitable sequestering agents are e.g. ethylenediamine tetraacetate, amino-polyphosphonates (such as those in the DEQUESTTM range). Phosphates and a wide variety of other poly-functional organic acids and salts can also optionally be employed. Preferred sequestering agents are selected from dipicolinic acid, ethylenediamine tetra acetic acid (EDTA) and its salts, hydroxyethylidene diphosphonic acid (Dequest 2010), ethylenediamine tetra(methylene-phosphonic acid) (Dequest 2040), diethylene-triamine penta(methylene-phosphonic acid) (Dequest 2060) and their salts. Sequestering agents are generally used in an amount of 0.01-5%, preferably 0.01-2%.
• the cleaning compositions according to the invention may also usefully contain a sequestering agent suitable for binding Ca ions.
• Suitable sequestering agents for this purpose are well known in the art and include compounds such as: alkali metal tripolyphosphate, pyrophosphate and ortho-phosphate, sodium nitrilotriacetic acid salt, sodium methylglycine-diacetic acid salt, alkali metal citrate, carboxymethyl malonate, carboxymethyloxysuccinate, tartrate, mono- and di-succinate and oxydisuccinate.
• Ca sequestering agents are preferably used in an amount of 0.05-6% of the composition. For most sequestering agents an amount of up to 1% is suitable, more preferably up to 0.5%.
• the inorganic phosphate sequestering agents are suitably used in an amount of up to 6%.
• the composition contains a thickening system which will improve the composition's ability to cling to a non-horizontal surface, thus increasing the contact time of the composition with the soiled surface.
• Many thickening systems are known from the art of thickening hypochlorite bleach compositions. Such systems often consist of one or more detergent surfactants in combination with an electrolyte such as an inorganic salt. Examples of such thickening systems are described in EP-A-079697, EP-A-110544, EP-A-137551, EP-A-145084, EP-A-244611, EP-A-635568, WO95/08611, DE-A-19621048 and the literature cited therein.
• suitable thickening systems comprise various polymeric substances such as natural and chemically modified polysaccharides and synthetic polymers such as those of (meth)acrylic acid or maleic acid or copolymers thereof with other monomers.
• synthetic polymers are e.g. sold under the trademarks: ACUSOL, CARBOPOL, POLYGEL, RHEOVIS, STRUCTURE and ALCOGUM.
• Another way to improve cling of the final composition to a non-horizontal surface is to cause it to foam on dispensing through the addition of a foaming surfactant and the use of an appropriate dispensing device such as foaming trigger sprays known in the art.
• the invention also provides liquid cleaning compositions consisting of at least two liquid partial compositions which are held separate from each other in a single container comprising at least two chambers or reservoirs or compartments (hereinafter referred to as 'chambers') wherein at least one partial composition comprises a peroxygen compound, at least one partial composition comprises a cationic nitrile and at least one partial composition comprises a pH adjusting compound which on mixing of the partial compositions is able to set the pH of the final composition to a value between 6 and 10, preferably between 7 and 9.
• Each partial composition has a pH such that the components of that partial composition are adequately stable on storage.
• the partial composition containing the cationic nitrile has pH of at most 6, more preferably at most 5.
• the cationic nitrile and the peroxygen compound are preferably not contained in the same partial composition.
• the invention also provides liquid cleaning compositions obtained through mixing of the above mentioned liquid partial compositions. Furthermore, the invention provides a container comprising two or more chambers holding the liquid partial compositions.
• a 'partial composition' is defined as a solution of a component, or a mixture of more, but not all, components of the final composition, which solution is held in a separate chamber of the container containing the total composition. Two or more partial compositions together make up the final composition according to this aspect of the invention.
• a container suitable for holding the hard surface cleaning compositions according to this aspect of the invention has at least as many separate chambers as the number of partial compositions making up the total composition.
• Such container may have one outer wall embracing all chambers which are separated from each other by partition walls inside the container or, alternatively, it may be made up of a plurality of separate containers, equivalent to the chambers, which are held together by some external means, such as a connecting part of the walls or a sleeve surrounding them, in such a way that they can be held and handled as one container.
• a dispensing system is provided in that each chamber is provided with an outlet opening through which the partial composition is dispensed.
• outlet openings may all lead to a separate mixing chamber in which the dispensed amounts of the partial compositions mix just before being applied to the substrate through a dispensing opening in the mixing chamber.
• the outlet openings may all lead to the outside of the container in such a way that the dispensed amounts of the partial compositions are all applied simultaneously to the same area of the substrate so as to mix while being applied to the substrate or immediately after application onto the substrate.
• the outlet openings will generally be positioned in close proximity to each other such that all partial compositions are poured, squirted or sprayed onto the same area of the substrate in one action.
• the outlet openings may be provided with a nozzle system designed to further improve the mixing of the partial components on leaving the container.
• the container may be provided with a multiple spray system able to either produce a single spray of a mixture of all the partial compositions or simultaneous sprays of each partial composition directed to the same area of a substrate whereafter the partial compositions mix on the substrate.
• the container preferably comprises no more than two chambers each holding a partial composition which compositions together make up the final composition. This implies that for the same reasons the compositions according to this aspect of the invention are preferably made up of two partial compositions. Additionally the container may comprise a mixing chamber as outlined above.
• the amounts of the partial compositions making up the final composition need not necessarily all be equal as long as care is taken that the concentration of each component in each of the partial compositions is chosen such that on mixing of the envisaged amounts of the partial compositions the right concentration of each component is present in the final composition.
• the volume of each chamber of the container is adapted to the amount of the partial composition contained in that chamber which is required to make up the total amount of the final composition.
• the total liquid volume of the final composition to be obtained from the container in general will be determined by the total volume of the container, excluding the volume of the mixing chamber, if present.
• the dispensing or outlet openings or other dispensing means of the various chambers in the container are dimensioned such that one single dispensing action dispenses the right amounts of all partial compositions necessary to properly make up the final in which each component is present in the required concentration.
• the dispensing or spray system may be so dimensioned that the final composition is dispensed as a foam.
• the containers will generally have a total volume of 0.1 - 2 litres, preferably at least 0.25 l, but preferably not more than 1.5 l.
• two-chamber containers preferably have chambers of about equal volume, holding about equal amounts of each of the two partial compositions.
• compositions according to the invention may be present in the compositions according to the invention, such as hydrotropes, antimicrobially active compounds or components to improve their consumer appeal such as perfumes and dyes.
• hydrotropes such as hydrotropes, antimicrobially active compounds or components to improve their consumer appeal such as perfumes and dyes.
• antimicrobially active compounds such as antimicrobially active compounds or components to improve their consumer appeal such as perfumes and dyes.
• Many other optional components customary in the art of cleaning compositions may be present as well.
• compositions according to the invention give excellent cleaning on a variety of soils, such as common kitchen soils. They are able to bleach the well-known stains of black mould often occurring in damp spaces and are therefore very suitable for bathroom cleaners. Furthermore, at pH 6.5 or above the cationic nitriles according to the invention effectively boost the antimicrobial properties of peroxides, particularly hydrogen peroxide, thus giving the compositions according to the invention improved hygienic properties. For this purpose a peroxide/nitile ratio of between 2:1 and 1:5 is preferred. The combination is active against gram-negative as well as gram-positive bacteria.
• the process of removing soil as well as black mould stains comprises the step of applying a cleaning composition as described above to the surface to be cleaned.
• a cleaning composition as described above to the surface to be cleaned.
• the cleaning compositions are freshly prepared just before being applied to the surface.
• a conveniently procedure for this comprises the application of the composition from a multi-chamber container as described above.
• compositions may be applied to the surface in any convenient way. They are preferably applied directly to the surface, such as by spraying, pouring or any similar operation, but they may also first be applied to a cleaning implement, such as a wipe, cloth or towel, whereafter the surface is cleaned with the implement.
• a cleaning implement such as a wipe, cloth or towel
• compositions comprising the N-methylmorpholinium-acetonitrile methosulphate (MMA)/hydrogen peroxide bleach system and various surfactants were tested on their ability to bleach black mould
• MMA N-methylmorpholinium-acetonitrile methosulphate
• hydrophile solutions were all freshly prepared just before testing so as to mimic compositions obtained by mixing appropriate partial compositions on dispensing. In order to obtain reproducible results an autoclaved mould paste was used for the testing.
• a small amount of the 'mould paste' was applied to the surface of large porous ceramic tiles and a small amount of distilled water added. This mixture was evenly spread across and rubbed into the surface of the tiles using a flexible plastic spatula. The final appearance of the soiled tiles was a uniform dark grey. The tiles were left to dry overnight in the dark and then the large tiles were cut into smaller test pieces using a standard 'tile cutter'.
• test solution A fixed quantity of the test solution was allowed to drop onto the surface and allowed to soak into the tile.
• the test solution was allowed to remain in contact with the soil for a fixed contact time, i.e. 3 minutes or 20 minutes at ambient temperature, after which the test pieces were immersed in 1.0M sodium thiosulphate solution for 10 minutes (to quench the reaction and prevent further bleaching).
• the test pieces were then immersed in distilled water for 10 minutes before rinsing with further distilled water and air-drying.
• Test pieces were assessed for the level of mould bleaching by an expert panel, using an integer scale running from 0 (no decolorisation) to 6 (complete bleaching). Panel test data for each system was collated and analysed statistically to provide mean scores for each test system. Each test (bleaching) system was tested using at least 3 replicate tiles.
• compositions A-F were tested on A . niger and C cladosporoides.
• the composition contents and the bleach scores are set out in table 1 below.
• the pH of the compositions was adjusted to 8.0 using NaOH.
• compositions containing amineoxide surfactant scored worse than the compositions containing octyl sulphate in bleaching both molds. It is also clear from the results that C. cladosporoides is most difficult to bleach and compositions containing amine oxide hardly give an acceptable bleach result on this mould.
• compositions G-L containing 0.5% or 1% MMA were tested on C. cladosporoides.
• the composition contents and the bleach scores are set out in tables 2A and 2B below.
• the pH of the compositions was adjusted to 8.0.
• compositions containing amine oxide or ethoxylated alkohol nonionic surfactants or the cationic surfactant scored significantly worse than the compositions containing octyl sulphate in bleaching C. cladosporoides.
• compositions Q-U were tested on C. cladosporoides .
• the composition contents and the bleach scores are set out in table 3 below.
• the pH of the compositions was adjusted to 8.0.
• the composition containing the amine oxide surfactant has inferior bleaching properties compared to the sulphate and sulphonate surfactants.

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

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Cited By (4)

Citations (1)

• 2001
  • 2001-04-26 EP EP01303808A patent/EP1253190A1/de not_active Withdrawn

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