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
  • C11D3/26—Organic compounds containing nitrogen
  • C11D3/30—Amines; Substituted amines ; Quaternized amines
• • 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
  • C11D17/0013—Liquid compositions with insoluble particles in suspension
• • 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
  • C11D3/18—Hydrocarbons

Definitions

• the invention relates to pourable, homogenous, abrasive, aqueous liquid detergent compositions containing a particulate abrasive which are suited to the cleaning of hard surfaces.
• Hard surface cleaners containing abrasive particles are well known.
• Typical compositions comprise one or more surfactants in solution and a plurality of abrasive particles dispersed therein.
• Typical abrasive materials include minerals such as calcite or dolomite and other materials of relatively high density. In this art it is generally considered necessary to ensure that the abrasive particles remain in suspension in the composition in order that the composition need not be vigorously shaken before use and that sedimentation, or even cementing of precipitated particles, is prevented.
• one or more surfactant components act as a suspending agent, usually in combination with a dissolved electrolyte.
• the presence of the electrolyte causes the surfactant component (s) to thicken by the establishment of a lamellar phase.
• These compositions are generally formulated at a pH above 9.0 especially where calcite is used as the abrasive.
• Surfactants employed as suspending agents in liquid abrasive cleaners have included, alkyl benzene sulphonates, alcohol sulphates, alcohol ethoxylates, alkyl amido ethoxylates, fatty acid soaps and secondary alkyl sulphonates. Combinations of these surfactants, together with electrolytes are used to form a suspending system as is well known in the art.
• the fine structure of these suspending systems generally consists of spherical structures ranging from 0.05 to about 10 microns in diameter. These structures are believed to comprise concentric shells of alternating bilayers of surfactant molecules spaced apart by thin water layers.
• the suspending system is not the only structure which surfactants can form in the presence of water.
• the above-mentioned surfactants can also form micellar structures which are viscous but are not capable of suspending particles.
• compositions of surfactant and water may separate into two or more mixed phases with different physical properties. Exactly which structure is adopted by a particular surfactant mix is strongly influenced by the ionic strength of electrolyte in the composition and some surfactant systems can be exceptionally sensitive to changes in ionic strength of the electrolyte.
• a further problem with liquid abrasive cleaners is their tendency to leave residues which are difficult to rinse away. This is a particular problem with compositions which contain insoluble abrasives. There is therefore a need to improve the performance of abrasive compositions in such as manner that the overall level of abrasive can be reduced so as to improve rinsing performance and reduce the possibility of surface damage by the abrasive.
• Solvents are well known components of non-abrasive cleaning compositions.
• Typical solvents used in cleaning compositions include, alcohols (such as ethanol), ethers (such as Butyl Cellosolve [TM] ) , paraffins (such as Isopar L [TM] ) , esters and terpenes (such as d-limonene) .
• Another known class of solvents are the alkanolamines .
• EP503219A (P&G) relates to a cleaning composition containing 0.1 - 10% of an alkanolamine.
• alkanolamine solvent at significant levels in a liquid abrasive cleaner. It is believed that alkanolamines have both electrolyte and solvent properties and can influence the structure of the suspending phase. Consequently, as the temperature of the composition changes, on storage or during transportation, the level of effective electrolyte in the composition will also change and this can result in the breakdown of the suspending phase and precipitation of abrasive particles or even phase-separation of the composition.
• the present invention provides a liquid abrasive cleaning composition of pH 7-13 which comprises:
• the alkanolamine acts both as a base and a solvent which improves cleaning and so allows the level of suspended abrasive to be reduced. In turn this is believed to reduce the possibility of abrasive damage to surfaces and improve rinsing performance. It is believed that the presence of the hydrocarbon co-solvent is required to maintain the stability of the alkanolamine based composition when it is subjected to temperature cycling or storage at extremes of temperature.
• Alkanolamines for use in the compositions of the present invention can be mono- or poly-functional as regards the amine and hydroxy moieties.
• Preferred alkanolamines are generally of the formulation H 2 N-R ⁇ -OH where Ri is a linear or branched alkyl chain having 2-6 carbons.
• Suitable alkanolamines include:
• 2-amino-2-methyl-1-propanol mono- di- and tri- ethanolamine, mono-, di- and tri -isopropanolamine, and, dimethyl-, diethyl or dibutyl ethanolamine,
• cyclic alkanolamines such as morpholine can also be employed.
• alkanolamines include: 2-amino-2-methyl- 1-propanol, mono-ethanolamine and di-ethanolamine. These materials are believed to give improved cleaning on tough or aged soils. Of these materials 2-amino-2-methyl-l-propanol (AMP) is particularly preferred. Typical levels of alkanolamine in the compositions of the invention range from l-5%wt. Higher levels of solvent are less desirable as these may attack certain plastics materials. It is particularly preferred to use 2-amino-2-methyl-l- propanol at a level of l-3%wt.
• Suitable co-solvent include saturated and unsaturated, linear or branched hydrocarbons.
• Preferred materials include:
• Particularly suitable terpenes include d-limonene.
• Particularly preferred paraffins include the material available in the marketplace as 'Shellsol-T' [TM] .
• Typical levels of co-solvent range from 0.5-5%wt. It is particularly preferred to use terpines at levels l-3%wt. Some of these terpene materials, such as limonene, have the further advantage that they, or impurities present in them, exhibit insect-repellency . We have determined that the terpene materials give better performance at pH's below 11.
• the straight chain paraffins can be used at higher levels than the terpenes as these materials are less aggressive to plastics. The paraffins are believed to give better performance at pH's above 11.
• the ratio of the alkanolamine to the hydrocarbon co-solvent falls in the range 3:1-1:3, with ratios of 3:1 to 1:1 being particularly preferred.
• a portion of the co-solvent can be introduced as a perfume component, although the levels of co-solvent required will generally require the addition of higher levels of this component that would normally be present as a perfume ingredient in cleaning compositions.
• the terpenes are used in this manner as selected terpenes, such as limonene, have a pleasant citrus smell, whereas paraffins are generally odourless.
• a dispersed, suspended particulate phase is an essential ingredient of compositions according to the present invention.
• the dispersed suspended particulate phase comprises a particulate abrasive which is insoluble in the aqueous phase.
• the abrasive may be soluble and present in such excess that the solubility of the abrasive in the aqueous phase is exceeded and consequently solid abrasive exists in the composition.
• Preferred abrasives for use in general purpose compositions have a Moh hardness below 6 although higher hardness abrasives can be employed for specialist applications. Lower hardness materials generally give less surface damage.
• Suitable abrasives can be selected from, particulate zeolites, calcites, silicas, silicates, carbonates, aluminas, bicarbonates, borates, sulphates, and, polymeric materials such as polyethylene.
• Preferred average (weight average) particle sizes for the abrasive fall in the range 0.5-200 microns, with values of around 10-100 microns being preferred. In this range an acceptable compromise between good cleaning behaviour and low substrate damage is achieved.
• Preferred levels of abrasive range from 5-70wt% on product, preferably in the range 20-40wt%, most preferably >30wt%. Such levels of abrasive give effective cleaning and good rinsing.
• the most preferred abrasives are calcium carbonate (as calcite) , mixtures of calcium and magnesium carbonates (as dolomite) , sodium hydrogen carbonate, potassium sulphate, zeolite, alumina, hydrated alumina, feldspar, talc and silica.
• Calcite and dolomite are particularly preferred due to their low cost, suitable hardness and colour.
• composition according to the invention will comprise detergent actives which are generally chosen from both anionic and nonionic detergent actives.
• Suitable anionic detergent active compounds are water-soluble salts of organic sulphuric reaction products having in the molecular structure an alkyl radical containing from 8 to 22 carbon atoms, and a radical chosen from sulphonic acid or sulphur acid ester radicals and mixtures thereof.
• Suitable anionic detergents are sodium and potassium alcohol sulphates, especially those obtained by sulphating the higher alcohols produced by reducing the glycerides of tallow or coconut oil; sodium and potassium alkyl benzene sulphonates such as those in which the alkyl group contains from 9 to 15 carbon atoms; sodium and potassium secondary alkanesulphonates; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulphates; sodium and potassium salts of sulphuric acid esters of the reaction product of one mole of a higher fatty alcohol and from 1 to 6 moles of ethylene oxide; sodium and potassium salts of alkyl phenol ethylene oxide ether sulphate with from 1 to 8 units of ethylene oxide molecule and in which the alkyl radicals contain from 4 to 14 carbon atoms; the reaction product of fatty acids esterified with isethionic acid and
• the preferred water-soluble synthetic anionic detergent active compounds are the alkali metal (such as sodium and potassium) and alkaline earth metal (such as calcium and magnesium) salts of higher alkyl benzene sulphonates and mixtures with olefinsulphonates and higher alkyl sulphates, and the higher fatty acid monoglyceride sulphates.
• the most preferred anionic detergent active compounds are higher alkyl aromatic sulphonates such as higher alkyl benzene sulphonates containing from 6 to 20 carbon atoms in the alkyl group in a straight or branched chain, particular examples of which are sodium salts of higher alkyl benzene sulphonates or of higher- alkyl toluene, xylene or phenol sulphonates, alkyl naphthalene sulphonates, ammonium diamyl naphthalene sulphonate, and sodium dinonyl naphthalene sulphonate.
• higher alkyl aromatic sulphonates such as higher alkyl benzene sulphonates containing from 6 to 20 carbon atoms in the alkyl group in a straight or branched chain, particular examples of which are sodium salts of higher alkyl benzene sulphonates or of higher- alkyl toluene, xylene or
• the amount of synthetic anionic detergent active to be employed in the detergent composition of this invention will generally be from 1 to 25%, preferably from 2 to 20%, and most preferably from 2 to 15% by weight.
• Suitable nonionic detergent active compounds can be broadly described as compounds produced by the condensation of alkylene oxide groups, which are hydrophilic in nature, with an organic hydrophobic compound which may be aliphatic or alkyl aromatic in nature.
• the length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water- soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
• Particular examples include the condensation product of aliphatic alcohols having from 8 to 22 carbon atoms in either straight or branched chain configuration with ethylene oxide, such as a coconut oil ethylene oxide condensate having from 2 to 15 moles of ethylene oxide per mole of coconut alcohol; condensates of alkylphenols whose alkyl group contains from 6 to 12 carbon atoms with 5 to 25 moles of ethylene oxide per mole of alkylphenol; condensates of the reaction product of ethylenediamine and propylene oxide with ethylene oxide, the condensates containing from 40 to 80% of polyoxyethylene radicals by weight and having a molecular weight of from 5,000 to 11,000; tertiary amine oxides of structure R 3 N0, where one group R is an alkyl group of 8 to 18 carbon atoms and the others are each methyl, ethyl or hydroxyethyl groups, for instance dimethyldodecylamine oxide; tertiary phosphine oxides of structure
• the amount of nonionic detergent active to be employed in the detergent composition of the invention will generally be from 0.5 to 15%, preferably from 1 to 10%, and most preferably from 1 to 8% by weight.
• compositions contain an amount of both the anionic and the nonionic detergent active which is chosen, bearing in mind the level of electrolyte present, so as to provide a structured liquid detergent composition, ie. one which is 'self' thickened without necessarily employing any other thickening agent.
• the weight ratio of anionic detergent to nonionic detergent active may vary and will depend on their nature but is preferably in the range of from 1:9 to 9:1, ideally from 1:4 to 4:1.
• the detergent compositions will comprise from 2 to 10% by weight of a water-soluble, synthetic anionic sulphated or sulphonated detergent salt containing an alkyl radical having from 8 to 22 carbon atoms in the molecule, and from 0.5 to 8% by weight of an alkyleneoxylated nonionic detergent derived from the condensation of an aliphatic alcohol having from 8 to 22 carbon atoms in the molecule with ethylene oxide, such that the condensate has from 2 to 15 moles of ethylene oxide per mole of aliphatic alcohol.
• amphoteric, cationic or zwitterionic detergent actives in the compositions according to the invention.
• Suitable amphoteric detergent-active compounds that optionally can be employed are derivatives of aliphatic secondary and tertiary amines containing an alkyl group of 8 to 18 carbon atoms and an aliphatic radical substituted by an anionic water-solubilising group, for instance sodium 3-dodecylamino- propionate, sodium 3-dodecylaminopropane sulphonate and sodium N-2-hydroxydodecyl-N-methyl taurate.
• anionic water-solubilising group for instance sodium 3-dodecylamino- propionate, sodium 3-dodecylaminopropane sulphonate and sodium N-2-hydroxydodecyl-N-methyl taurate.
• Suitable cationic detergent-active compounds are quaternary ammonium salts having an aliphatic radical of from 8 to 18 carbon atoms, for instance cetyltrimethyl ammonium bromide.
• Suitable zwitterionic detergent-active compounds that optionally can be employed are derivatives of aliphatic quaternary ammonium, sulphonium and phosphonium compounds having an aliphatic radical of from 8 to 18 carbon atoms and an aliphatic radical substituted by an anionic water- solubilising group, for instance 3- (N,N-dimethyl-N- hexadecylammonium) propane-1-sulphonate betaine, 3-(dodecyl methyl sulphonium) propane-1-sulphonate betaine and 3- (cetyl ethyl phosphonium) ethane sulphonate betaine.
• detergent-active compounds are compounds commonly used as surface-active agents given in the well-known textbooks "Surface Active Agents", Volume I by Schwartz and Perry and “Surface Active Agents and Detergents", Volume II by Schwartz, Perry and Berch.
• the total amount of detergent active compound to be employed in the detergent composition of the invention will generally be from 1.5 to 30%, preferably from 2 to 15% by weight.
• the composition will be capable of stably suspending the particles of abrasive, so that the consumer does not need to agitate the composition, for example by shaking it, in order to re-suspend and re-distribute sedimented particles prior to use.
• the composition should have a viscosity at 200C of at least 5000 Pas at a shear rate of 3 x 10 "5 sec. "1 (as determined by Stokes Law) . This viscosity is generally sufficient to ensure that the particles of abrasive do not sediment on standing at 200C by more than 1 cm in one month.
• the composition according to the invention should also remain sufficiently fluid, so that it can readily be poured from a bottle or other container when required for use.
• the composition should preferably have a viscosity at 200C, measured using a rotational viscometer which does not exceed 10 Pas at a shear rate of 21 sec. "1 .
• the viscosity at 200C is no greater than 5 Pas at a shear rate of 21 sec "1 .
• Suitable rheological conditions to suit these criteria can be provided by judicial choice of anionic and nonionic detergent to provide a structured liquid having the requisite suspending properties, and/or by use of an appropriate amount of an alternative structuring agent such as is well known in the art .
• compositions according to the invention may optionally contain polymeric structuring agents to aid in providing appropriate rheological properties to maintain the undissolved salt or salts uniformly distributed in the composition and in enhancing their distribution and adherence of the composition to the hard surface to be cleaned.
• Preferred structuring agents include polysaccharides, such as sodium carboxymethyl cellulose and other chemically modified cellulose materials, xanthan gum and other non-flocculating structuring agents such as Biopolymer PS87 referred to in US Patent No. 4 329 448.
• Certain polymers such as a polymer of acrylic acid cross-linked with a poly functional agent, for example CARBOPOL R , can also be used as structuring agents.
• the amount of such structuring agents, when employed, to be used in compositions according to the invention can be as little as 0.001%, preferably at least 0.01% by weight of the composition.
• composition of the invention can optionally comprise from 0.1-1% of polymer.
• the composition according to the invention can contain other ingredients which aid in their cleaning performance.
• the composition can contain detergent builders other than the special water-soluble salts, as defined herein, such as nitrilotriacetates, polycarboxylates, citrates, dicarboxylic acids, water-soluble phosphates especially polyphosphates, mixtures of ortho- and pyrophosphate, zeolites and mixtures thereof.
• Such builders can additionally function as abrasives if present in an amount in excess of their solubility in water.
• the builder, other than the special water-soluble salts when employed preferably will form from 0.1 to 25% by weight of the composition.
• Metal ion sequestrants such as ethylenediaminetetraacetates, amino-polyphosphonates (DEQUEST R ) and phosphates and a wide variety of other poly-functional organic acids and salts, can also optionally be employed provided they are compatible with the abrasive material.
• a further optional ingredient for compositions according to the invention is a suds regulating material, which can be employed in compositions according to the invention which have a tendency to produce excessive suds in use.
• a suds regulating material is soap.
• Soaps are salts of fatty acids and include alkali metal soaps such as the sodium, potassium and ammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 10 to about 20 carbon atoms.
• Particularly useful are the sodium and potassium and mono-, di- and triethanolamine salts of the mixtures of fatty acids derived from coconut oil and ground nut oil.
• the amount of soap can form at least 0.005%, preferably 0.5% to 2% by weight of the composition.
• Fatty acid soaps such as Prifac 7901 [TM] have been found to be suitable for this purpose.
• a further example of a suds regulating material is an silica or a silicone oil. Where the hydrocarbons according to the present invention are present at sufficiently high levels these may themselves provide some or all of the required antifoaming activity.
• compositions according to the invention can also contain, in addition to the ingredients already mentioned, various other optional ingredients such as Colourants, whiteners, optical brighteners, soil suspending agents, detersive enzymes, compatible bleaching agents (particularly hypohalites) , gel- control agents, further freeze-thaw stabilisers, bactericides, preservatives (for example 1,2, benzisothiazolin-3-one) , and hydrotropes .
• various other optional ingredients such as Colourants, whiteners, optical brighteners, soil suspending agents, detersive enzymes, compatible bleaching agents (particularly hypohalites) , gel- control agents, further freeze-thaw stabilisers, bactericides, preservatives (for example 1,2, benzisothiazolin-3-one) , and hydrotropes .
• compositions according to the invention are formulated in the alkaline pH range, and will generally have a pH of from 9.5 to 12.5, preferably about 10 to 12 when calcite is used as the abrasive.
• the pH can be lower, but the pH should generally be above the (pK a of the alkanolamine) -1 and preferably be above the pK a of the alkanolamine.
• Alkalising agents such as sodium hydroxide and sodium carbonate and acids such as hydrochloric acid can be used to adjust and buffer the pH as desired.
• Preferred Compositions are:
• compositions according to the present invention comprise:
• an alkanolamines selected from the group comprising: 2-amino-2-methyl-l-propanol , mono- di- and tri- ethanolamine, mono-, di- and tri- isopropanolamine, dimethyl-, diethyl- or dibutyl- ethanolamine, and mixtures thereof,
• a co-solvent selected from the group comprising: C ⁇ 0 H ⁇ 6 terpenes, C ⁇ 0 -C 16 straight chain paraffins and mixtures thereof,
• abrasive selected from the group comprising: calcium carbonate, magnesium carbonates, zeolite, alumina, hydrated alumina, feldspar, talc, silica and mixtures thereof, and,
• compositions were performed using the following base compositions (as given in table 1) with varying levels of solvents as indicated in table 2.
• Compositions were prepared at pH 10 and pH 12 as indicated in table 1.
• compositions of table 1 were made up adding a total of 2% solvent which was either 2% amino-methyl propanol (AMP) or 1% amino methyl propanol plus a co-solvent.
• AMP amino-methyl propanol
• the stability of the compositions was determined during five weeks storage under ambient conditions and under various modified temperature conditions.
• the modified temperature conditions were:
• Failure marked in the columns headed 'temp' in table 2 indicates that the samples separated into two or more phases when stored under at least one of the modified temperature conditions. Failure marked in the column headed ' ambi ' in table 2 indicates that the samples separated into two or more phases when stored under ambient conditions.
• the examples with Shellsol T and limonene are embodiments of the invention the examples with benzyl alcohol, Butyl Digol [TM] (diethylene glycol mono n-butyl ether) and Dowanol PnB [TM] (propylene glycol mono n-butyl ether) are comparatives which show that not all solvents are suitable for use in the practice of the invention. TABLE 2: Storage Results
• compositions at pH 10 could be made using paraffin (Shellsol T) as the co- solvent.
• paraffin Shellsol T
• limonene was effective as a co-solvent.

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Citations (5)

• 1997
  • 1997-04-25 GB GBGB9708500.5A patent/GB9708500D0/en active Pending
• 1998
  • 1998-04-14 IL IL13253698A patent/IL132536A0/xx unknown
  • 1998-04-17 JP JP54654898A patent/JP2001522393A/ja active Pending
  • 1998-04-17 KR KR1019997009858A patent/KR20010012114A/ko not_active Application Discontinuation
  • 1998-04-17 SK SK1457-99A patent/SK145799A3/sk unknown
  • 1998-04-17 EP EP98924136A patent/EP0977826A1/en not_active Withdrawn
  • 1998-04-17 AU AU76448/98A patent/AU7644898A/en not_active Abandoned
  • 1998-04-17 ID IDW991265A patent/ID23146A/id unknown
  • 1998-04-17 TR TR1999/02656T patent/TR199902656T2/xx unknown
  • 1998-04-17 CA CA002287233A patent/CA2287233A1/en not_active Abandoned
  • 1998-04-17 PL PL98336419A patent/PL336419A1/xx unknown
  • 1998-04-17 BR BR9808969-2A patent/BR9808969A/pt not_active Application Discontinuation
  • 1998-04-17 HU HU0004833A patent/HUP0004833A2/hu unknown
  • 1998-04-17 WO PCT/EP1998/002276 patent/WO1998049261A1/en not_active Application Discontinuation
  • 1998-04-17 CN CN98806384A patent/CN1261399A/zh active Pending
  • 1998-04-22 ZA ZA9803392A patent/ZA983392B/xx unknown
  • 1998-04-24 AR ARP980101901A patent/AR015597A1/es unknown
  • 1998-05-15 TW TW087107565A patent/TW517084B/zh active

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