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WO1998026036A1 - Ameliorations concernant des produits de nettoyage legers aqueux - Google Patents

Ameliorations concernant des produits de nettoyage legers aqueux Download PDF

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Publication number
WO1998026036A1
WO1998026036A1 PCT/EP1997/006674 EP9706674W WO9826036A1 WO 1998026036 A1 WO1998026036 A1 WO 1998026036A1 EP 9706674 W EP9706674 W EP 9706674W WO 9826036 A1 WO9826036 A1 WO 9826036A1
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WO
WIPO (PCT)
Prior art keywords
surfactant
polymer
oil
complex
coalescence
Prior art date
Application number
PCT/EP1997/006674
Other languages
English (en)
Inventor
George Kerr Rennie
John William Harold Yorke
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Unilever Plc
Unilever N.V.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Unilever Plc, Unilever N.V. filed Critical Unilever Plc
Priority to BR9714139-9A priority Critical patent/BR9714139A/pt
Priority to CA002270374A priority patent/CA2270374A1/fr
Priority to AU55586/98A priority patent/AU721830B2/en
Priority to EP97952016A priority patent/EP0944703A1/fr
Publication of WO1998026036A1 publication Critical patent/WO1998026036A1/fr

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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
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid 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
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic 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
    • C11D1/146—Sulfuric 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
    • C11D1/29—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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • 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
    • C11D1/75—Amino oxides
    • 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
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/90—Betaines

Definitions

  • the present invention relates to aqueous light duty cleaning compositions and will be described herein with particular reference to hand dishwashing liquids.
  • compositions typically comprise, as the principal surfactant component, one or more surfactants selected from a relatively small group.
  • principal surfactants are typically selected from amongst primary alcohol sulphates (also known as primary alkyl sulphates) , secondary alkane sulphonates, linear alkyl benzene sulphonate, alkoxylated alcohols and alkyl ether sulphates.
  • polyol derived surfactants such as alkylpolyglucosides, glucosamides and other sugar based surfactants, as well as alkyl glyceryl derivatives.
  • hand dishwashing compositions are not structureds by the presence of a lamellar phase.
  • compositions In addition to these principal surfactants it is commonplace for compositions to comprise a so-called 'foam-booster', selected from a ine oxides, alkanolamides (particularly the mono and di ethanolamides and isopropanolamides) and other nitrogen-based surfactant compounds, including poly-hydroxy amides and betaines .
  • a so-called 'foam-booster' selected from a ine oxides, alkanolamides (particularly the mono and di ethanolamides and isopropanolamides) and other nitrogen-based surfactant compounds, including poly-hydroxy amides and betaines .
  • R is typically C8-C18 alkyl and n is typically 1-14, or the related alkyl ether sulphates of the general formula:
  • R is again alkyl and n is typically 1-5.
  • a large proportion (often some 80%wt) of the total surfactant system comprises ether sulphates, with the balance of the actives comprising one or more foam-boosters.
  • the overall active concentration on product typically varies from around 20% for 'economy' brands to around 40% for 'concentrated' products. Lower concentrations, down to 2% surfactant are known as are higher concentrations, up to 70% surfactant.
  • the product comprising very high levels of surfactant are still aqueous, but may be in the form of pastes, gels or bars.
  • a common problem in hand dishwashing is encountered when the soil removed from the articles being washed contains a significant level of fat, grease or other oily matter.
  • typical in use levels of surfactant of 0.04%wt are sufficient to remove grease from the articles and suspend it as droplets, however, coalescence of these droplets may occur to produce large and visible bodies of fatty material. These bodies of material are unsightly and can be redeposited on the articles being washed, the hands of the user or the bowl surface. The presence of visible droplets of fatty material may cause the user to believe that the wash liquor is spent and lead the user to discard the wash liquor causing unnecessary further use of products and release of surfactant into the environment.
  • EP 0221774 discloses the use of hydrophobic/hydrophilic linear block copolymers . Similar compositions are disclosed in EP 222557 (P&G, 1987) .
  • EP 0346995 and EP 0719857 disclose a large number of formulations which include 'deflocculating polymers'. All are lamellar dispersions as the function of the polymer is to stabilise the lamellar dispersion against phase separation.
  • EP 0415698 discloses fabric softening compositions which comprise an aqueous base and one or more fabric softening components.
  • Example II of this document discloses a composition which comprises 30% quaternary- fabric softener, 1-1.5% nonionic and 0.1-0.2% of a polymer.
  • Example X of this document discloses compositions with various quats, 0.5% polymer and 1.5-2.0%.
  • coalescence of oil droplets during the dishwashing process can be significantly retarded, without detriment to the spontaneous grease removal properties of the formulation, by the presence of selected polymers having a hydrophilic backbone and hydrophobic side chains.
  • the present invention provides a non-lamellar, unbuilt, aqueous, light duty cleaning composition
  • a non-lamellar, unbuilt, aqueous, light duty cleaning composition comprising:
  • surfactant selected from the group comprising: nonionic surfactant, a complex of anionic surfactant and zwitterionic surfactant, a complex of anionic surfactant and amphoteric surfactant and mixtures thereof, and,
  • a polymer comprising a negatively charged or neutral hydrophilic backbone with at least one hydrophobic and oil-soluble side chain.
  • ratio of polymer to surfactant falls in the range to 1:100-1:10.
  • a second aspect of the present invention provides a dishwashing process which comprises the step of treating the surfaces of the dishes with a composition as described above in neat or dilute form.
  • a third aspect of the present invention relates to the use of 0.02-7%wt of a polymer, comprising a negatively charged or neutral hydrophilic backbone with at least one hydrophobic and oil-soluble side chain as an oil-coalescence inhibitor in a non-lamellar, unbuilt light duty cleaning composition
  • a polymer comprising a negatively charged or neutral hydrophilic backbone with at least one hydrophobic and oil-soluble side chain as an oil-coalescence inhibitor in a non-lamellar, unbuilt light duty cleaning composition
  • surfactant selected from the group comprising: nonionic surfactant, a complex of anionic surfactant and zwitterionic surfactant, a complex of anionic surfactant and amphoteric surfactant and mixtures thereof, wherein the ratio of polymer to surfactant in said light duty cleaning composition falls in the range to 1:100-1:10.
  • a fourth aspect of the present invention provides a non- lamellar, light duty cleaning composition which comprises surfactant selected from the group comprising: nonionic surfactant, a complex of anionic surfactant and zwitterionic surfactant, a complex of anionic surfactant and amphoteric surfactant and mixtures thereof, and, a polymer, said polymer comprising a negatively charged or neutral hydrophilic backbone with at least one hydrophobic and oil-soluble side chain wherein the ratio of polymer to surfactant falls in the range to 1:100-1:10 and the extent of coalescence as defined herein is less than 20%.
  • surfactant selected from the group comprising: nonionic surfactant, a complex of anionic surfactant and zwitterionic surfactant, a complex of anionic surfactant and amphoteric surfactant and mixtures thereof, and, a polymer, said polymer comprising a negatively charged or neutral hydrophilic backbone with at least one hydrophobic and oil-soluble side chain wherein the ratio of
  • the oil-soluble hydrophobic side chains of the polymer partition into oil droplets, while the hydrophilic backbone remains in the waterphase to stabilise the droplets against coalescence through a combination of steric hindrance and electrostatic repulsion.
  • the particular combinations of surfactants described above comprise non-charged surfactants and potentially surfactant complex-forming systems in which the charge of the anionic surfactant is in part shielded by the amphoteric or zwitterionic surfactant, this prevents significant complex formation between the anionic surfactant and the polymer which would otherwise inhibit the action of the polymer.
  • compositions of the present invention are non-lamellar.
  • the compositions of the present invention are single phase, isotropic systems.
  • compositions are preferably pourable liquids.
  • the viscosity of liquid compositions according to the invention is preferably in the range 200-300 cP at a shear rate of 21 reciprocal seconds as measured at a temperature of 25 Celcius using a Haake MV cup and bob. It is also believed possible to formulate products as pastes or gels or as powders to be dissolved in water prior to use.
  • the surfactant should comprise either nonionic surfactant or a surfactant blend which has the potential to form an anionic/ zwitterionic or anionic/amphoteric surfactant complex.
  • compositions according to the present invention comprise
  • surfactant comprising at least 5% on total surfactant of an alkylpolyglycoside
  • a polymer comprising a negatively charged or neutral hydrophilic backbone with at least one hydrophobic and oil-soluble side chain.
  • ratio of polymer to surfactant falls in the range to 1:100-1:10.
  • Preferred levels of APG are such that the composition comprises 30-40%wt of APG on total surfactant.
  • Preferred APG's have an alkyl chain comprising C_ . -i 6 and it is preferred that more than 50%wt of the APG present in the compositions of the invention comprises a C ⁇ _ ⁇ 4 alkyl APG and that the majority of the remaining APG is C 8 -Ci 8 .
  • the preferred degree of polymerisation is 1.1-1.6, more preferably 1.3-1.5.
  • Suitable materials include GLUCOPON 600 (RTM ex HENKEL) .
  • compositions which comprises APG show exceptionally low levels of fatty coalescence.
  • nonionic surfactants are those with an HLB of 11-15 as these, in combination with the polymers, show particularly low rates of coalescence.
  • anionic surfactants primary alkyl sulphate and/or alkyl ether sulphate are preferred components of compositions according to the invention.
  • the ratio of ethoxylated to non-ethoxylated primary alkyl sulphate in (2) being such that the overall ratio of ethoxylated to non-ethoxylated primary alkyl sulphate (AES) in (1) + (2) is 0.5-2.5.
  • PAS primary alkyl sulphate
  • PAS- 3EO technical grade PAS- 3EO
  • materials such as technical grade ethoxylated PAS with low ethoxylation numbers comprise significant levels of unethoxylated PAS, i.e. a material equivalent to (1).
  • PAS-1EO can replace both (1) and (2) and therefore comprise substantially all of (a) in the above-mentioned description of the invention.
  • Preferred levels of the mixture of PAS and AES are such that the mixture comprises equal weights of the two components, preferably each present as 30-40% of the total surfactant present.
  • the average ethoxylation value of the mixture of primary alkyl sulphate and alkyl ether sulphate is 0.75-1.25 EO.
  • the preferred average ethoxylation level in the alkyl ether sulphate component taken alone is 2-4 EO .
  • the alkyl chain length of the PAS falls in the range C 8 -C ⁇ 6 .
  • the PAS has a C i2 -C ⁇ 3 average alkyl chain length.
  • the PAS is substantially linear.
  • Suitable materials include DOBANOL-23S [RTM] (ex. Shell) .
  • alkyl ether sulphates are materials of the general formula:
  • Ri is linear or branched, C 8 to C ⁇ 8 alkyl. More preferably the alkyl chain length of the AES falls in the range C 8 -Ci 6 . Preferably the AES has a C ⁇ 2 -C ⁇ 3 average alkyl chain length. Preferably the AES is substantially linear. Suitable materials include DOBANOL-23-3S (RTM, ex SHELL) .
  • Preferred amphoteric and zwitterionic surfactants include betaines and/or amine oxides. Betaines are preferred to amine oxides for environmental reasons .
  • the preferred level of betaine in the compositions according to the invention is around 5%wt on surfactant. Amidobetaines are particularly preferred.
  • amido betaines are propyl amido betaines of the general formula : R. CONH . CH 2 . CH 2 . CH 2 . N + (R 6 R 7 ) . CH 2 COO ⁇
  • R is straight or branched C 8 to C ⁇ 8 alkyl
  • R 6 is Ci to C 3 alkyl or Ci to C 3 hydroxyalkyl
  • R 7 is Ci to C 3 alkyl or C x to C 3 hydroxyalkyl;
  • the betaine has an alkyl chain length (R) of C ⁇ 2 _C ⁇ ,
  • Suitable materials include TEGO BETAINE L5351 (RTM ex. Goldschmidt) .
  • the polymers employed in the present invention have a negatively charged or neutral hydrophilic backbone with at least one hydrophobic and oil-soluble side chain .
  • Polymers having a negatively charged backbone are preferred. We have determined that these anionic charged polymers had the largest beneficial effect, slowing the rate of coalescence significantly.
  • Typical backbones are polycarboxylate polymers formed as polymers of one or more of acrylic acid, methacrylic acid, maleic acid, crotonic acid, itaconic acid, aconitic acid, citraconic acid.
  • Polymers having a nonionic backbone, such as those derived from vinyl methyl ether, vinyl alcohol, acrolein, allyl alcohol and vinyl acetic acid are also envisaged as being suitable for putting the invention into effect.
  • the backbone is essentially linear, more preferably, branching in the backbone is limited such that the main chain of the backbone contains over 75% of its mass.
  • the hydrophobic side chains are saturated and/or unsaturated alkyl chains having from 5-24 carbon atoms, preferably 6-18 carbon atoms, most preferably 8-16 carbon atoms,
  • Preferred polymers are those described in US 5147576.
  • One particularly preferred polymer is that available in the marketplace as Narlex DC1 (TM, ex. National Starch)
  • Hydrotropes are optional components. It is preferred that the level of hydrotrope is no more than 20% of the total surfactant content on product, e.g. for a product containing 20% surfactant, the hydrotrope level should preferably be less than 4% on product . Where hydrotropes are required they are preferably selected from conventional hydrotrope materials including one or more of lower alkanols, alkaryl sulphonates, including xylene sulphonates and/or ureas . Higher levels of hydrotrope are required if the surfactant actives present are of low quality.
  • Magnesium is an optional component of the formulations according to the present invention. It is believed that the presence of magnesium boosts the detergency of the anionic surfactants present in the formulation. Preferred magnesium levels are equivalent to 2-14% as MgSO 4 .7H0. Magnesium may be present as the counter ion for the surfactant or be added.
  • electrolytes can be present at levels of 0.1-5% by weight of the overall composition.
  • Particularly preferred amongst the electrolytes are alkali metal halides, carbonates, bicarbonates and sulphates.
  • the most preferred electrolyte is sodium chloride.
  • Sodium chloride is conveniently present at a level of 0.1-5%, as a viscosity modifier.
  • Ammonium salts may be present.
  • the preferred electrolyes for grease removal are magnesium and potassium ions .
  • ingredients which may also be used in compositions according to the present invention are opacifiers (e.g. ethylene glycol distearate) , thickeners (e.g., guar gum), antibacterial agents (e.g. formaldehyde or Bronapol (TM) ) , anti- tarnish agents, weak metal chelators (e.g. citrates, glycinates) , perfumes, abrasives (e.g. calcites and dolomites) and dyes.
  • opacifiers e.g. ethylene glycol distearate
  • thickeners e.g., guar gum
  • antibacterial agents e.g. formaldehyde or Bronapol (TM)
  • TM Bronapol
  • anti- tarnish agents e.g. formaldehyde or Bronapol (TM)
  • weak metal chelators e.g. citrates, glycinates
  • perfumes e.g.
  • compositions according to the present invention can further comprise a solvent, preferably, when present, at level of l-15%wt on product, more preferably at a level of 2-7% on product .
  • any solvent present is selected from: propylene glycol mono n-butyl ether, dipropylene glycol mono n-butyl ether, propylene glycol mono t-butyl ether, dipropylene glycol mono t- butyl ether, diethylene glycol hexyl ether, ethyl acetate, methanol, ethanol, isopropyl alcohol, ethylene glycol monobutyl ether, di-ethylene glycol monobutyl ether and mixtures thereof.
  • the solvent is either a glycol ether or a C 2 -C 5 alcohol solvent.
  • Particularly preferred solvents are selected from the group comprising ethanol (preferably as industrial methylated spirits) , propylene glycol mono n-butyl ether (available as 'Dowanol PnB ' [RTM]) and di-ethylene glycol monobutyl ether (available in the marketplace both as 'Butyl Digol ' [RTM] or 'Butyl Carbitol' [RTM]).
  • a further inessential component is alkylene glycol, typically present at a level of 0-10% on product, irrespective of the overall surfactant concentration.
  • Propylene glycol is particularly suitable as a hydrotrope and/or viscosity modifier and while it is typically present in hand dishwashing compositions known in the art it may be dispensed of in compositions according to the present invention.
  • compositions according to the present invention comprising 15-50% surfactant on product are formulated such that they comprise, on surfactant, :
  • compositions according to the present invention comprise 10-50%, preferably 15-35% surfactant on product, which surfactant comprises, on total surfactant:
  • Preferred total compositions as aqueous solutions, comprise:
  • PAS/AES mixture preferably sodium lauryl ether sulphate 1EO (MMW 339, C 12 38-48%, C i3 52-62%),
  • l-3%wt betaine preferably lauryl amido propyl betaine (MMW 342, C12 95%)
  • g >1% dyes, animicrobial agents (preferably including formaldehyde) .
  • NARLEX DC1 is a suitable material
  • the extent of coalescence is less than 20% when measured as follows: emulsions of olive oil in water were prepared with a phase ratio of 20:80 of the oil phase to the water phase, using a jet homogeniser (ex. LabPlant) at lOOpsi (7kg/m 2 ) to obtain an emulsion with reproducible droplet sizes in the 1-10 micron range in a water phase which is a 0.6%wt active solution obtained by dilution of a light duty cleaning composition which comprises surfactant selected from the group comprising: nonionic surfactant, a complex of anionic surfactant and zwitterionic surfactant, a complex of anionic surfactant and amphoteric surfactant and mixtures thereof, and, a polymer, said polymer comprising a negatively charged or neutral hydrophilic backbone with at least one hydrophobic and oil-soluble side chain, wherein the ratio of polymer to surfactant falls in the range to 1:100- 1:10: the extent of coalescence being determined
  • Fig 1 shows a plot of the relation between the percentage of coalescence which occurs under the conditions specified below and the time taken to remove the grease from the Petri-dish using the method specified below.
  • Fig 2 shows a plot of the relationship between the volume of coalescence which occurs under the conditions specified below and the zeta potential as defined below.
  • Fig 3 shows the effect of increasing water hardness on compositions in the presence of two different polymers.
  • Fig 4 shows the effect of changing the polymer type on the rate of coalescence in centrifuge experiments as compared with a control .
  • Fig 5 shows the effect of changing the properties of the nonionic on the rate of coalescence both in the presence of polymer DC1 and otherwise.
  • Gerol PEJ 594 Ethylene glycol/terephthallic acid sulphonate: (ex. Rhone-Poulenc)
  • DC1 Sodium acrylate/laurylmethacrylate (ex. ALCO /National Starch)
  • ALCO Sodium acrylate/laurylmethacrylate
  • the names given in the left-hand column are believed to be trademarks.
  • 'DC1' is one which comprises a negatively charged or neutral hydrophilic backbone with at least one hydrophobic and oil-soluble side chain.
  • APG Akylpolyglycoside (Glucopon 600 (RTM) ex Henkel) .
  • PAS Primary alkyl sulphate Dobanol 23s/30 [TM] ex Shell
  • Marlipal 013/30 Ethoxylated nonionic with Cll-13 alkyl and an average of 3EO (ex Huls) . Marlipal is believed to be a trademark.
  • Dobanol 91-5 Ethoxylated nonionic with C9-11 alkyl and an average of 5EO (ex Shell). Dobanol is a trademark.
  • Marlipal 013/80 Ethoxylated nonionic with Cll-13 alkyl and an average of 8EO (ex Huls) .
  • Example 1 Relation between extent of coalescence and rate of grease removal, and effect of calcium.
  • Each petri dish had a cross marked on it centrally using permanent ink.
  • Petri dishes were placed in a clean oven at 45 ⁇ 2°C for 5 minutes, removed from the oven and filled with 5mls of the fat (still maintained at 60 ⁇ 2°C ) ensuring uniform coverage. The dishes were left to cool at room temperature over a period of l%-2 hours before use.
  • test solution of products A-E as described below was prepared at the desired concentration (typically 0.04%AD, e.g. lgm/l t of a 40% AD concentrate) using water of a specific hardness (typically 5, 12 or 24 deg FH) and heated to 50°C in a water bath.
  • the hot test solution was poured into a large beaker (e.g. 2L) containing a layer of glass beads as insulation and minimising the volume of foam produced and placed back in the waterbath, the temperature being maintained at 50C.
  • the test petri dish was added; time keeping was started as soon as the dish was submerged in the test solution. At the point at which the solution broke through to the glass surface on the base of the petri dish the time was recorded. The time at which the fat in each quadrant was fully removed was also recorded. While a tiny amount of small fatty speckles may have been left on the dish: where these covered a negligible fraction of the base, they were be ignored.
  • Emulsions of olive oil in water were prepared with a phase ratio of 20:80 of the oil phase to the water phase, using a jet homogeniser (ex. LabPlant) at lOOpsi (7kg/cm 2 ) to obtain an emulsion with reproducible droplet sizes in the 1-10 micron range .
  • a jet homogeniser ex. LabPlant
  • lOOpsi 7kg/cm 2
  • the water phase used was a 0.6%wt active solution obtained by dilution of the compositions A-E as listed in tables la and lb below.
  • Typical droplet sizes for products A and B are given below in table lc. Concentrations in table lc are given on product not on surfactant. D[4,3] and D[3,2] are in microns.
  • the extent of coalescence which occurs in the presence of the formulations used was determined after centrifugation of 10ml samples in graduated centrifuge tubes for 800 mins at 2000rpm, under conditions so as to produce an acceleration of 895g.
  • the volume of coalesced oil was measured to obtain an indication of the degree of coalescence expressed as a number in ml.
  • the zeta potential is the potential at the plane of shear or slip, i.e. the plane which separates water of hydration from free water. Zeta potential was measured using a Malvern Zetasizer (TM) following the instructions supplied with it.
  • TM Malvern Zetasizer
  • Figure 1 shows a plot of the relationship between the percentage of coalescence (C%) which occurs under the conditions specified above and the time (T) taken to remove the grease from the Petri-dish using the method specified above. Experiments were performed in 12 FH water.
  • Figure 2 shows a plot of the relationship between the volume of coalescence (Cvol) which occurs under the conditions specified above and the zeta potential (zeta) using the method specified above. Experiments were performed both in 12 FH water.
  • markers at the heads of the arrows include the added polymer CP5, those at the tail do not.
  • the products used are specified by the letter used to identify them in tables la and lb.
  • Figure 3 shows the effect of increasing water hardness on composition E in the presence of CP5 and DC1 polymers. Experiments were performed in both 12 and 24 FH water, using product E at a surfactant concentration of 0.6g/l. The polymer concentration in g/1 is plotted against the volume of oil coalesced from the emulsion after spinning at 2000 rpm for 800 minutes .
  • Figures 4a and 4b show the effect of changing the polymer type on the rate of coalescence in the centrifuge as compared with the control in which the waterphase of the emulsion was derived from E as described above.
  • the concentration of surfactant was 0.6g/l and where polymer was present it was present at a level of 0.075g/l.
  • the control was an emulsion in which the waterphase was derived directly from E and did not contain any polymer.
  • Table 2 shows the volume of oil coalesced after 800min as described above in the presence of simple surfactant systems.
  • the systems have a total surfactant concentration of 0.6gm/litre and are 50/50 mixtures of the two surfactants found by reading down or across the table.
  • Good performance is generally associated with an oil volume coalesced of 0.2ml, or less.
  • Figures shown in bold and underlined in table 2 indicate formulations in which there is an improvement in the stability of the oil droplets in the presence of the polymer.
  • the presence of nonionics and amphoterics is beneficial, but that poor results are generally obtained with PAS a strongly charged anionic surfactant.
  • LES a less strongly charged anionic surfactant, shows some improvement over PAS .
  • APG and APB containing systems can be improved to give very low levels of coalescence, and in general it can be seen that the addition of the DCl polymer never causes a significant increase in the coalescence, while more often than not, improves the coalescence score.
  • Figure 5 shows the effect of changing the properties of the nonionic on the rate of coalescence both in the presence of polymer DCl and otherwise. Coalescence was measured as described above, i.e. by the centrifuge method using 24 FH water (i.e. moderately hard) to prepare the waterphase of the emulsion.
  • the surfactants used are a series of ethoxylated nonionics with increasing degrees of ethoxylation. This increase in ethoxylation has the effect of increasing the hydrophile/lipophile balance of the surfactant.

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  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)

Abstract

La coalescence de gouttelettes d'huile au cours du lavage de la vaisselle peut être fortement retardée, sans nuire aux propriétés de dégraissage spontanées de la formulation, à l'aide de polymères sélectionnés présentant un squelette hydrophile et des chaînes latérales hydrophobes. La présente invention concerne une composition de nettoyage légère, aqueuse, sans agent adoucissant et non lamellaire. Cette composition comprend (a) 2 -70 % d'un tensioactif sélectionné dans le groupe se composant d'un tensioactif non ionique, d'un complexe d'un tensioactif anionique et d'un tensioactif zwittérionique, un complexe d'un tensioactif anionique et d'un tensioactif amphotérique et des mélanges de ces derniers, et (b) 0;02 à 7 % d'un polymère comprenant un squelette hydrophile neutre ou à charge négative avec au moins une chaîne latérale soluble à l'huile et hydrophobe. Dans cette composition, le rapport du polymère sur les tensioactifs se situe dans la plage 1/100 - 1/10. L'invention a également pour objet un procédé qui comprend l'étape consistant à traiter les surfaces de la vaisselle avec une composition décrite. On pense que les chaînes latérales hydrophobes solubles à l'huile se séparent des polymères en gouttelettes d'huile, lorsque le squelette hydrophile reste dans la phase aqueuse pour stabiliser les gouttelettes contre la coalescence par une combinaison d'entrave stérique et de répulsion électrostatique.
PCT/EP1997/006674 1996-12-12 1997-11-21 Ameliorations concernant des produits de nettoyage legers aqueux WO1998026036A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BR9714139-9A BR9714139A (pt) 1996-12-12 1997-11-21 Composição de limpeza, processo para lavagem de louça, e, uso de 0,02% em peso de um polìmero.
CA002270374A CA2270374A1 (fr) 1996-12-12 1997-11-21 Ameliorations concernant des produits de nettoyage legers aqueux
AU55586/98A AU721830B2 (en) 1996-12-12 1997-11-21 Improvements relating to aqueous light duty cleaning compositions
EP97952016A EP0944703A1 (fr) 1996-12-12 1997-11-21 Ameliorations concernant des produits de nettoyage legers aqueux

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9625884.3 1996-12-12
GBGB9625884.3A GB9625884D0 (en) 1996-12-12 1996-12-12 Improvements relating to aqueous light duty cleaning compositions

Publications (1)

Publication Number Publication Date
WO1998026036A1 true WO1998026036A1 (fr) 1998-06-18

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1997/006674 WO1998026036A1 (fr) 1996-12-12 1997-11-21 Ameliorations concernant des produits de nettoyage legers aqueux

Country Status (9)

Country Link
EP (1) EP0944703A1 (fr)
AR (1) AR009661A1 (fr)
AU (1) AU721830B2 (fr)
BR (1) BR9714139A (fr)
CA (1) CA2270374A1 (fr)
GB (1) GB9625884D0 (fr)
HU (1) HUP0000563A3 (fr)
WO (1) WO1998026036A1 (fr)
ZA (1) ZA9710550B (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002020708A1 (fr) * 2000-09-08 2002-03-14 Unilever Plc Composition trois-en-un de detergent pour laver la vaisselle contenant un acide polycarboxylique
FR2826017A1 (fr) * 2001-06-15 2002-12-20 Cognis France Sa Melanges de tensioactifs
US8192552B2 (en) 2002-02-11 2012-06-05 Rhodia Chimie Detergent composition comprising a block copolymer
WO2013019940A3 (fr) * 2011-08-02 2013-06-13 The Procter & Gamble Company Composition d'extraction liquide-liquide utile dans le traitement de tensioactifs hydrosolubles
CN103702728A (zh) * 2011-08-02 2014-04-02 宝洁公司 用于表面活性剂味道和/或气味改善的方法
US8821845B2 (en) 2005-06-23 2014-09-02 Rhodia Chimie Concentrated ingredient for treating and/or modifying surfaces, and use thereof in cosmetic compositions
US9072671B2 (en) 2012-08-02 2015-07-07 The Procter & Gamble Company Process for oral care material taste and/or odor improvement
US9078826B2 (en) 2011-08-02 2015-07-14 The Procter & Gamble Company Water-soluble surfactant compositions having improved taste

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5529724A (en) * 1995-02-06 1996-06-25 Lever Brothers Company, Division Of Conopco, Inc. Structured liquid compositions comprising selected secondary alcohol sulfates and a deflocculating polymer

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5529724A (en) * 1995-02-06 1996-06-25 Lever Brothers Company, Division Of Conopco, Inc. Structured liquid compositions comprising selected secondary alcohol sulfates and a deflocculating polymer

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002020708A1 (fr) * 2000-09-08 2002-03-14 Unilever Plc Composition trois-en-un de detergent pour laver la vaisselle contenant un acide polycarboxylique
US6521576B1 (en) 2000-09-08 2003-02-18 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Polycarboxylic acid containing three-in-one dishwashing composition
US6617302B2 (en) 2000-09-08 2003-09-09 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Polycarboxylic acid containing three-in-one dishwashing composition
FR2826017A1 (fr) * 2001-06-15 2002-12-20 Cognis France Sa Melanges de tensioactifs
WO2002102949A1 (fr) * 2001-06-15 2002-12-27 Cognis France S.A. Melanges d'agents tensioactifs
US7279456B2 (en) 2001-06-15 2007-10-09 Gognis France S.A. Surfactant mixtures
US8192552B2 (en) 2002-02-11 2012-06-05 Rhodia Chimie Detergent composition comprising a block copolymer
US8821845B2 (en) 2005-06-23 2014-09-02 Rhodia Chimie Concentrated ingredient for treating and/or modifying surfaces, and use thereof in cosmetic compositions
CN103702728A (zh) * 2011-08-02 2014-04-02 宝洁公司 用于表面活性剂味道和/或气味改善的方法
CN103717283A (zh) * 2011-08-02 2014-04-09 宝洁公司 可用于处理水溶性表面活性剂的液-液萃取组合物
US8697036B2 (en) 2011-08-02 2014-04-15 The Procter & Gamble Company Process for surfactant taste and/or odor improvement
WO2013019940A3 (fr) * 2011-08-02 2013-06-13 The Procter & Gamble Company Composition d'extraction liquide-liquide utile dans le traitement de tensioactifs hydrosolubles
US9078826B2 (en) 2011-08-02 2015-07-14 The Procter & Gamble Company Water-soluble surfactant compositions having improved taste
US10413844B2 (en) 2011-08-02 2019-09-17 The Procter & Gamble Company Liquid-liquid extraction composition useful in processing water-soluble surfactants
US10653601B2 (en) 2011-08-02 2020-05-19 The Procter & Gamble Company Water soluble surfactant composition having improved taste
US9072671B2 (en) 2012-08-02 2015-07-07 The Procter & Gamble Company Process for oral care material taste and/or odor improvement

Also Published As

Publication number Publication date
HUP0000563A2 (hu) 2000-08-28
AR009661A1 (es) 2000-04-26
HUP0000563A3 (en) 2001-02-28
GB9625884D0 (en) 1997-01-29
BR9714139A (pt) 2000-02-29
AU721830B2 (en) 2000-07-13
AU5558698A (en) 1998-07-03
CA2270374A1 (fr) 1998-06-18
EP0944703A1 (fr) 1999-09-29
ZA9710550B (en) 1999-05-24

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