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
  • 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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
• • 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
  • 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
  • C11D1/75—Amino oxides

Definitions

• the present invention relates to liquid detergent compositions suitable for use especially, but not exclusively, in fabric washing, shampoos, and above all, in manual dishwashing operations in both hard and soft water.
• Light-duty liquid detergent compositions such as are suitable for use in washing dishes are well-known. Many of the formulations in commercial use at the present time are based on a sulphonate-type anionic detergent, especially an alkyl benzene sulphonate, in conjunction with an alkyl polyethoxy sulphate (alkyl ether sulphate).
• the sulphonate-type detergent generally predominates.
• Protein denaturation by surfactants is considered to be one of the major causes of skin irritation and skin roughness induced by surfactants (G Imokawa et al. JOACS 52 , 484-489, Dec 1975).
• the degree of surfactant denaturation of protein depends on the type of surfactants and their concentration.
• dishwashing formulations that are on the market which are less interactive with protein and hence considered to be milder are those based on a combination of ether sulphates and amine oxides. See for example US-A-3 928 249 (Procter & Gamble). In place of amine oxides, betaines can also be used. See for example US 4 554 098.
• such formulations - particularly with amine oxides - are expensive, not only because the active ingredients are expensive, but also because they require a large amount of expensive hydrotropes such as xylenesulphonate and/or ethanol to produce liquids which are stable and of acceptable viscosity.
• EP 0232153 discloses detergent compositions based upon a mixture of anionic and nonionic surfactants together with lather boosters, at least some of the anionic surfactants being alkyl ether sulphate.
• nonionic surfactants in order to produce a mild system because such surfactants are inert towards proteins in the skin and because nonionic-containing formulations require lesser amounts of expensive hydrotropes.
• Nonionics have also been shown to have a good soil removing potential, particularly of greasy soils often found on dishes.
• nonionics as a class are low foamers and produce unstable lather.
• GB 2 165 855 discloses mild nonionic-based light duty liquid detergents wherein the nonionic component exceeds 50% by weight of the total detergent content.
• such high nonionic-based formulations would have foam performance deficiencies.
• the present invention is based on the realisation that cost-effective mild liquid dishwashing formulations with adequate performance can be obtained by careful choice of the active ingredients and their preparation, in particular by restricting the main anionic detergent active present and including also selected amounts of alkyl ether sulphate, lather boosters and non-ionic detergent active material.
• a stable detergent composition in liquid or gel form containing from 10 to 80% by weight of an active detergent mixture and also containing water, the active detergent mixture comprising:-
• At least a major proportion of the component (a) is selected from secondary alkane sulphonate, alkylbenzene sulphonate, primary alkyl sulphate, fatty acid ester sulphonate, dialkylsulphosuccinate and 2-alpha­ olefin sulphonate.
• compositions of the invention can give performance in detergency tests as good as those of conventional compositions containing alkyl benzene sulphonate, but are considerably milder.
• the concentration of the active detergent mixture may be as high as desired in the range 10 to 80%, provided that a stable liquid or gel product can be obtained, the range of 5 to 60% by weight is preferred, and aqueous liquid compositions with an active detergent mixture in the range of 5 to 40% by weight are of especial interest.
• Secondary alkane sulphonate may generally be produced by a free radical reaction, either a sulphochlorination reaction (Reed reaction) of a paraffin RH + SO2 + Cl2 ⁇ RSO2Cl + HCl followed by hydrolysis and neutralisation, or by a sulphoxidation reaction RH + SO2 + 1 ⁇ 2 O2 ⁇ RSO3H followed by neutralisation.
• Reed reaction a sulphochlorination reaction
• the secondary alkane sulphonate component (a) will normally be a mixture of materials of different alkyl chain lengths, of the formula R1R2CHSO3X where R1 and R2 which may be the same or different are each a straight or branched chain alkyl group having at least one carbon atom, the alkyl chain length (ie. total number of carbon atoms of R1 and R2 plus 1) preferably being in the range 13 to 18, and X is a solubilising cation.
• R1R2CHSO3X where R1 and R2 which may be the same or different are each a straight or branched chain alkyl group having at least one carbon atom, the alkyl chain length (ie. total number of carbon atoms of R1 and R2 plus 1) preferably being in the range 13 to 18, and X is a solubilising cation.
• An example of such material is SAS 60 of Hoechst (SAS is a Trade Mark) which is produced by a sulphoxidation process
• a suitable secondary alkane sulphonate produced by a sulphochlorination process is Mersolat (trade mark) of Bayer.
• Alkylbenzene sulphonate for use in component (a) is preferably derived from an alkylbenzene with a C8 to C16 primary or secondary alkyl group. This may in particular be C8 to C13 alkyl. Suitable alkylbenzene sulphonates are Dobs 102 of Shell and Marlon A of Huls.
• Primary alkyl sulphate is preferred (primary alcohol sulphate) for use in component (a) and is preferably of the formula ROSO3X where R is a C8 to C18 primary alkyl group and X is a solubilising cation. Suitable is Dobanol 23A of Shell in which R is predominantly C12 and C13. As well be explained in more detail below alkyl sulphate is a constituent of alkyl ether sulphates which provide component (b).
• Suitable detergent-active dialkyl sulphosuccinates are compounds of the formula wherein each of R1 and R2, which may be the same or different, represents a straight-chain or branched-chain alkyl group having 3 to 12 carbon atoms, preferably from 4 to 10 carbon atoms and more preferably from 6 to 8 carbon atoms, and X represents a solubilising cation.
• the alkyl groups R1 and R2 are preferably straight-chain or (in mixtures) predominantly straight-chain.
• dialkyl sulphosuccinates that may advantageously be used in the composition of the invention are the C6/C8 unsymmetrical materials described and claimed in GB 2 105 325 (Unilever); the dioctyl sulphosuccinate/dihexyl sulphosuccinate mixtures described and claimed in GB 2 104 913 (Unilever); and the mixtures of symmetrical and unsymmetrical dialkyl sulphosuccinates described and claimed in GB 2 108 520 (Unilever).
• alpha-olefin sulphonates will generally be in the range having from twelve to sixteen carbon atoms.
• Liporan 440 a C14 alpha-olefin sulphonate from Lion Corporation, Japan.
• Appropriate fatty acid ester sulphonates are of formula where R1 is straight or branched C8 to C16 alkyl R2 is straight or branched C1 to C4 alkyl and X is a solubising cation R1 is preferably C10 to C12 and R2 is preferably butyl.
• Component (a) of the active detergent mixture may also include one or more other detergent actives used in liquid compositions, for example alkyl glyceryl ether sulphonates, or alkyl sarcosinates.
• the amount is preferably less than half of component (a), more preferably not more than a quarter of it.
• the second essential component (b) of the active detergent mixture is alkyl ether sulphate (sometimes called alcohol ether sulphate or alkyl polyethoxy sulphate) having at least one ethylene oxide residue per molecule.
• alkyl ether sulphate which is a mixture of materials of the general formula: R - (OCH2CH2) n OSO3X wherein R is a C10 to C18 primary or secondary alkyl group, X is a solubilising cation, and n , the average degree of ethoxylation, is from 1 to 5, preferably from 3 to 4. Particularly preferred values of n are 3 and 4.
• R3 is preferably a C10 to C16 alkyl group.
• n represents an average.
• the unethoxylated material is, of course, alkyl sulphate and this contributes to component (a).
• alkyl sulphate in any alkyl ether sulphate will depend on average degree of ethoxylation n .
• n 3
• alkyl sulphate typically constitutes 15 to 20% of the mixture, and less than this when n is 4 or more.
• the proportion of alkyl sulphate is low, it may prove convenient to ignore it. Nevertheless, it contributes to component (a).
• alkyl sulphate typically constitutes 30% of the mixture provided as "alkyl ether sulphate".
• Such a mixture can provide both component (b) and component (a), with the latter then consisting entirely of alkyl sulphate.
• alkyl ether sulphate with an average degree of ethoxylation below 1.5. Unless the alkyl sulphate content of the ether sulphate is providing much or the whole of component (a), it is preferred that the alkyl ether sulphate is provided by material with an average of at least 2 or 2.5 ethylene oxide residues per molecule.
• Alkyl ether sulphate contains molecules with differing numbers of ethylene oxide residues in a statistical distribution.
• the proportion of molecules with a single ethylene oxide residue will not be substantially greater than the proportion with two ethylene oxide residues, nor the proportion with the most frequently encountered number of ethylene oxide residues (if this is more than two). Therefore this feature is an observable characteristic of component (b). If the average degree of ethoxylation is 2 or more, as preferred, the proportion of molecules with a single ethylene oxide residue will be less than the proportion with two ethylene oxide residues and the proportion with the most frequently encountered number.
• Preferred alkyl ether sulphates of the component (b), excluding alkyl sulphate, are mixtures of compounds of the above formula R-(OCH2CH2) n -OSO3X in which n is any positive integer, with the proviso that the average EO value is less than 5.
• Examples of preferred alkyl ether sulphates for use in the present invention are Dobanol (Trade Mark) 23-3 from Shell in which the degree of ethoxylation (n) is 3 and the equivalent material in which the degree of ethoxylation is 4. These materials which are based on C12-C13 (50% of each) primary alcohol (about 75% straight chain, 25% 2-methyl branched).
• Another preferred material is an alkyl ether sulphate based on Lial (Trade Mark) 123 from Chimica Augusta, which is a branched chain primary alcohol with a degree of ethoxylation of 3 to 4 and with a similar alkyl chain length distribution to Dobanol 23.
• Empicol MD Trade Mark
• Albright and Wilson with degree of ethoxylation of 4 and based on middle-cut coconut alkyl group.
• a suitable example of a secondary alcohol ether sulphate is a material derived from an alcohol such as Tergitol 15/S/3 (trade mark) of Union Carbide (this material itself is not at present available).
• the conventional process of manufacture of secondary alkyl ether sulphates is such that there is only a very small quantity of alkyl sulphate in the product.
• Component (b) provides at least 12% of the active detergent mixture, preferably it provides at least 20 or 30%. It preferably provides not more than 40% of the active detergent mixture. However, component (b) could form up to 50% of the mixture if component (b) contributes substantially or wholly to component (a).
• the solubilising cations of the anionic detergent actives of components (a) and (b), denoted as X in the formulae above, may be any which provide the desired solubility of the anionic material.
• Monovalent cations such as alkali metal ions, ammonium and substituted ammonium are typical.
• Divalent ions giving adequate solubility may be used, and especially magnesium ions may be present to improve soft water performance and can be incorporated as magnesium salt of the anionic actives or as inorganic magnesium salts, or in the hydrotrope system.
• Component (c) is a betaine or amine oxide or a mixture thereof. It is preferred to avoid using substantial amounts of these, especially amine oxides, for the sake of economy and consequent cost effectiveness.
• the amount of amine oxide is not more than 10% by weight of the active detergent mixture.
• the amount of betaine is not more than 30% by weight of this mixture.
• the total amount of amine oxide and betaine is preferably not more than 30% and more preferably not more than 15% or 10% by weight of the active detergent mixture. It is preferred to use betaines alone.
• Suitable betaines include simple betaines of formula and amido betaines of formula:
• R is a C8 to C18 straight or branched alkyl group. It may be a lauryl group or a middle cut coconut alkyl group.
• R6 and R7 are each C1 to C3 alkyl or C1 to C3 hydroxyalkyl. Examples of sulphobetaines have the above formulae with -CH2CO ⁇ 2 replaced by -(CH2)3SO ⁇ 3 or
• a suitable simple betaine is Empigen BB from Albright & Wilson. It has the formula quoted above in which R is C12 to C14 alkyl, derived from coconut, and R6 and R7 are both methyl. Also preferred is Tego L7 from Goldsmidt, which has a whole coconut alkyl group.
• Suitable amine oxides have the formula R R6 R7 N-O wherein R is a straight or branched chain C8 to C18 alkyl group and R6 and R7 are each C1 to C3 alkyl, or C1 to C3 hydroxyalkyl.
• a suitable amine oxide is Empigen OB from Albright & Wilson. In it R is middle-cut coconut alkyl and R6 and R7 are both methyl.
• Component (d) is one or more water-soluble non-ionic detergent active materials, eg. materials conventionally used in detergent formulations.
• the betaines and amine oxides of component (c) do not form part of component (d).
• Component (d) is preferably a polyalkoxylated material, notably it is one or more ethoxylated non-ionic detergent active materials. It is then desirable that such material should have an HLB value in the range from 12.0 to 16.0.
• Component (d) may be a polyethoxylated aliphatic alcohol having an alkyl chain length of from C8 to C18 preferably C8 to C16, and an average degree of ethoxylation of from 4 to 14.
• Suitable nonionic detergents include short-chain high-foaming ethoxylated alcohols of the general formula R - (OCH2CH2) m - OH wherein R is an alkyl group, preferably straight-chain, having from 8 to 18 better 8 to 16 and yet more preferably 9 to 12, carbon atoms, and the average degree of ethoxylation m is from 5 to 14, more preferably 6 to 12.
• An especially preferred nonionic detergent is Dobanol 91-8 from Shell, in which R is C9-C11 (predominantly straight-chain) and m is 8, or alternatively Lialet C11-10 EO.
• R is a secondary alkyl having from 8 to 18, preferably 11-15, carbon atoms and m is from 5 to 14 preferably 6-12.
• An example is Tergitol 15/S/12 of Union Carbide (not available at present) or the material of the Softanol A series (from Japan Catalytic).
• the polyethoxylated alcohol mixture is stripped, to reduce odour imparted to the composition.
• component (d) is an ethoxylated alkanolamide of the general formula R-CO- (R8)(OCH2CH2O) p H wherein R is a straight or branched alkyl having from 7 to carbon atoms, R8 is an ethyleneoxy or propyleneoxy group Y is hydrogen or -R8(CH2CH2O) q H p is 1 or more and q is 0, 1 or more R may be lauryl or coconut alkyl.
• R is a straight or branched alkyl having from 7 to carbon atoms
• R8 is an ethyleneoxy or propyleneoxy group
• Y is hydrogen or -R8(CH2CH2O) q H p is 1 or more and q is 0, 1 or more R may be lauryl or coconut alkyl.
• Examples of ethoxylated alkanolamide are Amidox L5 and Amidox C5 from Stepan Chemical Company.
• component (d) is ethoxylated alkylphenols and ethoxylated fatty acids, ie. polyethyleneglycol esters of fatty acids.
• Component (d) constitutes at least 35% by weight of the active detergent mixture, but less than 50%.
• Optionally present within the active detergent mixture of the composition of the invention may be one or more mono- or dialkanolamides, preferably C8 to C18, more preferably C10-C18 carboxylic acid mono- or di(C2-C3) alkanolamides.
• These have the general formulae R4 - CO - NHR5 and R4 - CO - N(R5)2 respectively wherein R4 is a C7-C17 aliphatic group, preferably straight-chain and preferably saturated, and R5 is a hydroxyethyl or hydroxypropyl group. R5 is preferably a 2-hydroxyethyl group.
• Materials of this type are generally made from fatty acids of natural origin and contain a range of molecules having R4 groups of different chain lengths; for example, coconut ethanolamides consist predominantly of C12 and C14 material, with varying amounts of C8,C10, C16 and C18 material. Preferred are ethanolamides derived from so-called middle cut coconut fatty acid, most preferably from lauric acid.
• the mono- and di-ethanolamides may range from 5% to 20% of the detergent mixture.
• the liquid detergent compositions of the invention will generally need to contain one or more hydrotropes.
• Hydrotropes are materials present in a formulation to control solubility, viscosity, clarity and stability but which themselves make no active contribution to the performance of the product.
• hydrotropes include lower aliphatic alcohols, especially ethanol; urea; lower alkylbenzene sulphonates such as sodium, toluene and xylene sulphonates and combinations of these. Preferred are alcohol, urea and xylene sulphonate. Hydrotropes are expensive and take up room in a formulation without contributing to its performance, and it is therefore desirable to use as small quantities of them as possible.
• amine oxides as mentioned above requires a large amount of alcohol as hydrotrope. For this reason and because of expense, it is preferred to avoid the use of a substantial amount of any tertiary amine oxide in the present invention.
• the weight of hydrotrope in the composition is not more than 12% of the weight of the active detergent mixture.
• compositions of the invention may also contain the usual minor ingredients such as perfume, colour, preservatives and germicides.
• the stable liquid detergent compositions of the invention may be used for all normal detergent purposes especially where foaming is advantageous, for example, fabric washing products, general purpose domestic and industrial cleaning compositions, carpet shampoos, car wash products, personal washing products, shampoos, foam bath products, and above all, manual dishwashing.
• Foaming performance was assessed by means of a modified Schlachter-Dierkes test based on the principle described in Fette und Seifen 1951, 53 , 207.
• a 100 ml aqueous solution of each material tested, having a concentration of 0.04% active detergent in 24°H water (French hardness) at 45°C was rapidly oscillated using a vertically oscillating perforated disc within a graduated cylinder.
• increments (0.2 g) of soil 9.5 parts commercial cooking fat, 0.25 partsoleic acid 0.25 parts stearic acid and 10 parts wheat starch in 120 parts water
• the result was recorded as the number of soil increments (NSI score): a score difference of 6 or less is generally regarded as insignificant.
• NAI score number of soil increments
• a comparison of wheatgerm acid phosphatase (WGAP) test and flex wash test results indicated that formulations giving less than 50% enzyme inhibition under the test conditions are substantially mild; any mildness differences between products giving ⁇ 40% inhibition do not show any detectable mildness differences in flex wash test, indicating that the enzyme test is very sensitive an that in a real life situation there is a threshold level of protein denaturation below which all actives and products are indistinguishably mild.
• the results of the WGAP test are expressed as percentage inhibition (ie 100% minus percentage activity remaining). Water gave no inhibition at all, ie 100% of activity remained.
• compositions of the present invention give a combination of mildness and performance.
• compositions of the present invention give a combination of mildness and performance.

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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)
• Detergent Compositions (AREA)
• Cosmetics (AREA)

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• 1989
  • 1989-03-10 GB GB898905551A patent/GB8905551D0/en active Pending
• 1990
  • 1990-03-06 CA CA002011578A patent/CA2011578C/en not_active Expired - Fee Related
  • 1990-03-08 ES ES90302490T patent/ES2088964T3/es not_active Expired - Lifetime
  • 1990-03-08 AU AU51150/90A patent/AU625979B2/en not_active Ceased
  • 1990-03-08 DE DE69027055T patent/DE69027055T2/de not_active Expired - Fee Related
  • 1990-03-08 EP EP90302490A patent/EP0387063B1/de not_active Expired - Lifetime
  • 1990-03-09 ZA ZA901850A patent/ZA901850B/xx unknown
  • 1990-03-09 KR KR1019900003119A patent/KR950002351B1/ko not_active Expired - Fee Related
  • 1990-03-09 IN IN55/BOM/90A patent/IN170595B/en unknown
  • 1990-03-09 JP JP2059762A patent/JPH0726115B2/ja not_active Expired - Lifetime
  • 1990-03-09 BR BR909001138A patent/BR9001138A/pt not_active IP Right Cessation
  • 1990-03-09 MY MYPI90000379A patent/MY106323A/en unknown
• 1991
  • 1991-09-19 ID IDP33291A patent/ID963B/id unknown

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