CA2011578C - Detergent compositions - Google Patents
Detergent compositionsInfo
- Publication number
- CA2011578C CA2011578C CA002011578A CA2011578A CA2011578C CA 2011578 C CA2011578 C CA 2011578C CA 002011578 A CA002011578 A CA 002011578A CA 2011578 A CA2011578 A CA 2011578A CA 2011578 C CA2011578 C CA 2011578C
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- Prior art keywords
- alkyl
- aes
- detergent
- active
- mixture
- Prior art date
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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
- 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
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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)
Abstract
A liquid detergent composition suitable especially for dishwashing by hand. The composition contains from 10 to 80%wt of an active detergent mixture of (a) primary alkyl sulphate (PAS), (b) alkyl ether sulphate (AES), (c) water soluble nonionic detergent active material and (d) betaine and/or amine oxide, and also water, wherein:
(i) the AES has an average ethoxylation value of between 1 and 5, and weight ratio of PAS:AES is in the range 2:1-1:3; and, (ii) the molar ratio of PAS to said betaine and/or amine oxide is in the range 3:1-1:3; and, (iii) the nonionic detergent comprises more than 35%, but less than 50% by weight of the active detergent mixture.
Compositions of the invention can provide a combination of good performance and good mildness.
(i) the AES has an average ethoxylation value of between 1 and 5, and weight ratio of PAS:AES is in the range 2:1-1:3; and, (ii) the molar ratio of PAS to said betaine and/or amine oxide is in the range 3:1-1:3; and, (iii) the nonionic detergent comprises more than 35%, but less than 50% by weight of the active detergent mixture.
Compositions of the invention can provide a combination of good performance and good mildness.
Description
DETERGENT COMPOSITIONS
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.
The term "dishes" as used herein means any utensils involved in food preparation or consumption which may be required to be washed to free them from food particles and other food residues, greases, proteins, starches, gums, dyes, oils and burnt organic residues.
2s 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.
The use of conventional dishwashing liquids based on 3~ alkyl benzene sulphonate/alkyl ether sulphate or on alkyl sulphate/alkyl ether sulphate is seen to have deleterious influence on the hand condition of users. Hence mildness - in washing-up liquid is considered a desirable quality, and many specially formulated products on the market make claims for it.
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 lo denaturation of protein depends on the type of surfactants and their concentration.
At present, the 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. However, 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.
2s EP 02321S3 (Unilever) 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.
It is preferred to include high amounts of 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. However, nonionics as a class are low foamers and produce unstable lather.
GB 2 165 855 (Colgate) discloses mild nonionic-based light duty liquid detergents wherein the nonionic component exceeds 50% by weight of the total detergent content. However, for reasons stated above, such high nonionic-based formulations would have foam performance deficiencies.
US 4 554 098 (Colgate~ mentioned above discloses a mild dishwashing formulation based on an alkyl ether sulphate containing an average of 5 to 12 moles of ethylene oxide in the molecule. However, such ether sulphates are not commercially easily available. Also, it is believed that the dioxane level in ether sulphate raw material increases with the increase in E0 content of ether sulphate. Therefore, for ease of commercial exploitation the use of widely used and generally 25 available ether sulphates containina less than 5 E0 is preferred.
Therefore there is need for the development of more cost-effective mild dishwashing formulations, which are 30 based on relatively less expensive detergent raw materials and which also require lesser amounts of expensive hydroptropes.
The present invention is based on the realisation 35 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 delergent active present and including also selected amounts of alkyl ether sulphate, lather boosters and non-ionic deLergent active material.
According to the present invention, a stable delergellt composition in liquid or gel form containing from 10 to 80%wt of an active delergellt mixture of (a) primary alkyl sulphate (PAS), (b) alkyl ether sulphate (AES), (c) water soluble nonionic dele~,ent active material and (d) betaine and/or amine oxide, and also water, wherein:
(i) the AES has an average ethoxylation value of between 1 and 5, and weight ratio of PAS:AES is in the range 2:1-1:3; and, (ii) the molar ratio of PAS to said betaine and/or amine oxide is in the range 3:1-1:3; and, (iii) the nonionic deleL~nt comprises more than 35%, but less than 50% by weight of the active deler~,ent mixture.
For reasons of cost-effectiveness, and availability of materials, primary alkyl sulphate is ~electe-l as component (a).
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.
.`B
~5~ 2n~ 78 It is particularly surprising that mildness of predominantly nonionic-based formulations can wholly be maintained by substituting a substantial portion of the nonionic with ether sulphates containing less than 5 EO, but enhancing the foam performance significantly and thus improving cost effectiveness.
Although in principle the concentration of the active detefgent 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 deteL~ t mixture in the range of 5 to 40% by weight are of special interest.
Primary alkyl sulphate (primary alcohol sulphate) for use in component (a) is preferably of the formula where R is a Cg to Clg primary aLtcyl group and X is a solubilising cation.
-B
2011~78 which R is predominantly C12 and C13. As will beexplained 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 COORl COOR2 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.
Among dialkyl sulphosuccinates th~t 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).
Appropriate alpha-olefin sulphonates will generally be in the range having from twelve to sixteen carbon ~ atoms.
, , ~ C3302 An example of such a material is Liporan 440, a C14 alpha-olefin sulphonate from Lion Corporation, Japan.
Appropriate fatty acid ester sulphonates are of formula Rl CH C2R2 where R1 is straight or branched C8 to C16 alkyl R2 is straight or branched Cl 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. This will normally be provided by incorporating into the composition an alkyl ether sulphate which is a mixture of materials of the general formula:
R - (OCH2CH2)n OS03X
~ C3302 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. In any given alkyl ether sulphate, a range of differently ethoxylated materials, and some unethoxylated material, will be present and the value of n represents an average. The unethoxylated material is, of course, alkyl sulphate and lo this contributes to component (a).
The amount of alkyl sulphate in any alkyl ether sulphate will depend on average degree of ethoxylation n.
When n is 3, alkyl sulphate typically constitutes 15 to 20% of the mixture, and less than this when n is 4 or more. When the proportion of alkyl sulphate is low, it may prove convenient to ignore it. Nevertheless, it contributes to component (a).
When the average degree of ethoxylation is 2, 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.
~2 have found that it is not feasible to use 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. In an alkyl ether sulphate where the average degree of ethoxylation is 1.5 or greater, 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 lo 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 E0 value is less than 5.
Examples of preferred alkyl ether sulphates for use 2s in the present invention are Dobanol (Trade Mark) 23-3 from Shell in which the deyree 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. Also preferred is Empicol MD (Trade Mark) -10- 2oll~78 from 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, ~fererably it provides at least 20 or 30%. It prerelably 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 deler~,ent 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 ty-pical. 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 ~y~lem.
Component (d) 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.
Prefelably then the amount of amine oxide is not more than 10% by weight of the active delelgellt mixture. Preferably ,. -~ B
B
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 - CONH CH2CH2cH2l CH2 2 In both formulae R is a C8 to C18 straight or branched alkyl group. It may be a lauryl group or a - middle cut coconut ~lkyl group. R6 and R7 are each C1 to C3 alkyl or C1 to C3 hydroxyalkyl. Examples of sulphobetaines have the above formulae with -CH2C0 2 replaced by TH
( 2)3 3 -CH2 CHSH2 S0 3 A suitable simple betaine is Empigen BB from Albright & Wilson.
It has the formula quoted above in which R is C12 - Cl4 alkyl, derived &om coconut, and R6 and R7 are both methyl. Also preferred is Tego L7 from Goldsmidt (Tego is a trade mark), which has a whole coconut alkyl group.
Suitable amine oxides have the formula wherein R is a straight or branched chain Cg to C1g8 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 (Empigen is a trade mark).
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 delergent active materials, eg. materials conventionally used in delergellt formulations. The betaines and amine oxides of component (d) do not form part of component (c).
Component (c) 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 16Ø
Component (c) may be a polyethoxylated aliphatic alcohol having an alkyl chain length of from Cg to Clg preferably Cg to Cl6, and an average degree of ethoxylation of from 4 to 14. Suitable nonionic detergellts include short-chain high-foaming ethoxylated alcohols of the general formula R- (OCH2CH2)m-OH
.~
~I......... B
~.
, 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 delerg~llt is Dobanol 91-8 from Shell, in which R is Cg-Cll (predominantly straight-chain) and m is 8, or alternatively Lialet Cll-10 EO.
Alternative suitable materials are those in which R is a secondary alkyl having from 8 to 18, preferably 11-15, carbon atoms an _ is from 5 to 14 ~re~elably 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).
Preferably the polyethoxylated alcohol mixture is stripped, to reduce odour imparted to the composition.
Another possibility for the component (c) is an ethoxylated alkanolamide of the general formula R-CO-N(E~g)(OCH2CH2O)pH
wherein R is a straight or branched alkyl having from 7 to 18 carbon atoms, R8 is an ethyleneoxy or propyleneoxy group Y is hydrogen or -Rg(CH2CH2O)qH
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 (Amidox is a trade mark).
~r~
: B
-14- 2û11578 Further possibilities for component (c) are ethoxylated alkylphenols and ethoxylated fatty acids, ie. polyethyleneglycol esters of fatty acids.
Component (c) constitutes at least 35% by weight of the active deLerg~.lt mixture, but less than 50%.
- Optionally present within the active delergent mixture of the composition of the invention may be one or more mono- or dialkanolamides, preferably Cg to C1g, more preferably C1o-C1g carboxylic acid mono- or di(C2-C3) alkanolamides. These have the general formulae R4 - CO - NHRs and R4 - CO- N(Rs)2 respectively wherein R4 is a C7-C17 aliphatic group, ~referably straight-chain and prerelably saturated, and Rs 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 Cg, C1o, C16 and C1g material. Prefelred are ethanolamides derived from so-called middle cut coconut fatty acid, most ~referably from lauric acid.
The mono- and di-ethanolamides may range from 5% to 20% of the delergent mixture.
As well as the active detergent mixture and water, the liquid delergent compositions of the invention will generally need to contain one or more hydrotropes.
. . . .
-:
B 2011~78 ~ ,.
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. Examples of 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.
For example, the use of 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.
In preferred forms of this invention the weight of hydrotrope in the composition is not more than 12~ of the weight of the active detergent mixture.
The compositions of the invention may also contain 25 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 30 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.
. ~
. .~ , l ~
The invention is further illustrated by the following non-limiting Examples.
EXAMPLES
Examples 1-4 The foaming performance and mildness of various aqueous formulations were compared. These formulations I
lo and II falling within the scope of the present application were compared with a comparable composition (A) containing over 50~ by weight of nonionic active.
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 24H water (French hardness) at 45C was rapidly oscillated using a vertically oscillating perforated disc within a graduated cylinder. After the initial generation of foam, 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) were added at 15 second intervals (10 seconds' mild agitation and 5 seconds' rest) until the foam collapsed. The result was recorded as the number of soil increments (NSI score): a score difference of 6 or less is generally regarded as insignificant. Each result was typically the average of 3 or 4 runs.
Several in-vitro and in-vivo methods for evaluating protein denaturation potency of surfactants and their mixtures have been reported (see Miyazowa et al, Int J Cos 35 Sci 6 33-46 1984, and the references cited therein). One 2û11`~78 B 1~
such method is the study of interaction of detergents with acid phosphatase enzyme either from skin (Prottey et al, Int J Cos Sci 6 263-273 1984) or from Wheatgerm (Tanaka et al, Anal Biochem 66 489-498 1975).
In vivo mildness of formulations can be assessed using a flex wash test. In this test neat products were rubbed on the forearm of panellists and rinsed. The process was repeated four times a day for five days and the level of erythema developed was assessed by trained assessors.
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.
2011~78 I II _ Lialet 123-3S1 10 Lialet 123-4S _ 10 Dobanol 23-A - - 8 Lialet 123-S 5 5 Lialet C11 lOE0 15 15 22 Empigen BB 6 6 6 lo Empigen LME 4 4 4 Plunger Test (0.04~ AD) WGAP Inhibition 23 21 12 1 - Alkyl Ether Sulphate 2 - Primary Alkyl Sulphate 3 - Nonionic 4 - Betaine 5 - Ethanolamide The Examples show that formulations I and II give a greater foaming performance than A. Altnough ~ WGAP
inhibition of A is less than I and II, the effective mildness is no different, as explained above. Thus compositions of the present invention give a combination of mildness and performance.
-.' ~ 19 -`- B C3302 The Examples show that formulations I and II give a greater foaming performance than A. Although % WGAP
inhibition of A is less than I and II, the effective mildness is no different, as explained above. Thus compositions of the present invention give a combination of mildness and performance.
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.
The term "dishes" as used herein means any utensils involved in food preparation or consumption which may be required to be washed to free them from food particles and other food residues, greases, proteins, starches, gums, dyes, oils and burnt organic residues.
2s 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.
The use of conventional dishwashing liquids based on 3~ alkyl benzene sulphonate/alkyl ether sulphate or on alkyl sulphate/alkyl ether sulphate is seen to have deleterious influence on the hand condition of users. Hence mildness - in washing-up liquid is considered a desirable quality, and many specially formulated products on the market make claims for it.
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 lo denaturation of protein depends on the type of surfactants and their concentration.
At present, the 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. However, 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.
2s EP 02321S3 (Unilever) 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.
It is preferred to include high amounts of 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. However, nonionics as a class are low foamers and produce unstable lather.
GB 2 165 855 (Colgate) discloses mild nonionic-based light duty liquid detergents wherein the nonionic component exceeds 50% by weight of the total detergent content. However, for reasons stated above, such high nonionic-based formulations would have foam performance deficiencies.
US 4 554 098 (Colgate~ mentioned above discloses a mild dishwashing formulation based on an alkyl ether sulphate containing an average of 5 to 12 moles of ethylene oxide in the molecule. However, such ether sulphates are not commercially easily available. Also, it is believed that the dioxane level in ether sulphate raw material increases with the increase in E0 content of ether sulphate. Therefore, for ease of commercial exploitation the use of widely used and generally 25 available ether sulphates containina less than 5 E0 is preferred.
Therefore there is need for the development of more cost-effective mild dishwashing formulations, which are 30 based on relatively less expensive detergent raw materials and which also require lesser amounts of expensive hydroptropes.
The present invention is based on the realisation 35 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 delergent active present and including also selected amounts of alkyl ether sulphate, lather boosters and non-ionic deLergent active material.
According to the present invention, a stable delergellt composition in liquid or gel form containing from 10 to 80%wt of an active delergellt mixture of (a) primary alkyl sulphate (PAS), (b) alkyl ether sulphate (AES), (c) water soluble nonionic dele~,ent active material and (d) betaine and/or amine oxide, and also water, wherein:
(i) the AES has an average ethoxylation value of between 1 and 5, and weight ratio of PAS:AES is in the range 2:1-1:3; and, (ii) the molar ratio of PAS to said betaine and/or amine oxide is in the range 3:1-1:3; and, (iii) the nonionic deleL~nt comprises more than 35%, but less than 50% by weight of the active deler~,ent mixture.
For reasons of cost-effectiveness, and availability of materials, primary alkyl sulphate is ~electe-l as component (a).
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.
.`B
~5~ 2n~ 78 It is particularly surprising that mildness of predominantly nonionic-based formulations can wholly be maintained by substituting a substantial portion of the nonionic with ether sulphates containing less than 5 EO, but enhancing the foam performance significantly and thus improving cost effectiveness.
Although in principle the concentration of the active detefgent 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 deteL~ t mixture in the range of 5 to 40% by weight are of special interest.
Primary alkyl sulphate (primary alcohol sulphate) for use in component (a) is preferably of the formula where R is a Cg to Clg primary aLtcyl group and X is a solubilising cation.
-B
2011~78 which R is predominantly C12 and C13. As will beexplained 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 COORl COOR2 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.
Among dialkyl sulphosuccinates th~t 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).
Appropriate alpha-olefin sulphonates will generally be in the range having from twelve to sixteen carbon ~ atoms.
, , ~ C3302 An example of such a material is Liporan 440, a C14 alpha-olefin sulphonate from Lion Corporation, Japan.
Appropriate fatty acid ester sulphonates are of formula Rl CH C2R2 where R1 is straight or branched C8 to C16 alkyl R2 is straight or branched Cl 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. This will normally be provided by incorporating into the composition an alkyl ether sulphate which is a mixture of materials of the general formula:
R - (OCH2CH2)n OS03X
~ C3302 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. In any given alkyl ether sulphate, a range of differently ethoxylated materials, and some unethoxylated material, will be present and the value of n represents an average. The unethoxylated material is, of course, alkyl sulphate and lo this contributes to component (a).
The amount of alkyl sulphate in any alkyl ether sulphate will depend on average degree of ethoxylation n.
When n is 3, alkyl sulphate typically constitutes 15 to 20% of the mixture, and less than this when n is 4 or more. When the proportion of alkyl sulphate is low, it may prove convenient to ignore it. Nevertheless, it contributes to component (a).
When the average degree of ethoxylation is 2, 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.
~2 have found that it is not feasible to use 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. In an alkyl ether sulphate where the average degree of ethoxylation is 1.5 or greater, 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 lo 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 E0 value is less than 5.
Examples of preferred alkyl ether sulphates for use 2s in the present invention are Dobanol (Trade Mark) 23-3 from Shell in which the deyree 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. Also preferred is Empicol MD (Trade Mark) -10- 2oll~78 from 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, ~fererably it provides at least 20 or 30%. It prerelably 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 deler~,ent 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 ty-pical. 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 ~y~lem.
Component (d) 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.
Prefelably then the amount of amine oxide is not more than 10% by weight of the active delelgellt mixture. Preferably ,. -~ B
B
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 - CONH CH2CH2cH2l CH2 2 In both formulae R is a C8 to C18 straight or branched alkyl group. It may be a lauryl group or a - middle cut coconut ~lkyl group. R6 and R7 are each C1 to C3 alkyl or C1 to C3 hydroxyalkyl. Examples of sulphobetaines have the above formulae with -CH2C0 2 replaced by TH
( 2)3 3 -CH2 CHSH2 S0 3 A suitable simple betaine is Empigen BB from Albright & Wilson.
It has the formula quoted above in which R is C12 - Cl4 alkyl, derived &om coconut, and R6 and R7 are both methyl. Also preferred is Tego L7 from Goldsmidt (Tego is a trade mark), which has a whole coconut alkyl group.
Suitable amine oxides have the formula wherein R is a straight or branched chain Cg to C1g8 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 (Empigen is a trade mark).
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 delergent active materials, eg. materials conventionally used in delergellt formulations. The betaines and amine oxides of component (d) do not form part of component (c).
Component (c) 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 16Ø
Component (c) may be a polyethoxylated aliphatic alcohol having an alkyl chain length of from Cg to Clg preferably Cg to Cl6, and an average degree of ethoxylation of from 4 to 14. Suitable nonionic detergellts include short-chain high-foaming ethoxylated alcohols of the general formula R- (OCH2CH2)m-OH
.~
~I......... B
~.
, 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 delerg~llt is Dobanol 91-8 from Shell, in which R is Cg-Cll (predominantly straight-chain) and m is 8, or alternatively Lialet Cll-10 EO.
Alternative suitable materials are those in which R is a secondary alkyl having from 8 to 18, preferably 11-15, carbon atoms an _ is from 5 to 14 ~re~elably 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).
Preferably the polyethoxylated alcohol mixture is stripped, to reduce odour imparted to the composition.
Another possibility for the component (c) is an ethoxylated alkanolamide of the general formula R-CO-N(E~g)(OCH2CH2O)pH
wherein R is a straight or branched alkyl having from 7 to 18 carbon atoms, R8 is an ethyleneoxy or propyleneoxy group Y is hydrogen or -Rg(CH2CH2O)qH
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 (Amidox is a trade mark).
~r~
: B
-14- 2û11578 Further possibilities for component (c) are ethoxylated alkylphenols and ethoxylated fatty acids, ie. polyethyleneglycol esters of fatty acids.
Component (c) constitutes at least 35% by weight of the active deLerg~.lt mixture, but less than 50%.
- Optionally present within the active delergent mixture of the composition of the invention may be one or more mono- or dialkanolamides, preferably Cg to C1g, more preferably C1o-C1g carboxylic acid mono- or di(C2-C3) alkanolamides. These have the general formulae R4 - CO - NHRs and R4 - CO- N(Rs)2 respectively wherein R4 is a C7-C17 aliphatic group, ~referably straight-chain and prerelably saturated, and Rs 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 Cg, C1o, C16 and C1g material. Prefelred are ethanolamides derived from so-called middle cut coconut fatty acid, most ~referably from lauric acid.
The mono- and di-ethanolamides may range from 5% to 20% of the delergent mixture.
As well as the active detergent mixture and water, the liquid delergent compositions of the invention will generally need to contain one or more hydrotropes.
. . . .
-:
B 2011~78 ~ ,.
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. Examples of 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.
For example, the use of 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.
In preferred forms of this invention the weight of hydrotrope in the composition is not more than 12~ of the weight of the active detergent mixture.
The compositions of the invention may also contain 25 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 30 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.
. ~
. .~ , l ~
The invention is further illustrated by the following non-limiting Examples.
EXAMPLES
Examples 1-4 The foaming performance and mildness of various aqueous formulations were compared. These formulations I
lo and II falling within the scope of the present application were compared with a comparable composition (A) containing over 50~ by weight of nonionic active.
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 24H water (French hardness) at 45C was rapidly oscillated using a vertically oscillating perforated disc within a graduated cylinder. After the initial generation of foam, 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) were added at 15 second intervals (10 seconds' mild agitation and 5 seconds' rest) until the foam collapsed. The result was recorded as the number of soil increments (NSI score): a score difference of 6 or less is generally regarded as insignificant. Each result was typically the average of 3 or 4 runs.
Several in-vitro and in-vivo methods for evaluating protein denaturation potency of surfactants and their mixtures have been reported (see Miyazowa et al, Int J Cos 35 Sci 6 33-46 1984, and the references cited therein). One 2û11`~78 B 1~
such method is the study of interaction of detergents with acid phosphatase enzyme either from skin (Prottey et al, Int J Cos Sci 6 263-273 1984) or from Wheatgerm (Tanaka et al, Anal Biochem 66 489-498 1975).
In vivo mildness of formulations can be assessed using a flex wash test. In this test neat products were rubbed on the forearm of panellists and rinsed. The process was repeated four times a day for five days and the level of erythema developed was assessed by trained assessors.
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.
2011~78 I II _ Lialet 123-3S1 10 Lialet 123-4S _ 10 Dobanol 23-A - - 8 Lialet 123-S 5 5 Lialet C11 lOE0 15 15 22 Empigen BB 6 6 6 lo Empigen LME 4 4 4 Plunger Test (0.04~ AD) WGAP Inhibition 23 21 12 1 - Alkyl Ether Sulphate 2 - Primary Alkyl Sulphate 3 - Nonionic 4 - Betaine 5 - Ethanolamide The Examples show that formulations I and II give a greater foaming performance than A. Altnough ~ WGAP
inhibition of A is less than I and II, the effective mildness is no different, as explained above. Thus compositions of the present invention give a combination of mildness and performance.
-.' ~ 19 -`- B C3302 The Examples show that formulations I and II give a greater foaming performance than A. Although % WGAP
inhibition of A is less than I and II, the effective mildness is no different, as explained above. Thus compositions of the present invention give a combination of mildness and performance.
Claims (7)
1. A stable detergent composition in liquid or gel form containing from 10 to 80%wt of an active detergent mixture of (a) primary alkyl sulphate (PAS), (b) alkyl ether sulphate (AES), (c) water soluble nonionic detergent active material and (d) betaine and/or amine oxide, and also water, wherein:
(i) the AES has an average ethoxylation value of between 1 and 5, and weight ratio of PAS:AES is in the range 2:1-1:3; and, (ii) the molar ratio of PAS to said betaine and/or amine oxide is in the range 3:1-1:3; and, (iii) the nonionic detergent comprises more than 35 % , but less than 50 % by weight of the active detergent mixture.
(i) the AES has an average ethoxylation value of between 1 and 5, and weight ratio of PAS:AES is in the range 2:1-1:3; and, (ii) the molar ratio of PAS to said betaine and/or amine oxide is in the range 3:1-1:3; and, (iii) the nonionic detergent comprises more than 35 % , but less than 50 % by weight of the active detergent mixture.
2. A composition according to claim 1 wherein the weight ratio of PAS:AES is in the range 2:1 to 1:2.
3. A composition according to claim 1 wherein the total amount of amine oxide and betaine is not more than 20% by weight of the active detergent mixture.
4. A composition according to claim 1 wherein component (d) contains substantially no amine oxide.
5. A composition according to claim 1 wherein the AES is provided by a mixture of materials of the general formula:
R-(OCH2CH2)n-OSO3X
wherein R is a C10 to C18 alkyl group, X is a solubilising cation, and n, the average degree of ethoxylation, is from 2 to 5.
R-(OCH2CH2)n-OSO3X
wherein R is a C10 to C18 alkyl group, X is a solubilising cation, and n, the average degree of ethoxylation, is from 2 to 5.
6. A detergent composition according to claim 1 the AES is provided by a primary alkyl ether sulphate in which the alkyl groups R are such that less than 20% of material of alkyl chain length C14 and above is present, and the average degree of ethoxylation n is from 3 to 5.
7. A composition according to claim 1 wherein the nonionic (c) is a material of chain length less than C12.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8905551.1 | 1989-03-10 | ||
| GB898905551A GB8905551D0 (en) | 1989-03-10 | 1989-03-10 | Detergent compositions |
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|---|---|
| CA2011578A1 CA2011578A1 (en) | 1990-09-10 |
| CA2011578C true CA2011578C (en) | 1995-04-25 |
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ID=10653110
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|---|---|---|---|
| CA002011578A Expired - Fee Related CA2011578C (en) | 1989-03-10 | 1990-03-06 | Detergent compositions |
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| JP (1) | JPH0726115B2 (en) |
| KR (1) | KR950002351B1 (en) |
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| CA2004812A1 (en) * | 1988-12-12 | 1990-06-12 | Michael Massaro | Detergent composition comprising betaine and ether sulphate |
| AU661682B2 (en) * | 1991-04-15 | 1995-08-03 | Colgate-Palmolive Company, The | Light duty liquid detergent compositions |
| US5320783A (en) * | 1992-11-04 | 1994-06-14 | The Procter & Gamble Company | Detergent gels containing ethoxylated alkyl sulfate surfactants in hexagonal liquid crystal form |
| PE4995A1 (en) * | 1993-06-30 | 1995-03-01 | Procter & Gamble | DETERGENT GEL CONTAINING ETHOXYLATED ALKYL SULPHATES AND SECONDARY SULPHONATES |
| AU678007B2 (en) * | 1993-07-09 | 1997-05-15 | Colgate-Palmolive Company, The | High foaming nonionic surfactant based liquid detergent |
| NZ260848A (en) * | 1993-07-09 | 1996-08-27 | Colgate Palmolive Co | High foaming liquid detergent comprising as nonionic surfactant an alkyl or fatty acid sorbitan ether with an ethylene oxide condensate, or an alkylphenolether of an ethylene oxide/propylene oxide condensate, a betaine and an ethoxylated alkyl ether sulphate |
| ATE318304T1 (en) | 1993-10-08 | 2006-03-15 | Novozymes As | AMYLASE VARIANTS |
| KR100314403B1 (en) * | 1994-06-22 | 2002-04-06 | 손 경 식 | Liquid detergent composition |
| GB9509452D0 (en) * | 1995-05-10 | 1995-07-05 | Unilever Plc | Light duty cleaning composititon |
| WO1997038071A1 (en) * | 1996-04-08 | 1997-10-16 | Colgate-Palmolive Company | Light duty liquid cleaning compositions |
| JP3609903B2 (en) * | 1996-07-09 | 2005-01-12 | 石原薬品株式会社 | Aqueous gel-like vehicle cleaner |
| EP0855438B1 (en) * | 1997-01-23 | 2004-01-07 | The Procter & Gamble Company | Detergent compositions with improved physical stability at low temperature |
| VN21741A1 (en) * | 2006-12-20 | 2010-01-25 | Unilever Nv | Dishwashing composition |
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| US3928249A (en) * | 1972-02-07 | 1975-12-23 | Procter & Gamble | Liquid detergent composition |
| US3929678A (en) * | 1974-08-01 | 1975-12-30 | Procter & Gamble | Detergent composition having enhanced particulate soil removal performance |
| CA1170949A (en) * | 1980-02-05 | 1984-07-17 | John B. Welch | Liquid detergent composition |
| DE3011550A1 (en) * | 1980-03-26 | 1981-10-01 | Henkel KGaA, 4000 Düsseldorf | LIQUID CLEANING AGENTS |
| CA1160133A (en) * | 1980-04-24 | 1984-01-10 | Anthony F. Martin | Liquid detergent compositions |
| JPS6039719B2 (en) * | 1982-05-11 | 1985-09-07 | 花王株式会社 | liquid cleaning composition |
| JPS594694A (en) * | 1982-06-30 | 1984-01-11 | ライオン株式会社 | Liquid detergent composition |
| EP0107946B1 (en) * | 1982-10-28 | 1987-03-11 | THE PROCTER & GAMBLE COMPANY | Liquid detergent compositions |
| JPS60197614A (en) * | 1984-03-21 | 1985-10-07 | Shionogi & Co Ltd | Shampoo composition of low irritation |
| ES8708009A1 (en) * | 1984-11-07 | 1987-09-01 | Procter & Gamble | Liquid detergent compositions. |
| GB8428149D0 (en) * | 1984-11-07 | 1984-12-12 | Procter & Gamble Ltd | Liquid detergent compositions |
| GB8602589D0 (en) * | 1986-02-03 | 1986-03-12 | Unilever Plc | Detergent compositions |
| DE3713962A1 (en) * | 1987-04-25 | 1988-11-10 | Henkel Kgaa | LAUNDRY TREATMENT AGENTS FOR OIL AND FAT SOILS |
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1989
- 1989-03-10 GB GB898905551A patent/GB8905551D0/en active Pending
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1990
- 1990-03-06 CA CA002011578A patent/CA2011578C/en not_active Expired - Fee Related
- 1990-03-08 ES ES90302490T patent/ES2088964T3/en not_active Expired - Lifetime
- 1990-03-08 AU AU51150/90A patent/AU625979B2/en not_active Ceased
- 1990-03-08 EP EP90302490A patent/EP0387063B1/en not_active Expired - Lifetime
- 1990-03-08 DE DE69027055T patent/DE69027055T2/en not_active Expired - Fee Related
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- 1990-03-09 BR BR909001138A patent/BR9001138A/en not_active IP Right Cessation
- 1990-03-09 MY MYPI90000379A patent/MY106323A/en unknown
- 1990-03-09 JP JP2059762A patent/JPH0726115B2/en not_active Expired - Lifetime
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1991
- 1991-09-19 ID IDP33291A patent/ID963B/en unknown
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| IN170595B (en) | 1992-04-18 |
| AU625979B2 (en) | 1992-07-23 |
| AU5115090A (en) | 1990-09-13 |
| EP0387063A3 (en) | 1991-09-04 |
| JPH0333197A (en) | 1991-02-13 |
| JPH0726115B2 (en) | 1995-03-22 |
| DE69027055T2 (en) | 1996-12-12 |
| GB8905551D0 (en) | 1989-04-19 |
| KR950002351B1 (en) | 1995-03-16 |
| EP0387063A2 (en) | 1990-09-12 |
| ID963B (en) | 1996-09-27 |
| CA2011578A1 (en) | 1990-09-10 |
| ES2088964T3 (en) | 1996-10-01 |
| MY106323A (en) | 1995-05-30 |
| ZA901850B (en) | 1991-11-27 |
| EP0387063B1 (en) | 1996-05-22 |
| KR900014574A (en) | 1990-10-24 |
| BR9001138A (en) | 1991-03-05 |
| DE69027055D1 (en) | 1996-06-27 |
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