CA1303453C - Cleaning compositions - Google Patents

Cleaning compositions

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Publication number
CA1303453C
CA1303453C CA000479982A CA479982A CA1303453C CA 1303453 C CA1303453 C CA 1303453C CA 000479982 A CA000479982 A CA 000479982A CA 479982 A CA479982 A CA 479982A CA 1303453 C CA1303453 C CA 1303453C
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Prior art keywords
amphoteric
surfactant
composition according
composition
surfactants
Prior art date
Legal status (The legal status 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 status listed.)
Expired - Lifetime
Application number
CA000479982A
Other languages
French (fr)
Inventor
Eric Graham Fishlock-Lomax
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Nouryon Surface Chemistry AB
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Individual
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88Ampholytes; Electroneutral compounds
    • C11D1/94Mixtures with anionic, cationic or non-ionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88Ampholytes; Electroneutral compounds

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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

ABSTRACT

Cleaning Compositions Cleaning compositions (Particularly liquid water-based compositions such as liquid detergents and hard surface cleaners) are described which contain at least two principal amphoteric surfactants and at least one non-ionic surfactant. One of the two amphoteric surfactants is of the acylamino type and the other is of the alkylamino or alkoxypropylamino type.

Description

~3~

CLEANING COMPOSITIONS

This invention concerns compositions ~or cleaning a wide range of items including hard surfaces and soft goods such as textiles both for commercial and home use.
The invention is primarily concerned with liquid water-based cleaning compositions such as liquid detergents, carpet cleaners, dishwashing liquids and hard surface cleaners, but the same principles are equally applicable to solid compositions for example in powder form.
Prior to this invention various suggestions have been made for obtaining synergistic detergency between one amphoteric and one or more nonionic surfactants. To my surprise I have found con5iderable further benefits of synergistic detergency, low temperature cleaning, and improved compatibility characteristics by using more than one principal (cleaning) amphoteric surfactant with at least one non-ionic surfactant.
The invention thus provicles a cleaning composition (preferably in liquid water-based form) which comprises at least two amphoteric suractants and at least one non-ionic surfactant.
These compositions offer many advantages including particular:
GS a) Improved detergency at low concentrations and low cost ~) Very wide applicability to various cleaning uses c~ Outstanding detergency at low temperatures with consequent energy saving d) Ability to produce highly concentrated liquid detergent compositions even in the presence of alkaline builder - 13al3453 e) Wide compatibility of the detergent system with many types of additives normally used in detergent compositions to confer specific additional properties.
Depending on the intended use, the compositions may also contain additives conventionally included in cleaning formulations. For example other surfactant may be adde~ for specific properties, for examples to add bactericidal properties, to boost foam or to confer softening properties. A further feature of this invention is the ease of incorporation of such additional surfactants without problems such as surfactant compatibility and stability of the formulation. Other additives may include alkaline builders to improve detergency, chelating or sequestering agents to avoid problems with heavy metal ions, optical brightening agents, solvents, dyes and perfumes.
The amphoteric surfactants may be of the type having the general formula (I) R-(CO) -(OCH2CH2C~2)n~ (CHR )x)y ~ Q ~I) where R is a C8_20 hydrocarbyl group, optionally substituted, R is H or Cl 6 alkyl;
B ls H, C16 alkyl or C16 alkyl substituted by hydroxy or amino, or a group Q as defined below;
Q is an anionic moiety;
~ is 2 to 6;
y is 0 to 5;
z to 0 or 1; and n is 0 or 1 (z being 0 when n is 1).
The compositions generally contain one or more (first3 amphoteric surfactant(s) in which z is 0 and preferably one or more (second) amphoteric surfactant(s) in which z is 1.
~, ~L3~3~5~

~ n these compounds, R may for example be a straight or branched alkyl or alkenyl group;
a or cycloalkyl-alkyl (e.g. cyclohexyl-alkyl) group;
an aralkyl or arallsenyl group in which the alkyl or alkenyl portion contains at least 6 carbon atoms;
or the hydrocarbyl portion of a resinic acid containing at least two fused rings, e.g~ as in the tricyclic pine resin acids such as abietic acid.
R is preferably a C10 16 alkyl group, e.g.
a C12 group and an example of a branched chain group is C16H33CH(CH3) . The aliphatic portion of R may for example be the hydrocarbyl portion of lauric or coconut fatty acidt both of which contain high portion of C12 constituents. An example lS of an unsaturated R group is oleyl. R may for example be substituted by hydroxy, as in hydroxystearyl, or by -COOH (e.g. at the 2- positiQn).
In most surfactants of the ~ormula(1) type, n is 0.
Rl is usually a hydrogen atom, but may be an alkyl group such as methyl.
When B is an alkyl group, it may have 1 6, preferably 2 - 4, carbon atoms, and is preferably a straight chain group. Examples of such groups are me~hyl and ethyl. The alkyl group may be substituted, for example by hydroxy, as 2-hydroxyethyl, or by amino.
~ he group Q may or example be of the formula -R COOM where R is a Cl 6 alkyl~ne group (su¢h as methylene or ethylene) and M is hydrogen or an alkali metal, alkaline earth metal, ammonium or substituted ammonium ion te.g. mono-, di- or tri-hydroxyethylammonium)~ M is preferably sodium, and R is preferably methylene.
For the purposes of this invention, and because o the change of ionic properties with pH shown by amphoteric surfactants, the free -COOH group ~IL3~3 is considered equivalent to -COONa or -COOK and ammonium or amine or other carboxylic acid salts.
The composition of this invention preferably contains a first amphoteric surfactant of formula (1) where R is a C8_20 hydrocarbyl group derived from coco or tallow fatty acids;
Rl is H, B is H or Q as defined below Q is an anionic moiety, preferably CH2COONa or 10 --2CH2CEI2COONa, x is 2 to 4, y is 0 to 4, z is 0, and n is 0;
in combination with a second amphoteric surfactant of formula (I) where:
R is a C8 20 hydrocarbyl group derived from COCOf oleic or tall oil fatty acid, R1 is H, B is H, hydroxyethyl or a group Q as defined below, Q is an anionic moiety, preferably C~2COONa or CH2CH2COONa, x is 2, y is 1, z is 1, and n is 0.
Commercially available examples o~ the first amphoteric surfactant include Deriphat*151, Deriphat-154, and the full sodium salts of Deriphat 151C, Deriphat 161C, Amphoram*CPl, Diamphoram*CPl, Triamphoram*
CPl, and Polyamphoram*CPl and Ampholak QTE (Deriphats available from Henkel, Amphorams from Ceca and Ampholak QTE from Amphoterics International Ltd.).
Commercially available examples of the second amphoteric surfactant include products classed as cocoamphoglycinate or cocoamphopropionate (and similar products made from the other fatty acids listed), or cocamphocarboxyglycinate or cocoam~hocarboxy-* Trademark ~3`~3 propionate (and similar products made from theother fatty acids listed), for example Miranol CM, C~M or C2MSF.
In general the relative (weight) concentrations of the two amphoteric surfactants used is from 90:10 to 10:90, preferably 3:1 to 2:1 (first amphoteric:
second amphoteric).
The non-ionic surfactants used are preferably ethylene oxide or propylene oxide/ethylene oxide adducts of alkylphenols (e.g~ nonylphenol) or long chain alcohols or alkylamines (e.g. C12_14 alcohols or C12_18 alkylamines). ~he weight ratio of the principal amphoteric surfactants to the non-ionic surfactant(s) is generally from 10:1 to 1:2, preferably from 2.5:1 to 1.5:1 (e.g. about 2:1).
The non-ionic surfactant may for example be a nonylphenol-ethylene oxide adduct containing 6 -12 moles ethylene oxide, a C12 1~ alcohol-ethylene oxide adduct containing 7 - 10 moles ethylene oxide, a C12 18 alkylamine-ethylene oxide adduct containing 7 - 15 moles ethylene oxide or an e~uivalent ethylene oxide/propylene oxide block copolymer adduct.
When a second non-ionic sur~actant is included, it is may be o the same general type but is preferably more lipophilic than the main non~ionic surfactant.
The second material may for example be a nonylphenol-ethylene oxide adduct containing 4 - 6 moles ethylene oxide, a C12_1~ alcohol-ethylene oxide adduct containing 4 - 6 moles ethylene oxide, a C12_18 a1kY1amine ethylene oxide adduct containing 2 - 5 mole~ ethylene oxide or an equivalent ethylene oxide/propylene oxide block copolymer adduct. A second non-ionic surfactant of this kind i~ generally used at a lower concentration than the first, for example, the weight ratio of the first to second surfactants may generally be from 100:1 to 60:40 or 70:30 in compositions containing a builder.

* Trademark '~3~3 One of the advantages of the invention is that the choice of non-ionic surfactant is not as critical as in conventional detergent systems, for example as regards the balance of detergent properties and water solubility required particularly in built systems. The amphoteric surfactants also solubilise the non-ionic surfactants in formulations containing a builder.
The compositions may also contain, depending on the intended use, additives such as builders (e.g. sodium metasilicate (anhydrous or pentahydrate), tetrapotassium pyrophosphate, caustic soda or nitrilotri-acetic acid), chelating or seque~tering agents (e.g. trisodium nitrilotriacetic acid, tetrasodium ethylenediamine tetracetic acid and trisodium hydroxy-ethylethylenediamine triacetic acid), solvents (e.g. glycolethers such as butyl glycol ether, butyl cellosolve), fabric conditioners (e.g. quaternary ammonium salts, such as a di-fatty (usually tallow) dimethylammonium chloride (e.g. Arquad 2 ~T) or a di-fatty (usually tallow) imidazoline methosulphate or ethosulphate ~uaternary salt (e.g. Ammonyx 4080 (Millmaster-Onyx), Imisoft*75 (M & S Chemicals) ~ Ampholak TQ (Amphoterics International)), foam boosters (such as alkyl betaines or amine oxides, e.g. Emigen BB & BT, Aromox DMDC (Akzo~ and Empigen*
OB (Albright & Wilson), Ammonyx LO and CDO (Millmaster-Onyx~, bactericides (e.g. a bactericidal surfactant such as a benzalkonium chloride (e.g. Imiquat BKC) or BTC 2125), optical brighteners (e.g. Tinopal*
CBS-X & Tinopal 5BMS-X ICiba)), dyes and perfumes.
The quantity of such additives used will vary according to the application and the nature of the particular additive. In general however liquid systems may contain 1-40% of a builder, 1-20% chelating agent, 1-10% solvent, 1-5~ fabric conditioner, 1-5% foam booster, 1-5% bactericide, 0.1-1% optical brightener and 0.1-1~ dyes and /or * Trademark ~L3~i3 perumes (percentages herein are by weight unless otherwise stated).
Liquid compositions which do not contain a builder may for example contain up to 50 % of the principal amphoteric surfactants and up to 25 % non-ionic surfactants, e.g. up to 40% first amphoteric surfactant, up to 10% second amphoteric surfactant, up to 20~ first non-ionic surfactant and up to 5% second non-ionic surfactant.
(Percentages given herein for the amphoteric and non-ionic surfactants are on the basis of 30%
active for the amphoterics and 100% active for the non-ionics; lactive' refers to concentration relative to the undiluted material).
Liquids detergents of the invention may for example have the following compositions:

General Preferred First amphoteric 10-25% 18-22 Second amphoteric 2-6% 3-5%
Non-ionic surfactant(s)3-15% 8-~%
.i Builder 1-40% 10-20~
Chelating agen~ 1-20~ 5-10%
Fabric conditioner 1-5% 2-4%
Optical brightener 0.1-1% 0.2-0.6%
Dye, perfume 0.1~-1% 0.2-0.6%
Water to ~00%
It will be appreciated that the overall compositions can be varied widely within the above ranges.
The preferred concentration ranges reer to compositions of conventional dilution, but one of the advantages of the invention is that it offers the possibility of very highly concentrated solutions. Such compositions may for example contain up to 35~ ~e.g. 20-35~) of the builder te.g. sodium metasilicate), up to 90% (e.g. 10-50%) of the two principal amphoteric ~3~3~3 surfactants (e.g. 9-40% of the first type and 1-15% of the second type) and up to 15~ (e.g. 3-15%) of non-ionic surfactant(s). Examples of such compositions are BuilderFirst Second Non-ionic Water Amphoteric Amphoteric 30% 9~ 1% 3% 57~
25% 17% 5% 8% 46%
22~ 23% ~ 11% 40%
Hard surface cleaners of the invention may for example have the following composition:

General Preferred Amphoteric - 1 2~8~ 3-5%
Amphoteric - 2 1-4% 1.5-2.5$
Non-ionic surfactant(s) 1-6% 2-4~
20 Solvent 1-5% 2-4%
Builder 0-15% 8-12 Foam booster 1-5% 2-4~
Bactericide 1-5~ 2-4%
Water to 100%
The following examples illustrate the invention.
Example 1 A hard surface cleaner was made using 4%
of the first type of amphoteric (Ampola~ YCE), 2% of the second type of amphoteric (e.g. cocoampho-glycinate) together with 2% nonyl phenol 9 mole ethoxylate and 1% nonyl phenol 5.5 mole ethoxylate.
This basic surfactant composition together with builders such as sodium metasilicate pentahydrate or tetra potassium pyrophosphate (10%) gave excellent cleaning results. Furthermore it was found possible to incorporate a bactericide of the 'benzalkonium chloride' type (3~) as well as a solvent such as * Trademark i';.~, .

~303~53 g butyl glycol ether (3%). Higher concentrations of the same type of formulation were easily possible without loss of stability. The results obtained were such as to give considerably better performance that conventional hard surface cleaners.
3-5% of amine oxide and about 2% NaCl was also found useful to increase the viscosity of this formulation, as well as increasing flash foam.
Furthermore, such products are normally based on anionic and nonionic surfactants where inclusion of a cationic bactericide gives problems of compatibility.
Also, the amount of alkaline electrolyte which can be included in conventional products is limited by the level of surfactant (and vice versa). In such cases the addition of hydrotrope such as sodium xylene sulphonate is necesary in substantial amounts to confer stability.
Example 2 A liquid laundry detergent was prepared using, as base surfactant compositionr 16% of the first type of amphoteric and 4~ of the second type of amphoteric (as in ~xample 1) together with 8% nonyl phenol 9 mole ethoxylate and 2% nonyl phenol 5.5 mole ethoxylate. This was formulated with 15%
sodium metasilicate pentahydrate, 2~ chelating agent (sodium nitrilotriacetic acid), and optional brighteners (0.4%), dye and perfume.
Washing at 30C, or even 20C, gave superior results as compared to both to a conventional type of liquid laundry detergent based on anionic and nonionic surfactants and also conventional powder detergents, both as regards detergency and whit~ning.
Furthermore, because of the compatibility of the surfactant system described in this invention, it was found possible to include easily a cationic bactericide of the type mentioned above and also a cationic fabric conditioning product (3~ Ampholak TQ, described as a di-fatty imidazoline ~uaternary).

Since the amphoteric surfactants used were calculated to be 30~ active, the net active content of the surfactant base described was only about one quarter of the active content of the comparative conventional laundr~ detergent and functioned better when used at only half the dosage level of the latter under the same conditions.
It was also found possible to prepare the compositions of Example 2 in more concentrated form, containing for example up to and over twice the stated concentrations of the various ingredients.
Furthermore, it is well known that conventional liquid laundry detergents of about 40~ active surfactant content and above require the addition of solubiliser or hydrotrope to confer stability and the addition of alkaline builder to such a system is virtually impossible without total loss of stability. The type o~ formulation described in this invention, however, provided a considerably better performing detergent composition into which alkaline builder was easily included.
By use of combinations of two types of amphoteric surfactant together with one or more nonionic surfactants it was found possible to obtain excellent detergency even at low temperature coupled with ease of incorporation into alkaline 'built' products and with greater flexibility regarding the possible incorporation of useful cationic additives. Not only does this offer better performance at lower cost but further savings are possible by omission of otherwise non-functional ingredients such as solubilisers and hydrotropes. Such is the ease of formulation with this system that it is possible to produce highly concentrated products or combinations of products, thus reducing the weight and volume of product for a given purpose, reducing the amount of water needed in such products and thus offering cheaper packaging costs, and offering energy saving by possible use at lower temperatures.

Claims (9)

1. A cleaning composition which comprises at least two amphoteric surfactants and at least one non-ionic surfactant, the amphoteric surfactants being of the type having the general formula (I) (I) where R is a C8-20 hydrocarbyl group, optionally substituted by hydroxy or carboxyl;
R1 is H or C1-6 alkyl;
B is H, C1-6 alkyl, C1-6 alkyl substituted by hydroxy or amino, or a group Q as defined below;
Q is -R2 COOM where R2 is a C1-6 alkylene group and M
is -H or an alkali metal, alkaline earth metal or ammonium ion or an ammonium ion substituted by up to three hydroxyethyl substituents x is 2 to 6;
y is 0 to 5;
z is 0 or 1; and n is 0 or 1 (z being Q when n is 1);
the composition containing at least a first amphoteric surfac-tant as defined above in which z is 0 and a second amphoteric surfactant in which z is 1.
2. A composition according to claim 1 which contains a first amphoteric surfactant of formula (1) where R is a C8-20 hydrocarbyl group derived from coco or tallow fatty acids;
R1 is H, B is H or Q as defined below Q is -CH2COONa or -CH2CH2COONa, x is 2 to 4, y is 0 to 4, z is 0, and n is 0;
in combination with a second amphoteric surfactant of formula (I) where:

R is a C8-20 hydrocarbyl group derived from coco, oleic or tall oil fatty acid, Rl is H, B is H, hydroxyethyl or a group Q as defined below, Q is -CH2COONa or CH2CH2COONa, x is 2, y is 1, z is 1, and n is 0.
3. A composition according to claim 1 which contains two non-ionie surfactants, the second of which is more lipophilic than the first and is present at a lower concentration than the first.
4. A composition according to claim 1 in which the weight ratio of the first amphoteric surfactant to the second amphoteric surfactant is from 3:1 to 2:1 and the weight ratio of the first and seeond amphoteric surfactants to the non-ionie surfactant(s) is from 2.5:1 to 1.5:1.
5. A composition according to claim 1 which eontains one or more builders, chelating or sequestering agents, solvents, fabric conditioners, foam boosters, baeterieides, optical brightners, dyes or perfumes as additives.
6. A composition according to claim 1 in the form of a liquid water-based composition.
7. A composition according to claim 1 in the form of a liquid detergent having the composition A or B below, by weight:
A B
First amphoteric 10-25% 18-22%
Second amphoteric 2-6% 3-5%
Non-ionic surfactant(s) 3-15% 8-12%
Builder 1-40% 10 20%
Chelating agent 1-20% 5-10%
Fabric conditioner 1-5% 2-4%
Optical brightener 0.1-1% 0.2-0.6%
Dye, perfume 0.1%-1% 0.2-0.6 Water to 100%
8. A composition according to claim 1 in the form of a highly concentrated liquid detergent containing 10-50% of the first and second amphoteric surfactants, 3-15% of the non-ionic surfactant(s) and 20-35% of the builder, by weight.
9. A composition according to claim 1 in the form of a hard surface cleaner having the composition A or B below, by weight A B

First amphoteric 2-8% 3-5%
Second amphoteric 1-4% 1.5-2.5%
Non-ionic surfactant(s) 1-6% 2-4%
Solvent 1-5% 2-4%
Builder 0-15% 8-12%
Foam booster 1-5% 2-4%
Bactericide 1-5% 2-4%
Water to 100%
CA000479982A 1984-04-25 1985-04-24 Cleaning compositions Expired - Lifetime CA1303453C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB848410501A GB8410501D0 (en) 1984-04-25 1984-04-25 Cleaning compositions
GB8410501 1984-04-25

Publications (1)

Publication Number Publication Date
CA1303453C true CA1303453C (en) 1992-06-16

Family

ID=10560027

Family Applications (1)

Application Number Title Priority Date Filing Date
CA000479982A Expired - Lifetime CA1303453C (en) 1984-04-25 1985-04-24 Cleaning compositions

Country Status (7)

Country Link
EP (1) EP0162600B1 (en)
AT (1) ATE37040T1 (en)
AU (1) AU573335B2 (en)
CA (1) CA1303453C (en)
DE (1) DE3564820D1 (en)
GB (1) GB8410501D0 (en)
ZA (1) ZA853104B (en)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8410503D0 (en) * 1984-04-25 1984-05-31 Fishlock Lomax E G Shampoo compositions
GB8522413D0 (en) * 1985-09-10 1985-10-16 Amphoterics International Ltd Surfactants
SE463211B (en) * 1987-10-26 1990-10-22 Berol Nobel Ab DETAILS COMPOSITION CONTAINING A COMBINATION OF AMPOTAIR LINING AND ZEOLITE
SE8802506L (en) * 1988-07-05 1990-01-06 Berol Nobel Nacka Ab NEW SOCIETIES OF THEIR PREPARATION AND APPLICATION
US5156761A (en) * 1988-07-20 1992-10-20 Dorrit Aaslyng Method of stabilizing an enzymatic liquid detergent composition
US5500151A (en) * 1988-10-07 1996-03-19 Colgate-Palmolive Co. Heavy duty fabric softening laundry detergent composition
DE68928569D1 (en) * 1989-11-06 1998-03-05 Colgate Palmolive Co Softening heavy-duty detergent composition for laundry
SE8904177D0 (en) * 1989-12-11 1989-12-11 Berol Nobel Nacka Ab TVAETTMEDELSKOMPOSITION
SE469428B (en) * 1991-11-21 1993-07-05 Berol Nobel Ab LIQUID DISCHARGE COMPOSITION CONTAINING ANIONIC TENSID AND A COMBINATION OF THREE TYPES OF AMPOTATED SOCIETIES
US5269974A (en) * 1992-09-01 1993-12-14 The Procter & Gamble Company Liquid or gel dishwashing detergent composition containing alkyl amphocarboxylic acid and magnesium or calcium ions
EP0689582B1 (en) * 1993-03-19 1998-08-26 The Procter & Gamble Company Acidic liquid detergent compositions for bathrooms
US5384063A (en) * 1993-03-19 1995-01-24 The Procter & Gamble Company Acidic liquid detergent compositions for bathrooms
US5399280A (en) * 1993-07-22 1995-03-21 The Procter & Gamble Company Acidic liquid detergent compositions for bathrooms
EP0728177B1 (en) * 1993-11-12 2000-03-01 The Procter & Gamble Company Liquid hard surface detergent compositions containing amphoteric detergent surfactant and perfume
US5801139A (en) * 1997-06-05 1998-09-01 Lever Brothers Company, Division Of Conopco, Inc. Process for making bar compositions comprising novel chelating surfactants
US5869441A (en) * 1997-06-05 1999-02-09 Lever Brothers Company, Division Of Conopco, Inc. Bar compositions comprising novel chelating surfactants
DE10343730A1 (en) * 2003-09-22 2005-04-21 Clariant Gmbh Highly concentrated aqueous solution of amphoteric surfactants

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8410503D0 (en) * 1984-04-25 1984-05-31 Fishlock Lomax E G Shampoo compositions

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Publication number Publication date
EP0162600A1 (en) 1985-11-27
ZA853104B (en) 1985-12-24
AU573335B2 (en) 1988-06-02
ATE37040T1 (en) 1988-09-15
DE3564820D1 (en) 1988-10-13
GB8410501D0 (en) 1984-05-31
EP0162600B1 (en) 1988-09-07
AU4168985A (en) 1985-10-31

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