CA2035984A1 - Topical composition - Google Patents
Topical compositionInfo
- Publication number
- CA2035984A1 CA2035984A1 CA002035984A CA2035984A CA2035984A1 CA 2035984 A1 CA2035984 A1 CA 2035984A1 CA 002035984 A CA002035984 A CA 002035984A CA 2035984 A CA2035984 A CA 2035984A CA 2035984 A1 CA2035984 A1 CA 2035984A1
- Authority
- CA
- Canada
- Prior art keywords
- phosphate
- mono
- composition according
- surfactant
- ether
- 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.)
- Abandoned
Links
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
- A61K8/442—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof substituted by amido group(s)
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/55—Phosphorus compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/10—Washing or bathing preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/02—Preparations for cleaning the hair
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
- Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
Abstract
Abstract A composition suitable for topical application to the skin or hair, comprises:
a. a monoalkyl or monoalkyl phosphate surfactant, b. a dialkyl or dialkenyl phosphate surfactant; and c. a co-surfactant chosen from alkylamidopropyl betaines and alkylamphoglycinates.
a. a monoalkyl or monoalkyl phosphate surfactant, b. a dialkyl or dialkenyl phosphate surfactant; and c. a co-surfactant chosen from alkylamidopropyl betaines and alkylamphoglycinates.
Description
2~33~
TOPICAL COMPOSITION
FIELD OF THE INVENTION
The invention relates to compositions suitable for topical application to the skin (including the mucosae), and to the hair. In particular, the invention is concerned with highly improved detergent compositions suitable for cleansing the whole body surface, including the mouth.
BACKGROUND TO THE INVENTION ~ PRIOR ART
The`damaging effect of conventional detergents used to wash the body surface, particularly where young,.
tender or damaged skin is involved, has been the subject of intense study for many years in a search for milder-to-the-skin products, which not only cleanse the skin efficiently, but also leave the skin with a pleasant smooth silky feel after the skin surface has been dried off.
The use of certain mono- and di-alkyl phosphate salts for this purpose has been advocated in view of 3s their mild characteristics, but some of this group of salts are used as antifoam agents because of their lather suppressant properties, and would therefore require careful formulation if lather control is not required.
To this end, US patent No. 4,139,485 (Kao Soap Co.
Ltd.) describes a detergent composition having low irritation properties on human skin, wherein the surfactant component is dialkyl or dialkenyl phosphate salt (DAP) and/or monoalkyl or monoalkenyl phosphate salt (MAP), each alkyl or alkenyl group having from 10 to 16 carbon atoms), the weight ratio of 'DAP' to 'MAP' being from 20:80 to 0:100. This system is stated to possess good detergency.
Also, US patent No. 4,526,710 tKao Corporation), report a study to improve properties of detergent composition which make use of anionic phosphate surface active agents, which Kao maintain are highly innoxious and particularly mild to the skin. As a result, Kao have found that when phosphate ester salts having a specific ion pair, notably mono- or di-alkyl (C8-18) phosphates, are used in combination with alkanol amine salts of ( higher fatty acids and alkyl amine oxides, the detergency and foaming characteristics are remarkably improved.
2s Also, US patent No. 4,758,376 (Kao) discloses an alternative composition, comprising an alkanolamine salt of a mono or dialkyl (C8-18) phosphate or mixtures thereof, to that described in US patent No. i,526,710 in which the problem of poor foaming due to the dialkyl phosphate salt is dealt with by incorporating with the phosphate a compound chosen from an amidoamine amphoteric surfactant or hydroxysulphobetaine, or an aliphatic lactylate or glycolate.
3s ~3~9~
TOPICAL COMPOSITION
FIELD OF THE INVENTION
The invention relates to compositions suitable for topical application to the skin (including the mucosae), and to the hair. In particular, the invention is concerned with highly improved detergent compositions suitable for cleansing the whole body surface, including the mouth.
BACKGROUND TO THE INVENTION ~ PRIOR ART
The`damaging effect of conventional detergents used to wash the body surface, particularly where young,.
tender or damaged skin is involved, has been the subject of intense study for many years in a search for milder-to-the-skin products, which not only cleanse the skin efficiently, but also leave the skin with a pleasant smooth silky feel after the skin surface has been dried off.
The use of certain mono- and di-alkyl phosphate salts for this purpose has been advocated in view of 3s their mild characteristics, but some of this group of salts are used as antifoam agents because of their lather suppressant properties, and would therefore require careful formulation if lather control is not required.
To this end, US patent No. 4,139,485 (Kao Soap Co.
Ltd.) describes a detergent composition having low irritation properties on human skin, wherein the surfactant component is dialkyl or dialkenyl phosphate salt (DAP) and/or monoalkyl or monoalkenyl phosphate salt (MAP), each alkyl or alkenyl group having from 10 to 16 carbon atoms), the weight ratio of 'DAP' to 'MAP' being from 20:80 to 0:100. This system is stated to possess good detergency.
Also, US patent No. 4,526,710 tKao Corporation), report a study to improve properties of detergent composition which make use of anionic phosphate surface active agents, which Kao maintain are highly innoxious and particularly mild to the skin. As a result, Kao have found that when phosphate ester salts having a specific ion pair, notably mono- or di-alkyl (C8-18) phosphates, are used in combination with alkanol amine salts of ( higher fatty acids and alkyl amine oxides, the detergency and foaming characteristics are remarkably improved.
2s Also, US patent No. 4,758,376 (Kao) discloses an alternative composition, comprising an alkanolamine salt of a mono or dialkyl (C8-18) phosphate or mixtures thereof, to that described in US patent No. i,526,710 in which the problem of poor foaming due to the dialkyl phosphate salt is dealt with by incorporating with the phosphate a compound chosen from an amidoamine amphoteric surfactant or hydroxysulphobetaine, or an aliphatic lactylate or glycolate.
3s ~3~9~
While investigating Kao's teaching further, particularly their stipulation in US patent No. 4,139,485 that the weight ratio of mono- to di-alkyl phosphate salt cannot fall below 80:20, without loss of foaming power, Applicants have now discovered that a greater proportion S by weight of the dialkyl phosphate salt of Kao can be tolerated without significant loss of lather volume, provided there is also present a special co-surfactant.
The compositions so obtained are accordingly capable of producing a superior lather volume and an outstanding lo lather creaminess. Also, the composition is so mild to the skin that it can safely be used for cleansing the mucosae, such as the mouth and the vagina, and other more delicate skin areas. It can also be used in shampoos for frequent, e.g. daily, hair washing, without risk of scalp irritation or damage attributable to harsher products.
In addition to these excellent attributes, the ease of rinsing from hair or skin and superior silky-smooth after-use skin feel properties of the compositions, including freedom from skin roughness and erythema, have great consumer appeal.
( DErINITION OF THE INVENTION
Accordingly, the invention provides a composition suitable for topical application to the skin or hair, which comprises:
(a) from 1 to 99~ by weight of monoalkyl or monoalkenyl phosphate surfactant having the structure (1):
2 ~ 3 ~ 9 ~ ~
The compositions so obtained are accordingly capable of producing a superior lather volume and an outstanding lo lather creaminess. Also, the composition is so mild to the skin that it can safely be used for cleansing the mucosae, such as the mouth and the vagina, and other more delicate skin areas. It can also be used in shampoos for frequent, e.g. daily, hair washing, without risk of scalp irritation or damage attributable to harsher products.
In addition to these excellent attributes, the ease of rinsing from hair or skin and superior silky-smooth after-use skin feel properties of the compositions, including freedom from skin roughness and erythema, have great consumer appeal.
( DErINITION OF THE INVENTION
Accordingly, the invention provides a composition suitable for topical application to the skin or hair, which comprises:
(a) from 1 to 99~ by weight of monoalkyl or monoalkenyl phosphate surfactant having the structure (1):
2 ~ 3 ~ 9 ~ ~
R -(CH2cH2)c P \ (1) OZ
S (b) from 1 to 50~tbY weight of dialkyl or dialkenyI phosphate surfactant having the structure (2):
RO2-(OCH2CH2)a \ ¦¦ (2) P OX
R3-(CH2CH2)b /
lS where Rl is chosen from branched or unbranched alkyl and alkenyl groups having an average of from lO to 18 carbon atoms;
where RO2 and RO3 are each chosen from branched or unbranched alkyl and alkenyl groups having an average of from lO to 18 carbon atoms;
X, Y and Z are.each chosen from H,-alkali 2s metal, ammonium and substituted a~monium counterions;
a and b are each chosen from 0 or a value of from 1 to lO, notably 1 to 4, especially l or 2; and c is chosen from 0 or a value of from l to 4, especially 1 or 2; and (c) from l to 50% by weight of a co-surfacta~t chosen from:
2~3~
S (b) from 1 to 50~tbY weight of dialkyl or dialkenyI phosphate surfactant having the structure (2):
RO2-(OCH2CH2)a \ ¦¦ (2) P OX
R3-(CH2CH2)b /
lS where Rl is chosen from branched or unbranched alkyl and alkenyl groups having an average of from lO to 18 carbon atoms;
where RO2 and RO3 are each chosen from branched or unbranched alkyl and alkenyl groups having an average of from lO to 18 carbon atoms;
X, Y and Z are.each chosen from H,-alkali 2s metal, ammonium and substituted a~monium counterions;
a and b are each chosen from 0 or a value of from 1 to lO, notably 1 to 4, especially l or 2; and c is chosen from 0 or a value of from l to 4, especially 1 or 2; and (c) from l to 50% by weight of a co-surfacta~t chosen from:
2~3~
i. alkylamidopropyl betaines, having the structure (11) R04 C N (CH2)3 - I - CH2C
and ii. alkylamphoglycinates, having the structure (12):
15R04 C- -N _ (CH2)2 N , (CH2)2oH (12) R -20where R 4 is C10_16 alkyl R05 and R06 are the same or different and are chosenfrom CH2COO and (CH.232coo .
DISCLOSURE OF THE INVENTION
2s The Monoalkyl or Monoalkenyl Phosphate Surfactant The composition according to the invention comprises monoalkyl or monoalkenyl phosphate surfactant having the structure (1):
~o 3s O OY
(OCH2cN2)Co p~ (1) S OZ
where R01 is chosen from branched or unbranched alkyl and alkenyl groups having from 10 to 18 carbon atoms;
lo Y and Z are each chosen from H, alkali metal, ammonium and substituted ammonium counterions; and c is chosen from 0 or a value of from 1 to 4.
Examples of the monoalkyl and monoalkenyl phosphate moiety include:
mono-n-decyl phosphate mono-n-dodecyl phosphate=(mono-lauryl phosphate) mono-n-tetradecyl phosphate=(monomyristyl phosphate) .mono-n-hexadecyl phosphate.
mono-n-octadecyl phosphate mono-(diethyleneglycol-mono-n-dodecyl ether) - phosphate mono-(ethyieneglycol-mono-n-decyl ether) phosphate mono-n-tetradecenyl phosphate mono-n-hexadecenyl phosphate mono-n-octadecenyl phosphate mono-n-decenyl phosphate mono-n-dodecenyl phosphate mono-(triethyleneglycol-mono-n-dodecenyl ether) 3 S ~
and ii. alkylamphoglycinates, having the structure (12):
15R04 C- -N _ (CH2)2 N , (CH2)2oH (12) R -20where R 4 is C10_16 alkyl R05 and R06 are the same or different and are chosenfrom CH2COO and (CH.232coo .
DISCLOSURE OF THE INVENTION
2s The Monoalkyl or Monoalkenyl Phosphate Surfactant The composition according to the invention comprises monoalkyl or monoalkenyl phosphate surfactant having the structure (1):
~o 3s O OY
(OCH2cN2)Co p~ (1) S OZ
where R01 is chosen from branched or unbranched alkyl and alkenyl groups having from 10 to 18 carbon atoms;
lo Y and Z are each chosen from H, alkali metal, ammonium and substituted ammonium counterions; and c is chosen from 0 or a value of from 1 to 4.
Examples of the monoalkyl and monoalkenyl phosphate moiety include:
mono-n-decyl phosphate mono-n-dodecyl phosphate=(mono-lauryl phosphate) mono-n-tetradecyl phosphate=(monomyristyl phosphate) .mono-n-hexadecyl phosphate.
mono-n-octadecyl phosphate mono-(diethyleneglycol-mono-n-dodecyl ether) - phosphate mono-(ethyieneglycol-mono-n-decyl ether) phosphate mono-n-tetradecenyl phosphate mono-n-hexadecenyl phosphate mono-n-octadecenyl phosphate mono-n-decenyl phosphate mono-n-dodecenyl phosphate mono-(triethyleneglycol-mono-n-dodecenyl ether) 3 S ~
phosphate mono-(ethyleneglycol-mono-n-tetradecenyl ether) phosphate mono-7-methyldecyl phosphate mono-5-methyldodecenyl phosphate . .
mono-6,6-dimethyltetradecyl phosphate mono-(ethyleneglycol-mono-n-octadecyl ether) phosphate mono-(diethyleneglycol-mono-n-octadecenyl ether) phosphate mono-(polyethyleneglycol~5EO]-monooleyl ether) phosphate mono-(polyethyleneglycol[3EO]-monolauryl ether) phosphate The monoalkyl phosphate surfactant is preferably a monolauryl phosphate salt.
The amount of the monoalkyl or monoalkenyl phosphate surfactant which is present in the composition according 2n to the invention is from l to 99%, preferably from 2 to 50% by weight of the composition, yet more preferably from 10% to 40% by weight of the composition.
The DialkYl or Dialkenyl Phosphate Surfactant The composition according to the invention also comprises dialkyl or dialkenyl phosphate surfactant having the structure (2):
O
RO2-(OCH2CH2)a O \ ¦¦
P OX (2) R -(CH2CH2)b ~ ~`.J~
mono-6,6-dimethyltetradecyl phosphate mono-(ethyleneglycol-mono-n-octadecyl ether) phosphate mono-(diethyleneglycol-mono-n-octadecenyl ether) phosphate mono-(polyethyleneglycol~5EO]-monooleyl ether) phosphate mono-(polyethyleneglycol[3EO]-monolauryl ether) phosphate The monoalkyl phosphate surfactant is preferably a monolauryl phosphate salt.
The amount of the monoalkyl or monoalkenyl phosphate surfactant which is present in the composition according 2n to the invention is from l to 99%, preferably from 2 to 50% by weight of the composition, yet more preferably from 10% to 40% by weight of the composition.
The DialkYl or Dialkenyl Phosphate Surfactant The composition according to the invention also comprises dialkyl or dialkenyl phosphate surfactant having the structure (2):
O
RO2-(OCH2CH2)a O \ ¦¦
P OX (2) R -(CH2CH2)b ~ ~`.J~
where R02 and R03 are each chosen from branched or unbranched alkyl and alkenyl groups having an average of from 10 to 18 carbon atoms;
S X is chosen from H, alkali metal, ,i ammonium and substituted ammonium counterions; and , a and b are each chosen from 0 or a lo value of from 1 to 10.
, Examples of the dialkyl and dialkenyl phosphate moiety include:
di-n-decyl phosphate di-n-dodecyl phosphate (dilauryl phosphate) di-n-tetradecyl phosphate .(dimyristyl phosphate) di-n-hexadecyl phosphate - di-n-octadecyl phosphate di-n-dodecenyl phosphate di-(7-methyldecyl) phosphate di-(ethyleneglycol-mono-n-octadecyl ether) .phosphate 2s di-(diethyleneglycol-mono-n-octadecenyl ether) . phosphate di-(polyethyleneglycol~SE0~-monooleyl ether) phosphate di-~polyethyleneglycol r 3E0~-monolauryl ether) phosphate The preferred dialkyl phosphate salt, is triethanolammonium dilauryl phosphate.
The amount of the dialkyl or dialkenyl phosphate salt which is present in the composition according to the - g -- J3130 invention is from 1 to 50%, preferably from 1 to 20% or even lO~ by weight, of the composition.
The weight ratio of the monoalkyl or monoalkenyl phosphate salt to the dialkyl or dialkenyl phosphate S surfactant is from 95:5 to 25:75, preferably 85:15 or 7~:25 to 50:50. Thetotal weigh~ ofthetwosurfa~ctants may be 2- ~Q 50%
of the composition.
The Co-surfactant The composition according to the invention also comprises a co-surfactant chosen from:
i. alkvlamidopro~Yl betaines, having the structure (11~:
R04 C _ N --(CH2)3 N~ _ CH2C00 (11) - and zs - . .
ii. alkylamphoglycinates, and having the structure (12):
R04 C- N - -(CH2)2 _ N - (C~2)2H
where R04 is C10 16 alkyl R05 and R06 are the same or different and are chosen from CH2Coo and (CH2)2C00 .
~ 6~ Y_~ 3 ~
An example of the alkamidopropyl betaine having the structure (11) is:
cocoamidopropyl betaine (e.g. TEGOBETAIN L7, ex Goldschmidt).
s Examples of the alkylamphoglycinate having the structure - (12) are:
cocoamphodiacetate (e.g. MIRANOL C2M-NP, ex Miranol InC . ~
cocoamphodipropionate (e.g. MIRANOL C2M-SF, ex Miranol Inc.) The amount of co-surfactant which is present in the composition according to the invention is from l to 50~, preferably from 2% or even 5% to 40~ by weight of the composition.
Water - The composition according to the invention also comprises an amount of water to act as a vehicle for the mono- and di-alkyl or -alkenyl phosphate surfactants and to enable them to be provided at a concentration suitable for convenient topical application to human skin.
The amount of water present in the composition of the invention is accordingly up to 99~, preferably from 5 to ~9% by weight of the composition.
~o Supplementarv Surfactant The composition according to the invention can also optionally comprise a supplementary surfactant, further 3s ~ L3 to modify the surfactant properties attributable to the mono- and di-alkyl or -alkenyl phosphate salts.
Examples of supplementary surfactants include anionic surfactants other than the phosphate salts defined herein, as well as nonionic, amphoteric and zwitterionic surfactants.
.
Anionic supplementary surfactants ( lo Particularly preferred supplementary surfactants, when employed, are anionic surfactants, examples of which are set out hereinafter.
i. Fatty acid soap supplementary surfactant The composition according to the invention can optionally comprise, as a supplementary surfactant one or more soaps which are water-soluble or water-dispersable alkali metal salts of an organic acid, especially a sodium or a potassium salt, or the corresponding ammonium or substituted ammonium salt. Examples of suitable organic acids are natural or synthetic alkanoic acids having from 10 to 22 carbon atoms, especially the fatty - acids of triglyceride oils such as tallow and coconut oil.
For solid products, such as powders, bars or tablets, the preferred soap is a soap of tallow fatty acids, that is fatty acids derived from tallow class fats, for example beef tallow, mutton tallow, lard, palm oil and some vegetable butters. Minor amounts of up to about 30%, preferably 10 to 20%, by weight of sodium soaps of nut oil fatty acids derived from nut oils, for example coconut oil and palm kernel oil, may be admixed with the sodium tallow soaps, to improve their lathering 2~3~
and solubility characteristics if desired. Whereas tallow fatty acids are predominantely C14 and C18 fatty acids, the nut oil fatty acids are of shorter chain length and are predominantly C10-Cl4 fatty acids.
For liquid or gel products, the preferred soaps are predominantely Cl0_l4 fatty acids derived from nut oils, or alternatively, from synthetic alkanoic acids.
The soaps can be provided as a preformed ingredient for the composition, or they can be formed in situ during the manufacture of the composition by reaction of suitable fatty acids and an alkali.
The amount of fatty acid soap which can be present 1 in the composition according to the invention is up to 90%, preferably from 2 to 80~ by weight of the composition, yet more preferably-from 2 to 20% by weight.
ii. Non-soa~ anionic su~plementary surfactants The composition according to the invention can also optionally comprise one or more non-soap anionic supplementary surfactants, examples of which include:
The alkali metal salts of organic sulphuric reaction products having an alkyl or acyl radical containing from 8-22 carbon atoms and a sulphonic acid or sulphuric acid ester group. Specific examples of these synthetic anionic surfactants are the sodium, ammonium, potassium or triethanolammonium alkyl sulphates, especially those obtained by sulphating the higher alcohols (C8-C18), sodium coconut oil fatty acid monoglyceride sulphates and sulphonates; sodium or potassium salts of sulphuric esters of the reaction product of one mole of a higher fatty alcohol ~e.g. tallow or coconut oil alcohols) and 2 ~ 3 J ~
1-12 moles of ethyleneoxide; sodium or potassium salts of alkyl phenol ethylene oxide ether sulphate with 1-10 units of ethylene oxide per molecule and in which the alkyl group contains from 8 to 12 carbon atoms, sodium alkyl glyceryl ether sulphonates, the reaction product of fatty acids having from 10 to 22 carbon atoms esterified with isethionic acid and neutralised with sodium hydroxide; water soluble salts of condensation products of fatty acids with N-methyl taurine.
Especlally preferred non-soap anionic co-surfactants include:
alkylaryl sulphonates, such as sodium alkyl benzene sulphonate (e.g. TEEPOL CM44, available from Shell).
alkyl sulphates, such as sodium lauryl sulphate te.g.
EMPICOL CX, available from Albright & Wilson), and triethanolomine lauryl sulphate (e.g. ENPICOL TL40/T, available from Albright & Wilson).
alkylether sulphates, such as sodium lauryl ether ( sulphate (e.g. ENPICOL ESB70, available from Albright &
Wilson).
alkyl sulphonates, such as sodium alkane (C13-18) sulphonate (e.g. HOSTAPU~ SAS 30, available from Hoechst).
olefin sulphonates, such as sodium olefin sulphonate (C15-18) (e.g. HOSTAPUR OS,available from Hoechst).
2 ~3 Sarcosinates, having the structure (3):
R - C -N -CH2COOM (3) where R3 is chosen from C6 14 alkyl, and ( lO M is a counterion chosen from alkali metals, ammonium, substituted ammonium, such as alkanolammonium.
An example of sarcosinates having the structure (3), sodium lauryl sarcosinate (e.g. HAMPOSYL L-95, available from Grace).
Taurides, having the structure (4):
O
( 4 11 R C r ' N - (CH2)2SO3M (4) zs where R4 is chosen from C8 18 alkyl An example of taurides having the structure (4) is:
coconut methyl taurine (e.g. FENOPON TC 42, available from GAF).
5 Isethionates, having the structure (5):
R ~ C - O (CH2)2S03M (5) where R5 is chosen from C8_18 alkyl-An example of isethionates having the structure (5) is:
sodium acyl isethionate (e.g. JORDAPON C1, available from Jordan).
(, 10 Monoalkyl sulphosuccinates, having the structure (6):
R6- 0 - C ~ CH2CH COOM (6) I
where R6 is chosen from clO_20 alkyl-Examples of monoalkyl sulphosuccinates having this structure (6) include:
sodium lauryl sulphosuccinate (e.g. EMPICOL SLL, available from Albright & Wilson) magnesium alkyl sulphosuccinate (e.g. ELFANOL 616 Mg, available from AKZO), sodium lauryl ethoxysulphosuccinate (e.g.
EMPICOL SDD, available from Albright & Wilson) coconut monoethanolamide ethoxysulphosuccinate, (e.g. EMPICOL SGG) disodium lauryl polyglycolether sulphosuccinate (e.g. SURTAGENE S30, available from CHEM-Y) polyethyleneglycol sulphosuccinate (e.g. REWOPOL
2~3~
SBFA 30, available from REWO).
Dialkyl sulphosuccinates, having the structure (7):
R7 _ o _ C ~ CH2CH COOR8 (7) ( lo where R7 and R8 are the same or different, and are are chosen from C6_14 alkyl-An example of dialkyl sulphosuccinate having the structure (7) is:
sodium dioctyl sulphosuccinate (e.g. EMCOL 4500 available from Witco).
Acyl lactylates, having the structure (8):
O H O
R9 - C - (O - C - Cln- OM (8) CH
2s 3 where R9 is chosen from C6_16 alkyl-An example of acyl lactates having the structure (8) is decanoyl lactate (e.g. PATIONIC 122A, available from Patterson, C.J.).
3s 2 ~
Acvlated -amino acids, such as sodium lauroyl glutamate (e.g. ACYLGLUTAMATE LS-ll, available from Ajinomoto Co. Inc.).
EthYl carboxylates, such as alkyl C12_14O(E0)40CH2C02Na (e.g. AKYP0 ~LM 38, available from AKZ0).
Nonionic supplementary surfactants ( 10 A composition according to the invention can also comprise nonionic supplementary surfactants which are compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. Examples of nonionic supplementary surfactants include:
i. The polyethylene oxide condensates of alkyl phenols having from 6 to 12 carbon atoms, either straight or branched chain, with ethylene oxide, which is present in amounts of from 10 to 60 moles of ethylene oxide per mole of alkylphenol.
ii. The condensation product of aliphatic alcohols having from 8 to 18 carbon atoms, straight or branched chain, with ethyleneoxide, for example, a coconut alcohol ethyleneoxide condensate having from 10 to 13 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from 10 to 14 carbon atoms.
iii. Long chain tertiary amineoxides having the structure (9):
- RlORllR12N __~
2 ~ 3 3 $~ ~
where R10 contains an alkyl, alkenyl or monohydroxyalkyl radical of from 8 to 18 carbon atoms, from 0 to 10 éthylene oxide moieties and from 0 to 1 glyceryl moiety, and Rl1 and R12 contain from 1 to 3 carbon atoms and up to 1 hydroxy group, for example, methyl, ethyl, propyl, hydroxyethyl, or hydroxypropyl groups.
Especially preferred examples of nonionic supplementary surfactants include:
(' 10 alkvlethoxylates, such as the DOBANOL series, available from Shell;
esterethoxylates, such as the TAGAT series, available from Goldschmidt;
alkYlalkanolamides, such as coconut monoethanolamide (e.g. EMPILAN CME, available from Albright & Wilson), and coconut diethanolomide, (e.g. EMPILAN CDE, available from Albright & Wilson).
- suaar esters, such as sucrose laurate and methyl glucose laurate (available from Grillo-Werke A.G.) esters of glycols, such as ethylene g~ycol mono stearate.
esters of glycerol, such as glyceryl mono stearate.
~0 ethoxylated sorbitan esters, such as the TWEEN series (available from ICI).
amine oxides, such as alkyldimethyl amine oxide (e.g.
EMPIGEN OB, available from Albright & Wilson) and alkylethoxydimethyl amine oxide (e.g. EMPIGEN OY, available from Albright & Wilson).
~ ~ 3 J ~
~witterionic and AmPhoteric supplementary surfactants The composition according to the invention can also contain zwitterionic supplementary surfactants, which are derivatives of aliphatic quaternary ammonium, phosphonium and sulphonium compounds in which the aliphatic radicals can be straight or branched chain, and where one aliphatic substituent contains from 8 to 18 carbon atoms, and one contains an anionic water-solubilising group, such as carboxyl, sulphonate, sulphate, phosphate or ( lO phosphonate.
Examples of zwitterionic supplementary surfactant include:
lS 4-[N,N-di(2-hydroxyethyl)-N-octadecylammonio]-butane-1-carboxylate, and 5-N,N-di(3-hydroxypropyl)-N-hexadecylammonio]-2-hydroxypentane-1-sulphate.
Particularly preferred zwitterionic supplementary surfactants are betaines, preferred examples of which are:
2s Alkyl betaines, having the structure (10):
R - N - CH2C (lO) where R16 i5 C10 16 alkyl.
An example of alkyl betaines having the structure ~lO) is:
~3~
lauryldimethyl betaine (e.g. EMPIGEN BB, available from Albright & Wilson).
Sultaines, having the structure (13):
R - N - CH2~ CH- CH2 - 5O3 (13) , - CH3 '10 where R21 is chosen from C12 16 alkyl or alkylamido.
An example of sultaines having the structure (13) is:
cocoamidopropylhydroxysultaine (e.g. CYCLOTERIC
BET-CS, available from Alcolac).
The amount of supplementary surfactant when present in the compositions according to the invention is usually up to 50%, preferably from 1 to 40~ by weight.
It is envisaged that the amount of non-soap supplementary surfactant will generally not exceed the amount of the specified co-surfactant.
Optional thickenina aaent The composi~ion according to the invention can also comprise a polymer thickener in an amount sufficient to adjust the viscosity of the composition, so as to facilitate dispensing it conveniently onto the body surface.
Examples of polymer thickeners include:
anionic cellulose materials, such as sodium carboxy methyl cellulose;
anionic polymers such as carboxy vinyl polymers, for examples Carbomer 940 and 941;
~3~9~
- ~1 - J3130 nonionic cellulose materials, such a methyi cellulose and hydroxy propyl methyl cellulose;
cationic cellulose materials, such as Polymer JR
400;
cationic gum materials, such as Jaguar C13S;
other gum materials such as gum acacia, gum tragacanth, locust bean gum, guar gum and carrageenan; proteins, such as albumin and protein hydrolysates;
and ( 10 clay materials, such as bentonite, hectorite, magnesium aluminium silicate, sodium magnesium silicate and a synthetic complex clay having the generic formula:
lS 8 g5.1 0.6H4.624] Na~0 6~ an example of which is Laponite, available from Laporte Industries.
The amount of thickening agent which can optionally be employed in the composition according to the invention is normally from 0.05 to 5%, preferably 0.1 to 1% by weight of the composition.
Preservative, The composition according to the invention can also optionally comprise a preservative to prevent microbial spoilage, especially biodegradation of the alkyl phosphate salt. It is accordingly apparent that the composition containing the alkyl phosphate salt may be prone to attack by bacteria, moulds and fungi and other microbial influences. There is therefore a risk that the shelf-life of the composition might be unacceptably short ~ a ~ L.~
due to the biodegradation or spoilage, unless there is included in the composition a bactericide, fungicide or other microbicide in an amount sufficient to inhibit or prevent the said biodegradation or spoilage, or unless other steps are taken to preserve the composition.
Examples of preservatives include:
(i) Chemical preservatives, such as ethanol, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, lo sodium propionate and the methyl, ethyl, propyl and butyl esters of p~hydroxybenzoic acid 2-bromo-2-nitropropane-1,3-diol, phenoxyethanol, dibromodicyanobutane, formalin and Triclosan. The amount of chemical preservative optionally to be incorporated in the composition according to the invention will generally be from 0.05 to 5%, preferably from 0.1 to 2% by weight, the amount chosen being sufficient to arrest microbial proliferation.
(ii) Water activity depressants, such as glycerPl, propylene glycol, sorbitol, sugars and salts, for examples alkali metal halides, sulphates and ( carboxylates. When employing a water activity depressant, sufficient should be incorporated in the composition according to the invention to reduce the water activity (~ w) from 1 to <0.9, preferably to ~0.85 and most preferably < 0.8, the lowest of these values being that at which yeasts, moulds and fungi will not proliferate.
~o Further optional inqredients The composition according to the invention can also contain other optional adjuncts, that is ingredients other than the main ingredients already defined which are 2~3~
conventionally employed in compositions for topical application to human skin. These adjuncts, when present, will normally form the balance of the composition.
Examples of optional adjuncts include vehicles, the selection of which will depend on the required product form of the composition. Typically, the vehicle when present, will be chosen from diluents, dispersants or carriers for the dialkyl or dialkenyl phosphate salt so ( lO as to ensure an even distribution of it when applied to the skin.
Compositions according to this invention can include water as a vehicle, usually with at least one other cosmetically-acceptable vehicle.
Vehicles other than water that can be used in compositions according to the invention can include liquids or solids as emollients, solvents, humectants, thickeners and powders. Examples of each of these types of vehicles, which can be used singly or as mixtures of one or more vehicles, are as follows:
Emollients, such as stearyl alcohol, glyceryl monolaurate, glyceryl monoricinoleate, glyceryl monostearate, propane-1,2-diol, butane-1,3-diol, docosan-1,2-diol, mink oil, cetyl alcohol, isopropyl isostearate, stearic acid, isobutyl palmitate, isocetyl stearate, oleyl alcohol, isopropyl laurate, hexyl laurate, decyl oleate, octadecan-2-ol, isocetyl alcohol, eicosanyl alcohol, behenyl alcohol, cetyl palmitate, silicone oils such as dimethylpolysiloxane, di-n-butyl sebacate, isopropyl myristate, isopropyl palmitate, 3s isopropyl stearate, butyl stearate, polythylene glycol, triethylene glycol, lanolin, cocoa butter, corn oil, 2 ~
cotton seed oil, tallow, lard, olive oil, palm kernel oil, rapeseed oil, safflower seed oil, soybean oil, sunflower seed oil, olive oil, sesame seed oil, coconut oil, arachis oi.l, castor oil, acetylated lanolin alcohols, petroleum, mineral oil, butyl myristate, isostearic acid, palmitic acid, isopropyl linoleate, lauryl lactate, myristyl lactate, decyl oleate, myristyl myristate;
Propellants, such as trichlorofluoromethane, lo dichlorodifluoromethane, dichlorotetrafluoroethane, monochlorodifluoromethane, trichlorotrifluoroethane, propane, butane, isobutane, dimethyl ether, carbon dioxide, nitrous oxide;
Solvents, such as ethyl alcohol, methylene chloride, isopropanol, acetone, castor oil, ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, dimethyl sulphoxide, dimethyl formamide, tetrahydrofuran;
Humectants, such as glycerin, sorbitol, sodium 2-pyrrolidone-5-carboxylate, soluble collagen, dibutyl 2s phthalate, g.elatin;
Powders, such as chalk, talc, fullers earth, kaolin, starch, gums, colloidal silicon dioxide, sodium polyacrylate, tetra alkyl and/or trialkyl aryl ammonium smectites, chemically modified magnesium aluminium silicate, organically modified montmorillonite clay, hydrated aluminium silicate, fumed silica, carboxyvinyl polymer, sodium carboxymethyl cellulose, ethylene glycol monostearate.
3s ~ ~ 3 ~3~Ll The cosmetically acceptable vehicle, when present, will usually form from 0.01 to 99.9%, preferably from 50 to 98% by weight of the composition, and can, in the absence of other cosmetic adjuncts, form the balance of the composition.
s PRODUCT FORM OF THE COMPOSITION
The composition according to the invention can take the form of a liquid or gel, intended to be dispensed 10 from a capped container such as a bottle, roll-on applicator or tube, or a pump-operated or propellant driven aerosol dispenser, as a skin cleanser, shower product, bath additive or shampoo. The composition can also take for form of a powder or a solid such as a stick, preferably housed in a suitable capped holder with a wind-up or push-up action similar to a lip stick, or a bar or tablet, with or without fatty acid soaps, intended to be used for washing instead of a conventional soap bar.
The invention also provides a closed container containing a detergent composition as herein defined.
Process for preparinq the Composition - The invention also provides a process for preparing the composition of the type defined herein, which process comprises the steps of:
(i) preparing a mixture comprising one or more dialkyl and/or dialkenyl phosphate surfactants, as defined herein, and one or more monoalkyl and/or monoalkenyl phosphate surfactants, as defined herein, and one or more co-surfactants, as defined herein; and 2 ~ 3 .3 9 ~ ~
(ii) subsequently packaging the mixture into containers.
Use of the composition The composition according to the invention is intended primarily as a personal washing product for cleansing the face and other sensitive parts of the body surface, including the mucosae. It can also be used for washing the hair as well as the skin.
In use, a small quantity, for example from I to 5 ml, of the composition is either rubbed between the hands, together with water to form a foam, which is then used for washing, or applied via a flannel or sponge to the area to be cleansed, or the foam is generated lS directly on that area. The foam is subsequently rinsed away with clean water.
.. . . . .
:SO
EXAMPLES
The invention is further illustrated by reference to the following examples.
Example 1 The foaming of three lauryl phosphate mixtures was investigated. Foaming was measured in vitro by the Ross-Miles procedure. A 0.3~ by weight concentration of the alkyl phosphate mixture in water was used, at 20C
and pH 7.5. Foam is generated by a standard method and the volume of foam is measured as a height in a cylinder.
Foaming was also measured by a trained panel who formed a lather in a standard procedure representing use of the mixture, diluted to 4.5% by weight alkyl phosphate(s), as a product for cleaning the skin. Each panellist estimated the volume and creaminess of the lather as scores on a scale. The lather was also collected and its volume measured.
Results are set out in the following Table 1. The values for estimated/perceived volume and creaminess are totals of panel scores.
TABLE 1 - FOAM PROPERTIES OF MAP:DAP RATIOS
Ratio of In vitro In vivo MAP:DAP Foam Measured Estimated Perceived alkyl ~ lauryl Height (mm) Volume (ml) /Volume Creaminess 100 : 0 153 30 118 124 3075 : 25 135 28 96 99 60 : 40 92 23 52 60 It is apparent that the presence of dialkyl phosphate inhibits foaming.
28 - ~ 3 '~
Example 2 A mixture of monolauryl phosphate and dilauryl phosphate in 75:25 weight ratio was mixed with each of a range of surfactants. The foaming of the resulting mixtures was tested by the Ross-Miles method as in Example 1.
Each test solution contained 0.30% of the alkyl phosphate mixture and 0.06% of the other surfactant(s).
The surfactants used and the foam heights are set out in the following Table 2.
These results shows that cocoamidopropyl betaine (CAPB) gave superior foaming and more than overcame the antifoam effect of the dilauryl phosphate.
- 29 - J3130 ~ $ ~
Co-active Trade Name Manufacturer Foam Heiqht (mmL
CAPB Tegobetaine L7 Goldschm;dt 154 Lauryl Sulpho- Nikkol LSA Nikko Chemicals 52 acetate Disodium Lauryl Rewopol SBFA Rewo 136 Ethoxy Sulpho-succinate Secondary n-Alkyl Hostapur SAS Hoechst 132 Sulphonate Sodium N-Cocoyl-N- Fenopon TC42 Rhone- 136 Methyl Taurate Poulenc C9-Cll (6EO) Dobanol 91-6 Shell 129 Alcohol Ethoxylate Sodium Lauryl Empicol ES8 70 Albright & Wilson 141 Ether (2EO) Sulphate Coconut Oi Ethanol- Cyclomide CD Witco 99 amide/Coconut Fatty Acid Sodium Alkyl PEG-10 Marlinat CMlOS Huls 136 Acetate Sodium Isostearyl Crolactil 515L Croda 121 Lactylate Saponin Glycoside Agrofoam SO Paroxite 141 TEA Lauryl Sulphate Empicol TL40/% Albright & Wilson 106 Coconut Mono Empilan CME Albright & Wilson 28 Ethanolamide Lauryl/Myristyl Empigen 08 Albright & Wilson 18 Dimethyl Amine Oxide .. , - : , ~3 ~"~
Example 3 Mixtures of monolauryl phosphate and dilauryl phosphate were mixed with cocoamidoporpyl betaine (CAPB) and diluted to an aqueous solution containing 4.5~ by weight alkyl phosphates and n. 8~ by weight CAPB. These solutions were assessed by a trained panel as in Example 1.
At the same time a commercial product was diluted to the same alkyl phosphate concentration and tested as a comparison. This product contained mono and dialkyl phosphates in a ratio of >80 : <20 (i.e. a mixture containing more than 80~ MAP).
The results are set out in the following Table 3.
MAP:DAPCo-active Measured Estimated/Perceived RatioVolume (ml) Volume Creaminess 75:25CAPB 43 123 109 60:40CAPB 36 118 113 Commercial Product 25 95 133 2~
Example 4 Mixtures of monolauryl phosphate and dilauryl phosphate were mixed with other materials and assessed by a trained panel for ease of lathering, lather volume and lather creaminess. The commercial product mentioned in Example 3 was also assessed by the panel. In each case the concentration of alkyl phosphates was 4.5~ by weight.
The other materials contained in the mixtures were 0.8% by weight of cocoamidopropyl betaine (CAPB, Tegobetaine L7) or 0.8% by weight of cocoamphodipropionate (Miranol C2M-SF) and 0.4~ by weight of cationic cellulosic polymer JR400.
The results (total panel scores) are set out in the following Table 4.
System Ease of Volume Creaminess Foaming MAP:DAP (75:25) 108.498.2 81.9 MAP:DAP (75:25) + CAPB 141.2 107.1 96.9 MAP:DAP (75:25) + CAPB + 135.0 137.4 141.2 polymer JR400 MAP:DAP (60.40) + Miranol133.0 129.9 130.6 C2M-SF ~ polymer JR400 Commercial produat 130.0130.0 140.0 The mixtures containing CAP~, with and without polymer JR400, were tested for zein solubilisation.
This test, first described by Gotte in Proc. Int. Congr.
Surface Active Subs. 4th, Brussels, 3 83-90, 1964, tests the liberation of zein (protein from corn kernel~ on exposure to surfactant. The result is expressed as 2~3~
percentage nitrogen in supernatant solution and correlates with harshness towards skin.
The results were:
MAP:DAP (75:25) + CAPB 0.68% N
above plus 0.4% polymer JR400 0.60% N
- Thus inclusion of polymer enhanaes mildness.
1~ Exam~le 5 This Example illustrates a body cleansing liquid product suitable for use in the shower.
The product contains the following ingredients:
Inaredients % w/w triethanolamine di-n-lauryl phosphate 18 triethanolamine mono-n-lauryl phosphate 18 cocoamphodiacetate (MIRANOL C2M-NP) 10 preservative 2 water to loo - 25 This product can be used for cleansing the whole body surface, including the hair, for example under the shower, a convenient amount of say 5ml being placed in the palm of the hand prior to distributing over the body surface with added water to create a lather with superior 3~ volume and creaminess characteristics.
The properties of the above product (the Test product) were tested against another product from which the cocoamphodiacetate was omitted (the Control product).
-- 33 ~
In this comparative test, strips of polyurethane foam were impregnated with equal quantities of the product according to the invention or the comparative product free from co-surfactant, each product first being diluted with tap water so that the concentration of alkyl phosphate in each case was 1~ by weight.
Each member of a panel of twenty assessors was then asked to produce a foam by manually kneeding one strip containing the Test product and the other containinq the Control product. Each panelist was then asked to decide which of the two samples gave the greater lather volume and the better lather creaminess. None of the panelists knew which sample was which.
The results of this test showed that the lather volume and lather creaminess of the Test product according to the invention containing triethanolamine di-n-lauryl phosphate, triethanolamine mono-n-lauryl phosphate and the cocoampho diacetate was superior to that containing only the triethanolamine di-n-lauryl phosphate and triethanolamine mono-n-lauryl phosphate, this difference being significantly different at the 95%
level.
2s From this test it was concluded that the product according to the invention, the Test product, was superior to the Control product.
~o ~35~
Examples 6 toll illustrate body shampoos for use in the shower or when bathing.
Example 6 96 w/w triethanolammonium monolauryl phosphate 18 triethanolammonium dilauryl phosphate 6 cocoamphodipropionate ~MIRANOL C2M-SF) 5 ~ ~
lo triethanolammonium laurate triethanolammonium myristate 2 lauryldimethylamine oxide 2 myristyldiethylamine oxide 0.5 cationised cellulose 0.1 propylene glycol 10 water to 100 Example,Z
% w/w triethanolamine monolauryl phosphate 21 triethanolamine dilauryl phosphate 9 cocoamidopropyl betaine (TEGOBETAINE L7) 8 lauryl dimethylbetaine 3 ethylene glycol monostearate 1.5 propylene glycol 2.5 preservative, perfume, dyes q.v.
water to 100%
~o ~ ~ 3 Example 8 ~ w/w sodium mono-(diethyleneglycol-mono-n-dodecyl ether) phosphate 10 sodium di-(diethyleneglycol-mono-n-dodecyl ether? phosphate 10 cocoamphodiacetate 12 triethanolammonium laurate triethanolammonium myristate 2 alkyldialkylamine oxide (EMIGEN OB
30% active) 8.3 cationised cellulose 0.1 propylene glycol 10 lS water to 100 Example 9 % w/w triethanolammonium mono-(ethyleneglycol-mono-n-decyl ether) phosphate 10 triethanolammonium s di-(ethyleneglycol-~ono-n-octadecenyl.
ether) phosphate 8 cocoamphodipropionate (MIRANOL C2M-SF) 9 lauryl dime~hylbetaine 3 ~0 ethylene glycol monostearate 1.5 propylene glycol 2.5 preservative, perfume, dyes q.v.
water to 100%
2~3'~
Example 10 triethanolammonium S mono-(ethyleneglycol-mono-n-decyl ether) phosphate 20 triethanolammonium di-(ethyleneglycol-mono-n-octadecyl ether) phosphate 3 cocoamidopropyl betaine (TEGOBETAINE ~7) 10 triethanolammonium laurate triethanolammonium myristate2 alkyldialkylamine oxide (EMIGEN OB) 30% active) 8.3 lS cationised cellulose 0.1 propylene glycol 10 water to 100 Example 11 % w~w sodium mono-(7-methyldecyl) phosphate 18 sodium di-(7-methyldecyl) phosphate 12 cocoamphodiacetate . . 15 -lauryl dimethylbetaine 3 ethylene glycol monostearate 1.5 propylene glycol 2.5 preservative, perfume, dyes q.v.
water to 100%
Examples<12,13 & 14 The following three examples illustrate soap-containing products in accordance with the invention.
s In each case, the products were made in accordance with standard soap manuPacture. The product of Example 8 yielded a flaked product which could not readily be pressed into a bar, as the flakes were not sufficiently cohesive. With the products of Examples 9 and 10, bars were formed following the usual plodding, extrusion and stamping that is conventional in soap bar manufacture.
These soap products had the following formulations:
lS
Examples Ingredient 12 13 14 (% by weight) Hardened Tallow Soap S9 54 80/20 tallow-coco soap - 7 66 sodium dilauryl phosphate 4 -6 2 sodium monolauryl phosphate 12 15 17 cocoamidopropyl betaine (TEGOBETAINE L7~ 5 8 10 water 20 10 5 ~o
S X is chosen from H, alkali metal, ,i ammonium and substituted ammonium counterions; and , a and b are each chosen from 0 or a lo value of from 1 to 10.
, Examples of the dialkyl and dialkenyl phosphate moiety include:
di-n-decyl phosphate di-n-dodecyl phosphate (dilauryl phosphate) di-n-tetradecyl phosphate .(dimyristyl phosphate) di-n-hexadecyl phosphate - di-n-octadecyl phosphate di-n-dodecenyl phosphate di-(7-methyldecyl) phosphate di-(ethyleneglycol-mono-n-octadecyl ether) .phosphate 2s di-(diethyleneglycol-mono-n-octadecenyl ether) . phosphate di-(polyethyleneglycol~SE0~-monooleyl ether) phosphate di-~polyethyleneglycol r 3E0~-monolauryl ether) phosphate The preferred dialkyl phosphate salt, is triethanolammonium dilauryl phosphate.
The amount of the dialkyl or dialkenyl phosphate salt which is present in the composition according to the - g -- J3130 invention is from 1 to 50%, preferably from 1 to 20% or even lO~ by weight, of the composition.
The weight ratio of the monoalkyl or monoalkenyl phosphate salt to the dialkyl or dialkenyl phosphate S surfactant is from 95:5 to 25:75, preferably 85:15 or 7~:25 to 50:50. Thetotal weigh~ ofthetwosurfa~ctants may be 2- ~Q 50%
of the composition.
The Co-surfactant The composition according to the invention also comprises a co-surfactant chosen from:
i. alkvlamidopro~Yl betaines, having the structure (11~:
R04 C _ N --(CH2)3 N~ _ CH2C00 (11) - and zs - . .
ii. alkylamphoglycinates, and having the structure (12):
R04 C- N - -(CH2)2 _ N - (C~2)2H
where R04 is C10 16 alkyl R05 and R06 are the same or different and are chosen from CH2Coo and (CH2)2C00 .
~ 6~ Y_~ 3 ~
An example of the alkamidopropyl betaine having the structure (11) is:
cocoamidopropyl betaine (e.g. TEGOBETAIN L7, ex Goldschmidt).
s Examples of the alkylamphoglycinate having the structure - (12) are:
cocoamphodiacetate (e.g. MIRANOL C2M-NP, ex Miranol InC . ~
cocoamphodipropionate (e.g. MIRANOL C2M-SF, ex Miranol Inc.) The amount of co-surfactant which is present in the composition according to the invention is from l to 50~, preferably from 2% or even 5% to 40~ by weight of the composition.
Water - The composition according to the invention also comprises an amount of water to act as a vehicle for the mono- and di-alkyl or -alkenyl phosphate surfactants and to enable them to be provided at a concentration suitable for convenient topical application to human skin.
The amount of water present in the composition of the invention is accordingly up to 99~, preferably from 5 to ~9% by weight of the composition.
~o Supplementarv Surfactant The composition according to the invention can also optionally comprise a supplementary surfactant, further 3s ~ L3 to modify the surfactant properties attributable to the mono- and di-alkyl or -alkenyl phosphate salts.
Examples of supplementary surfactants include anionic surfactants other than the phosphate salts defined herein, as well as nonionic, amphoteric and zwitterionic surfactants.
.
Anionic supplementary surfactants ( lo Particularly preferred supplementary surfactants, when employed, are anionic surfactants, examples of which are set out hereinafter.
i. Fatty acid soap supplementary surfactant The composition according to the invention can optionally comprise, as a supplementary surfactant one or more soaps which are water-soluble or water-dispersable alkali metal salts of an organic acid, especially a sodium or a potassium salt, or the corresponding ammonium or substituted ammonium salt. Examples of suitable organic acids are natural or synthetic alkanoic acids having from 10 to 22 carbon atoms, especially the fatty - acids of triglyceride oils such as tallow and coconut oil.
For solid products, such as powders, bars or tablets, the preferred soap is a soap of tallow fatty acids, that is fatty acids derived from tallow class fats, for example beef tallow, mutton tallow, lard, palm oil and some vegetable butters. Minor amounts of up to about 30%, preferably 10 to 20%, by weight of sodium soaps of nut oil fatty acids derived from nut oils, for example coconut oil and palm kernel oil, may be admixed with the sodium tallow soaps, to improve their lathering 2~3~
and solubility characteristics if desired. Whereas tallow fatty acids are predominantely C14 and C18 fatty acids, the nut oil fatty acids are of shorter chain length and are predominantly C10-Cl4 fatty acids.
For liquid or gel products, the preferred soaps are predominantely Cl0_l4 fatty acids derived from nut oils, or alternatively, from synthetic alkanoic acids.
The soaps can be provided as a preformed ingredient for the composition, or they can be formed in situ during the manufacture of the composition by reaction of suitable fatty acids and an alkali.
The amount of fatty acid soap which can be present 1 in the composition according to the invention is up to 90%, preferably from 2 to 80~ by weight of the composition, yet more preferably-from 2 to 20% by weight.
ii. Non-soa~ anionic su~plementary surfactants The composition according to the invention can also optionally comprise one or more non-soap anionic supplementary surfactants, examples of which include:
The alkali metal salts of organic sulphuric reaction products having an alkyl or acyl radical containing from 8-22 carbon atoms and a sulphonic acid or sulphuric acid ester group. Specific examples of these synthetic anionic surfactants are the sodium, ammonium, potassium or triethanolammonium alkyl sulphates, especially those obtained by sulphating the higher alcohols (C8-C18), sodium coconut oil fatty acid monoglyceride sulphates and sulphonates; sodium or potassium salts of sulphuric esters of the reaction product of one mole of a higher fatty alcohol ~e.g. tallow or coconut oil alcohols) and 2 ~ 3 J ~
1-12 moles of ethyleneoxide; sodium or potassium salts of alkyl phenol ethylene oxide ether sulphate with 1-10 units of ethylene oxide per molecule and in which the alkyl group contains from 8 to 12 carbon atoms, sodium alkyl glyceryl ether sulphonates, the reaction product of fatty acids having from 10 to 22 carbon atoms esterified with isethionic acid and neutralised with sodium hydroxide; water soluble salts of condensation products of fatty acids with N-methyl taurine.
Especlally preferred non-soap anionic co-surfactants include:
alkylaryl sulphonates, such as sodium alkyl benzene sulphonate (e.g. TEEPOL CM44, available from Shell).
alkyl sulphates, such as sodium lauryl sulphate te.g.
EMPICOL CX, available from Albright & Wilson), and triethanolomine lauryl sulphate (e.g. ENPICOL TL40/T, available from Albright & Wilson).
alkylether sulphates, such as sodium lauryl ether ( sulphate (e.g. ENPICOL ESB70, available from Albright &
Wilson).
alkyl sulphonates, such as sodium alkane (C13-18) sulphonate (e.g. HOSTAPU~ SAS 30, available from Hoechst).
olefin sulphonates, such as sodium olefin sulphonate (C15-18) (e.g. HOSTAPUR OS,available from Hoechst).
2 ~3 Sarcosinates, having the structure (3):
R - C -N -CH2COOM (3) where R3 is chosen from C6 14 alkyl, and ( lO M is a counterion chosen from alkali metals, ammonium, substituted ammonium, such as alkanolammonium.
An example of sarcosinates having the structure (3), sodium lauryl sarcosinate (e.g. HAMPOSYL L-95, available from Grace).
Taurides, having the structure (4):
O
( 4 11 R C r ' N - (CH2)2SO3M (4) zs where R4 is chosen from C8 18 alkyl An example of taurides having the structure (4) is:
coconut methyl taurine (e.g. FENOPON TC 42, available from GAF).
5 Isethionates, having the structure (5):
R ~ C - O (CH2)2S03M (5) where R5 is chosen from C8_18 alkyl-An example of isethionates having the structure (5) is:
sodium acyl isethionate (e.g. JORDAPON C1, available from Jordan).
(, 10 Monoalkyl sulphosuccinates, having the structure (6):
R6- 0 - C ~ CH2CH COOM (6) I
where R6 is chosen from clO_20 alkyl-Examples of monoalkyl sulphosuccinates having this structure (6) include:
sodium lauryl sulphosuccinate (e.g. EMPICOL SLL, available from Albright & Wilson) magnesium alkyl sulphosuccinate (e.g. ELFANOL 616 Mg, available from AKZO), sodium lauryl ethoxysulphosuccinate (e.g.
EMPICOL SDD, available from Albright & Wilson) coconut monoethanolamide ethoxysulphosuccinate, (e.g. EMPICOL SGG) disodium lauryl polyglycolether sulphosuccinate (e.g. SURTAGENE S30, available from CHEM-Y) polyethyleneglycol sulphosuccinate (e.g. REWOPOL
2~3~
SBFA 30, available from REWO).
Dialkyl sulphosuccinates, having the structure (7):
R7 _ o _ C ~ CH2CH COOR8 (7) ( lo where R7 and R8 are the same or different, and are are chosen from C6_14 alkyl-An example of dialkyl sulphosuccinate having the structure (7) is:
sodium dioctyl sulphosuccinate (e.g. EMCOL 4500 available from Witco).
Acyl lactylates, having the structure (8):
O H O
R9 - C - (O - C - Cln- OM (8) CH
2s 3 where R9 is chosen from C6_16 alkyl-An example of acyl lactates having the structure (8) is decanoyl lactate (e.g. PATIONIC 122A, available from Patterson, C.J.).
3s 2 ~
Acvlated -amino acids, such as sodium lauroyl glutamate (e.g. ACYLGLUTAMATE LS-ll, available from Ajinomoto Co. Inc.).
EthYl carboxylates, such as alkyl C12_14O(E0)40CH2C02Na (e.g. AKYP0 ~LM 38, available from AKZ0).
Nonionic supplementary surfactants ( 10 A composition according to the invention can also comprise nonionic supplementary surfactants which are compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. Examples of nonionic supplementary surfactants include:
i. The polyethylene oxide condensates of alkyl phenols having from 6 to 12 carbon atoms, either straight or branched chain, with ethylene oxide, which is present in amounts of from 10 to 60 moles of ethylene oxide per mole of alkylphenol.
ii. The condensation product of aliphatic alcohols having from 8 to 18 carbon atoms, straight or branched chain, with ethyleneoxide, for example, a coconut alcohol ethyleneoxide condensate having from 10 to 13 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from 10 to 14 carbon atoms.
iii. Long chain tertiary amineoxides having the structure (9):
- RlORllR12N __~
2 ~ 3 3 $~ ~
where R10 contains an alkyl, alkenyl or monohydroxyalkyl radical of from 8 to 18 carbon atoms, from 0 to 10 éthylene oxide moieties and from 0 to 1 glyceryl moiety, and Rl1 and R12 contain from 1 to 3 carbon atoms and up to 1 hydroxy group, for example, methyl, ethyl, propyl, hydroxyethyl, or hydroxypropyl groups.
Especially preferred examples of nonionic supplementary surfactants include:
(' 10 alkvlethoxylates, such as the DOBANOL series, available from Shell;
esterethoxylates, such as the TAGAT series, available from Goldschmidt;
alkYlalkanolamides, such as coconut monoethanolamide (e.g. EMPILAN CME, available from Albright & Wilson), and coconut diethanolomide, (e.g. EMPILAN CDE, available from Albright & Wilson).
- suaar esters, such as sucrose laurate and methyl glucose laurate (available from Grillo-Werke A.G.) esters of glycols, such as ethylene g~ycol mono stearate.
esters of glycerol, such as glyceryl mono stearate.
~0 ethoxylated sorbitan esters, such as the TWEEN series (available from ICI).
amine oxides, such as alkyldimethyl amine oxide (e.g.
EMPIGEN OB, available from Albright & Wilson) and alkylethoxydimethyl amine oxide (e.g. EMPIGEN OY, available from Albright & Wilson).
~ ~ 3 J ~
~witterionic and AmPhoteric supplementary surfactants The composition according to the invention can also contain zwitterionic supplementary surfactants, which are derivatives of aliphatic quaternary ammonium, phosphonium and sulphonium compounds in which the aliphatic radicals can be straight or branched chain, and where one aliphatic substituent contains from 8 to 18 carbon atoms, and one contains an anionic water-solubilising group, such as carboxyl, sulphonate, sulphate, phosphate or ( lO phosphonate.
Examples of zwitterionic supplementary surfactant include:
lS 4-[N,N-di(2-hydroxyethyl)-N-octadecylammonio]-butane-1-carboxylate, and 5-N,N-di(3-hydroxypropyl)-N-hexadecylammonio]-2-hydroxypentane-1-sulphate.
Particularly preferred zwitterionic supplementary surfactants are betaines, preferred examples of which are:
2s Alkyl betaines, having the structure (10):
R - N - CH2C (lO) where R16 i5 C10 16 alkyl.
An example of alkyl betaines having the structure ~lO) is:
~3~
lauryldimethyl betaine (e.g. EMPIGEN BB, available from Albright & Wilson).
Sultaines, having the structure (13):
R - N - CH2~ CH- CH2 - 5O3 (13) , - CH3 '10 where R21 is chosen from C12 16 alkyl or alkylamido.
An example of sultaines having the structure (13) is:
cocoamidopropylhydroxysultaine (e.g. CYCLOTERIC
BET-CS, available from Alcolac).
The amount of supplementary surfactant when present in the compositions according to the invention is usually up to 50%, preferably from 1 to 40~ by weight.
It is envisaged that the amount of non-soap supplementary surfactant will generally not exceed the amount of the specified co-surfactant.
Optional thickenina aaent The composi~ion according to the invention can also comprise a polymer thickener in an amount sufficient to adjust the viscosity of the composition, so as to facilitate dispensing it conveniently onto the body surface.
Examples of polymer thickeners include:
anionic cellulose materials, such as sodium carboxy methyl cellulose;
anionic polymers such as carboxy vinyl polymers, for examples Carbomer 940 and 941;
~3~9~
- ~1 - J3130 nonionic cellulose materials, such a methyi cellulose and hydroxy propyl methyl cellulose;
cationic cellulose materials, such as Polymer JR
400;
cationic gum materials, such as Jaguar C13S;
other gum materials such as gum acacia, gum tragacanth, locust bean gum, guar gum and carrageenan; proteins, such as albumin and protein hydrolysates;
and ( 10 clay materials, such as bentonite, hectorite, magnesium aluminium silicate, sodium magnesium silicate and a synthetic complex clay having the generic formula:
lS 8 g5.1 0.6H4.624] Na~0 6~ an example of which is Laponite, available from Laporte Industries.
The amount of thickening agent which can optionally be employed in the composition according to the invention is normally from 0.05 to 5%, preferably 0.1 to 1% by weight of the composition.
Preservative, The composition according to the invention can also optionally comprise a preservative to prevent microbial spoilage, especially biodegradation of the alkyl phosphate salt. It is accordingly apparent that the composition containing the alkyl phosphate salt may be prone to attack by bacteria, moulds and fungi and other microbial influences. There is therefore a risk that the shelf-life of the composition might be unacceptably short ~ a ~ L.~
due to the biodegradation or spoilage, unless there is included in the composition a bactericide, fungicide or other microbicide in an amount sufficient to inhibit or prevent the said biodegradation or spoilage, or unless other steps are taken to preserve the composition.
Examples of preservatives include:
(i) Chemical preservatives, such as ethanol, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, lo sodium propionate and the methyl, ethyl, propyl and butyl esters of p~hydroxybenzoic acid 2-bromo-2-nitropropane-1,3-diol, phenoxyethanol, dibromodicyanobutane, formalin and Triclosan. The amount of chemical preservative optionally to be incorporated in the composition according to the invention will generally be from 0.05 to 5%, preferably from 0.1 to 2% by weight, the amount chosen being sufficient to arrest microbial proliferation.
(ii) Water activity depressants, such as glycerPl, propylene glycol, sorbitol, sugars and salts, for examples alkali metal halides, sulphates and ( carboxylates. When employing a water activity depressant, sufficient should be incorporated in the composition according to the invention to reduce the water activity (~ w) from 1 to <0.9, preferably to ~0.85 and most preferably < 0.8, the lowest of these values being that at which yeasts, moulds and fungi will not proliferate.
~o Further optional inqredients The composition according to the invention can also contain other optional adjuncts, that is ingredients other than the main ingredients already defined which are 2~3~
conventionally employed in compositions for topical application to human skin. These adjuncts, when present, will normally form the balance of the composition.
Examples of optional adjuncts include vehicles, the selection of which will depend on the required product form of the composition. Typically, the vehicle when present, will be chosen from diluents, dispersants or carriers for the dialkyl or dialkenyl phosphate salt so ( lO as to ensure an even distribution of it when applied to the skin.
Compositions according to this invention can include water as a vehicle, usually with at least one other cosmetically-acceptable vehicle.
Vehicles other than water that can be used in compositions according to the invention can include liquids or solids as emollients, solvents, humectants, thickeners and powders. Examples of each of these types of vehicles, which can be used singly or as mixtures of one or more vehicles, are as follows:
Emollients, such as stearyl alcohol, glyceryl monolaurate, glyceryl monoricinoleate, glyceryl monostearate, propane-1,2-diol, butane-1,3-diol, docosan-1,2-diol, mink oil, cetyl alcohol, isopropyl isostearate, stearic acid, isobutyl palmitate, isocetyl stearate, oleyl alcohol, isopropyl laurate, hexyl laurate, decyl oleate, octadecan-2-ol, isocetyl alcohol, eicosanyl alcohol, behenyl alcohol, cetyl palmitate, silicone oils such as dimethylpolysiloxane, di-n-butyl sebacate, isopropyl myristate, isopropyl palmitate, 3s isopropyl stearate, butyl stearate, polythylene glycol, triethylene glycol, lanolin, cocoa butter, corn oil, 2 ~
cotton seed oil, tallow, lard, olive oil, palm kernel oil, rapeseed oil, safflower seed oil, soybean oil, sunflower seed oil, olive oil, sesame seed oil, coconut oil, arachis oi.l, castor oil, acetylated lanolin alcohols, petroleum, mineral oil, butyl myristate, isostearic acid, palmitic acid, isopropyl linoleate, lauryl lactate, myristyl lactate, decyl oleate, myristyl myristate;
Propellants, such as trichlorofluoromethane, lo dichlorodifluoromethane, dichlorotetrafluoroethane, monochlorodifluoromethane, trichlorotrifluoroethane, propane, butane, isobutane, dimethyl ether, carbon dioxide, nitrous oxide;
Solvents, such as ethyl alcohol, methylene chloride, isopropanol, acetone, castor oil, ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, dimethyl sulphoxide, dimethyl formamide, tetrahydrofuran;
Humectants, such as glycerin, sorbitol, sodium 2-pyrrolidone-5-carboxylate, soluble collagen, dibutyl 2s phthalate, g.elatin;
Powders, such as chalk, talc, fullers earth, kaolin, starch, gums, colloidal silicon dioxide, sodium polyacrylate, tetra alkyl and/or trialkyl aryl ammonium smectites, chemically modified magnesium aluminium silicate, organically modified montmorillonite clay, hydrated aluminium silicate, fumed silica, carboxyvinyl polymer, sodium carboxymethyl cellulose, ethylene glycol monostearate.
3s ~ ~ 3 ~3~Ll The cosmetically acceptable vehicle, when present, will usually form from 0.01 to 99.9%, preferably from 50 to 98% by weight of the composition, and can, in the absence of other cosmetic adjuncts, form the balance of the composition.
s PRODUCT FORM OF THE COMPOSITION
The composition according to the invention can take the form of a liquid or gel, intended to be dispensed 10 from a capped container such as a bottle, roll-on applicator or tube, or a pump-operated or propellant driven aerosol dispenser, as a skin cleanser, shower product, bath additive or shampoo. The composition can also take for form of a powder or a solid such as a stick, preferably housed in a suitable capped holder with a wind-up or push-up action similar to a lip stick, or a bar or tablet, with or without fatty acid soaps, intended to be used for washing instead of a conventional soap bar.
The invention also provides a closed container containing a detergent composition as herein defined.
Process for preparinq the Composition - The invention also provides a process for preparing the composition of the type defined herein, which process comprises the steps of:
(i) preparing a mixture comprising one or more dialkyl and/or dialkenyl phosphate surfactants, as defined herein, and one or more monoalkyl and/or monoalkenyl phosphate surfactants, as defined herein, and one or more co-surfactants, as defined herein; and 2 ~ 3 .3 9 ~ ~
(ii) subsequently packaging the mixture into containers.
Use of the composition The composition according to the invention is intended primarily as a personal washing product for cleansing the face and other sensitive parts of the body surface, including the mucosae. It can also be used for washing the hair as well as the skin.
In use, a small quantity, for example from I to 5 ml, of the composition is either rubbed between the hands, together with water to form a foam, which is then used for washing, or applied via a flannel or sponge to the area to be cleansed, or the foam is generated lS directly on that area. The foam is subsequently rinsed away with clean water.
.. . . . .
:SO
EXAMPLES
The invention is further illustrated by reference to the following examples.
Example 1 The foaming of three lauryl phosphate mixtures was investigated. Foaming was measured in vitro by the Ross-Miles procedure. A 0.3~ by weight concentration of the alkyl phosphate mixture in water was used, at 20C
and pH 7.5. Foam is generated by a standard method and the volume of foam is measured as a height in a cylinder.
Foaming was also measured by a trained panel who formed a lather in a standard procedure representing use of the mixture, diluted to 4.5% by weight alkyl phosphate(s), as a product for cleaning the skin. Each panellist estimated the volume and creaminess of the lather as scores on a scale. The lather was also collected and its volume measured.
Results are set out in the following Table 1. The values for estimated/perceived volume and creaminess are totals of panel scores.
TABLE 1 - FOAM PROPERTIES OF MAP:DAP RATIOS
Ratio of In vitro In vivo MAP:DAP Foam Measured Estimated Perceived alkyl ~ lauryl Height (mm) Volume (ml) /Volume Creaminess 100 : 0 153 30 118 124 3075 : 25 135 28 96 99 60 : 40 92 23 52 60 It is apparent that the presence of dialkyl phosphate inhibits foaming.
28 - ~ 3 '~
Example 2 A mixture of monolauryl phosphate and dilauryl phosphate in 75:25 weight ratio was mixed with each of a range of surfactants. The foaming of the resulting mixtures was tested by the Ross-Miles method as in Example 1.
Each test solution contained 0.30% of the alkyl phosphate mixture and 0.06% of the other surfactant(s).
The surfactants used and the foam heights are set out in the following Table 2.
These results shows that cocoamidopropyl betaine (CAPB) gave superior foaming and more than overcame the antifoam effect of the dilauryl phosphate.
- 29 - J3130 ~ $ ~
Co-active Trade Name Manufacturer Foam Heiqht (mmL
CAPB Tegobetaine L7 Goldschm;dt 154 Lauryl Sulpho- Nikkol LSA Nikko Chemicals 52 acetate Disodium Lauryl Rewopol SBFA Rewo 136 Ethoxy Sulpho-succinate Secondary n-Alkyl Hostapur SAS Hoechst 132 Sulphonate Sodium N-Cocoyl-N- Fenopon TC42 Rhone- 136 Methyl Taurate Poulenc C9-Cll (6EO) Dobanol 91-6 Shell 129 Alcohol Ethoxylate Sodium Lauryl Empicol ES8 70 Albright & Wilson 141 Ether (2EO) Sulphate Coconut Oi Ethanol- Cyclomide CD Witco 99 amide/Coconut Fatty Acid Sodium Alkyl PEG-10 Marlinat CMlOS Huls 136 Acetate Sodium Isostearyl Crolactil 515L Croda 121 Lactylate Saponin Glycoside Agrofoam SO Paroxite 141 TEA Lauryl Sulphate Empicol TL40/% Albright & Wilson 106 Coconut Mono Empilan CME Albright & Wilson 28 Ethanolamide Lauryl/Myristyl Empigen 08 Albright & Wilson 18 Dimethyl Amine Oxide .. , - : , ~3 ~"~
Example 3 Mixtures of monolauryl phosphate and dilauryl phosphate were mixed with cocoamidoporpyl betaine (CAPB) and diluted to an aqueous solution containing 4.5~ by weight alkyl phosphates and n. 8~ by weight CAPB. These solutions were assessed by a trained panel as in Example 1.
At the same time a commercial product was diluted to the same alkyl phosphate concentration and tested as a comparison. This product contained mono and dialkyl phosphates in a ratio of >80 : <20 (i.e. a mixture containing more than 80~ MAP).
The results are set out in the following Table 3.
MAP:DAPCo-active Measured Estimated/Perceived RatioVolume (ml) Volume Creaminess 75:25CAPB 43 123 109 60:40CAPB 36 118 113 Commercial Product 25 95 133 2~
Example 4 Mixtures of monolauryl phosphate and dilauryl phosphate were mixed with other materials and assessed by a trained panel for ease of lathering, lather volume and lather creaminess. The commercial product mentioned in Example 3 was also assessed by the panel. In each case the concentration of alkyl phosphates was 4.5~ by weight.
The other materials contained in the mixtures were 0.8% by weight of cocoamidopropyl betaine (CAPB, Tegobetaine L7) or 0.8% by weight of cocoamphodipropionate (Miranol C2M-SF) and 0.4~ by weight of cationic cellulosic polymer JR400.
The results (total panel scores) are set out in the following Table 4.
System Ease of Volume Creaminess Foaming MAP:DAP (75:25) 108.498.2 81.9 MAP:DAP (75:25) + CAPB 141.2 107.1 96.9 MAP:DAP (75:25) + CAPB + 135.0 137.4 141.2 polymer JR400 MAP:DAP (60.40) + Miranol133.0 129.9 130.6 C2M-SF ~ polymer JR400 Commercial produat 130.0130.0 140.0 The mixtures containing CAP~, with and without polymer JR400, were tested for zein solubilisation.
This test, first described by Gotte in Proc. Int. Congr.
Surface Active Subs. 4th, Brussels, 3 83-90, 1964, tests the liberation of zein (protein from corn kernel~ on exposure to surfactant. The result is expressed as 2~3~
percentage nitrogen in supernatant solution and correlates with harshness towards skin.
The results were:
MAP:DAP (75:25) + CAPB 0.68% N
above plus 0.4% polymer JR400 0.60% N
- Thus inclusion of polymer enhanaes mildness.
1~ Exam~le 5 This Example illustrates a body cleansing liquid product suitable for use in the shower.
The product contains the following ingredients:
Inaredients % w/w triethanolamine di-n-lauryl phosphate 18 triethanolamine mono-n-lauryl phosphate 18 cocoamphodiacetate (MIRANOL C2M-NP) 10 preservative 2 water to loo - 25 This product can be used for cleansing the whole body surface, including the hair, for example under the shower, a convenient amount of say 5ml being placed in the palm of the hand prior to distributing over the body surface with added water to create a lather with superior 3~ volume and creaminess characteristics.
The properties of the above product (the Test product) were tested against another product from which the cocoamphodiacetate was omitted (the Control product).
-- 33 ~
In this comparative test, strips of polyurethane foam were impregnated with equal quantities of the product according to the invention or the comparative product free from co-surfactant, each product first being diluted with tap water so that the concentration of alkyl phosphate in each case was 1~ by weight.
Each member of a panel of twenty assessors was then asked to produce a foam by manually kneeding one strip containing the Test product and the other containinq the Control product. Each panelist was then asked to decide which of the two samples gave the greater lather volume and the better lather creaminess. None of the panelists knew which sample was which.
The results of this test showed that the lather volume and lather creaminess of the Test product according to the invention containing triethanolamine di-n-lauryl phosphate, triethanolamine mono-n-lauryl phosphate and the cocoampho diacetate was superior to that containing only the triethanolamine di-n-lauryl phosphate and triethanolamine mono-n-lauryl phosphate, this difference being significantly different at the 95%
level.
2s From this test it was concluded that the product according to the invention, the Test product, was superior to the Control product.
~o ~35~
Examples 6 toll illustrate body shampoos for use in the shower or when bathing.
Example 6 96 w/w triethanolammonium monolauryl phosphate 18 triethanolammonium dilauryl phosphate 6 cocoamphodipropionate ~MIRANOL C2M-SF) 5 ~ ~
lo triethanolammonium laurate triethanolammonium myristate 2 lauryldimethylamine oxide 2 myristyldiethylamine oxide 0.5 cationised cellulose 0.1 propylene glycol 10 water to 100 Example,Z
% w/w triethanolamine monolauryl phosphate 21 triethanolamine dilauryl phosphate 9 cocoamidopropyl betaine (TEGOBETAINE L7) 8 lauryl dimethylbetaine 3 ethylene glycol monostearate 1.5 propylene glycol 2.5 preservative, perfume, dyes q.v.
water to 100%
~o ~ ~ 3 Example 8 ~ w/w sodium mono-(diethyleneglycol-mono-n-dodecyl ether) phosphate 10 sodium di-(diethyleneglycol-mono-n-dodecyl ether? phosphate 10 cocoamphodiacetate 12 triethanolammonium laurate triethanolammonium myristate 2 alkyldialkylamine oxide (EMIGEN OB
30% active) 8.3 cationised cellulose 0.1 propylene glycol 10 lS water to 100 Example 9 % w/w triethanolammonium mono-(ethyleneglycol-mono-n-decyl ether) phosphate 10 triethanolammonium s di-(ethyleneglycol-~ono-n-octadecenyl.
ether) phosphate 8 cocoamphodipropionate (MIRANOL C2M-SF) 9 lauryl dime~hylbetaine 3 ~0 ethylene glycol monostearate 1.5 propylene glycol 2.5 preservative, perfume, dyes q.v.
water to 100%
2~3'~
Example 10 triethanolammonium S mono-(ethyleneglycol-mono-n-decyl ether) phosphate 20 triethanolammonium di-(ethyleneglycol-mono-n-octadecyl ether) phosphate 3 cocoamidopropyl betaine (TEGOBETAINE ~7) 10 triethanolammonium laurate triethanolammonium myristate2 alkyldialkylamine oxide (EMIGEN OB) 30% active) 8.3 lS cationised cellulose 0.1 propylene glycol 10 water to 100 Example 11 % w~w sodium mono-(7-methyldecyl) phosphate 18 sodium di-(7-methyldecyl) phosphate 12 cocoamphodiacetate . . 15 -lauryl dimethylbetaine 3 ethylene glycol monostearate 1.5 propylene glycol 2.5 preservative, perfume, dyes q.v.
water to 100%
Examples<12,13 & 14 The following three examples illustrate soap-containing products in accordance with the invention.
s In each case, the products were made in accordance with standard soap manuPacture. The product of Example 8 yielded a flaked product which could not readily be pressed into a bar, as the flakes were not sufficiently cohesive. With the products of Examples 9 and 10, bars were formed following the usual plodding, extrusion and stamping that is conventional in soap bar manufacture.
These soap products had the following formulations:
lS
Examples Ingredient 12 13 14 (% by weight) Hardened Tallow Soap S9 54 80/20 tallow-coco soap - 7 66 sodium dilauryl phosphate 4 -6 2 sodium monolauryl phosphate 12 15 17 cocoamidopropyl betaine (TEGOBETAINE L7~ 5 8 10 water 20 10 5 ~o
Claims (21)
1. A composition suitable for topical application to the skin or hair, which comprises:
(a) from 1 to 99% by weight of monoalkyl or monoalkenyl phosphate surfactant having the structure (1):
(1) (b) from 1 to 50% by weight of dialkyl or dialkenyl phosphate surfactant having the structure (2):
(2) where R01 is selected from the group consisting of branched or unbranched alkyl and alkenyl groups having an average of from 10 to 18 carbon atoms;
R02 and R03 are each selected from the group consisting of branched or unbranched alkyl and alkenyl groups having an average of from 10 to 18 carbon atoms;
X, Y and Z are each selected from the group consisting of hydrogen alkali metal, ammonium and substituted ammonium counterions;
a and b are each o or a value of from 1 to 10; and c is 0 or a value of from 1 to 4; and (c) from: 1 to 50% by weight of a co-surfactant selected from the group consisting of i. alkylamidopropyl betaines, having the structure (11) (11) and ii. alkylamphoglycinates, having the structure (12):
(12) where R04 is C10-16 alkyl R05 and R06 are the same or different and are selected from CH2COO- and (CH2)2COO-.
(a) from 1 to 99% by weight of monoalkyl or monoalkenyl phosphate surfactant having the structure (1):
(1) (b) from 1 to 50% by weight of dialkyl or dialkenyl phosphate surfactant having the structure (2):
(2) where R01 is selected from the group consisting of branched or unbranched alkyl and alkenyl groups having an average of from 10 to 18 carbon atoms;
R02 and R03 are each selected from the group consisting of branched or unbranched alkyl and alkenyl groups having an average of from 10 to 18 carbon atoms;
X, Y and Z are each selected from the group consisting of hydrogen alkali metal, ammonium and substituted ammonium counterions;
a and b are each o or a value of from 1 to 10; and c is 0 or a value of from 1 to 4; and (c) from: 1 to 50% by weight of a co-surfactant selected from the group consisting of i. alkylamidopropyl betaines, having the structure (11) (11) and ii. alkylamphoglycinates, having the structure (12):
(12) where R04 is C10-16 alkyl R05 and R06 are the same or different and are selected from CH2COO- and (CH2)2COO-.
2. A composition according to claim 1, in which the monoalkyl phosphate moiety of the dialkyl phosphate surfactant is selected from the group consisting of:
mono-n-decyl phosphate mono-n-dodecyl phosphate=(mono-lauryl phosphate) mono-n-tetradecyl phosphate=(monomyristyl phosphate) mono-n-hexadecyl phosphate mono-n-octadecyl phosphate.
mono-(diethyleneglycol-mono-n-dodecyl ether) phosphate mono-(ethyleneglycol-mono-n-decyl ether) phosphate mono-n-tetradecenyl phosphate mono-n-hexadecenyl phosphate mono-n-octadecenyl phosphate mono-n-decenyl phosphate mono-n-dodecenyl phosphate mono-(triethyleneglycol-mono-n-dodecenyl ether) phosphate mono-(ethyleneglycol-mono-n-tetradecenyl ether) phosphate mono-7-methyldecyl phosphate mono-5-methyldodecenyl-phosphate mono-6,6-dimethyltetradecyl phosphate mono-(ethyleneglycol-mono-n-octadecyl ether) phosphate mono-(diethyleneglycol-mono-n-octadecenyl ether) phosphate mono-(polyethyleneglycol[5E0]-monooleyl ether) phosphate mono-(polyethyleneglycol[3EO]-monolauryl ether) phosphate
mono-n-decyl phosphate mono-n-dodecyl phosphate=(mono-lauryl phosphate) mono-n-tetradecyl phosphate=(monomyristyl phosphate) mono-n-hexadecyl phosphate mono-n-octadecyl phosphate.
mono-(diethyleneglycol-mono-n-dodecyl ether) phosphate mono-(ethyleneglycol-mono-n-decyl ether) phosphate mono-n-tetradecenyl phosphate mono-n-hexadecenyl phosphate mono-n-octadecenyl phosphate mono-n-decenyl phosphate mono-n-dodecenyl phosphate mono-(triethyleneglycol-mono-n-dodecenyl ether) phosphate mono-(ethyleneglycol-mono-n-tetradecenyl ether) phosphate mono-7-methyldecyl phosphate mono-5-methyldodecenyl-phosphate mono-6,6-dimethyltetradecyl phosphate mono-(ethyleneglycol-mono-n-octadecyl ether) phosphate mono-(diethyleneglycol-mono-n-octadecenyl ether) phosphate mono-(polyethyleneglycol[5E0]-monooleyl ether) phosphate mono-(polyethyleneglycol[3EO]-monolauryl ether) phosphate
3. A composition according to claim 1 in which the monoalkyl phosphate surfactant is mono-n-dodecyl phosphate salt.
4. A composition according to claim 1 in which the monoalkyl or monoalkenyl phosphate surfactant forms from 2 to 50% by weight of the composition.
5. A composition according to claim 1 in which the dialkyl phosphate moiety of the dialkyl phosphate surfactant is selected from the group consisting of:
di-n-decyl phosphate di-n-dodecyl phosphate (dilauryl phosphate) di-n-tetradecyl phosphate (dimyristyl phosphate) di-n-hexadecyl phosphate di-n-octadecyl phosphate di-n-dodecenyl phosphate di-(7-methyldecyl) phosphate di-(ethyleneglycol-mono-n-octadecyl ether) phosphate di-(diethyleneglycol-mono-n-octadecenyl ether) phosphate di-(polyethyleneglycol[5EO]-monooleyl ether) phosphate di-(polyethyleneglycol[3EO]-monolauryl ether) phosphate
di-n-decyl phosphate di-n-dodecyl phosphate (dilauryl phosphate) di-n-tetradecyl phosphate (dimyristyl phosphate) di-n-hexadecyl phosphate di-n-octadecyl phosphate di-n-dodecenyl phosphate di-(7-methyldecyl) phosphate di-(ethyleneglycol-mono-n-octadecyl ether) phosphate di-(diethyleneglycol-mono-n-octadecenyl ether) phosphate di-(polyethyleneglycol[5EO]-monooleyl ether) phosphate di-(polyethyleneglycol[3EO]-monolauryl ether) phosphate
6. A composition according to claim 1 in which the dialkyl phosphate surfactant is a sodium, a potassium or a triethanolamine salt.
7. A composition according to claim 1 in which the dialkyl phosphate surfactant forms from 1 to 10% by weight of the composition.
8. A composition according to claim 1 in which the weight ratio of the monoalkyl or monoalkenyl phosphate surfactant to the dialkyl or dialkenyl phosphate surfactant is from 95:5 to 25:75.
9. A composition according to claim 1 in which the weight ratio of the monoalkyl or monoalkenyl phosphate surfactant to the dialkyl or dialkenyl phosphate surfactant is from 75:25 to 50:50.
10. A composition according to claim 1 which further comprises a supplementary anionic surfactant.
11. A composition according to claim 1 which further comprises a supplementary nonionic surfactant.
12. A composition according to claim 1 which further comprises a supplementary zwitterionic surfactant.
13. A composition according to claim 1 which is a liquid or gel product
14. A composition according to claim 13, which further comprises a polymeric thickener.
15. A composition according to claim 13 which is a washing product suitable-for topical application to the face.
16. A composition according to claim 1 which is a shampoo;
17. A composition according to claim 1 which is a powder
18, A composition according to claim 1 which is a bar or tablet suitable for washing the skin.
19. A process for preparing a composition according to claim 1 which process comprises the steps of:
i. preparing a mixture comprising:
a. 1 to 99% by weight of one or more monoalkyl or monoalkenyl phosphate surfactants having the structure (1):
(1) b. 1 to 50% by weight of one or more dialkyl or dialkenyl phosphate surfactants having the structure (2):
(2) R01 is selected from the group consisting of branched or unbranched alkyl and alkenyl groups having an average of from 10 to 18 carbon atoms where R02 and R03 are each selected from the group consisting of branched or unbranched alkyl and alkenyl groups having an average of from 10 to 18 carbon atoms;
X, Y and Z are each selected from the group consisting of H, alkali metal, ammonium and substituted ammonium counterions;
a and b are each 0 or a value of from 1 to 10;
c is 0 or a value of from 1 to 4;
and c. 1 to 50% by weight of a co-surfactant selected from the group consisting of i. alkylamidopropyl betaines, having the structure (11):
(11) and ii. alkylamphoglycinates, having the structure (12):
(12) where R04 is C10-16 alkyl R05 and R06 are the same or different and are selected from the group consisting of CH2COO- and (CH2)2COO-; and iii. subsequently packaging the composition so formed into containers.
i. preparing a mixture comprising:
a. 1 to 99% by weight of one or more monoalkyl or monoalkenyl phosphate surfactants having the structure (1):
(1) b. 1 to 50% by weight of one or more dialkyl or dialkenyl phosphate surfactants having the structure (2):
(2) R01 is selected from the group consisting of branched or unbranched alkyl and alkenyl groups having an average of from 10 to 18 carbon atoms where R02 and R03 are each selected from the group consisting of branched or unbranched alkyl and alkenyl groups having an average of from 10 to 18 carbon atoms;
X, Y and Z are each selected from the group consisting of H, alkali metal, ammonium and substituted ammonium counterions;
a and b are each 0 or a value of from 1 to 10;
c is 0 or a value of from 1 to 4;
and c. 1 to 50% by weight of a co-surfactant selected from the group consisting of i. alkylamidopropyl betaines, having the structure (11):
(11) and ii. alkylamphoglycinates, having the structure (12):
(12) where R04 is C10-16 alkyl R05 and R06 are the same or different and are selected from the group consisting of CH2COO- and (CH2)2COO-; and iii. subsequently packaging the composition so formed into containers.
20. A method of washing human skin or hair characterised by the use of a composition according to claim 1.
21. The composition suitable for topical application as claimed in claim 1 and substantially as described herein.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB909003199A GB9003199D0 (en) | 1990-02-13 | 1990-02-13 | Topical composition |
| GB9003199.8 | 1990-02-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2035984A1 true CA2035984A1 (en) | 1991-08-14 |
Family
ID=10670884
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002035984A Abandoned CA2035984A1 (en) | 1990-02-13 | 1991-02-08 | Topical composition |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US5139781A (en) |
| EP (1) | EP0442701B1 (en) |
| JP (1) | JPH04211009A (en) |
| KR (1) | KR960014786B1 (en) |
| AT (1) | ATE137111T1 (en) |
| AU (1) | AU631721B2 (en) |
| BR (1) | BR9100584A (en) |
| CA (1) | CA2035984A1 (en) |
| DE (1) | DE69118944T2 (en) |
| GB (1) | GB9003199D0 (en) |
| IN (1) | IN172847B (en) |
| MY (1) | MY105314A (en) |
| ZA (1) | ZA911067B (en) |
Families Citing this family (36)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9204175D0 (en) * | 1992-02-27 | 1992-04-08 | Unilever Plc | Cleansing composition |
| US5334387A (en) * | 1993-02-23 | 1994-08-02 | Colgate-Palmolive Company | Topical composition comprising mono and dialkyl phosphates with a cosurfactant |
| US5387372A (en) * | 1993-03-05 | 1995-02-07 | Colgate-Palmolive Company | Composition for cleansing body with high foaming action |
| DE4412235A1 (en) * | 1993-04-16 | 1994-10-20 | Colgate Palmolive Co | Body cleansing composition |
| ZA951012B (en) * | 1994-02-14 | 1996-08-08 | Colgate Palmolive Co | Composition |
| US5441671A (en) * | 1994-03-01 | 1995-08-15 | Chesebrough-Pond's Usa Co., Division Of Conopco, Inc. | Skin cleansing composition |
| US5635462A (en) * | 1994-07-08 | 1997-06-03 | Gojo Industries, Inc. | Antimicrobial cleansing compositions |
| WO1996014145A1 (en) * | 1994-11-04 | 1996-05-17 | Croda, Inc. | Fatty alcohol phosphate ester emulsifier compositions |
| US5556630A (en) * | 1995-01-03 | 1996-09-17 | Chesebrough-Pond's Usc Co., Division Of Conopco, Inc. | Cold creams containing acyl lactylates |
| US5605676A (en) * | 1995-06-26 | 1997-02-25 | Colgate-Palmolive Company | Oral composition exhibiting improved uptake and retention of antibacterial compounds on dental tissue surfaces |
| ES2126495B1 (en) * | 1996-11-05 | 1999-12-01 | Kao Corp Sa | CONCENTRATED AQUEOUS COMPOSITIONS OF BETA-TYPE SURFACTANTS AND THEIR PROCEDURE FOR OBTAINING. |
| US5800803A (en) * | 1997-02-10 | 1998-09-01 | Colgate-Palmolive Company | Oral composition exhibiting enhanced uptake by dental tissue of noncationic antibacterial agents |
| DE19707800A1 (en) | 1997-02-27 | 1998-09-03 | Clariant Gmbh | Mixtures of alkyl phosphoric acid esters and their use as cosmetic and pharmaceutical emulsifiers |
| DE19711452A1 (en) | 1997-03-19 | 1998-09-24 | Sca Hygiene Paper Gmbh | Moisture regulator-containing composition for tissue products, process for the production of these products, use of the composition for the treatment of tissue products and tissue products in the form of wetlaid, including TAD or airlaid (non-woven) based on flat carrier materials predominantly containing cellulose fibers |
| ATE210954T1 (en) * | 1997-08-18 | 2002-01-15 | Neubourg Stephanie | FOAM SKIN PROTECTION CREAM |
| ZA989994B (en) * | 1997-11-10 | 1999-05-05 | Kimberly Clark Co | Wet wipes containing a mono alkyl phosphate |
| US6030931A (en) * | 1998-02-03 | 2000-02-29 | Chesebrough-Pond's Usa Co., Division Of Conopco, Inc. | Foaming cleansing skin product |
| US6262130B1 (en) | 1998-11-24 | 2001-07-17 | Rhodia, Inc. | High solids, pumpable aqueous compositions of high monoalkyl phosphate ester salt content |
| US9139731B2 (en) | 1999-11-12 | 2015-09-22 | The Procter & Gamble Company | Compositions and methods for improving overall tooth health and appearance |
| US6673358B1 (en) | 1999-12-16 | 2004-01-06 | Kimberly-Clark Worldwide, Inc. | Wet wipes containing a mono alkyl phosphate |
| US6649578B1 (en) * | 2000-01-28 | 2003-11-18 | Applied Carbo Chemicals Inc. | Di-carboxy alkyl phosphate esters in personal care applications |
| DE10035207A1 (en) * | 2000-07-20 | 2002-01-31 | Beiersdorf Ag | Shaped soap product containing talc, one or more fatty acids in the form of their alkali soaps and one or more amphoteric surfactants in the absence of alky / olig) glycosides |
| DE10035211A1 (en) * | 2000-07-20 | 2002-01-31 | Beiersdorf Ag | Shaped soap product containing talc, one or more fatty acids in the form of their alkali soaps and one or more nonionic surfactants in the absence of alkyl (oligo) glycosides |
| US6566408B1 (en) * | 2000-08-01 | 2003-05-20 | Rhodia, Inc. | Aqueous surfactant compositions of monoalkyl phosphate ester salts and amphoteric surfactants |
| ATE341391T1 (en) | 2001-06-04 | 2006-10-15 | Rhodia | PUMPABLE LIQUID SURFACTANT COMPOSITIONS COMPRISING ALKANOLAMIN SALTS OF ALKYLPHOSPHATE ESTERS |
| US7838447B2 (en) * | 2001-12-20 | 2010-11-23 | Kimberly-Clark Worldwide, Inc. | Antimicrobial pre-moistened wipers |
| JP4173712B2 (en) * | 2002-04-12 | 2008-10-29 | 花王株式会社 | Cleaning composition |
| WO2004092315A1 (en) * | 2003-04-14 | 2004-10-28 | Kao Corporation | Cleaning agent composition |
| JP4663540B2 (en) * | 2006-02-07 | 2011-04-06 | 花王株式会社 | Hair treatment agent |
| WO2009078857A1 (en) * | 2007-12-17 | 2009-06-25 | Colgate-Palmolive Company | Cleansing bars |
| WO2011031807A2 (en) * | 2009-09-11 | 2011-03-17 | The Procter & Gamble Company | Methods and compositions for hydrophobic modification of oral cavity surfaces |
| US8729137B2 (en) | 2009-12-23 | 2014-05-20 | Colgate-Palmolive Company | Cleansing bar |
| BR112015013012A2 (en) | 2012-12-07 | 2017-07-11 | Colgate Palmolive Co | bar soap composition and method for its manufacture |
| EP3221439B1 (en) | 2014-12-05 | 2019-03-20 | Colgate-Palmolive Company | Cleansing bars with phenoxyethanol |
| AU2014412810B2 (en) | 2014-12-05 | 2018-04-19 | Colgate-Palmolive Company | Cleansing bars with taurine |
| EP3383358B1 (en) | 2015-12-31 | 2021-05-19 | Colgate-Palmolive Company | Cleansing bars |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2758093A (en) * | 1948-06-22 | 1956-08-07 | Textilana Corp | Laundering compositions containing ortho-phosphoric acid esters |
| JPS5326806A (en) * | 1976-08-24 | 1978-03-13 | Kao Corp | Low irritating detergent composition |
| JPS5846160B2 (en) * | 1978-07-13 | 1983-10-14 | 花王株式会社 | Shampoo - Composition |
| US4375421A (en) * | 1981-10-19 | 1983-03-01 | Lever Brothers Company | Viscous compositions containing amido betaines and salts |
| JPS5874798A (en) * | 1981-10-28 | 1983-05-06 | 花王株式会社 | Shampoo composition |
| JPS5943517B2 (en) * | 1981-12-14 | 1984-10-22 | 花王株式会社 | liquid cleaning composition |
| JPS6191137A (en) * | 1984-10-11 | 1986-05-09 | Kao Corp | External drug composition |
| ES2026844T3 (en) * | 1985-11-28 | 1992-05-16 | Kao Corporation | A DETERGENT COMPOSITION. |
| JPH0246639B2 (en) * | 1985-12-12 | 1990-10-16 | Kao Corp | SENJOZAISOSEIBUTSU |
| JP2566446B2 (en) * | 1988-06-15 | 1996-12-25 | サンスター株式会社 | Transparent detergent composition |
| LU87249A1 (en) * | 1988-06-17 | 1990-02-28 | Oreal | COMPOSITION FOR INDUCING AND STIMULATING HAIR GROWTH AND / OR BRAKING HAIR LOSS, BASED ON AN AMPHOTERIC SURFACTANT AND A PYRIMIDINE DERIVATIVE |
| GB8828017D0 (en) * | 1988-12-01 | 1989-01-05 | Unilever Plc | Topical composition |
| GB8828013D0 (en) * | 1988-12-01 | 1989-01-05 | Unilever Plc | Topical composition |
| GB9000704D0 (en) * | 1990-01-12 | 1990-03-14 | Unilever Plc | Topical composition |
-
1990
- 1990-02-13 GB GB909003199A patent/GB9003199D0/en active Pending
-
1991
- 1991-02-08 CA CA002035984A patent/CA2035984A1/en not_active Abandoned
- 1991-02-08 AU AU70867/91A patent/AU631721B2/en not_active Ceased
- 1991-02-08 BR BR919100584A patent/BR9100584A/en not_active Application Discontinuation
- 1991-02-08 IN IN42BO1991 patent/IN172847B/en unknown
- 1991-02-12 AT AT91301125T patent/ATE137111T1/en not_active IP Right Cessation
- 1991-02-12 DE DE69118944T patent/DE69118944T2/en not_active Expired - Fee Related
- 1991-02-12 MY MYPI91000229A patent/MY105314A/en unknown
- 1991-02-12 EP EP91301125A patent/EP0442701B1/en not_active Revoked
- 1991-02-13 KR KR91002428A patent/KR960014786B1/en not_active IP Right Cessation
- 1991-02-13 ZA ZA911067A patent/ZA911067B/en unknown
- 1991-02-13 US US07/655,517 patent/US5139781A/en not_active Expired - Fee Related
- 1991-02-13 JP JP3041243A patent/JPH04211009A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0442701A3 (en) | 1993-04-14 |
| US5139781A (en) | 1992-08-18 |
| JPH04211009A (en) | 1992-08-03 |
| AU7086791A (en) | 1991-08-15 |
| DE69118944D1 (en) | 1996-05-30 |
| KR960014786B1 (en) | 1996-10-19 |
| GB9003199D0 (en) | 1990-04-11 |
| IN172847B (en) | 1993-12-11 |
| EP0442701A2 (en) | 1991-08-21 |
| ATE137111T1 (en) | 1996-05-15 |
| AU631721B2 (en) | 1992-12-03 |
| BR9100584A (en) | 1991-10-29 |
| MY105314A (en) | 1994-09-30 |
| KR910015285A (en) | 1991-09-30 |
| EP0442701B1 (en) | 1996-04-24 |
| ZA911067B (en) | 1992-10-28 |
| DE69118944T2 (en) | 1996-09-19 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |