Abstract: An liquid cleansing composition is disclosed that contains a specific levels of polyol(s), monoalkyl sulfosuccinate surfactant(s), N-acyl amino acid(s) or salt(s) thereof, and optionally monoalkyl phosphate(s) that provides excellent user properties including fast rinsing, squeaky clean feel and excellent lather.
J6941/C
FORM - 2
THE PATENTS ACT, 1970
(39 of 1970)
&
The Patents Rules, 2003
COMPLETE SPECIFICATION
(See Section 10 and Rule 13)
LIQUID CLEANSING COMPOSITION WITH UNIQUE SENSORY PROPERTIES
HINDUSTAN UNILEVER LIMITED, a company incorporated under the Indian Companies Act, 1913 and having its registered office at Hindustan Lever House, 165/166, Backbay Reclamation, Mumbai -400 020, Maharashtra, India
The following specification particularly describes the invention and the manner in which it is to be performed
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LIQUID CLEANSING COMPOSITION WITH UNIQUE SENSORY PROPERTIES
The present invention relates to detergent compositions
suitable for topical application for cleansing the human
body, such as the skin and hair. In particular, it relates
to stable liquid cleansing compositions containing a
specific combination of polyol(s), monoalkyl
sulfosuccinate(s) , n-acyl amino acid surfactant(s) and
optionally monoallkyl phosphate(s).
Prior art skin cleansers modify the way the skin feels after
the shower by depositing materials such as oils or polymers.
However, such cleansers often have disadvantageous sensory
or physical properties, such as a slimy feel and/or poor
lather. Stability problems are observed with other
combinations of hydrophilic emollients and surfactants.
EP patent application No.1235890 entitled Stable, High Glycerol Liquids Comprising N-Acyl Amino Acids and/or Salts
and issued to Arai et al. discloses high content glycerol liquid compositions comprising N-acyl amino acids and/or salts and defined sulfosuccinic acid monoesters, and a method of enhancing the stability of high content glycerin compositions comprising N-acyl amino acids or salt's thereof
and sulfosuccinic acid monoesters.
Surprisingly it has been discovered that by incorporating specific emollients and surfactants in specific amounts in a cleanser formulation, excellent sensory and lather properties' can be obtained simultaneously.
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In a first aspect of the invention, there is provided a cleansing composition including but not limited to:
- about 30 % to 54 % by wt. of total polyol(s);
preferably at least about 35 % by wt.;
- about 5 % to 10 % by wt. of total normal C10 to C16 mono alkyl sulfosuccinate (s), and
- about 0.6 % to 9 % by wt. of N-acyl amino acid(s) or salt(s) of such acid(s) or a blend there of; preferably
about 1 % to 9 % by wt.
In a further aspect of the invention, there is provided a method for cleansing the skin or hair with a quick rinsing cleansing composition having durable lather, including but 15 not limited to the steps of:
a. applying the durable lathering composition
containing about 30 % to 54 % by wt. of total
polyol(s); about 5 % to 10 % by wt. of total normal
C10 to C16 mono alkyl sulfosuccinate (s) , and about
20 0.6 % to 9 % by wt. of N-acyl amino acid(s) or
salt(s) of such acid(s) or a blend there of to the skin or hair;
b. rinsing the composition from the skin or hair; and
c. drying the skin or hair.
25
In a further aspect, of the invention, .there is provided a cleansing composition including but not limited, to:
about 30 % to 54 % by wt. of total polyol(s); preferably 30 at least about 35 % by wt.;
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about 5 % to 10 % by wt. of total normal C10 to C16 mono alkyl sulfosuccinate(s), and
about 0.6 % to 9 % by wt. of N-acyl amino acid(s) or 5 salt(s) of such acid(s) or a blend there of; preferably about 1 % to 9 % by wt.
In a preferred embodiment, the inventive composition further includes at least about 2 % to 5 % by wt. of total normal C8
10 to C24 mono alkyl phosphate(s). Advantageously the
composition further includes at least about 15 % by wt. of water (preferably at least about 30 %• by wt. of water) . Preferably the ratio of total mono alkyl sulfosuccinate(s) to total mono alkyl phosphate (s) is in the range of about
15 1:10 to about 10.: 1, more preferably in the range of about 9:2 to about 2:9. Advantageously the ratio of total mono alkyl sulfosuccinate(s) to total N-acyl amino acid surfactant(s) is in the range of about 1:10 to about 10:1, preferably in the range of about 9:3 to about 3:9.
20
In a further preferred embodiment, the polyol(s) is/are selected from glycerin, diglycerin, ethoxylated glycerin, propoxylated glycerin,, propylene glycol, dipropylene glycol, polypropylene glycol, polyethylene glycol, sorbitol,
25 hydroxypropyl sorbitol hexylene glycol, 1,3-butylene glycol or 1,2,6-hexanetriol or blends thereof and/or the monoalkyl sulfosuccinate(s) is/are selected from CIO, C12 or C14 monoalkyl sulfosuccinate(s) or blends thereof. When present, the mono alkyl phosphate (s) can be in either the
30 acid or neutralized form, preferably where the alkyl group ■ is in the range of C6 to C20. Advantageously the N-acyl
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amino acid surfactant(s) has/have alkyl chain length (s) in the range of C8 to C16.
In a further preferred embodiment, the inventive composition 5 has a viscosity is in the. range of about 5,000 to 1,000,000 cps at 25°C as' measured via the T-bar method. Preferably the composition further includes about 0.1 % to 15 % by wt. of an ordered liquid crystalline phase inducing structurant inducing a liquid crystalline phase in the composition. 10 More preferably the ordered liquid crystalline phase cleansing composition is a lamellar composition.
Advantageously the ordered liquid crystalline phase inducing structurant is selected from a C8 to C24 alkenyl or a
15 branched alkyl fatty acid or ester thereof, a C8 to C24
alkenyl or a branched alkyl alcohol or ether thereof, a C5 to C14 linear alkyl fatty acid, trihydroxystearin, or derivatives or mixtures thereof. Advantageously the ordered liquid crystalline phase inducing structurant is selected
20 from lauric acid, oleic acid, palm kernel acid, 'palm fatty acid, coconut acid, isostearic acid, or derivatives or mixtures thereof.
In a further preferred embodiment, the inventive composition 25 includes cationic polymer(s) in a total concentration of greater than about 0.1 % by wt. (preferably greater than about 0.2, 0.5', 1 or 2 %. by wt.). Preferably the composition further includes less than about 4 % by wt. of total tri- and diglyceride oil(s), more preferably less than 30 about 1 % by wt.'of total tri-and diglyceride oil(s)).
Advantageously the composition further includes less than
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about 1 % by wt. of diakylene glycol(s), preferably less than about 0.8 % by wt. of diakylene glycol(s). More preferably the composition further includes less than about 5 % by wt. of soap(s), preferably less than about 4, 3, 2, 5 or 1 % by wt. of soap(s).
In a further aspect of the invention there is provided a method for cleansing the skin or hair with a quick rinsing cleansing composition having durable lather, including but
10 not limited to the steps of applying to the skin, or hair the durable lathering composition including at least about 30 % to 54 % by wt. of total polyol(s); about 5 % to 10 % by wt. of total normal C10 to C16 mono alkyl sulfosuccinate (s) , and about 0.6 % to 9 % by wt. of N-acyl amino acid(s) or salt(s)
15 of such acid(s) or a blend there of; rinsing the composition from the skin or hair; and drying the skin or hair.
Preferably the inventive compositions have at least one sensory attribute as defined in the Panel Test Method for
20 Sensory and Physical Properties protocol described below that is superior compared to comparative composition (s) . More preferably the inventive compositions have at least 2, 3, 4 or more sensory attributes with superior properties. Advantagously the inventive compositions are found to be
25 stable according the stablity criteria summarized below compared to comparative composition(s). These attributes preferably include one or more of the following: ease of . pouring, thickness, amount of lather, creaminess of lather, ease of rinse, and slippery wet as defined below.
30
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Surfactants are an essential component of the inventive cleansing composition. They are compounds that have hydrophobic and hydrophilic portions that act to reduce the • surface tension of the aqueous solutions they are dissolved 5 in. In addition to the surfactants required by the
invention, other useful surfactants can be added to the inventive composition and can include anionic, nonionic, amphoteric, and cationic surfactants, and blends thereof.
10 The cleansing composition of the present invention contains monoalkyl sulfosuccinate(s) (e.g., C6-C22 sulfosuccinates); N-acyl amino acids and optionally monoalkyl phosphate(s) (e.g. C8-C24 alkyl phosphates).
15 Acyl groups in the N-acyl amino acids and salts thereof which are suitable for the purposes of the present invention have 6 to 24 carbon atoms; for example, lauryl, myristyl, palmityl, or the like is included. The amino acids include glutamic acid, glycine and beta-alanine. The salts include alkali
20 metal salts, hydroxyalkyl substituted ammonium salts and
ammonium salts. The hydroxyalkyl substituted ammonium salts may preferably have 1 to 3 carbon atoms in the hydroxyalkyl' group. N-acyl-N-alkyl amino acids are also included in the term "N-acyl amino acids" used herein. The alkyl groups in
25 the N-acyl-N-alkyl amino acids may preferably have 1 to 3 carbon atoms and include methyl, ethyl, propyl, and isopropyl. These N-acyl amino acids and salts thereof may be used independently or as a combination of two or more.
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Preferred N-acyl amino acids and salts thereof may include N-acyl amino acids such as N-lauroylglutamic acid, N-myristoylglutamic acid, N-palmitoyl-alpha-glutamic acid, N-myristoyl-beta- alanine, N-palmitoyl-beta-alanine, N-acyl N-5 alkyl amino acids such as N- lauroyl-N-ethylglycine, N-lauroyl-N-isopropylglycine, N-lauroylsarcosine, N-myristoylsarcosine, N-palmitoylsarcosine, N-lauroyl-N-methyl-beta- alanine, as well as their alkali metal salts and hydroxyal.kyl-substituted ammonium salts. 10
Monoalkyl sulfosuccinates having the formula:
R402CCH2CH(S03M)C02M
15 are usefully employed in the invention as described, above
4 wherein R ranges from Cio-Cie alkyl and M is a solubilizing
cation.
Other anionic detergent actives which may be used include 20 aliphatic sulfonates, such as a primary alkane (e.g., C8-C22) sulfonate, primary alkane (e.g., C8-C22) disulfonate, C8-C22
alkene sulfonate, C8-C22 hydroxyalkane sulfonate or alkyl
glyceryl ether sulfonate (AGS); or aromatic sulfonates such as alkyl benzene sulfonate. 25
The anionic may also be an alkyl sulfate (e.g., C12-C18 alkyl
sulfate) or an alkyl ether sulfate (including alkyl glyceryl ether sulfates). Among the alkyl ether sulfates are those having the formula:
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RO(CH2CH20)nS03M
wherein R is an alkyl or alkenyl having 8 to 18 carbons, preferably 12 to 18 carbons; n has an average value of greater than 1.0, preferably greater than 3; and M is a solubilizing cation such as sodium, potassium, ammonium or substituted ammonium. Ammonium and sodium lauryl ether sulfates are preferred.
10
The anionic, may also include dialkyl sulfosuccinates (e.g., C5-C22 sulfosuccinates), alkyl and acyl taurates, alkyl and
acyl sarcosinates, sulfoacetates, C8-C24 dialkyl phosphates,
alkyl phosphate esters and alkoxyl alkyl phosphate esters,
15 acyl lactates, C8-C22 monoalkyl succinates and maleates,
sulphoacetates, alkyl glucosides and acyl isethionates, and the like.
Amide-MEA sulfosuccinates of the formula:
20
R4CONHCH2CH202CCH2CH(SO3M)C02M
o
5
4 may be used wherein R ranges from C8-C22 alkyl, and M is a
solubilizing cation may be used.
Sarcosinates are generally indicated by the formula:
R1CON(CH3)CH2C02M,
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1 wherein R ranges from C8-C20 alkyl and M is a solubilizing
cation.
Taurates are generally identified by formula:
5
R2CONR3CH2CH2S03M
2 3
wherein R ranges from CB-C20 alkyl, R ranges from C3.-C4
alkyl and M is a solubilizing cation. 10
The inventive cleansing composition may contain Cs-Cis acyl
isethionates. These esters are prepared by reaction between alkali metal isethionate with mixed aliphatic fatty acids having from 6 to 18 carbon atoms and an iodine value of less 15 than 20. At least 75 % of the mixed fatty acids have from 12 to 18 carbon atoms and up to 25 % have from 6 to 10 carbon atoms.
The acyl isethionate may be an alkoxylated isethionate such 20 as is described in Ilardi et al., U.S. Patent No. 5,393,466, entitled "Fatty Acid Esters of Polyalkoxylated isethonic acid"; issued February 28, 1995; hereby incorporated by reference. This compound has the general formula:
25 RC-0(0)-C(X)H-C (Y)H2-(OCH-CHQ)m-S03M+
wherein R is an alkyl group having 8 to 18 carbons, m is an integer from 1 to 4, X and Y are hydrogen or an alkyl group
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having 1 to 4 carbons and M is a monovalent cation such as for example sodium, potassium or ammonium.
One or more amphoteric surfactants may be used in this 5 invention. Amphoteric surfactants are preferably used at levels as low as 1 % or 2 % by wt., and at levels as high as 6 % or 8 % by wt. Such surfactants include at least one acid group. This may be a carboxylic or a sulphonic acid group. They include quaternary nitrogen, and therefore are '10 quaternary amido acids. They should generally include an alkyl or alkenyl group of 7 to 18 carbon atoms. They will usually comply with an overall structural formula:
R1-[-C(0)-NH(CH2)n-]m-N+-(R2)(R3)X-Y
15
1 ">
where R is alkyl or alkenyl of 7 to 18 carbon atoms; R and
3 R are each independently alkyl, hydroxyalkyl or carboxyalkyl
of 1 to 3 carbon atoms; n is 2 to 4; m is 0 to 1; X is alkylene of 1 to 3 carbon atoms optionally substituted with
20 hydroxyl; and Y is -CC>2~ or -SO3-
Suitable amphoteric surfactants within the above general formula include simple betaines of formula:
25 R1-N+-(R2)(R3)CH2C02~
and amido betaines of formula:
R1-CONH(CH2)n-N+-(R2)(R3)CH2C02"
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where n is 2 or 3.
12 3
In both formulae R , R and R are as defined previously.
5 R may in particular be a mixture of Ci2 and C14 alkyl
groups derived from coconut oil so that at least half,
1 preferably at least three quarters of the groups R have 10
2 3 to 14 carbon atoms. R and R are preferably methyl.
A further possibility is that the amphoteric detergent is a 10 sulphobetaine of formula:
R1-N+-(R2) (R3) (CH2)3S03~
or 15
R1-CONH(CH2)m-N+-(R2)(R3)(CH2)3S03~
-(CH2)3SG3
where m is 2 or-3, or variants of these in which
is replaced by: 20
-CH2C(OH)(H)CH2S03~
12 3 In these formulae R , Rfc and R are as discussed previously.
25 Amphoacetates and diamphoacetates are also intended to be
covered in possible zwitterionic and/or amphoteric compounds which may be used such as e.g., sodium lauroamphoacetate, sodium cocoamphoacetate, and blends thereof, and the like.
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One or more nonionic surfactants may also be used in the cleansing composition of the present invention. Nonionic surfactants are preferably used at levels as low as 1 % or 2 % by wt. and at levels as high as 5 % or 6 % by wt. The 5 -nonionics which may be used include in particular the
reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols, acids, amides or alkylphenols with alkylene oxides, especially ethylene oxide either alone or with 10 propylene oxide.
Specific nonionic detergent compounds include alkyl (C6-C22) phenols ethylene oxide condensates, the condensation products of aliphatic (Cs-Cis) primary or secondary linear
15 or branched alcohols with ethylene oxide, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine. Other so-called nonionic detergent compounds include long chain tertiary amine oxides, long chain tertiary phosphine oxides and
20 dialkyl sulphoxide, and the like.
The nonionic may also be a sugar amide, such as a polysaccharide amide. Specifically, the surfactant may be one of the lactobionamides described in U.S. Patent No.
25 5,389,279 to Au et al. titled ""Compositions Comprising
Nonionic Glycolipid Surfactants" issued February 14, 1995, which is hereby incorporated by reference; or it may be one . of the sugar amides described in Patent No. 5,009,814 to Kelkenberg, titled "Use of N-Poly Hydroxyalkyl Fatty Acid
30 Amides as Thickening Agents for Liquid Aqueous Surfactant
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Systems" issued April 23, 1991, hereby incorporated into the subject application by reference.
A useful component in compositions according to the 5 invention is a cationic skin feel agent or polymer which may be a cationic skin conditioning agent, such as for example cationic celluloses. Cationic polymers are preferably used at levels as low as about 0.2 % or 0.3 %, and at levels as high as about 0.8 % or 1 % by wt.
10
Cationic cellulose is available from Amerchol Corp. (Edison, NJ, USA) in their Polymer JR (trade mark) and LR (trade mark) series of polymers, as salts of hydroxyethyl cellulose reacted with trimethyl ammonium substituted epoxide,
15 referred to in the industry (CTFA) as Polyquaternium 10. Another type of cationic cellulose includes the polymeric quaternary ammonium salts of hydroxyethyl cellulose reacted with lauryl dimethyl ammonium-substituted epoxide, referred to in the industry (CTFA) as Polyquaternium 24. These
20 materials are available from Amerchol Corp. (Edison, NJ, USA) under the tradename Folymer LM-200.
A particularly suitable type of cationic polysaccharide polymer that can be used is a cationic guar gum derivative,
25 such as guar hydroxypropyltrimoniuin chloride (Commercially, available from Rhone-Poulenc in their JAGUAR trademark series). Examples are JAGUAR C13S, which has a low degree of substitution of the cationic groups and high viscosity, JAGUAR C15, having a moderate degree of substitution and a
30 low viscosity, JAGUAR C17 . (high degree of substitution, high viscosity), JAGUAR C16, which is a hydroxypropylated
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cationic guar derivative containing a low level of substituent groups as well as cationic quaternary ammonium groups, and JAGUAR 162 which is a high transparency, medium viscosity guar having a low degree of substitution. 5
Particularly preferred cationic polymers are JAGUAR C13S, JAGUAR C15, JAGUAR CI7 and JAGUAR CI6 and JAGUAR CI62, especially Jaguar C13S. Other cationic skin feel agents known in the art may be used, provided that they are 10 compatible with the inventive formulation.
One or more cationic surfactants may also be used in the cleansing composition. Cationic surfactants may be used at levels as low as about 0.1, 0.3, 0.5 or 1 %, and at levels 15 as high as 2, 3, 4 or 5 % by wt.
Examples of cationic detergents are the quaternary ammonium compounds such as alkyldimethylammonium halogenides. Other suitable surfactants which may be used are described in U.S.
20 Patent No. 3,723,325 to Parran Jr. titled "Detergent Compositions Containing Particle Deposition Enhancing Agents" issued March, 27, 1973; and "Surface Active Agents and Detergents" (Vol. I & II) by Schwartz, Perry & Berch, both of which are also incorporated into the subject
25 application by reference.
In addition, the inventive cleansing composition of the invention may include 0 to 15 % by wt. optional ingredients as follows: perfumes; sequestering agents such as 30 tetrasodium ethylenediaminetetraacetate (EDTA), EHDP or
mixtures in an amount of 0.01 % to 1 %, preferably 0.01 % to
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0.05 %; and coloring agents, opacifiers and pearlizers such
as zinc stearate, magnesium stearate, Ti02, EGMS (ethylene
glycol monostearate) or Lytron 621 (Styrene/Acrylate copolymer) and the like/ all of which are useful in 5 enhancing the appearance or cosmetic properties of the product.
The compositions may further comprise antimicrobials such as
2-hydroxy-4,2', 4' trichlorodiphenylether (DP300);
10 preservatives such as dimethyloldimethylhydantoin (Glydant XL1000), parabens, sorbic acid etc., and the like.
The compositions may also comprise coconut acyl mono- or diethanol amides as suds boosters, and strongly ionizing 15 salts such as sodium chloride and sodium sulfate may also be used to advantage.
Antioxidants such as, for example, butylated hydroxytoluene (BHT) and the like may be used advantageously in amounts of 20 about 0.01 % or higher if appropriate.
Moisturizers (also known as hydrophilic emollients) that also are humectants such as polyhydric alcohols, e.g. glycerine and propylene glycol, and the like; and polyols 25 such as the polyethylene glycols listed below and the like are used as described above.
Polyox WSR-205 ' PEG 14M,
Polyox WSR-N-60K PEG 45M, or
30 Polyox WSR-N-750 PEG 7M.
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Hydrophobic emollients may be used at levels that do not alter the unique sensory properties of the invention. Preferably, hydrophobic emollients are used below about 1, 0.5, 0.1, or 0.01 % by wt., or not at all. 5
The term "emollient" (also considered to be conditioning compounds according to the invention) is defined as a substance which softens or improves the elasticity, appearance, and youthfulness of the skin (stratum corneum) 10 by either increasing its water content, adding, or replacing lipids and other skin nutrients, or both, and keeps it soft by retarding the decrease of its water content.
Useful hydrophobic emollients include the following: 15 (a) silicone oils and modifications thereof such as linear and cyclic polydimethylsiloxanes; amino, alkyl, alkylaryl, and aryl silicone oils; (b) fats and oils including natural fats and oils such as jojoba, soybean, sunflower, rice bran, avocado, almond, 20 olive, sesame, persic, castor, coconut, mink oils; cacao fat; beef tallow, lard; hardened oils obtained by hydrogenating the aforementioned oils; and synthetic mono-, di- and triglycerides such as myristic acid glyceride and 2-ethylhexanoic acid glyceride; 25 (c) waxes such as carnauba, spermaceti, beeswax, lanolin, and derivatives thereof;
(d) hydrophobic and hydrophillic plant extracts;
(e) hydrocarbons such as liquid paraffins, vaseline, microcrystalline wax, ceresin, squalene, pristan and
30 mineral oil;
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(f) higher fatty acids such as lauric, myristic, palmitic, stearic, behenic, oleic, linoleic, linolenic, lanolic, isostearic, arachidonic and poly unsaturated fatty acids (PUFA); 5 (g) higher alcohols such as lauryl, cetyl, stearyl, oleyl, behenyl, cholesterol and 2-hexydecanol alcohol; (h) esters such as cetyl octanoate, myristyl lactate, cetyl lactate, isopropyl myristate, myristyl myristate,. isopropyl palmitate, isopropyl adipate, butyl stearate, 10 decyl oleate, cholesterol isostearate, glycerol
monostearate, glycerol distearate, glycerol tristearate, alkyl lactate, alkyl citrate and alkyl tartrate; (i) essential oils and extracts thereof such as mentha,
jasmine, camphor, white cedar, bitter orange peel, ryu, 15 turpentine, cinnamon, bergamot, citrus unshiu, calamus, pine, lavender, bay, clove, hiba, eucalyptus, lemon, starflower, thyme, peppermint, rose, sage, sesame, ginger, basil, juniper, lemon grass, rosemary, rosewood, avocado, grape, grapeseed, myrrh, cucumber, watercress, 20 calendula, elder flower, geranium, linden blossom,
amaranth, seaweed, ginko, ginseng, carrot, guarana, tea tree, jojoba, comfrey, oatmeal, cocoa, neroli, vanilla, green tea, penny royal, aloe vera, menthol, cineole, eugenol, citral, citronelle, borneol, linalool, 25 geraniol, evening primrose, camphor, thymol, spirantol, penene, limonene and terpenoid oils; (j) mixtures of any of the foregoing components, and the like.
30 The inventive cleansing composition preferably possesses an ordered liquid crystalline microstructure, preferably a
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lamellar microstructure structure. The rheological behavior of all surfactant solutions, including liquid cleansing solutions, is strongly dependent on the microstructure, i.e., the shape and concentration■of micelles or other self-5 assembled structures in solution.
When there is sufficient surfactant to form micelles (concentrations above the critical micelle concentration or CMC), for example, spherical, cylindrical (rod-like or
10 discoidal), spherocylindrical or ellipsoidal micelles may
form. As surfactant concentration increases, ordered liquid crystalline phases such as lamellar phase, hexagonal phase, cubic phase or L3 sponge phase may form. The lamellar phase, for example, consists of alternating'surfactant
15 bilayers and water layers. These layers are not generally flat, but fold to form submicron spherical onion like structures called vesicles or liposomes. The hexagonal phase, on the other hand, consists of long cylindrical micelles arranged in a hexagonal lattice. In general, the 20 microstructure of most personal care products consist of either spherical micelles; rod micelles; or a lamellar dispersion.
As noted above, micelles may be spherical or rod-like.
25 Formulations having spherical micelles tend to have a low viscosity and exhibit Newtonian shear behavior (i.e., viscosity stays constant as a function of shear rate; thus, if easy pouring of product is desired, the solution is less viscous and, as a consequence, it doesn't suspend as well).
30 In these systems, the viscosity increases linearly with surfactant concentration.
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Rod micellar solutions are more viscous, because movement of the longer micelles is restricted. At a critical shear rate, the micelles align and the solution becomes shear thinning. Addition of salts increases the size of the rod 5 micelles thereof, increasing zero shear viscosity (i.e., viscosity when sitting in a bottle) which helps suspend particles, but also increases critical shear rate (i.e. the point at which the product becomes shear thinning; higher critical shear rates means the product is more difficult to 10 pour).
Lamellar dispersions differ from both spherical and rod-like micelles because they can have high zero shear viscosity (because of the close packed arrangement of constituent 15 lamellar droplets), yet these solutions are very shear thinning (readily dispense on pouring). That is, the solutions can become thinner than rod micellar solutions at moderate shear rates.
20 In formulating liquid cleansing compositions, therefore, there is the choice of using' rod-micellar solutions (whose zero shear viscosity,-e.g., suspending ability, is not very good and/or are not very shear thinning); or lamellar dispersions (with higher zero shear viscosity, e.g. better
25 suspending, and yet are very shear thinning). Such lamellar compositions are characterised by high zero shear viscosity (good for suspending and/or structuring) while simultaneously being very shear thinning such that they readily dispense in pouring. Such compositions possess a
30 "heaping", lotion-like appearance, which conveys signals of enhanced moisturization.
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When rod-micellar solutions are used, they also often require the use of external structurants to enhance viscosity and to suspend particles (again, because they have lower zero shear viscosity than lamellar phase solutions). 5 For this, carbomers and clays are often used. At higher shear rates (as in product dispensing, application of the product to the body, or rubbing with hands), since the rod-micellar solutions are less shear thinning, the viscosity of the solution stays high, and the product can be stringy and
10 thick. Lamellar dispersion based products, having higher zero shear viscosity, can more readily suspend emollients, and are typically more creamy. In general, lamellar phase compositions are easy to identify by their characteristic focal conic shape and oily streak texture, while hexagonal
15 phase exhibits angular fan-like texture. In contrast, micellar phases are optically isotropic.
It should be understood that lamellar phases may be formed in a wide variety of surfactant systems using a wide variety
20 of lamellar phase "inducers" as described, for example, in U.S. Pat. No. 5,952,286 issued to Puvvada, et al., on September, 14, 1999. Generally, the transitions from micelle to lamellar phase are functions of effective average area of headgroup of the surfactant, the length of the
25 extended tail, and the volume of tail. Using branched
surfactants, or surfactants with smaller headgroups or bulky tails are also effective ways of inducing transitions from rod micellar to lamellar.
30 One way of characterizing ordered liquid crystalline
dispersions includes measuring viscosity at low shear rate
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(using for example a Stress Rheometer) when additional inducer (e.g., oleic acid or isostearic acid) is used. At higher amounts of inducer, the low shear viscosity will significantly increase. 5
Another way of measuring ordered liquid crystalline dispersions is using freeze fracture electron microscopy. Micrographs generally will show ordered liquid crystalline microstructure and close packed organization of the lamellar 10 droplets (generally in size range of about 2 microns).
In a preferred embodiment, the inventive ordered liquid crystalline phase composition preferably has a low shear viscosity in the range of about 40,000 to about 300,000 15 centipoises (cps) measured at 0.5 RPM using T-bar spindle A at 25°C using the procedure described below. More preferably the viscosity range is about 50,000 to about 150,000 cps.
Advantageously, active agents other than conditioning agents 20 such as emollients or moisturizers defined above may be
added to the cleansing composition in a safe and effective amount during formulation to treat the skin during the use of the product. These active ingredients may be advantageously selected from antimicrobial and antifungal 25 actives, vitamins, anti-acne actives; anti-wrinkle, anti-skin atrophy and skin repair actives; skin barrier repair actives; non-steroidal cosmetic soothing actives; artificial tanning agents and accelerators; skin lightening actives; sunscreen actives; sebum stimulators; sebum inhibitors; 30 anti-oxidants; protease inhibitors; skin tightening agents; anti-itch ingredients; hair growth inhibitors; 5-alpha
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reductase inhibitors; desquamating enzyme enhancers; anti-glycation agents; topical anesthetics, or mixtures thereof; and the like.
5 These active agents may be selected from water soluble
active agents, oil soluble active agents, pharmaceutically-acceptable salts and mixtures thereof. Advantageously the agents will be soluble or dispersible in the cleansing composition. The term "active agent" as used herein means
10 personal care actives which can be used to deliver a benefit to the skin and/or hair and which generally are not used to confer a conditioning benefit, as is conferred by humectants and emollients previously described herein. The term "safe and effective amount" as used herein, means an amount of
15 active agent high enough to modify the condition to be
treated or to deliver the desired skin care benefit, but low enough to avoid serious side effects.
The term "benefit", as used herein, means the therapeutic, 20 prophylactic, and/or chronic benefits associated with treating a particular condition with one or more of the active agents described herein. What is a safe and effective amount of the active agent ingredient will vary with the specific active agent, the ability of the active to 25 penetrate through the skin, the age, health condition, and skin condition of the user, and other like factors.
Preferably the composition of the present invention comprises from about 0.01 % to about 50 %, more preferably 30 from about 0.05 % to about 25 %, even more preferably 0.1 %
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to about 10 %, and most preferably 0.1 % to about 5 %, by weight of the active agent component.
Anti-acne actives can be effective in treating acne 5 vulgaris, a chronic disorder of the pilosebaceous follicles. Non-limiting examples of useful anti-acne actives include the keratolytics such as salicylic acid (o-hydroxybenzoic acid), derivatives of salicylic acid such as 5-octanoyl salicylic acid and 4 methoxysalicylic acid, and resorcinol; 10 retinoids such as retinoic acid and its derivatives (e.g., cis and trans) ; sulfur-containing D and L amino acids and their derivatives and salts, particularly their N-acetyl derivatives, mixtures thereof and the like.
15 Anti-microbial and anti-fungal actives can be effective to prevent the proliferation and growth of bacteria and fungi. Non-limiting examples of anti-microbial and anti-fungal actives include b-lactam drugs, quinolone drugs, ciprofloxacin, norfloxacin, tetracycline, erythromycin,
20 amikacin, 2, 4, 4 '-trichloro-2 '-hydroxy diphenyl ether,
3,4,4'- trichlorobanilide, phenoxyethanol, triclosan; triclocarban; and mixtures thereof and the like.
Anti-wrinkle, anti-skin atrophy and skin repair actives can 25 be effective in replenishing or rejuvenating the epidermal layer. These actives generally provide these desirable skin care benefits by promoting or maintaining the natural process of desquamation. Non-limiting examples of anti-wrinkle and anti-skin atrophy actives include vitamins, 30 minerals, and skin nutrients such as milk, vitamins A, E,
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and K; vitamin alkyl esters, including vitamin C alkyl esters; magnesium, calcium, copper, zinc and other metallic components; retinoic acid and its derivatives (e.g., cis and trans); retinal; retinol; retinyl esters such as retinyl 5 acetate, retinyl palmitate, and retinyl propionate; vitamin B 3 compounds (such as niacinamide and nicotinic acid), alpha hydroxy acids, beta hydroxy acids, e.g. salicylic acid and derivatives thereof (such as 5-octanoyl salicylic acid, heptyloxy 4 salicylic acid, and 4-methoxy salicylic acid); 10 mixtures thereof and the like.
Skin barrier repair actives are those skin care actives which can help repair and replenish the natural moisture barrier function of the epidermis. Non-limiting examples of
15 skin barrier repair actives include lipids such as
cholesterol, ceramides, sucrose esters and pseudo-ceramides as described in European Patent Specification No. 556,957; ascorbic acid; biotin; biotin esters; phospholipids, mixtures thereof, and the like.
20
Non-steroidal cosmetic soothing actives can be effective in preventing or treating inflammation of the skin. The soothing active enhances the skin appearance benefits of the present invention, e.g., such agents contribute to a more
25 uniform and acceptable skin tone or color. Non-limiting examples of cosmetic soothing agents include the following categories: propionic acid derivatives; acetic acid derivatives; fenamic acid derivatives; mixtures thereof and the like. Many of these cosmetic soothing actives are
30 described in U.S. Pat. No. 4,985,459 to Sunshine et al.,
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issued Jan. 15, 1991, incorporated by reference herein in its entirety.
Artificial tanning actives can help in simulating a natural 5 suntan by increasing melanin in the skin or by producing the appearance of increased melanin in the skin. Non-limiting examples of artificial tanning agents and accelerators include dihydroxyacetaone; tyrosine; tyrosine esters such as ethyl tyrosinate and glucose tyrosinate; mixtures thereof, 10 and the like.
Skin lightening actives can actually decrease the amount of melanin in the skin, or provide such an effect by other mechanisms. Non-limiting examples of skin lightening 15 actives useful herein include aloe extract, alpha-glyceryl-L-ascorbic acid, aminotyroxine, ammonium lactate, glycolic acid, hydroquinone, 4 hydroxyanisole, mixtures thereof, and the like.
20 Also useful herein are sunscreen actives. A wide variety of sunscreen agents are described in U.S. Pat. No. 5,087,445, to Haffey et al., issued Feb. 11, 1992/ U.S. Pat. No. 5,073,372, to Turner et al., issued Dec. 17, 1991; U.S. Pat. No. 5,073,371, to Turner et al. issued Dec. 17, 1991; and
25 Segarin, et al., at Chapter VIII, pages 189 et seq., of Cosmetics Science and Technology, all of which are incorporated herein by reference in their entirety. Non-limiting examples of sunscreens which are useful in the compositions of the present invention are those selected
30 from octyl methoxyl cinnamate (Parsol MCX) and butyl methoxy benzoylmethane (Parsol 1789), 2-ethylhexyl p-
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methoxycinnamate, 2-ethylhexyl N,N-dimethyl-p-aminobenzoate, p- aminobenzoic acid, 2-phenylbenzimidazole-5-sulfonic acid, oxybenzone, mixtures thereof, and the like.
5 Sebum stimulators can increase the production of sebum by the sebaceous glands. Non-limiting examples of sebum stimulating actives include bryonolic acid, dehydroetiandrosterone (DHEA), orizanol, mixtures thereof, and the like.
10 Sebum inhibitors can decrease the production of sebum by the sebaceous glands. Non-limiting examples of useful sebum inhibiting actives include aluminum hydroxy chloride, corticosteroids, dehydroacetic acid and its salts, dichlorophenyl imidazoldioxolan (available from Elubiol),
15 mixtures thereof, and the like.
Also useful as actives in the present invention are protease inhibitors. Protease inhibitors can be divided into two general classes; the proteinases and the peptidases.
20 Proteinases act on specific interior peptide bonds of
proteins, and peptidases act on peptide bonds adjacent to a free amino or carboxyl group on the end of a protein, and thus cleave the protein from the outside. Protease inhibitors suitable for use in the present invention
25 include, but are not limited to, proteinases such as serine proteases, metalloproteases, cysteine proteases, and aspartyl protease, and peptidases, such as carboxypepidases, dipeptidases and aminopepidases, mixtures thereof and the like.
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Other useful as active ingredients in the present invention are skin tightening agents. Non-limiting examples of skin tightening agents which are useful in the compositions of the present invention include monomers which can bind a 5 polymer to the skin such as terpolymers of vinylpyrrolidone, (meth)acrylic acid and a hydrophobic monomer comprised of long chain alkyl (meth)acrylates, mixtures thereof, and the like.
10 Active ingredients in the present invention may also include anti-itch ingredients. Suitable examples of anti-itch ingredients which are useful in the compositions of the present invention include hydrocortisone, methdilizine and trimeprazineare, mixtures thereof, and the like.
15
Non-limiting examples of hair growth inhibitors which are useful in the compositions of the present invention include 17 beta estradiol, anti-angiogenic steroids, curcuma extract, cycloxygenase inhibitors, evening primrose oil,
20 linoleic acid and the like. Suitable 5-alpha reductase
inhibitors include ethynylestradiol and genistine, mixtures thereof and the like.
Non-limiting examples of desquamating enzyme enhancers which 25 are useful in the compositions of the present invention include alanine, aspartic acid, N methyl serine, serine, trimethyl glycine, mixtures thereof, and the like.
A non-limiting example of an anti-glycation agent which is 30 useful in the compositions of the present invention would be
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Amadorine (available from Barnet Products Distributor), and the like.
EXAMPLES
The invention will now be described in greater detail by way of the following non-limiting examples. The examples are for illustrative purposes only and not intended to limit the invention in any way. Physical test methods are described below.
Except in the operating and comparative examples, or where otherwise explicitly indicated, all numbers in this description indicating amounts or ratios of materials or conditions or reaction, physical properties of materials and/or use are to be understood as modified by the word "about".
Where used in the specification, the term "comprising" is intended to include the presence of stated features, integers, steps, components, but not to preclude the presence or addition of one or more features, integers, steps, components or groups thereof.
All percentages in the specification and examples are intended to be by weight unless stated otherwise.
Example 1
A series of inventive and comparative formulas A to I were made according to Table 1 using the procedure below in order to evaluate the effect of glycerin concentration on various
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sensory properties. The sensory properties were determined via trained panel testing using the procedure provided below and the results are summarized in Table 1. It was found that the inventive formulations provided overall superior 5 sensory and stability properties compared to the comparative formulations.
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Example 2
A series of inventive and comparative formulas F and J to P were made according to Table 2 using the procedure below in 5 order to evaluate the effect of C12 Disodium Sulfosuccinate concentration on various sensory properties. The sensory properties were determined via trained panel testing using the procedure provided below, and the results are summarized in Table 2. It was found that the inventive formulations 10 provided overall superior sensory and stability properties compared to the comparative formulations.
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Example 3
A series of inventive and comparative formulas F and Q to X were made according to Table 3 using the procedure below in 5 order to evaluate the effect of sodium cocoyl glycinate concentration on various sensory properties. The sensory properties were determined via trained panel testing using the procedure provided below and the results are summarized in Table 3. It was found that the inventive formulations 10 provided overall superior sensory and stability properties compared to the comparative formulations.
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Example 4
A series of inventive and comparative formulas F and Y to CC were made according to Table 4 using the procedure below in 5 order to evaluate the effect potassium monoalkyl phosphate concentration on various sensory properties. The sensory properties were determined via trained panel testing using the procedure provided below and the results are summarized in Table 4. It was found that the inventive formulations 10 provided overall superior sensory and stability properties compared to the comparative formulations.
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Example 5
A series of inventive formulas LA and DD to HH were made according to Table 5 using the procedure below. It was 5 found that the inventive formulations provided overall superior stability properties.
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Example 6
A series of comparative and inventive formulas II to LL were made according to Table 6 using the procedure below. The 5 sensory properties were determined via trained panel testing using the procedure provided below and the results are summarized in Table 6. It was found that the inventive formulations provided overall superior sensory and stability properties compared to the comparative formulations. 10
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- 40 -Procedure for Sample Preparation for Examples 1 to 6
1 Weigh DI water, Glycerin, EDTA-4Na and Glydant together
5 in the main mixer and begin mixing and heating to 55°C.
2 Add Merquat 3330 and Merquat 550 or Styleze to the main
mixer when it reaches 55°C and hold for 15 min.
10 3 Heat to 80°C slowly. Then slowly add C12 Disodium Sulfosuccinate, NA Coocyl Glycinate, and mono alkyl phosphate to the main mixer and mix until completely dissolved.
15 4 Predisperse Ti02 with water, and when predispersed add to the main mixer and blend in.
5 Weigh fatty acids together and start heating and mixing
until mixture reaches 80°C.
20
6 Add fatty acid blend to the main mixer and mix for 15
min at 70-80°C.
7 Cool down to 4 0°C. 25
8 Slowly add perfume.
9 Let stand overnight before filling containers.
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Methods
Panel Test Method for Sensory and Physical Properties
A panel is assembled of 10 persons and trained according to the following instructions and definitions. The assessments for each attribute of all the panelists are added and the average calculated and reported.
Wash your palm with unper fumed control soap (Ivory® soap available from Procter and Gamble, or its equivalent) and wet.your face with water as required. Then provide individual assessments of test samples by selecting a value from the following numerical scales that most closely applies.
Before use
1. Ease of pouring from container.
0 5 10
Difficult Easy
2. Thickness
0 5 10
Thin Thick
Pour the product (about 1 ml) onto the palm.
Pour one teaspoonful of water onto the palm and dilute it 20
times with additional water.
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Make a lather between hands by rubbing hands together 10 times to evaluate the ease of lathering. Pour one teaspoonful of water onto palm and rub hands together again 30 times to evaluate amount of lather and rub 5 hands together 10 times to evaluate the creaminess of
lather. Then provide individual assessments of test samples by selecting a value from the following numerical scales that most closely applies.
10 Product in palm
3. Ease of diluting with water
15
0 Difficult
10
Easy
!0 4. Ease of lathering
Difficult
10 Easy
5. Lather amount
30
No lather
10 Copious lather
35
6. Creaminess of lather
0 Not creamy
10 Creamy
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5
Start washing the face with the pre-lathered product until it feels it is time to rinse. Then provide individual assessments of test samples by selecting a value from the following numerical scales that most closely applies.
Product on face
10
7. Ease of spreading
0 5 10
Difficult Easy
15
8. Stickiness
0 5 10
20 Not Sticky Sticky
9. Slippery
25
0 5 10
Not slippery Slippery
30 10. Lather amount
0 ' 5 10
35 No lather Copious lather
Rinse your face with water as needed until you feel it is time to dry it.
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Then provide individual assessments of test samples by selecting a value from the following numerical scales that most closely applies.
5 While rinsing
11. Ease of rinse
10
Difficult
10 Easy
15
Wet skin feel
12. Slippery
i—I—I—I
20
0 Not Slippery
10 Slippery
13. Dragginess
25
0
Not draggy
1 1 KH
10 Draggy
30 14. Cleanness
35
Not clean
10 Clean
15. Freshness
40 0
Not fresh
10 Fresh
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Dry the face with paper towel. Wait for 2 minutes.
Then provide individual assessments of test samples by selecting a value from the following numerical scales that 5 most closely applies.
10
Dry Skin Feel 16. Dryness
0 5 10
15 Not dry Dry
17. Smoothness
20
0 5 10
Not smooth Smooth
!5 18. Tightness
30
0 5 10
Not tight Tight
19. Pleasant
35 0 5 10
Not pleasant Pleasant
Attribute definitions for panel testing 40
Before using the product
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Ease of pouring
Difficult : It is difficult to dispense the product
when pouring it from the container. Easy : It is easy to dispense the product when
pouring it from the container.
2. Thickness Thin
Thick
: The appearance of the product is like
water. -.The appearance of the product is like
honey.
When product is used on the palm
3. Ease of diluting with water
Difficult : The product is difficult to mix with
water. Easy : The product is easy to mix with water.
4. Ease of lathering
Difficult : It takes a long time to lather between
the hands. Easy : It takes a short time to lather between
the hands.
Amount of lather
No lather : No lather appears when you rub the
product.between the hands Copious amount of lather ' : Copious lather appears when you rub the
product between the hands.
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6. Creaminess of lather
Not creamy : The appearance of the lather consists of
large and/or coarse bubbles.
Creamy : The appearance of the lather appears
creamy with fine uniformly sized bubbles.
When use the product is used on the arms
7. Ease of spreading the product
Difficult : The product is difficult to distribute
all over the forearm. Easy : The product is easy to distribute all
over the forearm.
8. Stickiness of the product
Not sticky : It is easy to lift fingers from the
skin. Sticky : Resistance is felt when fingers are
lifted from the skin.
9. Slippery
Not slippery : There is noticeable resistance felt when
the skin is rubbed with fingertips.
Slippery : There is no noticeable resistance felt
when the skin is rubbed with fingertips.
10. Amount of lather
No lather : No lather appears when the arms are
rubbed with the hands.
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Copious lather: Copious lather appears when the arms are
rubbed with the hands.
When rinsing the arms
10
11. Ease of rinse .Difficult
Easy
A great deal of water is required to remove product from the skin. Only a small amount of water is required to remove product from the skin.
Wet skin feel
12. Slippery 15 Not slippery
Slippery
: Resistance to motion is felt when the skin is stroked with finger tips.
: No resistance to motion is felt when the skin is stroked with finger tips.
20 13. Dragginess Not draggy
Draggy
no resistance to motion is felt when the skin is stroked with finger tips, resistance to motion is felt when the skin is stroked with finger tips.
25
30
14. Cleanliness Not clean
Clean
Sensation that dirt has not been completely removed from the skin. Sensation that dirt has been completely removed from the skin.
15. Freshness
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49 _
Not fresh Fresh
The feeling as if the skin is tired. The feeling as if the skin is on a mountaintop.
Dry skin feel
16. Dryness Not dry Dry
The skin feels supple and moist, The skin feels completely dry.
17. Smoothness Not smooth
Smooth
: resistance to motion is felt, when the skin is stroked with finger tips.
:the skin feels like silk when the skin is stroked with finger tips.
18. Tightness Tight
The skin feels as if it has shrunk across the face.
19. Pleasant Pleasant
A combined feeling of satisfaction and comfort is felt.
Stability Method
Samples may be stored at the following conditions and evaluated at the following evaluation points.
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Condition Time ■ Evaluations Evaluation Points
Approx. 25°C 12 weeks to 3 years Viscosity, Visual Initial1 day■1,2,4, 8,12 weeks,3 years.
40°C 12. weeks Visual only 1,2,4,8,12 weeks
50°C 1 week Viscosity, Visual 1 week .
-9°C/25°C cycle (24 hours at each temp.) 3 cycles (6 days) Viscosity, Visual 1 week
Viscosity: Measured by the method indicated for each example.
5 Visual evaluation: color, odor, and appearance.
A sample is considered stable if its viscosity and visual evaluation do not change significantly (i.e. greater than 20 % relative) from the initial measurements at all conditions. 0
T-bar Viscosity Measurement
Scope
5 This method covers the measurement of the viscosity of a preferred embodiment of the invention that has an ordered liquid crystalline phase.
Apparatus 0
Brookfield RVT Viscometer with Helipath Accessory; Chuck, weight and closer assembly for T-bar attachment;
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T-bar Spindle A;
Plastic cups diameter greater than 6.35 cm (2.5 inches).
Procedure 5
1. Verify that the viscometer and the helipath stand are
level by referring to the bubble levels on the back of
the instrument.
10 2. Connect the chuck/closer/weight assembly to the
Viscometer (Note the left-hand coupling threads).
3. Clean Spindle A with deionized water and pat dry with a
Kimwipe sheet. Slide the spindle in the closer and
15 tighten.
4. Set the rotational speed at 0.5 RPM. In case of a
digital viscometer (DV)' select the % mode and press
autozero with the motor switch on.
20
5. Place the product in a plastic cup with inner diameter
of greater than 6.35 cm (2.5 inches). The height of the
product in the cup should be at least 7.62 cm (3
inches). The temperature of the product should be 25°C.
25
6. Lower the spindle into the product approx. 6.4 mm (~l/4
inches). Set the adjustable stops of the helipath stand
so that the spindle does not touch the bottom of the
plastic cup or come out of the sample.
30
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7. Start the viscometer and allow the dial to make one or
two revolutions before turning on the Helipath stand.
Note the dial reading as the helipath stand passes the
middle of its downward traverse.
5
8. Multiply the dial reading by a factor of 4,000 and
report the viscosity reading in cps.
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- 53 -CLAIMS
1. A cleansing composition comprising:
5 a. 30 % to 54 % by wt. of total polyol(s);
b. 5 % to 10 % by wt. of total normal C10 to C16 mono alkyl sulfosuccinate(s), and
10 c. 0.6 % to 9 % by wt. of N-acyl amino acid(s) or salt(s) of such acid(s) or a blend thereof.
2. The composition according to claim 1 further comprising
at least 2 % to 5 % by wt. of total normal C8 to C24
15 mono alkyl phosphate(s).
3. The composition according to claim 1 or claim 2 further
comprising at least 15 % by wt. of water.
20 4. The composition according to claim 2 or claim 3 wherein the ratio of total mono alkyl sulfosuccinate (s) to total mono alkyl phosphate
| # | Name | Date |
|---|---|---|
| 1 | 1238-MUMNP-2007- PUBLICATION REPORT.pdf | 2022-02-14 |
| 1 | 1238-mumnp-2007-form 18(17-12-2007).pdf | 2007-12-17 |
| 2 | 1238-mumnp-2007-assignment(24-8-2007).pdf | 2018-08-09 |
| 2 | 1238-mumnp-2007-correspondence 1(17-12-2007).pdf | 2007-12-17 |
| 3 | 1238-MUMNP-2007_EXAMREPORT.pdf | 2018-08-09 |
| 4 | 1238-mumnp-2007-wo international publication report(16-8-2007).pdf | 2018-08-09 |
| 4 | 1238-mumnp-2007-claims.pdf | 2018-08-09 |
| 5 | 1238-mumnp-2007-pct-search report.pdf | 2018-08-09 |
| 5 | 1238-mumnp-2007-correspondence 2(25-6-2008).pdf | 2018-08-09 |
| 6 | 1238-MUMNP-2007-PCT-ISA-210(30-3-2009).pdf | 2018-08-09 |
| 6 | 1238-MUMNP-2007-CORRESPONDENCE 25-6-2008.pdf | 2018-08-09 |
| 7 | 1238-MUMNP-2007-OTHER DOCUMENT(30-3-2009).pdf | 2018-08-09 |
| 7 | 1238-MUMNP-2007-CORRESPONDENCE(30-3-2009).pdf | 2018-08-09 |
| 8 | 1238-mumnp-2007-form-pct-separate sheet-409.pdf | 2018-08-09 |
| 8 | 1238-mumnp-2007-correspondence(ipo)-(11-5-2011).pdf | 2018-08-09 |
| 9 | 1238-mumnp-2007-correspondence-others.pdf | 2018-08-09 |
| 9 | 1238-mumnp-2007-form-pct-ipea-416.pdf | 2018-08-09 |
| 10 | 1238-mumnp-2007-correspondence-received.pdf | 2018-08-09 |
| 10 | 1238-mumnp-2007-form-pct-ipea-409.pdf | 2018-08-09 |
| 11 | 1238-mumnp-2007-description (complete).pdf | 2018-08-09 |
| 11 | 1238-mumnp-2007-form-5.pdf | 2018-08-09 |
| 12 | 1238-mumnp-2007-form 2(title page)-(16-8-2007).pdf | 2018-08-09 |
| 12 | 1238-mumnp-2007-form-3.pdf | 2018-08-09 |
| 13 | 1238-mumnp-2007-form-1.pdf | 2018-08-09 |
| 13 | 1238-mumnp-2007-form-2.pdf | 2018-08-09 |
| 15 | 1238-mumnp-2007-form-1.pdf | 2018-08-09 |
| 15 | 1238-mumnp-2007-form-2.pdf | 2018-08-09 |
| 16 | 1238-mumnp-2007-form 2(title page)-(16-8-2007).pdf | 2018-08-09 |
| 16 | 1238-mumnp-2007-form-3.pdf | 2018-08-09 |
| 17 | 1238-mumnp-2007-form-5.pdf | 2018-08-09 |
| 17 | 1238-mumnp-2007-description (complete).pdf | 2018-08-09 |
| 18 | 1238-mumnp-2007-form-pct-ipea-409.pdf | 2018-08-09 |
| 18 | 1238-mumnp-2007-correspondence-received.pdf | 2018-08-09 |
| 19 | 1238-mumnp-2007-correspondence-others.pdf | 2018-08-09 |
| 19 | 1238-mumnp-2007-form-pct-ipea-416.pdf | 2018-08-09 |
| 20 | 1238-mumnp-2007-correspondence(ipo)-(11-5-2011).pdf | 2018-08-09 |
| 20 | 1238-mumnp-2007-form-pct-separate sheet-409.pdf | 2018-08-09 |
| 21 | 1238-MUMNP-2007-CORRESPONDENCE(30-3-2009).pdf | 2018-08-09 |
| 21 | 1238-MUMNP-2007-OTHER DOCUMENT(30-3-2009).pdf | 2018-08-09 |
| 22 | 1238-MUMNP-2007-CORRESPONDENCE 25-6-2008.pdf | 2018-08-09 |
| 22 | 1238-MUMNP-2007-PCT-ISA-210(30-3-2009).pdf | 2018-08-09 |
| 23 | 1238-mumnp-2007-correspondence 2(25-6-2008).pdf | 2018-08-09 |
| 23 | 1238-mumnp-2007-pct-search report.pdf | 2018-08-09 |
| 24 | 1238-mumnp-2007-claims.pdf | 2018-08-09 |
| 24 | 1238-mumnp-2007-wo international publication report(16-8-2007).pdf | 2018-08-09 |
| 25 | 1238-MUMNP-2007_EXAMREPORT.pdf | 2018-08-09 |
| 26 | 1238-mumnp-2007-correspondence 1(17-12-2007).pdf | 2007-12-17 |
| 26 | 1238-mumnp-2007-assignment(24-8-2007).pdf | 2018-08-09 |
| 27 | 1238-mumnp-2007-form 18(17-12-2007).pdf | 2007-12-17 |
| 27 | 1238-MUMNP-2007- PUBLICATION REPORT.pdf | 2022-02-14 |