CA2189835A1 - Spontaneously formed clear silicone microemulsions - Google Patents
Spontaneously formed clear silicone microemulsionsInfo
- Publication number
- CA2189835A1 CA2189835A1 CA002189835A CA2189835A CA2189835A1 CA 2189835 A1 CA2189835 A1 CA 2189835A1 CA 002189835 A CA002189835 A CA 002189835A CA 2189835 A CA2189835 A CA 2189835A CA 2189835 A1 CA2189835 A1 CA 2189835A1
- Authority
- CA
- Canada
- Prior art keywords
- microemulsion
- value
- methyl siloxane
- water
- hair
- 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
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- 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
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
- A61K8/894—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a polyoxyalkylene group, e.g. cetyl dimethicone copolyol
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
- A61K8/068—Microemulsions
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- 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
- A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
- A61K8/585—Organosilicon compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q15/00—Anti-perspirants or body deodorants
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y5/00—Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
- A61K2800/26—Optical properties
- A61K2800/262—Transparent; Translucent
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/41—Particular ingredients further characterized by their size
- A61K2800/413—Nanosized, i.e. having sizes below 100 nm
-
- 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
- A61Q5/12—Preparations containing hair conditioners
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
Abstract
A method of spontaneously forming a highly stable clear microemulsion by combining (i) water; (ii) a volatile cyclic methyl siloxane or volatile linear methyl siloxane;
and (iii) a silicone polyether surfactant. The amounts of each component are such that the composition is in the form of a microemulsion. The volatile methyl siloxane is present in the microemulsion in the form of particles having an average diameter of less than 100 nanometers. The resultant microemulsion is useful in personal care products.
and (iii) a silicone polyether surfactant. The amounts of each component are such that the composition is in the form of a microemulsion. The volatile methyl siloxane is present in the microemulsion in the form of particles having an average diameter of less than 100 nanometers. The resultant microemulsion is useful in personal care products.
Description
~ 21 8~835 ,, SPONTANEOUSLY FORMED CLEAR SLICONE MICROEMULSION
This invention is directed to an optically clear silicone ~ILu~u.,.~lLh~ll formed with very little mechanical energy for mixing the I I More particularly, a ternary UUII~ ;iiUll of water, a volatile cyclic or linear methyl siloxane (VMS), and short-chain or low molecular weight silicûne polyether, ~r ~ ' ~ provides optically clear ufi~lu~ lul.~ s when combined with only hand agitation.
It is well du, ' (US-A 4999398) that emulsions, especially silicone emulsions, are opaque, cloudy, and tend to separate on standing. Thus, the desirability ûf , which contain micro-particles in the droplet phase is to provide a measure of clarity.
As used herein, the term emulsion or Ill.Ll.l U~ Ul~;Oll means a dispersion of one immiscible liquid in another, in the form of droplets, with diarneters rl,U,UlU. ' ' 'y in the range of 100-1,000 U~UIUIII~L~I~ (0.1-1.0 ~lul.~.,t~.l/l,OOO-10,000 angstroms A). In contrast, a mi~, ~ ' means a transparent, thermod~ "y stable, dispersion of two or more immiscible liquids and a surfactant.
M;w u. ' are clear or transparent because they contain particles smaller than the wavelength of visible light, which is typically on order of 10-100 M;UIU~IIUID;UII~ may contain oil droplets dispersed in water (O/W), water droplets dispersed in oil (W/O), or they may be in the form of a 1,;~ structure.They are ..1 ,~ 1 by an ultra-low interfacial tension between the oil and water phases.
A lldcl U~ ulb;Oll is recognized by several of its inherent ~ 1-,, . .., 1 l~. ;~l ;, .~
which are that (i) it contains oil, water, and a surfactant; (ii) there is a high r n of surfactant relative to oil, (iu) the system is optically clear; (iv) the phases do not separate by c~ntrifi~g,Ati~ n; and (v) the sy$em forms blJ~ ' - '~/, Thus, for this invention, an emulsion is considered as containing particles having an average diameter of more than 100 l~llul..~;lul ~ (0.1 1111~1 Ulll~ l/l ,000 ~' 2 ~ 8~835 angstroms A), whereas a ".:~ contains particles having an average diameter of less than 100 (0.1 llli.,lUll~t~ /1,000 angstroms A). Clarity or ~l ~ t;.,~ is controlled to a great extent by the particle size of the dispersed phase. The scattering of light is dependent on the particle size. Therefore, clear or transparent CUlll~)UD;LiUllD
appear to be a single phase without droplets or particles when viewed with the naked eye.
While US-A 3299112 describes emulsions formed from water, a silicone oil and a silicone polyether, these emulsions are not clear, and they require input of substantial mechanical energy to prepare. Ful lll~llllul ~, in contrast to our invention, the ternary system in that patent is not a llfi~ oll, the silicone oil is not a volatile cyclic VMS; and while it does describe a linear silicone oil, it is not a volatile linear silicone!
Thus, the silicone oil of that reference ~UII ~ JOIIJD to R"3SiO(R"~SiO)2~SiR"3 where x is 10-1,000. Our l,u-l ~iD~)oll~illg volatile linear VMS has an "x" of 0-5, well below the range of the reference. In fact, we even found that where "x" exceeds 5, the emulsions tend not to be clear.
In addition, emulsions are recognized as inherently unstable systems and separate with time. In contrast, our llli~Jlu.,~ lD;ullD form ~r ' ~/ and are stable indefinitely. The order of addition of the l- - r ~ ' does not influence their formation, and simple hand shaking in the ~ l d~UI~ range of their stability is sufficient to cause the ,lU~ IUID;UIID to form.
~ These D~ / formed clear Illil.lU~ flD;U~ID have particular value in the personal care arena. Because of the unique volatility ~ ;UD of the VMS
component of our ternary system, it can be used alone, or blended with other cosmetic fluids, to form a variety of over-the-counter personal care products.
Thus, it is useful as a carrier in i __D~);ld~ and deodorants, since it leaves a dry feel, and does not cool the skin upon C~ )Uld~iOII. It is lubricious and will improve the properties of skin creams, skin care lotions, ., .. ,~ , facial treatments such as acne or wrinkle removers, personal and facial cleansers, bath oils, perfumes, colognes, sachets, sunscreens, pre-shave and after-shave lotions, shaving soaps and ~' 21 89835 shaving lathers. It can be used m hair shampoos, hair c~n~' ;, hair sprays, mousses, permanents, depilatories and cuticle coats, to enhance gloss and drying time and provide . .. " ,1 l; l ;. ,. .; . .~ benefits. In cosmetics, it functions as a leveling and spreading agent for pigments in make-ups, color cosmetics, ~ ' s, blushes, lipsticks, eyeliners, mascaras, oil removers, color cosmetic removers and powders. It is useful as a delivery system for oil and water soluble substances such as vitamins. When i~,vll~uld~d into sticks, gels, lotions, aerosols and roll-ons, our ternary ~ "J';~ imparts a dry, silky-smooth, payout.
In addition, because our *)V~ VU;~IY formed clear llf~ulv~ lul~;v.lo exhibit a variety of adYall~L~,_vu~ and beneficial properties such as (i) clarity, (ii) very small particle size, (iii) ultra-low interfacial tensions, (iv) the ability to combine properties of water and oil in a single 1- ~,, fluid, (v) shelf stability and (vi) ease of ~I r~Ja~ ioll, they have wide application but especially in . i~J..I b~ , deodorants, in perfumes as a carrier and in hair ~.. . 1; 1 ;. ). ,;. ,~
It is an object of this invention to form a clear Illi~l v~lllul.,;v~l by simplycombining (i) water; (ii) a volatile cyclic methyl siloxane or volatile linear methyl siloxane;
and (iii) a silicone polyether.
Surprisingly, we have discovered how to make clear products without involving the use of high shear, heretofore required to obtain the small particle size necessary to achieve clarity.
These clear Illi~,l(J~,l..JI~;Vlli:. form ~.". '..,..vu~ in the sense that they do not require energy input by means of mixing and shear devices. Thus, turbines, impellers, colloid mills, hnmr~g~ni7Prs or sonolators are not required to form these systems. It is only necessary that the appropriate amounts of the three crlmrc be added to a suitable container and the container be hand shaken. Of course, the cu.,.~,ul~ can be mixed or sheared with more energy input, and the microemulsions will still be obtained, but no advantage results firom such additional energy usage.
~' 21 89835 Our temary i.... "1~~~; l ;.., . contains water, a volatile cyclic or linear methyl siloxane (VMS), and a short-chain or low molecular weight silicone polyether. Those three ~...., .1...1 . : ~ are combined to form clear i.~ without the addition of other materials.
Thus, the claimed ~ .. is free of non-essential ingredients such as salts; co-surfactants, Illullchrd~u~y alcohols; and diols and triols such as ethylene glycol and glycerol. The elimination of such non-essential ingredien~s is especially beneficial and ddvoll~L~ u~ as it obviates the need for refractive index matching, often resorted to in the past to achieve clear or transparent products.
The three u. .".1,.~ are combined in any given order of addition. While heat enhances solubility, lowers surface tension and reduces viscosity, its application is also not required. Room ltul~,c.~lul~ (20-25~C /68-77~F.) is sufficient in most cases.
The oil component of our temary, ,.c,~lLiv.. is a volatile methyl siloxane (VMS), which is a low viscosity silicone fluid COIl~ -r ~' ~, to the average unit fommula (CH3),SiO(4 ,)n in which a has an average value of two or three. The fluid contains siloxane units joined by =Si-O-Si-- bonds. R,,~ ,.ltdlive units are .... " ...r .. ,~ "M"
units(CH3)3SiO~nand~ ' "'D"units(CH3)2SiO22. Thepresenceofl.,ir"...l;.-~"T" units CH3SiO3,2 results in the formation of branched cyclic volatile methyl siloxanes.
The presence of ~lldLUll~.liUI.dl "Q" units SiO4n results in the formation of branched linear volatile methyl siloxanes.
Linear VMS have the formula (CH3)3SiO{(CH3)2SiO},~Si(CH3h, and cyclic VMS have the formula {(CH3)2SiO}y, in which x is 0-5 and y is 3-6. Preferably, the volatile methyl siloxane has a boiling point less than 250~C. and a viscosity of 0.65-5.0 centistokes (mm2/s).
Some It;1111,.~,.1~21~iV~ volatile methyl siloxanes are:
~' 2 1 89835 H3C i O i O 'i CH3 Il) Linear -- x O (llj Cyclic CH
3 _ y H3C--i--~ ' i- ~ 'i CH3 (111) Branched Linear CH3 ~ CH3 H3C ' i CH3 H3C i O i O ''i CH3 (IVi BranchedCyclic H3C_ j. O i CH3 - .-- 21 89835 The cyclic volatile methyl siloxanes (II) have been assigmed the T ~ ' ~i Cosmetic Ingredient (INCI) name "CYCLOMETHICONE"
by The Cosmetics, Toiletries and Fragrance Association, Inc., (CTFA) Washington, DC.
Cyclic and linear methyl siloxanes are clear fluids, essentially odorless, non-toxic, non-greasy, non-stinging and non-irritating to skin. VMS leave ' "~/ no residue after thirty minutes at room LclulJ~dLulti (20-25~C./68-77~F.) when one gram is placed at the center of No. I circular filter paper of 185 millimeters diameter, supported at its perimeter in open room atmosphere. Volatile methyl siloxanes may be used alone or mixed together.
Mixtures result in solutions having cva~ , behaviors different from individual 'duids.
R~ e.~ Live linear volatile methyl siloxanes (I) are l~,Aaull~ y' " ' (MM) with a boiling point of 1 00~C., viscosity of 0.65 mm2/s, and formula Me3 SiOSiMe3; o.,L uucLhy ' ' (MDM) with a boiling point of 1 52~C ., viscosity of 1.04 mm2/s, and formula Me3SiOMe2SiOSiMe3; dc~alllcLllyl~ la~iluAaue (MD2M) witha boiling point of 194~C., viscosity of 1.53 mm2/s, and formula Me3SiO(Me2SiO)2SiMe3; dorlr~ - 1-- Il~y~ t ~ ,,I,r. (MD3M) with a boiling point of 229~C., viscosity of 2.06 mm2/s, and formulaMe3SiO(Me2SiO)3SiMe3;
lcll ad~,~.aul~ llyl~ lr (MD4M) with a boiling point of 245~C., viscosity of 2.63 mm~/s, and formula Me3SiO(Me2SiO)4SiMe3; and h ~ yll~ JAalle (MDsM) with a boiling point of 270~C., viscosity of 3 .24 mm2/s, and formula Me3SiO(Me2SiO)sSiMe3.
R~., ve cyclic volatile methyl siloxanes (II) are ' yL.y~ (D3) a solid with a boiling point of 134~C. and formula {(Me2)SiO} 3; octameth;dcy.,loL~iL a~ ,AL.._ (D4) with a boiling point of 1 76~C., viscosity of 2.3 mm2/s, and formula {(Me2)SiO}4; ' ' yh~y~ "l~ l .Y (Ds) with a boiling point of 210~C., viscosity of 3.87 mm2/s, and formula {(Me2)SiO}s; and ~lo~ y~ (D6) with a boiling point of 245~C., viscosity of 6.62 mm2/s, and formula ~(Me2)SiO}6.
~' 2 1 &9835 R~~ ld~ive branched volatile methyl siloxanes (III) and (IV) are ll~lA,lI-yl-3-{(~ .. 'yl)oxy}trisiloxane (M3T) with a boiling point of 192~C, viscosity of 1 57 mm2/s, and formula CloH3003Si4, hexamethyl-3,3,bis-{(Lli~ l,:.;lyl)oxy}trisiloxane(M4Q)withaboilingpointof222~C.,viscosityof2.86mtn2/s, and for~nula C12H3604Sis; and ~ 1 {(Ll;ll-~ lyl-'yl)oxy}
(MD3) with the formula CgH2404Si4.
One preferred VMS component of my ternary system is o~ h~ y~lu~ u~c [(CH3)2SiO]4. It has a viscosity of 2.3 centistokes (mm2/s) at 25~C., and is referred to as "D4" since it contains four r~ifimrtin~ "D'l units (CH3)2SiO2/2 shown as:
O i O
Four "D" unhs combine to form ' ~Icyclo-tetrasiloxane shown in either formula below:
H3C~ ~CH3 CH3 ~Si~
~j o H3C~ f \ ~ 3 CH3 H3C \~ ~/ CH3 ~' 2 ~ 89835 In the literature, D4 is often called CYCLOMETHICONE or TETRAMER. It has a higher viscosity of 2.3 rnm2/s (cs) and is thicker than water of 1.0 mm2/s (cs), yet o~ lyl~y~luleLl '~ needs 94% less heat to evaporate than water.
Another preferred VMS component of my ternary system is y~ (D5) often referred to as PENTAMER. It is shown structurally below:
H3C 3 Cl H3 \si--o--si/
H3C~¦ ¦ ~CH3 /si\ /si\
H3C ~--S~--~ CH3 A benefit offered by using VMS UUI~ ~ is that many local, state, , federal and ;. .I rl 1 l~ regulations, have restricted the use of certain chemicals, but VMS
is a suitable Ir.~ Thus, the Ellvi~u. .. II~dl Protection Agency (EPA) determined that volatile methyl siloxanes such as octarnethylcy~,lule~la~iloxane, ' ' ~k,y~,L)-p. . ~ rl(lrr~~lrthyl~yl ~ - L '~ '~ hexamethyldisiloxane, oc~ ~tl.y" ' and d~ llG~l!yl~e~l~ l;lu~ , were acceptable substitutes for the CFC-I 13 ~.I.Iolunuulu~.~boll (C2C13F3) and methyk,l.lulurullll (MCF). This d~ ; ", is limited to clearling in closed systems, for metal clearling, electronic clearling and precision cleaning "~ under the EPA's Sigaificant New AlternativesPolicy (SNAP).
~' 2~ 89835 In addition, the EPA excluded VMS as a volatile organic compound (VOC). Thus, they added VMS to a hst of compounds in 40 CPR 51.100(s), excluded from the definition of VOC, on the basis that VMS çr)mro~ have negligible to llu~u~ ..ic ozone formation. They pointed out that exempting VMS
from regulation as an ozone precursor contributes to ~ v~ ll of several importznt lallvilulllu~ goals, in that VMS might be used as a substitute for i...",l,,...,,.l~ listed as hazardous air pollutants (HAP). As they explained, that list met the need to develop substitutes for ozone depleting substances (ODS), and to attain National Ambient Air Quality Standards for ozone under Title I of the Clean Air Act.
The other component of our ternary system, m addition to water and VMS, is a short-chain or low molecular weight silicone polyether. R~ ,uldliv~ polyether structures are:
Rl Rl Rl Rl Rl-- i O 'i--O i O i Rl Rl Rl R2 Rl X Y
Rl Rl Rl Rl R2-- i O--''i O i O 'i R2 Rl Rl R2 Rl ~ 21 89835 ~o A cyclic polyether of the type shown below can also be used.
-i O i- O
--m -- --n In these structures, Rl represents an alkyl group containing 1-6 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, and hexyl; R2 represents the radical -(CH2)~0(C~H40)b(C3H60)cR3; x has a value of 0-3; y has a value of 1-3; z has a value of 0-2; m has a value of 3-5; n is one; a has a value of 3-6; b has a value of 4-20; c has a value of 0-5; and R3 is hydrogen atom, a methyl radical, or an acyl radical such as acetyl.
Preferably, Rl is methyl; b is 6-12; c is zero; and R3 is hydrogen atom.
C..~ .... of this invention may contain 5-70% by weight of surfactant, but most preferably, they contain 15-3 0% by weight of the surfactamt. The balance of the C~ iS oil and water, with the ~,. UpUI ~iu..., of oil and water generally falling between 40:60 to 80:20, or 0.4 to 0.8 as defined below for Ratio 1.
For purposes of this invention, the criteria used to determine optical clarity is whether text c~m be read with the naked eye through a two centimeter diameter bottle filled with the llfi~
As noted in the textbook Ml.,, . ' Theory and Practice, Edited by Leon M. Prince, Academic Press, Inc., Pages 7-10, New York (1977), the "Visual recognition of llfi-,l u~,..lulb;u.~s should not be taken lightly. In fact, the lllh,l U~.IUI..;Ull chemist should train himself carefully in this art. Use of sunlight rather than an artificial source of light is I r~ 1 The eye is better than a llli-~lu~,u~)e because the limit of resolution of a light lllh,lub~,u~e in blue light is only about 0.1 llm sû that droplets smaller than 0.14 ~lm cannot be seen".
Example I
We formed optically clear ll~ l u~ ,lblu..D ~u,..~ vu.,ly at l-,"~,u~.l dLUI tiDranging between 47-62~C. by merely adding to a container, 50 parts of de-ioni2ed water, 50 parts of ' "1~. 1~ ~I rl I ~ ? (D4) and 25 parts of silicone polyether. No mixing, stirring, shearing or input of mechanical energy for agitating the three ingredients was required. The polyether uull~D~Ju~ d to the compound Rl Rl Rl Rl Rl-- i O 'i- O i O 'i Rl Rl 1~1 R2 Rl X Y
where Rl was methyl, x was zero, y was one and R2 was -(CH2)3(0C2H4)80H. Text was able to be read through a two centimeter diameter bottle filled with the microemulsions. It was determined that the mi..l- ' contained particles having an average diameter of lessthan 100 (01 ~lU~lUII~ lb).
Example II
We repeated Example I and formed clear u~.lullb;ullb .,~ ..,..vu~/y at .~IdLUI~ ranging between 60-68~C. by merely combining in a container, 50 parts of 21 8~835 de-ionized water, S0 parts of ' ~ ,y. 1~ ~p~ (DS) and 25 parts of silicone polyether. The optical clarity was the same as obtained in Example I.
Example Ill We repeated Example I and formed clear Illh~lU~ UI,..JII~ ~u~ vu.~ly at ~tUl~ ld~UI~ ranging between 44-60~C. by merely combining in a container, 6û parts of de-ionized water, 40 parts of ~ ,L"~ (D4), and 17.65 parts of silicone polyether. The optical clarity was the same as obtained in Example I.
Example IV
We repeated Example III including the use of salt which is a non-essential ingredient. We formed clear u~lu!.. JI~S ~ y at I , dlUlt~ ranging between 20-30~C by merely combining in a container, 50 parts of an aqueous solution containing 15% sodium chloride, 50 parts of octamethyl.,y..lu~ a~ilu~ , (D4), and 17.65 parts of silicone polyether. The optical clarity was the same as obtained in Example m.
Example V
We repeated Example IV and formed clear ll h,lU~ ul~;OII~ ... vu.ly at ~ ,ld~UIU.~ ranging between 22-41~C. by merely combining in a container, 30 parts of an aqueous solution containing 15% sodium cbloride, 70 parts of octamethylcyclo-I~LI a~;lu~ (D4), and 25 parts of silicone polyether. The optical clarity was the same as obtained in Example IV.
Example VI
We repeated Example II and formed clear Illi~lU~llUI:~;Ull~ .~.uu~ .vu.~ly at ~tlll~llU11~ ranging between 30-85~C. by merely combining in a container, 50 parts of de-ionized water, 50 parts of d~,aull~ yl~,y~ (D5) and 66.67 parts of silicone polyether. The optical clarity was the same as obtained in Example II.
The following four examples illustrate preparation of clear allli~)~,l ~;1 all~.In Examples VII-X, an all~ J;lall~ active was hluul~uldled into our clear silicone Illi~/l U~lllUI~iO~ without input of mechanical energy for mixing the ..OIII~J~
2l 89835 Example VII
We repeated Example I and formed clear ~ ,..vu..ly at t~,.ll~)~d~UI1.~ ranging between 42-58~C. by merely combining in a container, 50 parts of an aqueous solution containing 25% of the a~ ~lL active Aluminum Cbl~l vl~yl~
(ACH-303), 50 parts of octamethyl~.,lui ' (D4) and 25 parts of silicone polyether. The optical clarity was the same as obtained in Example 1.
Example VIII
We repeated Example VII and formed clear Illi~ lUI..;~ ...V~.~VU.~Iy at i l __d~UI~ ranging between 36-69.6~C. by merely combining in a container, 50 parts of an aqueous solution containing 25% of the 'i l active Aluminum-Zirconium T~ u-uhydrex-Gly (ACH-370), 50 parts of o.,l~..~L;l~.y. .1. .l rl ~ (D4) and 28.2 parts of silicone polyether. The optical clarity was the same as obtained in Exarnple VII.
Exa[nple IX
We repeated Exalnple VII and formed clear llli.~lu~ VU,~/y at lelll~ dlul~,~ ranging between 30-46~C. by merely combining in a container, 50 parts of an aqueous solution containing 50% of the a~ J.,l ~;. all~ active Aluminum Chl~,. ullyll dLe (ACH-303), 50 parts of octamethyl~,y~.luleLl~ d..~ (D4) and 21.95 pa~ts of silicone polyether. The optical clarity was the same as obtained in Example VII.
Example X
We repeated Example VII and formed clear .. i.,. ~ VU.>ly at room I~ y~ld~UI~ by merely combining in a container, 63 parts of an aqueous solution containing 25% ofthe ~i *);ldllL active Aluminum Chlorohydrate (ACH-303) and 15%ofsodiumchloride~37partsofouldlll~lllyll~y~lu~lla~;hJ~dil~(D4)~and2o5partsof silicone polyether. The optical clarity was the same as obtained in Example VII.Other i, ,~.;.~...~ actives such as Aluminum ~f~cqll ' ~Jllydldle salts can be used in Examples VII-X. Suitable o~ products can be formulated containing a maximum use level of i I active of 20% by weight AZG and 25%
by weight ACH, on an anhydrous basis.
The following examples illustrate preparation of r~ o~ according to this invention using a linear volatile methyl siloxane instead of a cyclic volatile methyl siloxane.
Example Xl We repeated Example I and formed clear Illi.,lu~lllulDiol~s ,,~ uu.,~y at Le~ J.,.dLule~ ranging between 30-70~C. by merely combining in a container, 50 parts of de-ionized water, 50 parts of hexamethyhl;Dilu,.~l~ (~I) and 42.9 parts of Silicone polyether. The optical clarity was the same as obtained in Example 1.
Example Xll We repeated Example Xl and formed clear ~lli.,l c ' ~ Ju.~l,v at LellllJ~,IdLul." ranging between 43-56~C. by merely combining in a container, 50 parts of de-ionized water, 50 parts of hexamethyl('i ' (MM) and 1?.7 parts of silicone polyether. The optical clarity was the same as obtained in Example 1.
Table I provides a summary of Examples l-XII. In Table 1, Ratio I is the amount of oil divided by the amounts of oil and water. Ratio 2 is the amount of surfactant divided by the amounts of oil, water and surfactant. Percent Surfactant is obtained from the l l ' ' . (Ratio 2) divided by ( I -Ratio 2) X 100.
~ 21 89835 TA:BLE I
Example TU~ u~t:(oc) Ratio I RatiQ 2 % C~
47-62 0.5 0.2 25.0 Il 60-68 0 5 0.2 25.0 m 44-60 0.4 0.15 17.6 IV 20-30 0.5 0.15 17 6 V 22-41 0 7 0.2 25.0 Vl 30-85 0.5 0.4 66 7 Vll 42-58 0 5 0.2 25.0 VIII 36-69.6 0 5 0.22 28.2 IX 30-46 0.5 0.18 22.0 X 20-25 0 5 0.22 28.2 Xl 30-70 0.5 0.3 42.9 ~D[I 43-56 0.5 0.15 17 6 As seen in Table 1, c.-".,l..,- ';~ ...~ according to our invention are prepared at L~ UI .,., generally in the range of 20-85~C. They contain 5-70% by weight of surfactant, most preferably, 15-30% by weight ofthe surfactant; with the balance being oil andwater. TheF. UpUl~iUII~ of oilandwatergenerallyfallbetween40:60to80:20,orO.4 to 0.8 as defined above for Ratio 1.
Figure I is a ternary phase diagram of our system comprising water, octamethylcy.,lu~l~ilu,.al.e (D~) and the silicone surfactant, for tlf ~. . ",;";,.~ cu.,.~ui,;~iu..
ranges of U~,llll~l_ U~ prepared according to Example 7~111 of this invention. The are defined by the shaded area depicted in Figure I .
In Figure I, each of the corners represents 100 percent of the component labelled there. The side of the triangle directly opposite each corner represents zero percent of that c ul..r Lines parallel to the opposite side represent increasingamounts of that component as they become closer to the corner Any line drawn from the ~ 2 1 89835 corner of Component A to the opposite side represents varying the amount of Component A at a constant ratio of the other two romrr The Co~ o~;liull of any point within the shaded area is determined by drawing lines parallel to each of the three sides through the point. The amount of each component is then read from the; . . l r, .~ . . of each line with the side of the triangle which ~,U~ JUIId~ to that component, i.e. the side beginning at I ûû at each culll~o..~ L'~
corner.
Example XIII
We formed a number of optically clear Ill~,IU; ' ~ ,~IUU~ VI~ / at room l~ nil d~Ul~; (22~C.). In this example, ~ ,r~ ;. ,.. c~ v ~. of the invention were prepared, wherein the mixing ratio of the three r ~ -r; ~ ~ comprising water, oil and surfactant, was within the shaded area in Figure 1, i.e., the area surrounded by the lines connecting points A, B, C, D and E. We formed these .lli.,l.,.,~ l..;ull~ in the same manner as in Example 1. Thus, we merely added the three ingredients to a container. No mixing, stirring, shearing or input of mechanical energy for agitating the three ingredients was required. The polyether COllUi~lJU.IdC;l to the same compound used in Exarnple I. We were again able to read text through a two centimeter diameter bottle filled with these i-.l-'~""'l "'' They contained particles having an average diameter of less than lûû
ildllO.I.~,t~l ~ (û . I Uli~ l u---~
Example XIV - Comparison We repeated Example I and formed a number of emulsions at room d~Ul~. However, in this COMPARISON EXAMPLE, we used a silicone oil equivalent to the silicone oils described in US-A 3299112. Thus, the silicone oil I~UIll, ' ' to R''3SiO(R''2SiO)ySiR''3 with x being 10-I,ûûû. Although we followed the teaching in the above patent, we were not able to read text through a two centimeter diameter bottle filled with these comparative emulsions. One ~".I~u~ .l ofthis invention involves using a volatile linear VMS having an "x" of 0-5, well below the range - ~ 21 89835 of the above patent. In this CO~ARISON E7~AMPLE, we verified that where 'Ix' exceeds 5, the resultant, .lU~iUII~ are not clear.
This invention is directed to an optically clear silicone ~ILu~u.,.~lLh~ll formed with very little mechanical energy for mixing the I I More particularly, a ternary UUII~ ;iiUll of water, a volatile cyclic or linear methyl siloxane (VMS), and short-chain or low molecular weight silicûne polyether, ~r ~ ' ~ provides optically clear ufi~lu~ lul.~ s when combined with only hand agitation.
It is well du, ' (US-A 4999398) that emulsions, especially silicone emulsions, are opaque, cloudy, and tend to separate on standing. Thus, the desirability ûf , which contain micro-particles in the droplet phase is to provide a measure of clarity.
As used herein, the term emulsion or Ill.Ll.l U~ Ul~;Oll means a dispersion of one immiscible liquid in another, in the form of droplets, with diarneters rl,U,UlU. ' ' 'y in the range of 100-1,000 U~UIUIII~L~I~ (0.1-1.0 ~lul.~.,t~.l/l,OOO-10,000 angstroms A). In contrast, a mi~, ~ ' means a transparent, thermod~ "y stable, dispersion of two or more immiscible liquids and a surfactant.
M;w u. ' are clear or transparent because they contain particles smaller than the wavelength of visible light, which is typically on order of 10-100 M;UIU~IIUID;UII~ may contain oil droplets dispersed in water (O/W), water droplets dispersed in oil (W/O), or they may be in the form of a 1,;~ structure.They are ..1 ,~ 1 by an ultra-low interfacial tension between the oil and water phases.
A lldcl U~ ulb;Oll is recognized by several of its inherent ~ 1-,, . .., 1 l~. ;~l ;, .~
which are that (i) it contains oil, water, and a surfactant; (ii) there is a high r n of surfactant relative to oil, (iu) the system is optically clear; (iv) the phases do not separate by c~ntrifi~g,Ati~ n; and (v) the sy$em forms blJ~ ' - '~/, Thus, for this invention, an emulsion is considered as containing particles having an average diameter of more than 100 l~llul..~;lul ~ (0.1 1111~1 Ulll~ l/l ,000 ~' 2 ~ 8~835 angstroms A), whereas a ".:~ contains particles having an average diameter of less than 100 (0.1 llli.,lUll~t~ /1,000 angstroms A). Clarity or ~l ~ t;.,~ is controlled to a great extent by the particle size of the dispersed phase. The scattering of light is dependent on the particle size. Therefore, clear or transparent CUlll~)UD;LiUllD
appear to be a single phase without droplets or particles when viewed with the naked eye.
While US-A 3299112 describes emulsions formed from water, a silicone oil and a silicone polyether, these emulsions are not clear, and they require input of substantial mechanical energy to prepare. Ful lll~llllul ~, in contrast to our invention, the ternary system in that patent is not a llfi~ oll, the silicone oil is not a volatile cyclic VMS; and while it does describe a linear silicone oil, it is not a volatile linear silicone!
Thus, the silicone oil of that reference ~UII ~ JOIIJD to R"3SiO(R"~SiO)2~SiR"3 where x is 10-1,000. Our l,u-l ~iD~)oll~illg volatile linear VMS has an "x" of 0-5, well below the range of the reference. In fact, we even found that where "x" exceeds 5, the emulsions tend not to be clear.
In addition, emulsions are recognized as inherently unstable systems and separate with time. In contrast, our llli~Jlu.,~ lD;ullD form ~r ' ~/ and are stable indefinitely. The order of addition of the l- - r ~ ' does not influence their formation, and simple hand shaking in the ~ l d~UI~ range of their stability is sufficient to cause the ,lU~ IUID;UIID to form.
~ These D~ / formed clear Illil.lU~ flD;U~ID have particular value in the personal care arena. Because of the unique volatility ~ ;UD of the VMS
component of our ternary system, it can be used alone, or blended with other cosmetic fluids, to form a variety of over-the-counter personal care products.
Thus, it is useful as a carrier in i __D~);ld~ and deodorants, since it leaves a dry feel, and does not cool the skin upon C~ )Uld~iOII. It is lubricious and will improve the properties of skin creams, skin care lotions, ., .. ,~ , facial treatments such as acne or wrinkle removers, personal and facial cleansers, bath oils, perfumes, colognes, sachets, sunscreens, pre-shave and after-shave lotions, shaving soaps and ~' 21 89835 shaving lathers. It can be used m hair shampoos, hair c~n~' ;, hair sprays, mousses, permanents, depilatories and cuticle coats, to enhance gloss and drying time and provide . .. " ,1 l; l ;. ,. .; . .~ benefits. In cosmetics, it functions as a leveling and spreading agent for pigments in make-ups, color cosmetics, ~ ' s, blushes, lipsticks, eyeliners, mascaras, oil removers, color cosmetic removers and powders. It is useful as a delivery system for oil and water soluble substances such as vitamins. When i~,vll~uld~d into sticks, gels, lotions, aerosols and roll-ons, our ternary ~ "J';~ imparts a dry, silky-smooth, payout.
In addition, because our *)V~ VU;~IY formed clear llf~ulv~ lul~;v.lo exhibit a variety of adYall~L~,_vu~ and beneficial properties such as (i) clarity, (ii) very small particle size, (iii) ultra-low interfacial tensions, (iv) the ability to combine properties of water and oil in a single 1- ~,, fluid, (v) shelf stability and (vi) ease of ~I r~Ja~ ioll, they have wide application but especially in . i~J..I b~ , deodorants, in perfumes as a carrier and in hair ~.. . 1; 1 ;. ). ,;. ,~
It is an object of this invention to form a clear Illi~l v~lllul.,;v~l by simplycombining (i) water; (ii) a volatile cyclic methyl siloxane or volatile linear methyl siloxane;
and (iii) a silicone polyether.
Surprisingly, we have discovered how to make clear products without involving the use of high shear, heretofore required to obtain the small particle size necessary to achieve clarity.
These clear Illi~,l(J~,l..JI~;Vlli:. form ~.". '..,..vu~ in the sense that they do not require energy input by means of mixing and shear devices. Thus, turbines, impellers, colloid mills, hnmr~g~ni7Prs or sonolators are not required to form these systems. It is only necessary that the appropriate amounts of the three crlmrc be added to a suitable container and the container be hand shaken. Of course, the cu.,.~,ul~ can be mixed or sheared with more energy input, and the microemulsions will still be obtained, but no advantage results firom such additional energy usage.
~' 21 89835 Our temary i.... "1~~~; l ;.., . contains water, a volatile cyclic or linear methyl siloxane (VMS), and a short-chain or low molecular weight silicone polyether. Those three ~...., .1...1 . : ~ are combined to form clear i.~ without the addition of other materials.
Thus, the claimed ~ .. is free of non-essential ingredients such as salts; co-surfactants, Illullchrd~u~y alcohols; and diols and triols such as ethylene glycol and glycerol. The elimination of such non-essential ingredien~s is especially beneficial and ddvoll~L~ u~ as it obviates the need for refractive index matching, often resorted to in the past to achieve clear or transparent products.
The three u. .".1,.~ are combined in any given order of addition. While heat enhances solubility, lowers surface tension and reduces viscosity, its application is also not required. Room ltul~,c.~lul~ (20-25~C /68-77~F.) is sufficient in most cases.
The oil component of our temary, ,.c,~lLiv.. is a volatile methyl siloxane (VMS), which is a low viscosity silicone fluid COIl~ -r ~' ~, to the average unit fommula (CH3),SiO(4 ,)n in which a has an average value of two or three. The fluid contains siloxane units joined by =Si-O-Si-- bonds. R,,~ ,.ltdlive units are .... " ...r .. ,~ "M"
units(CH3)3SiO~nand~ ' "'D"units(CH3)2SiO22. Thepresenceofl.,ir"...l;.-~"T" units CH3SiO3,2 results in the formation of branched cyclic volatile methyl siloxanes.
The presence of ~lldLUll~.liUI.dl "Q" units SiO4n results in the formation of branched linear volatile methyl siloxanes.
Linear VMS have the formula (CH3)3SiO{(CH3)2SiO},~Si(CH3h, and cyclic VMS have the formula {(CH3)2SiO}y, in which x is 0-5 and y is 3-6. Preferably, the volatile methyl siloxane has a boiling point less than 250~C. and a viscosity of 0.65-5.0 centistokes (mm2/s).
Some It;1111,.~,.1~21~iV~ volatile methyl siloxanes are:
~' 2 1 89835 H3C i O i O 'i CH3 Il) Linear -- x O (llj Cyclic CH
3 _ y H3C--i--~ ' i- ~ 'i CH3 (111) Branched Linear CH3 ~ CH3 H3C ' i CH3 H3C i O i O ''i CH3 (IVi BranchedCyclic H3C_ j. O i CH3 - .-- 21 89835 The cyclic volatile methyl siloxanes (II) have been assigmed the T ~ ' ~i Cosmetic Ingredient (INCI) name "CYCLOMETHICONE"
by The Cosmetics, Toiletries and Fragrance Association, Inc., (CTFA) Washington, DC.
Cyclic and linear methyl siloxanes are clear fluids, essentially odorless, non-toxic, non-greasy, non-stinging and non-irritating to skin. VMS leave ' "~/ no residue after thirty minutes at room LclulJ~dLulti (20-25~C./68-77~F.) when one gram is placed at the center of No. I circular filter paper of 185 millimeters diameter, supported at its perimeter in open room atmosphere. Volatile methyl siloxanes may be used alone or mixed together.
Mixtures result in solutions having cva~ , behaviors different from individual 'duids.
R~ e.~ Live linear volatile methyl siloxanes (I) are l~,Aaull~ y' " ' (MM) with a boiling point of 1 00~C., viscosity of 0.65 mm2/s, and formula Me3 SiOSiMe3; o.,L uucLhy ' ' (MDM) with a boiling point of 1 52~C ., viscosity of 1.04 mm2/s, and formula Me3SiOMe2SiOSiMe3; dc~alllcLllyl~ la~iluAaue (MD2M) witha boiling point of 194~C., viscosity of 1.53 mm2/s, and formula Me3SiO(Me2SiO)2SiMe3; dorlr~ - 1-- Il~y~ t ~ ,,I,r. (MD3M) with a boiling point of 229~C., viscosity of 2.06 mm2/s, and formulaMe3SiO(Me2SiO)3SiMe3;
lcll ad~,~.aul~ llyl~ lr (MD4M) with a boiling point of 245~C., viscosity of 2.63 mm~/s, and formula Me3SiO(Me2SiO)4SiMe3; and h ~ yll~ JAalle (MDsM) with a boiling point of 270~C., viscosity of 3 .24 mm2/s, and formula Me3SiO(Me2SiO)sSiMe3.
R~., ve cyclic volatile methyl siloxanes (II) are ' yL.y~ (D3) a solid with a boiling point of 134~C. and formula {(Me2)SiO} 3; octameth;dcy.,loL~iL a~ ,AL.._ (D4) with a boiling point of 1 76~C., viscosity of 2.3 mm2/s, and formula {(Me2)SiO}4; ' ' yh~y~ "l~ l .Y (Ds) with a boiling point of 210~C., viscosity of 3.87 mm2/s, and formula {(Me2)SiO}s; and ~lo~ y~ (D6) with a boiling point of 245~C., viscosity of 6.62 mm2/s, and formula ~(Me2)SiO}6.
~' 2 1 &9835 R~~ ld~ive branched volatile methyl siloxanes (III) and (IV) are ll~lA,lI-yl-3-{(~ .. 'yl)oxy}trisiloxane (M3T) with a boiling point of 192~C, viscosity of 1 57 mm2/s, and formula CloH3003Si4, hexamethyl-3,3,bis-{(Lli~ l,:.;lyl)oxy}trisiloxane(M4Q)withaboilingpointof222~C.,viscosityof2.86mtn2/s, and for~nula C12H3604Sis; and ~ 1 {(Ll;ll-~ lyl-'yl)oxy}
(MD3) with the formula CgH2404Si4.
One preferred VMS component of my ternary system is o~ h~ y~lu~ u~c [(CH3)2SiO]4. It has a viscosity of 2.3 centistokes (mm2/s) at 25~C., and is referred to as "D4" since it contains four r~ifimrtin~ "D'l units (CH3)2SiO2/2 shown as:
O i O
Four "D" unhs combine to form ' ~Icyclo-tetrasiloxane shown in either formula below:
H3C~ ~CH3 CH3 ~Si~
~j o H3C~ f \ ~ 3 CH3 H3C \~ ~/ CH3 ~' 2 ~ 89835 In the literature, D4 is often called CYCLOMETHICONE or TETRAMER. It has a higher viscosity of 2.3 rnm2/s (cs) and is thicker than water of 1.0 mm2/s (cs), yet o~ lyl~y~luleLl '~ needs 94% less heat to evaporate than water.
Another preferred VMS component of my ternary system is y~ (D5) often referred to as PENTAMER. It is shown structurally below:
H3C 3 Cl H3 \si--o--si/
H3C~¦ ¦ ~CH3 /si\ /si\
H3C ~--S~--~ CH3 A benefit offered by using VMS UUI~ ~ is that many local, state, , federal and ;. .I rl 1 l~ regulations, have restricted the use of certain chemicals, but VMS
is a suitable Ir.~ Thus, the Ellvi~u. .. II~dl Protection Agency (EPA) determined that volatile methyl siloxanes such as octarnethylcy~,lule~la~iloxane, ' ' ~k,y~,L)-p. . ~ rl(lrr~~lrthyl~yl ~ - L '~ '~ hexamethyldisiloxane, oc~ ~tl.y" ' and d~ llG~l!yl~e~l~ l;lu~ , were acceptable substitutes for the CFC-I 13 ~.I.Iolunuulu~.~boll (C2C13F3) and methyk,l.lulurullll (MCF). This d~ ; ", is limited to clearling in closed systems, for metal clearling, electronic clearling and precision cleaning "~ under the EPA's Sigaificant New AlternativesPolicy (SNAP).
~' 2~ 89835 In addition, the EPA excluded VMS as a volatile organic compound (VOC). Thus, they added VMS to a hst of compounds in 40 CPR 51.100(s), excluded from the definition of VOC, on the basis that VMS çr)mro~ have negligible to llu~u~ ..ic ozone formation. They pointed out that exempting VMS
from regulation as an ozone precursor contributes to ~ v~ ll of several importznt lallvilulllu~ goals, in that VMS might be used as a substitute for i...",l,,...,,.l~ listed as hazardous air pollutants (HAP). As they explained, that list met the need to develop substitutes for ozone depleting substances (ODS), and to attain National Ambient Air Quality Standards for ozone under Title I of the Clean Air Act.
The other component of our ternary system, m addition to water and VMS, is a short-chain or low molecular weight silicone polyether. R~ ,uldliv~ polyether structures are:
Rl Rl Rl Rl Rl-- i O 'i--O i O i Rl Rl Rl R2 Rl X Y
Rl Rl Rl Rl R2-- i O--''i O i O 'i R2 Rl Rl R2 Rl ~ 21 89835 ~o A cyclic polyether of the type shown below can also be used.
-i O i- O
--m -- --n In these structures, Rl represents an alkyl group containing 1-6 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, and hexyl; R2 represents the radical -(CH2)~0(C~H40)b(C3H60)cR3; x has a value of 0-3; y has a value of 1-3; z has a value of 0-2; m has a value of 3-5; n is one; a has a value of 3-6; b has a value of 4-20; c has a value of 0-5; and R3 is hydrogen atom, a methyl radical, or an acyl radical such as acetyl.
Preferably, Rl is methyl; b is 6-12; c is zero; and R3 is hydrogen atom.
C..~ .... of this invention may contain 5-70% by weight of surfactant, but most preferably, they contain 15-3 0% by weight of the surfactamt. The balance of the C~ iS oil and water, with the ~,. UpUI ~iu..., of oil and water generally falling between 40:60 to 80:20, or 0.4 to 0.8 as defined below for Ratio 1.
For purposes of this invention, the criteria used to determine optical clarity is whether text c~m be read with the naked eye through a two centimeter diameter bottle filled with the llfi~
As noted in the textbook Ml.,, . ' Theory and Practice, Edited by Leon M. Prince, Academic Press, Inc., Pages 7-10, New York (1977), the "Visual recognition of llfi-,l u~,..lulb;u.~s should not be taken lightly. In fact, the lllh,l U~.IUI..;Ull chemist should train himself carefully in this art. Use of sunlight rather than an artificial source of light is I r~ 1 The eye is better than a llli-~lu~,u~)e because the limit of resolution of a light lllh,lub~,u~e in blue light is only about 0.1 llm sû that droplets smaller than 0.14 ~lm cannot be seen".
Example I
We formed optically clear ll~ l u~ ,lblu..D ~u,..~ vu.,ly at l-,"~,u~.l dLUI tiDranging between 47-62~C. by merely adding to a container, 50 parts of de-ioni2ed water, 50 parts of ' "1~. 1~ ~I rl I ~ ? (D4) and 25 parts of silicone polyether. No mixing, stirring, shearing or input of mechanical energy for agitating the three ingredients was required. The polyether uull~D~Ju~ d to the compound Rl Rl Rl Rl Rl-- i O 'i- O i O 'i Rl Rl 1~1 R2 Rl X Y
where Rl was methyl, x was zero, y was one and R2 was -(CH2)3(0C2H4)80H. Text was able to be read through a two centimeter diameter bottle filled with the microemulsions. It was determined that the mi..l- ' contained particles having an average diameter of lessthan 100 (01 ~lU~lUII~ lb).
Example II
We repeated Example I and formed clear u~.lullb;ullb .,~ ..,..vu~/y at .~IdLUI~ ranging between 60-68~C. by merely combining in a container, 50 parts of 21 8~835 de-ionized water, S0 parts of ' ~ ,y. 1~ ~p~ (DS) and 25 parts of silicone polyether. The optical clarity was the same as obtained in Example I.
Example Ill We repeated Example I and formed clear Illh~lU~ UI,..JII~ ~u~ vu.~ly at ~tUl~ ld~UI~ ranging between 44-60~C. by merely combining in a container, 6û parts of de-ionized water, 40 parts of ~ ,L"~ (D4), and 17.65 parts of silicone polyether. The optical clarity was the same as obtained in Example I.
Example IV
We repeated Example III including the use of salt which is a non-essential ingredient. We formed clear u~lu!.. JI~S ~ y at I , dlUlt~ ranging between 20-30~C by merely combining in a container, 50 parts of an aqueous solution containing 15% sodium chloride, 50 parts of octamethyl.,y..lu~ a~ilu~ , (D4), and 17.65 parts of silicone polyether. The optical clarity was the same as obtained in Example m.
Example V
We repeated Example IV and formed clear ll h,lU~ ul~;OII~ ... vu.ly at ~ ,ld~UIU.~ ranging between 22-41~C. by merely combining in a container, 30 parts of an aqueous solution containing 15% sodium cbloride, 70 parts of octamethylcyclo-I~LI a~;lu~ (D4), and 25 parts of silicone polyether. The optical clarity was the same as obtained in Example IV.
Example VI
We repeated Example II and formed clear Illi~lU~llUI:~;Ull~ .~.uu~ .vu.~ly at ~tlll~llU11~ ranging between 30-85~C. by merely combining in a container, 50 parts of de-ionized water, 50 parts of d~,aull~ yl~,y~ (D5) and 66.67 parts of silicone polyether. The optical clarity was the same as obtained in Example II.
The following four examples illustrate preparation of clear allli~)~,l ~;1 all~.In Examples VII-X, an all~ J;lall~ active was hluul~uldled into our clear silicone Illi~/l U~lllUI~iO~ without input of mechanical energy for mixing the ..OIII~J~
2l 89835 Example VII
We repeated Example I and formed clear ~ ,..vu..ly at t~,.ll~)~d~UI1.~ ranging between 42-58~C. by merely combining in a container, 50 parts of an aqueous solution containing 25% of the a~ ~lL active Aluminum Cbl~l vl~yl~
(ACH-303), 50 parts of octamethyl~.,lui ' (D4) and 25 parts of silicone polyether. The optical clarity was the same as obtained in Example 1.
Example VIII
We repeated Example VII and formed clear Illi~ lUI..;~ ...V~.~VU.~Iy at i l __d~UI~ ranging between 36-69.6~C. by merely combining in a container, 50 parts of an aqueous solution containing 25% of the 'i l active Aluminum-Zirconium T~ u-uhydrex-Gly (ACH-370), 50 parts of o.,l~..~L;l~.y. .1. .l rl ~ (D4) and 28.2 parts of silicone polyether. The optical clarity was the same as obtained in Exarnple VII.
Exa[nple IX
We repeated Exalnple VII and formed clear llli.~lu~ VU,~/y at lelll~ dlul~,~ ranging between 30-46~C. by merely combining in a container, 50 parts of an aqueous solution containing 50% of the a~ J.,l ~;. all~ active Aluminum Chl~,. ullyll dLe (ACH-303), 50 parts of octamethyl~,y~.luleLl~ d..~ (D4) and 21.95 pa~ts of silicone polyether. The optical clarity was the same as obtained in Example VII.
Example X
We repeated Example VII and formed clear .. i.,. ~ VU.>ly at room I~ y~ld~UI~ by merely combining in a container, 63 parts of an aqueous solution containing 25% ofthe ~i *);ldllL active Aluminum Chlorohydrate (ACH-303) and 15%ofsodiumchloride~37partsofouldlll~lllyll~y~lu~lla~;hJ~dil~(D4)~and2o5partsof silicone polyether. The optical clarity was the same as obtained in Example VII.Other i, ,~.;.~...~ actives such as Aluminum ~f~cqll ' ~Jllydldle salts can be used in Examples VII-X. Suitable o~ products can be formulated containing a maximum use level of i I active of 20% by weight AZG and 25%
by weight ACH, on an anhydrous basis.
The following examples illustrate preparation of r~ o~ according to this invention using a linear volatile methyl siloxane instead of a cyclic volatile methyl siloxane.
Example Xl We repeated Example I and formed clear Illi.,lu~lllulDiol~s ,,~ uu.,~y at Le~ J.,.dLule~ ranging between 30-70~C. by merely combining in a container, 50 parts of de-ionized water, 50 parts of hexamethyhl;Dilu,.~l~ (~I) and 42.9 parts of Silicone polyether. The optical clarity was the same as obtained in Example 1.
Example Xll We repeated Example Xl and formed clear ~lli.,l c ' ~ Ju.~l,v at LellllJ~,IdLul." ranging between 43-56~C. by merely combining in a container, 50 parts of de-ionized water, 50 parts of hexamethyl('i ' (MM) and 1?.7 parts of silicone polyether. The optical clarity was the same as obtained in Example 1.
Table I provides a summary of Examples l-XII. In Table 1, Ratio I is the amount of oil divided by the amounts of oil and water. Ratio 2 is the amount of surfactant divided by the amounts of oil, water and surfactant. Percent Surfactant is obtained from the l l ' ' . (Ratio 2) divided by ( I -Ratio 2) X 100.
~ 21 89835 TA:BLE I
Example TU~ u~t:(oc) Ratio I RatiQ 2 % C~
47-62 0.5 0.2 25.0 Il 60-68 0 5 0.2 25.0 m 44-60 0.4 0.15 17.6 IV 20-30 0.5 0.15 17 6 V 22-41 0 7 0.2 25.0 Vl 30-85 0.5 0.4 66 7 Vll 42-58 0 5 0.2 25.0 VIII 36-69.6 0 5 0.22 28.2 IX 30-46 0.5 0.18 22.0 X 20-25 0 5 0.22 28.2 Xl 30-70 0.5 0.3 42.9 ~D[I 43-56 0.5 0.15 17 6 As seen in Table 1, c.-".,l..,- ';~ ...~ according to our invention are prepared at L~ UI .,., generally in the range of 20-85~C. They contain 5-70% by weight of surfactant, most preferably, 15-30% by weight ofthe surfactant; with the balance being oil andwater. TheF. UpUl~iUII~ of oilandwatergenerallyfallbetween40:60to80:20,orO.4 to 0.8 as defined above for Ratio 1.
Figure I is a ternary phase diagram of our system comprising water, octamethylcy.,lu~l~ilu,.al.e (D~) and the silicone surfactant, for tlf ~. . ",;";,.~ cu.,.~ui,;~iu..
ranges of U~,llll~l_ U~ prepared according to Example 7~111 of this invention. The are defined by the shaded area depicted in Figure I .
In Figure I, each of the corners represents 100 percent of the component labelled there. The side of the triangle directly opposite each corner represents zero percent of that c ul..r Lines parallel to the opposite side represent increasingamounts of that component as they become closer to the corner Any line drawn from the ~ 2 1 89835 corner of Component A to the opposite side represents varying the amount of Component A at a constant ratio of the other two romrr The Co~ o~;liull of any point within the shaded area is determined by drawing lines parallel to each of the three sides through the point. The amount of each component is then read from the; . . l r, .~ . . of each line with the side of the triangle which ~,U~ JUIId~ to that component, i.e. the side beginning at I ûû at each culll~o..~ L'~
corner.
Example XIII
We formed a number of optically clear Ill~,IU; ' ~ ,~IUU~ VI~ / at room l~ nil d~Ul~; (22~C.). In this example, ~ ,r~ ;. ,.. c~ v ~. of the invention were prepared, wherein the mixing ratio of the three r ~ -r; ~ ~ comprising water, oil and surfactant, was within the shaded area in Figure 1, i.e., the area surrounded by the lines connecting points A, B, C, D and E. We formed these .lli.,l.,.,~ l..;ull~ in the same manner as in Example 1. Thus, we merely added the three ingredients to a container. No mixing, stirring, shearing or input of mechanical energy for agitating the three ingredients was required. The polyether COllUi~lJU.IdC;l to the same compound used in Exarnple I. We were again able to read text through a two centimeter diameter bottle filled with these i-.l-'~""'l "'' They contained particles having an average diameter of less than lûû
ildllO.I.~,t~l ~ (û . I Uli~ l u---~
Example XIV - Comparison We repeated Example I and formed a number of emulsions at room d~Ul~. However, in this COMPARISON EXAMPLE, we used a silicone oil equivalent to the silicone oils described in US-A 3299112. Thus, the silicone oil I~UIll, ' ' to R''3SiO(R''2SiO)ySiR''3 with x being 10-I,ûûû. Although we followed the teaching in the above patent, we were not able to read text through a two centimeter diameter bottle filled with these comparative emulsions. One ~".I~u~ .l ofthis invention involves using a volatile linear VMS having an "x" of 0-5, well below the range - ~ 21 89835 of the above patent. In this CO~ARISON E7~AMPLE, we verified that where 'Ix' exceeds 5, the resultant, .lU~iUII~ are not clear.
Claims (8)
1. A method for forming a microemulsion comprises combining (i) water;
(ii) a cyclic methyl siloxane having the formula {(CH3)2SiO}p or a linear methyl siloxane having the formula (CH3)3SiO{(CH3)2SiO}qSi(CH3)3 in which p is 3-6 and q is 0-5; and (iii) a silicone polyether having a formula selected from the group consisting of where R1 represents an alkyl group containing 1-6 carbon atoms; R2 represents the radical -(CH2)2O(C2H4O)b(C3H6O)cR3; x has a value of 0-3; y has a value of 1-3; z has a value of 0-2; m has a value of 3-5; n is one; a has a value of 3-6; b has a value of 6-12; c has a value of 0-5; and R3 is hydrogen atom, a methyl radical or an acyl radical.
(ii) a cyclic methyl siloxane having the formula {(CH3)2SiO}p or a linear methyl siloxane having the formula (CH3)3SiO{(CH3)2SiO}qSi(CH3)3 in which p is 3-6 and q is 0-5; and (iii) a silicone polyether having a formula selected from the group consisting of where R1 represents an alkyl group containing 1-6 carbon atoms; R2 represents the radical -(CH2)2O(C2H4O)b(C3H6O)cR3; x has a value of 0-3; y has a value of 1-3; z has a value of 0-2; m has a value of 3-5; n is one; a has a value of 3-6; b has a value of 6-12; c has a value of 0-5; and R3 is hydrogen atom, a methyl radical or an acyl radical.
2. A method according to claim 1 in which the methyl siloxane is present in the microemulsion in the form of droplets having an average diameter of less than 100 nanometers.
3. A method according to claim 1 in which the methyl siloxane is selected from octamethylcyclotetrasiloxane or decamethylcyclopentasiloxane.
4. A microemulsion obtainable by the method defined in claim 1.
5. A microemulsion prepared according to the method defined in claim 1, the microemulsion having a composition defined by and within the shaded area depicted in the annexed Figure 1.
6. A personal care product containing the microemulsion of claim 5 selected from the group consisting of antiperspirants, deodorants, skin creams, skin care lotions, moisturizers, acne removers, wrinkle removers, facial cleansers, bath oils, perfumes, colognes, sachets, sunscreens, pre-shave lotions, after-shave lotions, shaving soaps, shaving lathers, hair shampoos, hair conditioners hair sprays, mousses, permanents, depilatories, cuticle coats, make-ups, color cosmetics, foundations, blushes, lipsticks, eyeliners, mascaras, oil removers, cosmetic removers, delivery systems for oil and water soluble substances and powders, including products in the form of sticks, gels, lotions, aerosols and roll-ons.
7. A method according to claim 2 containing about 15-30% by weight of the silicone polyether, the proportions of methyl siloxane and water being between 40:60 to 80:20.
8. A method of improving the appearance of the hair or skin of a mammal comprising applying to said hair or skin the microemulsion of claim 4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/560,561 US5705562A (en) | 1995-11-20 | 1995-11-20 | Spontaneously formed clear silicone microemulsions |
| US08/560,561 | 1995-11-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2189835A1 true CA2189835A1 (en) | 1997-05-21 |
Family
ID=24238328
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002189835A Abandoned CA2189835A1 (en) | 1995-11-20 | 1996-11-07 | Spontaneously formed clear silicone microemulsions |
Country Status (11)
| Country | Link |
|---|---|
| US (2) | US5705562A (en) |
| EP (1) | EP0774482B1 (en) |
| JP (1) | JPH09183901A (en) |
| KR (1) | KR100421759B1 (en) |
| AU (1) | AU703229B2 (en) |
| BR (1) | BR9605612A (en) |
| CA (1) | CA2189835A1 (en) |
| DE (1) | DE69614637T2 (en) |
| ES (1) | ES2162983T3 (en) |
| MX (1) | MX9605682A (en) |
| TW (1) | TW327639B (en) |
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- 1995-11-20 US US08/560,561 patent/US5705562A/en not_active Expired - Lifetime
-
1996
- 1996-08-09 US US08/694,722 patent/US5707613A/en not_active Expired - Lifetime
- 1996-11-07 CA CA002189835A patent/CA2189835A1/en not_active Abandoned
- 1996-11-14 ES ES96308244T patent/ES2162983T3/en not_active Expired - Lifetime
- 1996-11-14 EP EP96308244A patent/EP0774482B1/en not_active Expired - Lifetime
- 1996-11-14 DE DE69614637T patent/DE69614637T2/en not_active Expired - Lifetime
- 1996-11-15 TW TW085114037A patent/TW327639B/en active
- 1996-11-18 AU AU71802/96A patent/AU703229B2/en not_active Ceased
- 1996-11-18 JP JP8306168A patent/JPH09183901A/en active Pending
- 1996-11-19 MX MX9605682A patent/MX9605682A/en unknown
- 1996-11-19 BR BR9605612A patent/BR9605612A/en not_active Application Discontinuation
- 1996-11-20 KR KR1019960056982A patent/KR100421759B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| AU703229B2 (en) | 1999-03-18 |
| JPH09183901A (en) | 1997-07-15 |
| US5707613A (en) | 1998-01-13 |
| EP0774482A3 (en) | 1997-07-30 |
| KR100421759B1 (en) | 2004-05-17 |
| TW327639B (en) | 1998-03-01 |
| AU7180296A (en) | 1997-05-29 |
| EP0774482B1 (en) | 2001-08-22 |
| EP0774482A2 (en) | 1997-05-21 |
| DE69614637D1 (en) | 2001-09-27 |
| ES2162983T3 (en) | 2002-01-16 |
| BR9605612A (en) | 1998-08-18 |
| KR970025692A (en) | 1997-06-24 |
| DE69614637T2 (en) | 2002-09-12 |
| US5705562A (en) | 1998-01-06 |
| MX9605682A (en) | 1997-05-31 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |
Effective date: 20040722 |