DE1617946A1 - Self-foaming homogeneous liquid mixture - Google Patents

Description

PATENT LAWYERS 161794g DWNG. RICHARD GLAWE. DIPING. KLAUS DELFS ■ DIPL-PH / S. DR. WALTER MOLL ^MDNCHEN MÖNCHEN

8 MÖNCHEN 26 2 HAMBURG

PO Box 37 WAITZSTR.

LIEBHERRSTR. 20 TEU (0411) 89 2255 TEL (0811J22i548

YOUR SIGN YOUR MESSAGE FROM OUR SIGNFM

SIGN Munich

^{AFFECT i} YARDIlET & COMPAMT LIMIIED

london / england

Self-foaming homogeneous liquid mixture

The invention relates to the production of self-viewing gauges homogeneous liquid mixtures that occur when spraying Form a foam with temporary resistance from suitable aerosol containers

cosmetic purposes are aerosol-foam mixtures proposed and used. It was stated that these mixtures were used in transparent containers or dispensers are suitable.

101821/201 ί ^0RiG? Pt- inspects)

However, the mixtures have the disadvantage that some of the constituents are separated out at low ambient temperatures. These formed an unsightly, heterogeneous layer or precipitate at the bottom of the aerosol. Such temperatures below 15 to 2O ⁰ C, often even below 5 ⁰ O, are frequently encountered at low Außenteraperaturea in the morning in the bathroom. These fillings, usually precipitations of the surface-active agents (surfactants) present, were so troublesome that at these low temperatures even the formation of foam was prevented.

The present invention provides and aims to overcome these shortcomings in the prior art starting to create an aerosol shower mix that works with remains clear at said low temperatures and avoids any noticeable precipitation in the container.

According to the invention, such a mixture should also be used created that does not cause a burning sensation on the skin and avoids any skin irritation and reddening of the skin «

According to the invention, the components the mixture are selected and dimensioned so that the

109323/2065

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generated foam collapses by itself in a very short time.

The invention is directed to the production of such liquid gauges at low pressure and with satisfactory clarity at extremely low Fm _c -; ebuivjsteciperaturea, so that the product remains clear and fluid over a wide temperature range and is therefore also suitable from an aesthetic point of view Aerosol containers made of clear glass, to be packed with plastic coated glass and clear plastic. Skin fresheners, aftershave lotions, shampoos and similarly rapidly collapsing foams have a much more elegant and attractive effect when they are contained in and dispensed from an aerosol container as a clear, uniform phase.

The problem is compounded in part by the fact that the grinding of the surfactant mainly to certain, im. Must limit commercially available mixtures of surfactants. In order to achieve the desired clarity at low temperature, special mixtures had to be used according to the invention suitable surface-active agents are developed, except for the other measures with regard to the composition, which will be explained in more detail later.

109823 / 20S & ^ t fi6W ^ original

burn open and skin irritation potential

Development work in this area has shown that high levels of alcohol (ie $ 55 to $ 65) cause considerable irritation to healthy skin and often cause reddening of the skin with repeated use. Since the agent has to be applied to the skin in a very large number of cosmetic applications, this is extremely undesirable. The effect is even more pronounced with aftershave foams that are applied to the skin after shaving.

For this reason the invention, foams were developed according to the fo an ethanol content of only 32 of 95 / ^ pc alcohol, or even lower have. Even alcohol contents that do not cause any particular irritation can sting the face. Therefore, because of the cosmetic elegance, foams with negligible skin irritation potential are required. Self-liquefying foam products according to the present invention which have been produced with an alcohol content in the range of 30 to 45% alcohol have no or only minimal burnability on the skin.

Foam stability and volatility

Another aspect of the mixtures according to the invention

8 ~ 2 3 ^{a 4/2} ~ 06

dung is the stability of the foam. The compositions customary up to now were very often much too stable. In contrast to the prior art, it was found according to the invention that suitable foams should be self-liquefying with a stability period of 10 to 60 seconds. There was indeed a love of this type among buyers, as more stable foams are also resistant to heating and often swell out between singers when used.The foam structure properties depend on the concentration and composition of the mixture of surfactants, the alcohol concentration and the type and type Concentration of the selected propellant from »

Components

The essential basic components of a rapidly collapsing foam with temporary stability are the following:

A) A mixture of alcohol ($ 30 to $ 55) and water, which serves as a carrier.

B) A mixture of surface active agents (surfactant) in concentrations of 0.4 to 5.0 wt -.% ·

G) Compatible gaseous hydrocarbons or halo-

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ΙΟΙ

genetically modified hydrocarbons, individually or as a mixture, in concentrations of 2 to 18 Grew .- / £,

In addition, any useful cosolvent can be used that does not affect the clarity or foam structure of the finished aerosol mixture.

A) The alcohol / water ratio

The surfactants normally used with these aerosols are selected to be soluble in alcohol and insoluble in water. The ratio of water to alcohol is then adjusted at room temperature to the point at which the mixture of surface-active agents is just insoluble in the alcohol-water mixture. The Eera natural, at which the concentrate becomes clear and homogeneous, usually coincides with the upper temperature at which a suitable foam is produced when the concentrate is sprayed out as an aerosol.

The term "alcohol ¹¹ relates to ethanol, methanol, isopropanol, which can replace a portion or the G-esaratmenge of the alcohol.

If lower alcohol levels are used, will

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then reduced fountains on the skin. It was therefore erf incTungsgeraäß assumed to use the lowest possible amount of alcohol in the mixture, which is compatible with the Requirement for clarity of the finished aerosol is still acceptable; This is achieved through the following measures:

1. Selection of surfactants with a good one Solubility in water-alcohol mixtures.

2. The use of glycols and ethers as couplers,

3. Increased blowing agent concentration

B) Choice of surfactant .

The texture of the foam and its stability are directly influenced by the concentration and choice of surfactant (s). However, it should not be required in any EaIl., More than 5 wt .- / α of surfactants in the total To use aerosol mixture, because higher contents of these additives stickiness as well as a heat dissipating In reality, utu only causes sensation on the skin act as solubilizing substitutes for alcohol. This substitution of alcohol can be more elegant Way can be achieved by using more! Propellants, GIy-

- 7 109823/2068.

col or water or a combination of these substances is used, so that the deposition of excessive amounts of esters on the skin is avoided. The choice between the suitable mixtures of surface-active agents is somewhat limited, since these must be solid substances that must be ^{clearly soluble in the finished aerosol mixture including the propellant down to 6 0} G, but in the concentrate (all other components with the exception of the propellant ) must be insoluble at temperatures up to 30 ° or more (if the foam is to be generated at higher temperatures).

Suitable mixtures of surface-active agents, which give the best clarity, contain saturated ^C ^ 2 " ^G 22""I fatty alcohols and non-ionic surface active agents, which are selected from the polyoxyethylene derivatives of fatty alcohols, Q ^ - Ogp-i 'fatty acids, ^etc. ^ lanolic acids and - alcohols made by reacting a suitable alcohol or acid with ethylene oxide or polyethylene oxide. Some typical examples of these mixtures are as follows:

Weight -Jq

a) Getyl alcohol 25 - 60

Pentaethoxy (5 moles of ethylene oxide) ^G 16 - 20 "fatty alcohol ether 75 - 40

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Weight -Yes

b) Cety! alcohol 53 - 66.0 diethoxy stearyl ether 53 - 20 Decaethoxy-stearyl-ether 20-14

c) Ceryl alcohol 50.0 polyethylene glycol (40 mol ethylene oxide) -laaolin, alcohol-ether 50.0

d) Dtethoxy-stearyl-ether 28-35 Oetyl alcohol 3-6 Polyäthylanglycol (25 mol Ethyleö-

oxy.d) - Laaolia alcohol ether 53 - 66

e) Arachidyl alcohol 6.0 polyoxyethylene (40 mol ethylene oxide) - lanolin alcohol ether
Diethoxy stearyl ether

f) Diethoxy-atearyl-ether Cety! alcohol

Mixtures of nonionic surfactants based on itethers or sorbitan fatty acid esters, with Ethylene oxide condensed saturated aliphatic

1QSS23 / 206S

71 .0 23 .0 54 at the 64 46 36

0., g-20 alcohols and ethanolin alcohols turned out to be just that if extremely effective surfactants, if good foam and clarity at low temperature in systems are desired which have lower alcohol contents. Examples of such systems are the following:

Wt .- ^

g) Mixture or Geraische of Pentaethoxy-Decaäthoxy-Getyl / Stearyl / Arachidyläthern 100.0

h) Diethoxy-stearyl-ether 25 - 48

Polyoxyethylene (40 mol ethylene oxide) lanolin alcohol ether 15 - 52

i) Tetraethoxy-stearyl-ether · 25

Polyoxyethylene (20 moles of ethylene oxide) sorbitan monolaurate 75

j) Tetraethoxy-cetyl / stearyl-ether 35 - 40

Decaethoxy-cetyl / stearyl-ether 65 - 60

G) The foaming agent

The solubility of the propellants in highly aqueous systems is a limitation of the latter variable,

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Monochloro-difluoro-J-ithan, difluoro-ethane, trichloro-monofluoro-methane unö dichloro-monofluoro-methane selected on the compatibility of the propellant with the concentrate to increase.

These more soluble propellants can often be mixed with other, less soluble gases such as dichloro-difluoro-methane and ietrafluor-Diehlor-ilthan can be used to to derive the best properties "of both types.

All other factors are the same, with the maximum concentration of propellant that the system can hold in a single liquid phase depending on the water content in the aerosol. Less water in the concentrate allows the dissolution γοη more blowing agent, but the foaming properties also depend on the water and poor foam development results if the water concentration is reduced to below 20 ° ß> if high G-Iy co Ige are not maintained (above 10 ·; ») are used to compensate for the low percentage of water.

The lowest pressures are found in such systems achieved with little water, which monochloro-bifluor-lthane

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or a combination of monochloro-difluoro-; ithan with Trichloro-monofluoromethane or with tetrafluoro-dichloroithane contain. Low pressures can also be achieved by mixtures of dichloro-dif luor-ethane with trichloro-ionofluoro-methane or Te met luor-dichloro-ethau, which "Ο ^ .. r./.-,> or contain less dichloro-dixluoro-iiethan, achieved will. The preferred prints were in -ueroicn. about 1 biü "!, Ο at," but under gev / iiJöea .Jodiayuu ^ n;: onaen the prints in the range of lü bi.i -1-0 pai lie ^ on.

The solvent solubility is also critical because The foam stability is a function of the solubility of the deodorant ireibmittelß in the aqueous alcoholic water.

Auxiliary ingredients (couplers, thinning agents, ij-ermiciae usv /.)

While the essential basic components of these improved foams consist of alcohol, water, blowing agents with a mixture of nonionic surfactants, other useful ingredients such as glycols, ethers and esters can be incorporated as additional couplers or emollients. Certain liquid surface-active agents, such as di- and 'Hriäthoxy-oläyläthe · ¹ and tetraethoxy lauryl ethers, although they are not structurally

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BATH 109823/206 5

turelle foaming agents are, in addition, "clarity bi, s down." to generate lower temperatures or allow them the use of higher propellant contents than otherwise achievable would be. Remedies, bacteriostatic agents and! other medications and emollients can also be used are incorporated for their usefulness, but do not form a critical part of the present invention. In each year, you can also use low-burning aids, such as those that can also be selected, and anti-irritants and anti-inflammatory agents such as polyvinyl pyrollidone or guaiac azulene can be incorporated.

The following specific examples illustrate The invention.

example 1

Wt .- ^ 95% ethanol 32.60 Surfactant mixture "g". 0.40 Glycerine '' 10.00 V / asaer 56.81 Cetyl iriethyl ammonium bromide 0.05 Perfume 0.14

When two grams of difluoro-iithane are poured into the bottle

109823/2065

are pressed, the concentrate clears and v / ird homogeneous. The finished one, provided with a _. Foam actuator Aerosol · produces a good, dense, fast-breaking one Foam which does not cause stinging even when repeatedly applied to the face. That finished aerosol is clear at temperatures as low as 6 ° 0.

Example 2

Weight -Yes

(95 ^ alcohol 51.0 (surfactant mixture "b" 2.7

0 (menthol. 0.1

(Perfume ° · ^ϋ

^ Hexachlorophene '0.1

^ Distilled water 34.9

^ Trichloro-monofluoro-methane 4.4

'Monochloro-Difluor-Athan, 6.1

The above concentrate ingredients (0) one after the Shaving foam is mixed together to form a uniform, gelled slurry and filled into clear aerosol bottles. Hach deal of rinsing to remove air, the bottles are marked with an a regular aerosol valve for gas bottles closed.

-H-

BATH

I09823 / 20S5

When the propellant mixture (P) is through, add the part the finished aerosol becomes a single one homogeneous liquid phase, which goes down to about 6 ° Ü It's clear. The pressure of the finished aerosol is 1.4 atm Hh ü, 14 atä at 21 ° 0. Generated when used after shaving the Lichaur *] ice an irritation and only sensation a tainiinal, moaentan burning.

■ jelspiel 3

Medical body freshening foam is prepared using the recipe given below, inserted into a Jclar aerosol bottle and flushed with a standardized u-LasflascheavxHriTET "" VerscbrtooB ^ enZTtachdeia mau first to>Jiiti'eriiuii ^ from Lui't. The heterogeneous concentrate is cleared by the addition of the propellant phase (P). The finished aerosol has a pressure of 1.7 J atü + ΰ, 14 atLi 'at 21 ° C and is clear down ^{to about 6 0 G.}

Hit a.3. ^ Enoi-'aten üchaumbetätiger provided, spreads A foam cloud emerges from the aerosol, which the desired foam properties and the desired (refuge has a usability of 30 to 60 seconds at Has ambient temperature.

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Applied to the skin, no irritation or burning is generated even after repeated application.,

95% ethanol

Surface active agent mixture "a"

Hexachlorophene

200

.70 1 .30 Q S. C. '■) ■ 45 * V

(Parf ätn.. _
CDistilled water
I '(i ^ onochlor-Dii'lu-or-Xtliati 3.3

Example 4-

The folienäe medical Iiotizentratproclukt l'är üie skin (0) is produced as in the previous examples and is at 21 ° ö a semi-solid, opaque ii The addition of the l'reibraittelgeraisches leads, via the above, to a clear, homogeneous aerosol with a pressure of only 1.27 atm + 0.14 atm at 21 ° C. The entire aerosol, packed in a clear, uncoated bottle, is clear at temperatures down to 6 ° 0 + 1 ° g. The "show cloud" is particularly fine-bubble and softened due to the presence of a slightly higher concentration of the surfactant.

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9i - _ui:?: Töö lthanol ... "· ^-;; 4-7.Ο.

Surface active agent. Mixture "el"_; /2..9 water _"," ■. ": -.. - ■"'■■ - - .-- "' -. 5Q.6

(PhyEidiniLimclaloricl 0.1

Paririm- '■■;....; - "■; .. ^'■: ^ Ö.9

AllantDiu - _ .0,1.-

('Triclxlor-Mouoflaor-Hethane ■ 4 · 4

i 6.Ί

To el oh YorteiLeii eier present iJrf iacluiii; numbers: iJan l'ehlea oinen burning of the skin "with wieäeriiOlteE application of the _tJ GticmraaerosolSj as moths of a! travel rope load frincti raned skin and" the avoidance of the. Formationa reddened nautatellen. ilia- an important advantage is found in the £ iar hcitdes Ae r os ο Is "at Ie mp era door β η de r ö-rij '<3 e no rd η ung • von.6 ° ti. ui-fj is achieved through Specially selected e olDürj.'lächonaktiver means, -by. Heralasetaen of:

haltfis, by denying the Ü-ehaltes Ba r; rittf.'i and ofirch selection üos. Irei Mittelgemlsches. -

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10 & 823/20 65 "

Claims (1)

Pat e η t a η s ρ r Lieh, e 1. Aerosol foam wet low pressures, consisting of .einem carrier, a mixture-surface-active agent and a propellant, characterized in that the carrier is a monohydric alcohol with 1 to 'J carbon atoms in the amount of about Ϊ5Ο to 55, Ό and water in there is sufficient amount in the concentrate to make 100 , J ; that the surface-active agent, which is present in an amount of about 0.4 to 5.0; j and is soluble in the mass at temperatures of about 6 ° O, was selected from the class of the ethereal alcohols having 12 to 22 carbon atoms and is combined with non-ionic, upper flüche active agents which ffettalkohola "the PoIyäthylenoxyd derivatives leave from the latter, the fatty acids, lanolin and Lanolinällcohole are selected;! and CTAB the in amounts of 2 to 1β '/ ά present propellant from eggs class' butane , Mono-chloro-difluoro-ii-thane, difluoro-iithane, trichloro-monofluoro-methane, dichloro-ionofluoro-i-ethane, dichloro ) Jlf. Luoro-methane and tetrafluoro-ilichloro-etiiane ;; e \ / ^r irt, v / oboi whose pressure is about 1 to 1, d at. 2 _f aerosol show races according to Anöpriicii "1, öaduroii; ■; ο Ic ο η η ζ eich η ο t, da ύ the oberfläolnui.-iktiye Mibtel ILther dar oorbitan fatty acid esters unci ta.it .ithylou- 109823/2065 oizyü includes condensed, saturated petal alcohols and lanolin alcohols. 3. Aerosol foam wet after. Claim 1, characterized g e ic e η η ζ e i c Ii η c t that the water-alcohol ratio so is that at ambient temperatures the G-emic the surface-active agent is completely soluble therein. 4. Aerosol foam compositions according to claim 1, characterized in that ρ; e'kennzeichne t that the amount of water is at least 20 -Jo . 5. AerOSOlschaummassen according to claim 1, characterized geke η η ζ eich η et that a substance from the class G-lycole, petroleum ether and fatty ester is anv / esend as a coupler. . 6. Aerosol clip compositions according to claim 1, characterized in that p; eke η n ζ eich η et, ■ that the aerosol foam breaks in about one minute. 7 | Aerosol foam xQassen according to claim 1, characterized S e k e η n z i c h η e t that the aerosol foam within of the range from about 6 ° to 50 ° 0 « 3. Aerosol clip compositions according to claim 1, characterized ■■■■ · ■ - '. _ 2 - · , BAD ORIGINAL 109823/2065, characterized in that the friction agent is a mixture of monochloro-difluoro-ethane with irichlor-monofluoro-methane is in approximately the same proportions, the alcohol concentration being low. 9. · Aerosol foam masses according to claim 1, characterized in that the ratios of Water / alcohol / propellant / surfactant like this are that the foam on the skin breaks down without the application of pressure from the temperature of the skin. .10, aerosol foam compositions according to claim 1, characterized in that they have the following approximate Have composition? Weight - ^G / o ■ Alcohol. 32.60 Pentaethoxy to Decaethoxy Getyl / Stearyl / arachidyl ether 0.40 Water 57.00 Glycerine 10.00 Difluor-Athan and 1I ₉ aerosol foam reactors according to claim 1, characterized in that they have the following approximate composition: Alcohol 51.0 • Cetyl / alcohol / MäthOxysteary lather /. · ■ · - Deoa ethoxystearyl ether. 2.7 Water 34- 9 and Irichlor-Monofluor-Methane with Monoohlor-Dif luor-iithaa, 12. Aerosol sciiaumtDassea according to claim 1, daäürch g e lc e η η ζ e i c h η e t that they are the following approximate Have composition; : - grew .- ^ " Alcohol, 5S.7Ö Cetylailcohol / Eentaäthöxy-Eeti ^ lkohol-ether 1.90 - · ■ - Mass? ν- / """'■ Ψ5 * 9 £> Böl ^ räthyleneglyool 20α Λ 9 Ί3 · AeropOlsohaumöKiesett according Aaspruch t ",. dadurcn ge e ic-ei .fi.α ζ η G et _fet: to satisfy the following approximate ZuBammensetzuttg _: 47 * 8 Polyethylene (25) & lygQl-iatiolInaIkoholather 2.9 . and Irichlor-Monofluor-Methane with Mpttoohlor- ^! Difluoroethane