DE1955556A1 - Suspending fluids - Google Patents

Description

The invention relates to suspending liquids, that is liquids which have the ability to transform into stable! Wise finely divided substances, for example solid finely divided material such as particles of silica, quartz, feldspar, kaolin, carborundum, encapsulated substances, insoluble? suspending active detergents, solid germicides and solid additives to prevent redeposition of dirt, globular material such as immiscible liquids, and gaseous material _} such as bubbles of immiscible gas for a reasonable time at temperatures in the range of -5 to 30 ° C. .

It is known that the suspending power of a liquid Mixture, which comprises a nonionic, surface-active agent and water, from the micellar action in depends on the aqueous solutions. If the concentration of the nonionic is low, a simple micella form, vrelche, predominates consists of a spherical aggregate of molecules of the active nonionics, with the water-soluble head groups are on its surface and the hydrocarbon chains form a liquid core, at higher concentrations the! spherical shape is replaced by a more stretched Hxcella-

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shape, these are cylindrical types (see J.Francois et al. J, Colloid Int.Sci · '2M, p. 293 (1966)). Simple mixtures from an active nonionic and water have no suspending power - the degree of interaction between the nonionic micelles is insufficient.

According to the invention, the suspending liquid comprises V / ater, a nonionic surfactant, as here defined, $ 0.01-0.2 of a soap and up to $ 2 of an additive, as will be defined here, the percentages being based on the liquid being by weight.

Presumably the active l'ionic and the soap form a mixed micelle which a. possess extremely active surfaces due to the smallness of the water-soluble group of the particular lionionics, and therefore a low degree of hydration of the micella surface. In practice, the small size of this water-soluble group makes the active ionionic too insoluble to be micelles to form, and the surprisingly small amount of soap acts as a cartoonizing agent, which is necessary to create a nicellar To produce solution of the ionic in the water.

The addition should "I adsorb on the micellar surface,

such an increase in micellar interaction within

to
of this mixed micellar solution, an increase which gives the liquids according to the invention their suspending power »

Suitable surface-active ITonionics are defined as those which have an HLB value of 10-12, in the hydrophobic part of the molecule have a total carbon number of 12-16 and are close to it, micelles in water at around 25 ⁰ G, or at temperatures which are suggested for storage and use, to form up to about 4O ⁰ O. The HLB value is the hydrophil-lypophil balance (see WCGriffin, J. Soc, Cosmetic Chemists, _1, (1949) page 311 The HLB value calculated for a surfactant is inaccurate and in practice ifonionics surface active agents whose HLB values are determined or calculated within the range of 10-12 are suitable

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for use in the preparation of the suspending liquids according to the invention as a function of. her Micellar capacity. The micelle-forming capacity is estimated in the usual way, that is by testing the solubility in distilled water at about 25 C (if this is the required temperature is) of 5% aqueous solutions the agents in any given rank or class of chemical structure. The active Konionic, which first showing a sharp decrease in haze relative to the chemically adjacent agents is noted. this marks the critical point in the series or class at which Kicella formation begins. The agent that is near is to form hicelles, is the one in the same rank or class whose HLB value is as half a unit below the so noted agent is calculated or determined.

For example, if the class of active honionics to be used is an ethylene oxide condensate, the HLB value is approximately equal to the percentage weight of ethylene oxide divided by 5 »Ss it is found that the condensate which shows the sharp drop in turbidity, which is what just forms a micellar solution, an additional ilthylei Oxydeinheit contains over the condensate, which is suitable for the production of the liquid according to the invention. One Ethylene oxide unit corresponds approximately to 1/2 an HLB unit,

Is intended to have up to a maximum temperature of about 4-0 ⁰ C Yienn the suspending liquid Suspendierverniögen at a higher temperature than about 30 G, is AEAs active Konionic having an HLB value of 10-12. un-j. selected by testing its solubility in distilled water at the required temperature. Of course, cooling these SxxEEjiäXEK suspending liquids can lead to a decrease in their susceptibility, and conversely, heating can adversely affect the suspending ability of liquids which contain Uonionies due to their

Solubility at 25 C were chosen. «The loss of suspension capacity is probably due to the destruction of the cylindrical kicelle and the formation of ku s.e Iiger

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Micelles, which act on the additive, but liquids with suspending ability does not result.

Suitable nonionic surface-active agents can be found in found in the following classes: fatty acid alkylolamides and alkylene oxide condensates of alkylphenols, aliphatic Alcohols, alkylamines, fatty acid alkylolamides and alkyl mercaptans, Ethylene oxide condensates are preferred »

Suitable active formulations for liquids for storage and use up to 30 ° C. Their calculated HLB values are listed in brackets, are: Monylphenol-7-ethylene oxide (11.6) pentadecanol-6-ethylene oxide (iO.8), alkyl (C _{12 -1} .) Amine-3-ethylene oxide (11.5), octylphenol-6-ethylene oxide (11.6), coconut oil monoethanolamide-2-ethylene oxide (10), alkyl (C _12-1 ,) alcohol-6-ethylene oxide (11 , 4) and lauric diethanolamide (10.0)

It should be noted that the 'specified in this list HLB values are those of the pure compounds. Commercial products often contain impurities and grime from the raw material and the extraction processes used. These can in a noticeable manner the HLB-Yfert change compared to that of the pure connection.

The active lionionic will generally be present in an amount of 5-15% by weight of the agent. The concentration is within these limits for different active Uonionics EchwarJcen because the micella shape varies with both the concentration and with the chemical nature of the Nonionics, which means that the optimal concentration for one agent may be 6tfo , but for another 6 $ insufficient and $ 10 will be the concentration required.

The soap ingredient can be obtained from the reaction of a base such as 1.) a hydroxide or carbonate of an alkali metal, e.g. Sodium, potassium or ammonium, and a fatty acid with one Alkyl radical of 11 to 18 carbon atoms, or 2.) an organic base such as diethanolamine with a fatty acid an alkyl radical of 11-18 carbon atoms. Natural sources of fatty acids, e.g. peanut oil and coconut oil can be used. The organic soap from diet hanoi -

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BATH ORIGINAL

amine laurate is preferred "which is obtained by neutralizing Lauric acid can be obtained with diethanolamine .. Others suitable soaps are sodium laurate, sodium stearate, diethanolamine oleate and potassium peanut oil soap,

The concentration of soap is between $ 0.01 and $ 0.2, preferably between $ 0.02 and $ 0.08 by weight of the composition.

The puncture of the additive has already been briefly discussed. It has been found that a molecule which has a high affinity for hydrocarbons and some affinity for water can bring about the enlargement in the micellar interaction which is necessary for the production of the suspending liquid according to the invention is effective Accordingly, the addition defined as a compound which is soluble in dodecane at least 10 percent, at 25 $ ⁰ C and in distilled water at 25 0 to an extent which is in the range of 0.01 to 2 weight . $ and does not disturb the ion balance »

Suitable additives are benzene, substituted benzenes, Uaphthalene, long-chain alcohols in which the chain length is from 8 to 14 carbon atoms, short-chain aliphatic paraffins in which the chain length is 6 to 8 carbon atoms is, unsaturated compounds with 6-14 carbon atoms, for example terpenes such as dipentene and terpinolene, and aliphatic amines with chain lengths of at least 8 carbon atoms »

Currently preferred additives, which are all soluble in dodecane to at least 10 $ and also in water in the amount given in brackets; Benzene (0.18), toluene (0.06), xylene (0.02), mitrobenzene (0.25), chlorobenzene (0.03), dibutyl phthalate (0.01), 3,5-dimethoxy-4- chlorobenzene (0.02) safrole (0.02), n-octyl alcohol (0.06), 2-ethylhexanol (0.02), lauryl alcohol (0.01), n-hexane (0.015), n-heptane (0 .01), cyclohexene (0.02), dipentene (0.04), terpinolene (0.04)? Decylamine (0.04). The solubility values given above relate to essentially pure compounds ' ;

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The ones to be used in the liquids according to the invention Amounts of additive are in the range of 0.03-2, preferably 0.5-1 wt. ^.

.Some organic acids, "for example lauric acid, are unsuitable as they have been found to upset the ionic balance of the cartoonizing agents. Organic Bases with a content of less than 8 carbon atoms are also unsuitable, for example n-hexylamine, Aniline and Cyclohexylamines Synthetic anionic detergents also disrupt the ionic balance and should be excluded.

It should be noted that some commercially available grades of active HOnionics meeting the preceding definition, which may contain one or the other essential component, Z ₀ as the S _{e e} j_f or the additive may be present already in the active Uonionic. For example, if lauric diethanolamide is chosen as the uonionic, many commercial types of this product inevitably include diethano-

amine laurate, that is a soap within the definition of a soap suitable for the suspending liquids according to the invention, which is probably also unavoidably present in the specified range. Likewise, if the active honionic is a commercially available ethylene oxide condensate of an alcohol, it may very well contain some unreacted alcohol. If this alcohol meets the criteria given above for the selection of the additive and is present in the prescribed quantities, then a suspending liquid can be created by simply adding this commercially available active ionionics and a soap to water. If the alcohol does not pass the test for the If the additive is selected according to the invention, then it should be removed before suspending liquids can be prepared from the commercially available ethylene oxide condensate of alcohol.

To produce the suspending liquids according to the invention, the active nonionic is dissolved in water, do you support τ · oh HinmifüimTit? rf pt> ff ο -i fo never comicellating

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Agent The additive is then added

The suspending liquids according to the invention can be used to permanently suspend finely divided I-Imaterial. The invention also relates to that resulting therefrom suspended funds.

The solid particles which can be consistently suspended vary in particle size over a wider range from 10 mm to about 5.0 mm in diameter. The upper limit depends on the density of the particles, in such a way that the more dense the particles are, the smaller the particle size required for a successful stable suspension. A particle size of 100 microns in diameter and a density of 2.5 g / cc, for example silica powder, can be easily and consistently suspended in the suspending liquids according to the invention. To determine if any given particulate material can be consistently suspended, the following equation can be used. This equation relates to densities to maximum particle size for suspensions. If d "is the density in g / cc of the particles to be suspended and d is the density of the suspending medium, then D is the diameter in microns of the largest particles to be suspended from the equation D (d _s - _Q ) = 150. Although particles of a larger diameter than that of the _obi:; sgemässen erfindun-en equation calculated size in the liquids can be suspended, the Juspensionszeit will be relatively shorter than that for -eilchen under this size '·

The suspending liquids according to the invention result Suspensions which are stable for at least 6 I ^ onaxes.

If pourable suspensions are desired, they can Liquids in! -! Throws of not more than 30 threads be present throughout the mixture. If pastes are required, then more than 70% by weight of the total mixture can be used finely divided solids in the suspension according to the invention Liquids are permanently suspended · The Srfin—

or ττΗ

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will give consistent pourable suspensions containing 5-5-5% by weight of the total mixture of particulate solids, although if desired less than 5% and down. to about 0.1 pounds, can be suspended. The suspending liquids for pourable suspensions are generally those with an apparent viscosity of 20 centipoises up to 3 poises, measured in the shear zone 5-1000 sec. ".

The suspending liquids according to the invention can Suspend liquid material immiscible in droplet form. The droplets can sigkeit through the suspending plus dispersed, their size by the viscosity the droplet liquid is determined. This provides a visual effect which can be used to indicate benefits to the consumer or just a pleasing one To represent appearance. The droplet size can zv / isch 10 "and 2 mm in diameter, preferably between 0.05 and 2 mm of ravages fluctuate, and the concentration increases from 0.1 to 20% by weight of the total liquid. Higher concentrations can reduce the distribution of the active ITonionics, the soap and the additive to the detriment of the _ Impair the ability to suspend. The migration of the soap to the interfaces is believed to be the reason for the V / irkun ^ -. The size of the droplets depends on the relative Viscosities and the energy introduced into the liquid during manufacture, i.e. from shaking or stirring, off.

The suspending liquids can consistently disperse gas bubbles, with suitable dimensions for such Bubbles that are less than about 150 microns in diameter. the Concentration can be from 0.002-0.1% by weight of the coat.

The invention will now be illustrated by examples of inventive suspending liquids described, wherein Water in all cases makes up the balance and the percentages of the total liquid are equal to those of the law The abbreviation EO means xethylene oxide.

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Examples Active honionic soap amine laurate 1955556 alcohol council as a contaminant e the —Q— 1fr. 10 $ Fonylphenol-7 EO Diethanol $ 0.02 Diethanol $ 0.08 $ 0.5 benzene supply 1 amine laurate amine laurate Additive 2 10 $ Pentadecanol-6 EO 0.03 $ Diethanol- Diethanol $ 0.03 $ 0.9 benzene $ 0.9 benzene The suspending capacity of the suspending agents according to the invention 2 amine laurate Liquids is stocked by the following 8 $ alkyl (O ₄ η _{H /)} ) amine Diethanol $ 0.05 $ 0.5 benzene $ 0.5 benzene specified suspensions. 3 3 EO ¹ ^ " ¹⁴ amine laurate 10 $ Octylphenol-6 EO $ 0.9 benzene 4- 1 $ benzene 10 $ alkyl (O _12-14 ) alcohol
get-6 EO $ 0.9 dipentene 5 $ 10 Pentadecanol-6 EO $ 0.9 Iiitro- 6th 10 $ ionylphenol-7 EO benzene $ 0.03 diethanolamine- $ 1 lauryl- 1 $ n-hexane 7th 10 $ Monylphenol-7 EO laurat $ 0.025 latrium- 8th 10 $ Fonylphenol-7 EO stearate $ 0.06 Hairium- 9 laurat $ 8 off-the-shelf $ 0.1 potassium laurine diethanolamide peanut oil soap 10 (commercially available) automatic application sness of $ 8 off-the-shelf Diethanolamine Lauric diethanolamide advice as a contaminant 11th inclination automatic on essence of Diethanolamine

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I No. composition Particle micron density g / cc Stability lei room temperature Suspending liquid / fine size (about 25 ⁰ O) part material > = 12th 8.5 $ l \ fonylphenol-7 EO § Just a small amount of clearer $ 0.017 Diethanolamine Laurate 20-50 2.6 Liquid on, the surface j 0.765ij benzene g / cc of the system after 6 months. That $ 15 kaolin suspended material was well ver UU pX
50-100 µ divides in bulk of the solution. 13th 9.0 $ Pentadecanol-6 EO 2 $ 1
$ 48:
$ 50 50 / u g / cc O $ 0.027 Diethanolamine Laurate
$ 0.45 benzene 2.4 Resistant after 6 months co
co $ 10 silica 50 u -80/1 14th 8 $ Nonylphenol-7 EO ^ ' & pt & $ 0.048 Sodium Laurate 2.7 g / cc Resistant after 6 months " N) $ 0.72 benzene $ 2
$ 48:
$ 50 100 ίι O
cn $ 20 oalcite I \ J \ J ΛΑ.
50-100 µ
50 ^ i O 15th 5.6 $ alkyl C, _{0 y1} amine-3 EO 50 µ Resistant after 6 months. One $ 0.056 Diethanolamine Laurate
$ 0.63 benzene
$ 30 silica 2 $ 1 - 80 ^ u 2.4 small amount of clear liquid
speed on the. Surface after
9 months. 16 6 $ Nonylphenol-7 EO 00 µ Resistant after 8 months, $ 0.06 K. Peanut Oil Soap
$ 0.3 benzene
$ 40 oalcite $ 48: 2.7 no visible sign of
Deposition. »
CC 17th $ 4.8 commercial laurine $ 50 50-100 JU 2.4 Resistant after 8 months, no cn diethanolamide * 50 µ * - 9 r Sign of deposition cn $ 0.6 benzene cn $ 40 silica cn
CD

Mr . Composition, particle size density Stability at room temperature • • Persistent after 6 months. cc Suspending liquid / fine- ^ u = · micron (about 25 ⁰ C) cn some material cn 18th 7.2 $ commercially available diethanol cn amid * 100-200 2.4 Resistant after 6 months, none cn 0.9 $ n-hexane, m / u Signs of deposition CD 10 $ Nfeosyl (fine silica) 19th $ 6.4 Commercially available B diethanol Although the maximum particle amid * 150-25Q µ 3.2 size for an optimal suspen $ 0.8 benzene sion with this density is 65 / U,
remained 'after 3 months $ 20 carborundum Particle still suspended Ö in the liquid and had it 'X; only $ 5 clear liquid ep ¹ . deposited on the surface. KJ ΓΌ $ 8 off-the-shelfB Dii ^; , tm..r: oi- O arnid * O $ 0.8 benzene O 1.0 $ silicone oil with a via sity of 1000, centipoise 0.5 mm 1.7 g / cc 0.02 $ oil soluble dye (in the SüikorrJl) Diethanolamine laurate, present as an impurity.

Claims (7)

-12-Pa t. denial of claims. 1. Suspending liquid containing water, a nonionic surface active agent and a Soap, characterized in that the nonionic surface-active agent has a KLB value of 10-12, has a total "number" of carbon atoms in its hydrophobic part of the molecule of 12-16 and is close to the formation of micelles at the temperature at which suspending power is required that the soap present in an amount of 0.01-0.2 wt. 56 of the liquid is and that in addition up to 25ε of an additive is added which is soluble in dodecane to at least 10 wt. # and in distilled water to an extent of 0.01-2 wt. and does not disturb the ionic equilibrium » 2. Liquid according to claim 1, characterized in that the nonionic surface-active Agent present in an amount of 5 * 15% by weight of the liquid is· 3 · Liquid according to claim 1 or 2, characterized in that the nonionic surface-active Agent is a fatty acid alkylolamide, preferably lauric diethanolamide « 4. Liquid according to claim 1 or 2, characterized in that the nonionic surface-active agent is an alkylene oxide condensate of an alkylphenol, an aliphatic alcohol, an alkylamine, a fatty acid alkylamus or an alkyl mercaptan, preferably a condensate of nonylphenol and 7 moles of ethylene oxide 'per mole of phenol, of the octylphenol and 6 moles of ethylene oxide per mole of phenol, the Pentadecanols and 6 moles of ethylene oxide per mole of alcohol, or an alkyl (C ₁₂ _-i4) amine with 3 mol of ethylene oxide per mol of amine, 5 · Liquid according to one of the preceding claims, thereby g e k e η η indicates that the soap is diethano] 009824/2000 BATH ORIGINAL -13- 1355556 6 »Liquid according to one of the preceding claims, characterized in that the soap is present in an amount of 0.02-0.08 percent by weight of the liquid. 7. Liquid naoh one of the preceding claims, characterized in that the additive a benzene, naphthalene, a long chain alcohol aliphatic alcohol with a carbon chain length of 8-14 carbon atoms or an aliphatic paraffin with a carbon chain length of 6-8 carbon atoms, 8 «Liquid naoh one of the preceding claims, characterized in that the additive is present in an amount of $ 0.5-1 of the liquid. 9 · A suspended compilation, consisting essentially of from a liquid according to the preceding Claims wherein finely divided material or liquid globules "are constantly suspended in the liquid. 00982472000