EP0020644A1 - Compositions pour produire des emulsions et des dispersions stables - Google Patents

Compositions pour produire des emulsions et des dispersions stables

Info

Publication number
EP0020644A1
EP0020644A1 EP79901645A EP79901645A EP0020644A1 EP 0020644 A1 EP0020644 A1 EP 0020644A1 EP 79901645 A EP79901645 A EP 79901645A EP 79901645 A EP79901645 A EP 79901645A EP 0020644 A1 EP0020644 A1 EP 0020644A1
Authority
EP
European Patent Office
Prior art keywords
water
carrageenan
iota
weight
active agent
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.)
Withdrawn
Application number
EP79901645A
Other languages
German (de)
English (en)
Inventor
Dimitri James Stancioff
Martin Colton Womer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
FMC Corp
Original Assignee
FMC Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by FMC Corp filed Critical FMC Corp
Publication of EP0020644A1 publication Critical patent/EP0020644A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/042—Gels
    • 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
    • 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
    • A61K8/73—Polysaccharides
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/38—Alcohols, e.g. oxidation products of paraffins

Definitions

  • the invention relates to an adjuvant which in aqueous form can be mixed with materials which are water-insoluble liquids or par iculate solids to form aqueous emulsions having a unique combination of properties.
  • the stability, or resistance to separation of such emulsions may be enhanced by thickening the aqueous phase, also known as the continuous or external phase, with thickeners to inhibit the collision of the particles of the dispersed phase, also known as the discontinuous or internal phase. Inhibition of such collisions lessens the likelihood of merger or coalescence of the dispersed particles into larger particles, which coalescence leads to complete separation.
  • Thickening the aqueous external phase also has been known to inhibit the settling or creaming of the dispersed particles which is caused by differences between the specific gravities of the internal phase and the external phase of the emulsion.
  • the thickeners used to inhibit separation have included vegetable gums and clays, including gelatin, cellulose derivatives, gum tragacanth, gum acacia, sodium alginate, Irish Moss and its extractive gums, kappa-carrageenan and lambda-carrageenan. These thick- eners have usually been used in combination with surface active agents. However, the introduction of such thick ⁇ eners in an amount sufficient to provide a substantial increase in stability has necessarily greatly increased the viscosity of the emulsion so that it is no longer useful for many of the purposes of the emulsion before thickening.
  • an aqueous thixo- tropic gel useful as a vehicle for dispersed substances may be prepared with a composition consisting essen- tially of iota-carrageenan, a sequestrant for calcium, and a water-soluble compound of calcium which slowly dissolves in water and releases calcium ions as described in Stancioff et al. U.S. Patent No. 3,562,176 issued February 9, 1971.
  • dispersions made with such gels lack the stability properties of emulsions made in accordance with the present invention.
  • Emulsions in which water is the external phase are used in many commercial products and may be desired to have a wide range of physical properties. These properties may be related to aesthetic appeal, ease and safety of use, and efficiency.
  • aqueous emulsions are often used in many commercial products and may be desired to have a wide range of physical properties. These properties may be related to aesthetic appeal, ease and safety of use, and efficiency.
  • aqueous emulsions are often
  • Emulsions of such agricultural chemicals may also need to be stable, not exhibiting coalescence or separation of the dispersed phase for several months whether stored at moderate temperatures (20 * to 30 * C) or subjected to repeated freezing and thawing, as may occur in the field.
  • Such aqueous emulsions often need to have low viscosity, less than 2,000 mPa-s (milli Pascal seconds) at 20 ⁇ C. as determined with a Brookfield LVT viscometer at 6 rpm; for ease of handling, mixing with other chemicals, or spraying onto crops.
  • aqueous emulsions often need to be readily diluted with water of any temperature from 1 ⁇ C to 45 ⁇ C without coalescence of the dispersed phase. Additionally, the proportion of dispersed internal phase may need to be as low as 1.0% of the total, on the basis of volume, or as great as 45% of the total on the basis of volume.
  • the present invention provides an adjuvant capable of forming aqueous emulsions and dispersions having a wide range of dispersed phase content of at least 1% preferably from 1 to 45% by volume with improved properties of low viscosity (less than 2,000 -4-
  • aqueous emulsions and dispersions have proper ⁇ ties desired for specific fields of utility, such as agricultural chemicals, cosmetics, pharmaceuticals-, dyes, monomers for emulsion polymerization, industrial and other products.
  • the present invention also offers the advantage that it makes it possible to provide an adjuvant containing no calcium ion but instead ammonium, potassium, barium or magnesium ions; this is advan ⁇ tageous because of the incompatibility of many emulsions with calcium. Moreover, it provides a way safely and economically to pre-emulsify biologically active or hazardous oils at a central location having bulk handling and containment facilities. In this way, simple containers and agitators may be used in the field to dilute the emulsion concentrate to the degree necessary to apply the effective emulsified ingredient at a safe, as well as effective level of addition per unit area.
  • the adjuvant of the present invention consists essentially of an aqueous solution of iota-carrageenan; a water soluble gel-inducing cation selected from the group consisting of ammonium, potassium, calcium, barium, or magnesium or mixtures thereof an amount equivalent to at least 4.8% by weight of the iota- carrageenan; and a water-soluble surface active agent which does not interact with iota-carrageenan in aqueous solution to form a precipitate and which is capable, when shaken together with water and the insoluble material to be emulsified in the absence of carrageenan, of forming a unstable dispersion of discrete particles of the material which, although separating readily from the water, do not coalesce to a substantial extent, which dispersion has a viscosity no greater than 200 mPa*s at 20 ⁇ C; the surface active agent is anionic, non-ionic, or amphoteric and amounts to 1.25 to 60 times the weight of the
  • an aqueous solution of iota-carrageenan (a sulfated algil polysaccharide) is mixed with a soluble surface active agent or agents as defined above in the presence of the specified soluble gel-inducing cations to produce an aqueous solution which is useful as an.adjuvant for making aqueous emul ⁇ sions of water-immiscible liquids and dispersions of particulate solids.
  • iota-carrageenan as employed herein means polysaccharides (as well as their salts with cations such as ammonium, alkali metals, or alkaline earth metals) composed essentially of glycosidically linked hexose units in the form of D-galactose and
  • polysaccharides are further distinguished by exhibiting in the infrared spectrum a strong absorption peak at 805-810 reciprocal centimeters, as well as the absorption peak at 845-850 reciprocal centimeters exhibited by common varieties of carrageenan, such as that extracted from Chondrus crispus.
  • the preferred polysaccharides which exhibit properties suitable for the practice of this invention are polysaccharides wherein the ratio of the absorption peak at 805-810 reciprocal centimeters rela ⁇ tive to the absorption peak at 845-850 reciprocal centi ⁇ meters is from 0.50 to 0.90, although the value of this ratio may range from 0.4 to 1.0.
  • the average number of ester sulfate groups in iota-carrageenan as determined by conventional analytical procedures in relation to hexose sugar units is high, namely, about 60% to about 125% of the number of hexose sugar units.
  • the usual sources of the iota-carrageenan that is employed in the practice of this invention are the following seaweeds: Genus and species;
  • the hexose composition of iota-carrageenan varies somewhat, depending on the type of seaweed from which the polysaccharide is obtained and on the process ⁇ ing conditions employed in its recovery from the seaweed. Extraction with alkali generally enhances gelling pro ⁇ perties and is normally, therefore, preferred. However, alkali extraction is not essential. Thus extraction using plain water is adequate. Generally, the ratio of D-galactose residues to 3,6-anhydro-D-galactose residue as determined by conventional analytical pro ⁇ cedures is from about 2:1 to about 1:1. The molecular weight of the polysaccharide may vary from about 20,000 to 1,000,000.
  • the soluble gel-inducing cation or cations of the present invention may be provided as a part of any soluble salt such as a chloride, a nitrate, a sulfate (for example calcium sulfate dihydrate), or it may be a part of the iota-carrageenan as in the case of calcium iota-carrageenan, or it may be a part of the surface- active agent, as in the case of potassium oleate or potassium stearate.
  • the amount of cation must be chemically equivalent to at least 4.8% by weight of the iota-carrageenan. There is no upper limit on the amount of cations, although there is nothing to be gained by employing more than an amount fully equivalent to the iota-carrageenan.
  • any anionic, nonionic or amphoteric surface active agent meeting the requirements specified above can be used, it should be noted that certain ones, notably those containing carboxyl salt groups such as fatty acid soaps, have a sequestering effect on divalent cations, rendering them insoluble for the purposes of the present invention. Consequently, when a material such as calcium iota-carrageenan is employed in combina ⁇ tion with a fatty acid soap the calcium is ineffective as a gel-inducing cation and another non-sequestered cation such as ammonium or potassium must be used.
  • fatty acid soap used may be a potassium or ammonium soap.
  • the first requirement of the surface active agent, its non-reactive character when mixed with iota- carrageenan can be determined simply by visual observa ⁇ tion of a solution containing 1% by weight of iota- carrageenan or salt thereof in water when there is mixed with it the selected surface-active agent in an amount equal to ten times the iota-carrageenan by weight. If no precipitate forms, the surface-active agent is satisfactorily non-reactive.
  • / WIPO .v capability can be readily determined by preparing a water solution containing 10%. by weight of the surface- active agent; into the solution at room temperature there is stirred 1% by volume of the water immiscible liquid of particulate solid which is desired to be emulsified, observing whether or not a dispersion is formed (even though it settles within a few minutes) and measuring the viscosity of the dispersion by means of a Brookfield Syncro-lectric LVT Viscometer at 6 rpm while the. solution is at approximately room temperature (20 * C); if a dispersion is formed and the viscosity is less than 200 mPa»s, the surface-active agent is effec ⁇ tive.
  • a preferred surface-active agent is a potassium soap of a long chain (12-20 carbon atoms) fatty acid such as potassium oleate or stearate mixed with a long chain (12-20 carbon atoms) fatty alcohol such as oleyl alcohol or hexadecyl alcohol, the amount of alcohol being from 0.1 to 10% by weight of the mixture with the potassium soap.
  • the combination of potassium oleate with oleyl alcohol is particularly desirable because it decreases the energy input required to emulsify a water immiscible liquid in the aqueous adjuvant and producing smaller, more uniform droplets of the dispersed material.
  • nonionic surface-active agents are sorbitan monopalmi- tate, polyoxyeth lene sorbitan monopalmitate, polyoxy- ethylene alkyl phenols, for example octylphenoxy- polyethoxy ethanol;
  • useful amphoteric surface-active agents include the sodium salt on N-coco beta-amino propionate; of the anionic surface-active agents, fatty acid soaps are particularly useful, such as the sodium, ammonium, or potassium soaps of fatty acids having from
  • a dilute solution of iota-carrageenan is first prepared by dispersing a salt of iota-carrageenan into the vortex of rapidly stirring water. While the sodium salt is readily soluble in water at 25 * C, the potassium, ammonium, calcium, barium or magnesium salt require heating to about 70"C to dissolve, after which the solution is cooled.
  • a solution of calcium iota-carrageenan may be prepared by the methods described in U.S. Patent No. 3,562,176, issued February 9, 1971.
  • the calcium salt need not be used, nor does calcium need to be present at any step in the invention, provided another gel-inducing cation is present such as ammonium, potassium, barium, or magnesium.
  • another gel-inducing cation such as ammonium, potassium, barium, or magnesium.
  • the presence of other non-gel-inducing soluble cations such as sodium is not objectionable..
  • To the iota-carrageenan solution is added the surface active agent or agents, and soluble salts of gel-inducing cations if an insufficient amount is associated with the carrageenan or surface-active agents, and the solution is stirred until all components have dissolved.
  • the solution so formed may contain all of the water to be present in the final emulsion, or any lesser portion of that water in which case it is a concentrated adjuvant which may be diluted with the remainder of the water at or before the time the water immiscible material is mixed with it to form the desired aqueous emulsion.
  • the aqueous adjuvant concen ⁇ trate contains the iota-carrageenan, gel-inducing cation, and surface-active agent in relative proportions as defined above but in higher concentrations than the diluted adjuvant or the finished emulsion.
  • the concen ⁇ tration of the iota-carrageenan in the finished emulsion should be from 0.2-0.8% by weight of the water present, the amount of soluble gel-inducing cation should be at least chemically equivalent to 4.8% of the amount of iota-carrageenan, and the concentration of the surface- active agent should be from 1 to' 20% by weight of the water present.
  • the diluted adjuvant containing the concen- trations of ingredients set forth above has exceptional utility as an aqueous adjuvant into which a water- immiscible liquid or particulate solid may readily be emulsified by simple mechanical stirring.
  • Emulsions prepared from the aqueous adjuvant of this invention may range in proportion of internal phase from 1% of the total on the basis of volume, to 45% of the total on the basis of volume, or higher.
  • Such emulsions are stable for more than one month when stored at room tem ⁇ perature and are also stable after freezing and thawing; they are dilutable in water at any temperature from
  • the pH of the aqueous adjuvant can vary over a considerable range depending upon the precise surface- active agent employed and the pH of the concentrated aqueous emulsion prepared from the adjuvant can also vary over a considerable range depending upon the precise nature of the water-insoluble material in the dispersed or internal phase of the emulsion as well as upon the nature of the surface-active agent present.
  • the pH is approximately 10-11, whereas when octylphenoxy-polyethoxy ethanol (Triton X-100 TM) is used as the surface-active agent, the pH is about 7.
  • This invention is particularly useful in the preparation of emulsions of low melting waxy material, allowing them to be emulsified in the liquid state and remain in a stable wax emulsion (that is, as a dispersion or emulsion of particulate solids) after cooling.
  • Oils that are, as a dispersion or emulsion of particulate solids
  • Q-v.PI which maintain their liquid state throughout the prac ⁇ tical temperature range, including non-polar oils such as -light paraffin oil as well as polar oils, are likewise kept in stable emulsions by the adjuvant prepared by this invention. Emulsions prepared in this way often remain stable for periods greater than one year without coalescence.
  • a concentrated aqueous emulsion was prepared by stirring into 6 parts by weight of the adjuvant,
  • a miticidal polar oil hexadecyl cyclopropane carbox late containing free hexadecanol as an impurity, sold under the trade name Cycloprate TM using a high speed propeller-type stirrer.
  • the result- ing emulsion had a pH of 10.1 and contained approxi ⁇ mately 45% by volume of dispersed or internal phase polar oil in the form of droplets having an average diameter of 10 micrometers.
  • the concentrated emulsion had a viscosity less than 2,000 mPa-s and measured as described above and was readily diluted with water 1:100 to form a dilute emulsion sprayable in conventional spray eq ⁇ ipment for use as a miticide.
  • the concentrated emul ⁇ sion was stable, displaying no coalescence of oil droplets after storage for three months at room temperature.
  • the concentrated emulsion was subjected to three successive freeze-thaw cycles (from -5 # C. to 42"C.) without any change in particle size. Dilution of the concentrated emulsion with 100 times its weight of ice cold water with minimal agitation was accomplished without loss of stability, both before and after subjection of the con- centrated emulsion to the three freeze-thaw cycles described above.
  • O PI emulsions displayed extreme creaming of the internal phase from the external phase. Unstable emulsions were also obtained when gelatin or gum acacia or Irish Moss were substituted for the iota-carrageenan in an amount sufficient to give the emulsions a viscosity approxi ⁇ mately equal to the viscosity of the emulsion containing iota-carrageenan.

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • General Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Chemical & Material Sciences (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Dispersion Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Dermatology (AREA)
  • Colloid Chemistry (AREA)

Abstract

Un adjuvant contenant de la iota-carraghenine, un cation produisant un gel a savoir de l'ammonium, du potassium, du calcium, du baryum, ou du magnesium, et des agents tensioactifs selectionnes anioniques, non ioniques ou amphoteres lorsqu'ils sont melanges avec de l'eau ou avec des liquides insolubles dans l'eau ou des solides a bas point de fusion forme une emulsion concentree contenant 1%-45% ou plus en volume de phases dispersees et ayant une viscosite inferieure a 2000 mPa.s a temperature ambiante, qui est stable pendant son stockage a temperature ambiante, et qui peut etre dilue dans l'eau sans perte de stabilite, et stable a de multiples cycles de congelation-decongelation.
EP79901645A 1978-12-08 1980-06-17 Compositions pour produire des emulsions et des dispersions stables Withdrawn EP0020644A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US96759878A 1978-12-08 1978-12-08
US967598 1978-12-08

Publications (1)

Publication Number Publication Date
EP0020644A1 true EP0020644A1 (fr) 1981-01-07

Family

ID=25513028

Family Applications (1)

Application Number Title Priority Date Filing Date
EP79901645A Withdrawn EP0020644A1 (fr) 1978-12-08 1980-06-17 Compositions pour produire des emulsions et des dispersions stables

Country Status (2)

Country Link
EP (1) EP0020644A1 (fr)
WO (1) WO1980001142A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5998812A (ja) * 1982-07-08 1984-06-07 Toyo Seikan Kaisha Ltd プラスチツクキヤツプの製造方法
GB8628068D0 (en) * 1986-11-24 1986-12-31 Unilever Plc Aqueous gel comprising carrageenan
WO1991007972A1 (fr) * 1989-11-29 1991-06-13 S.C. Johnson & Son, Inc. Appat aqueux gelifie pour insectes

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2619467A (en) * 1952-11-25 Detergent mixtures containing
US2765255A (en) * 1948-10-25 1956-10-02 Shell Dev Insecticidal emulsion concentrates
US3562176A (en) * 1967-11-28 1971-02-09 Marine Colloids Inc Production of thixotropic gels and composition therefor

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8001142A1 *

Also Published As

Publication number Publication date
WO1980001142A1 (fr) 1980-06-12

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