DE2728357A1 - PROCESS FOR THE PRODUCTION OF A STABLE SUSPENSION OF FINE DISTRIBUTED SOLID PARTICLES IN THE OIL PHASE IN AN OIL-IN-WATER EMULSION, FOR EXAMPLE A PIGMENTED STAIN - Google Patents

Description

Wpl.-lng. Heinz Bardehle ^ - «n ^, .. Patenian World £ IL OOD 7

22. Hmrslt. 15. TiL 2 »2S5S

IQ, TWStHKM 4

Munich, June 23, 1977

My reference: P 2530

Applicant: Gorivaerk AS

Birkemosevej I
6000 Kolding
Denmark

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Process for the production of a stable suspension of finely divided solid particles in the oil phase in an oil-in-water emulsion, for example a pigmented stain

The present invention relates to a method for producing a stable suspension of finely divided solids Particles in an oil-in-water emulsion. With this method, a stable suspension can be made more solid Create particles in a light fluid. The invention is described below in terms of penetrating pigmented Stains for the protection of wood and wood products explained in more detail, which are not or only to an insignificant degree for Layers or precipitation of pigments or other suspended solid particles tend to, but can for example can also be used in the manufacture of pigmented paints, abrasives, polishing agents, cleaning agents, etc.

When applying stain to a porous surface, for example a wood surface, one of the conditions for achieving good penetration is relative low viscosity of the liquid in relation to the rate of evaporation. Since in practice a short - If drying time is desired, the absolute viscosity must therefore be low. If the stain is by means of pigment particles is wholly or partially colored, these will sediment upon lingering according to Stokes law, which in practice interesting area is considered to be approximate, i.e. that the sedimentation speed is a function of the particles

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size and viscosity. As a result, the The stain must be subjected to a vigorous stirring process before use, which is why such agents are usually put in buckets and the like. be sold with good stirring possibility. In case stirring is not done thoroughly enough, color errors occur with regard to the nuance and color fastness in the Use of the product.

It is known to combat this problem in several ways .

The simplest method is to measure the particle size reduce colloidal dimensions so that sedimentation is negligible even over long periods of time. This method can only be used for particularly expensive products because the production of such a pigment dispersion is very expensive.

Another very used method is to add so-called "anti-sedimentation additives" to the pigment, for example different polar compounds to flocculate. This does not prevent precipitation; the sediment will but of such a character that he is particularly easy to stir up again. In extreme cases the pigment becomes ^ so vigorously flocculated that the product can even be sold in canisters that only require a quick shake before use. However, this flocculation of the pigment gives the treated surface a color gritty, unpleasant appearance, and the penetration possibilities of the actual pigment become strong reduced.

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A third possibility that can also be used is that
Viscosity by adding what is known as Thixotropic,
To make theological properties producing agents such as polyamide derivatives, colloidal silica etc. for types of pickling due to organic solvents dependent on the displacement force and time. As a result, the viscosity can be kept high during the dwell time, during the actual application instant and in a very short period of time that follows
receives the low value favorable for penetration. However, this method is limited to those cases in which very high displacement forces arise during application, for example application of a brush, and, because the viscosity reduction is very short in practice, does not provide any possibility of achieving a sufficiently deep penetration.

The purpose of the present invention is to provide a method, which does not suffer from the aforementioned disadvantages, in which a product with a good penetration ability and good protective effect can be achieved with regard to pickling
does not tend to layer or deposit the pigment even if it is left for a long time. In a more general sense, it is the purpose of the invention, stable suspensions of finely divided solid particles in the oil phase of an oil-in-water emulsion without a tendency to. to create significant rainfall.

This is achieved by the method according to the invention, which is characterized in that the finely divided solid
Particles in an oil phase in the presence of one or more
Dispersing aids that can make the surface of the particles oleophilic, as well as one or more steriech and / or

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Electrostatically stabilizing dispersants are rubbed out to form a stabilized suspension, after which this in an aqueous medium in the presence of one or more emulsifiers is emulsified in such a way that it is affected by the dispersing agent or agents mentioned and dispersing auxiliaries do not affect the stability of the oil phase produced. The particles thus ground the inner phase of a stable oil-in-water emulsion incorporated and held in this by the outer continuous phase of the emulsion then from a slightly liquid Liquid.

Surprisingly, it has been shown that by thus partly adding suitable oleophilic surface properties to the particles taught, partly suitable steric and / or electrostatic forces between the particles and between the particles and the interface layer for the aqueous phase of the emulsion are brought about, stable suspensions without or only with a very low tendency for the particles to precipitate when they stay.

one

Procedure that when viewed directly / certain similarity with the mentioned method, but after a closer analysis they show decisive differences and especially not on products with the achievable by the method according to the invention Long-term stability are aimed at or lead to such, are described in several publications:

DT-OS 22 12 521 describes a process for the production of an electrophoresis bath in emulsion form, in which the bath is, inter alia, a pigment suspension in a water-dissolved completely neutral

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added lized carboxylic acid. Aim the indicated cash register but on the retention of the pigment in the water phase, and the process is not on the production of long-term stable products directed.

Swedish patent specification No. 139,292 relates to a process for the production of plastic emulsions which can be used, for example, as glue or for fixing pigments on textiles. In Example 5, copper phthalocyanine blue is distributed in a concentrated emulsifier solution to which emulsifier, water and an aminoplast emulsion are also added. This emulsion, which thus does not contain the pigment in the inner phase of the emulsion because the aminoplast emulsion is prepared and added separately, is additionally thickened with an o / w emulsion of gasoline in an emulsifier solution of the type mentioned above. Here, too, it is by no means to be expected that the pigment will bind to the internal emulsion phase. "The features characteristic of the invention are therefore not present here at all.

Swedish patent specification No. 135,667 describes a process for the preparation of an emulsion concentrate which has to be diluted immediately before use, which is why the long-term stability is insignificant. Closer determined is the purpose of to prepare emulsions in whose internal phase water-insoluble Schutzmittel_ are achieved by a method in which it is desired to eliminate the possible negative influence on the emulsion stability due to interaction with the outer phase by a tedious stepwise correction for these interactions .

The possibility for dispersed active ingredients has now been described in detail, and nothing is said about the conditions for it

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mentioned, possibly a substance dispersed in the inner phase to stabilize against failures. There is therefore no similarity with the features characteristic of the invention.

DT-OS ZZ 36 757 describes an emulsion that can be used in particular as a spray liquid, which can be of the water-in (3l as well as the oil-in-water type, and in which, in one phase, particles of a substance with antibacterial, insecticidal, herbicidal or plant growth-modifying action are dispersed.

These fluids are said to be more stable than known products of the same Kind; the stability is only for / + 8 hours has been proven, and it is particularly emphasized that the products, unlike the known products, are easily redispersible are.

Part of the peculiarity of spray liquids is that they are specific Weight ratio and the volume ratio between the Sets phases within more precisely defined limits, partly a suitable non-ionic or anionic surface-active substance selects the one that is hydrophobic or hydrophilic, depending on your wishes, whether the particles should be in the oil or water phase.

It cannot be ruled out that for particles of substances the mentioned type in this way a sufficient stability or at least redispersibility for the intended use can be created; However, the applicant's tests have shown that the measures mentioned are effective for long-term stabilization of pigmented oil-in-water emulsions are quite inadequate.

None of the above-mentioned writings thus mentions the

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straight processes peculiar combination of a dispersing aid, that can make the particle surface oleophilic, a dispersant that can stabilize the internal phase of the emulsion, and of a compatible Eraulgatorsystein, which is the actual emulsion can stabilize.

In an oil-in-water emulsion of the type mentioned here, one can hold the particles in the inner phase and thus the stability of the suspension are determined in more detail according to the invention in the following manner bring about:

In order to ensure that the particles, for example the pigment particles, Made oleophilic, i.e. wetted better by oil than by water, they are according to the invention more surface-active in the presence of suitable surface-active substances Means rubbed out so that they are brought into this state, which is a prerequisite for the actual incorporation into the oil phase. These agents are referred to here and below as dispersing aids and, with regard to pigments, can also be referred to as pigment wetting agents will.

According to the invention, this can be achieved by treatment with one or more Surfactants are chosen from among nonionics Agents such as alkyl polyathoxylates and alkylaryl polyglycol ethers; ampholytic agents such as electroneutral salts of cation active and anion active. Groups, for example salts of Fatty amines with fatty acids or polycarboxylic acids; anion-active agents for example fatty alcohol sulfates, sulfiraides, alkylarylsulfonates, in particular alkylbenzene and naphthalene sulfonates, phosphate esters, metal naphthenates and metal salts of fatty acids; and cation-active Agents, for example quaternary ammonium compounds, alkylimide

zolBalzen and lecithin. These funds can also apply to the individual

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Teach particles an electrical surface charge, which in the event that the original potential (zeta potential) the particle is not large enough to cause an ajiti flocculation effect as a result of electrostatic repulsion. Thus, for example, the pigment particles are from the manufacturing process or often surrounded by a membrane of water from the point of view of storage, the purpose of which is to achieve good dispersion when rubbing out is to be displaced in the presence of the surfactant (s). Except for this change in surface properties According to the invention, the suspension of the particles formed in the oil phase of the actual particles can thereby continue stabilized so that the oil phase is added to the oil phase during the rubbing-out with electrostatic forces between the particles. These can be among the same types as the above oleophilizing dispersing aids be chosen apart from the nonionics.

It has been found, however, that the best stability of the suspension is achieved in the event that oil-soluble agents are added to the oil phase during the rubbing-out, which agents can also exert steric stabilization. Such agents are, for example, surface-active soluble polymers with polar character, for example polymers of oxidized unsaturated fatty acids and their esters or ethers, partially polymerized esters of polycarboxylic acids, for example alkyds, and styrene-, isocyanate- and silicone-modified editions thereof, acrylic-modified and / or epoxidized oils and resins, aldehyde condensation with amines and / or phenols and polyether and poly ^r vinyl derivatives. It has been found to be effective

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-sir

Stabilization usually only in the case of polymers with a molecular weight of about 1500 is observed and increases with increasing molecular weight up to about lo, oooo, after which the effect may decrease.

It should be noted that several of the types of surfactants mentioned Means exert both an electrostatic and a steric stabilization, as well as the actual particle surface influence can, which is why one may use the same or several different surface-active agents can use the dispersing aid.

The specific choice of surface-active agents depends, among other things, on the
Type of particles and the desired end product and can be determined by experiments by the person skilled in the art. A preferred combination in the production of pigmented stains is a dispersing aid with a hydrophobic group of cation-active character,
such as an amine, optionally in the form of an amine salt, in particular with a hydrophobic anion (electron neutral salt), or
in the form of an area ester such as a lecithin in combination with a sterically stabilizing surface-active polymer
as mentioned above.

For the process to run smoothly, it is of decisive importance that the particles are incorporated into a stable emulsion. This stability is achieved by adding one or more
Emulsifiers created that are steric and / or electrostatic
Generate forces between the individual particles of the inner phase (oil phase) in the emulsion. In that respect it is
It is of crucial importance that this stabilization of the emulsion is not at the expense of the stability of the suspension in the interior

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phase takes place, which is why rolcho jT.n'.ulg ■■ to; s are to be selected that do not affect the oil phase generated by the dispersants and auxiliaries.

These emulsifiers ionic oclei ¹ may be nonioniseber way can be one or enforce the two phases in the emulsion. For ionogenic (cat or anionic) species, electrostatic repulsion between the inner-phase drops plays an important role in stabilization, while the effect of nonionic species is mainly based on steric repulsion and is largely pH-independent. The stability is also influenced by the distribution of the surface-active agent between the 2 phases, and a so-called HT / :? is often used, especially for nonionic species. · Value (hydrophilliphophilic balance) calculated for the selection of the most suitable emulsifier for a given type of oil.

To achieve electrostatically acting forces during stabilization one or more surface-active, add substances acting in the outer phase and in the boundary layer for the inner phase, which under ionic emulsifiers and Protective colloids, such as alkyl aryl and alkyl sulfonates ^, their amine and metal salts, such as calcium alkyl aryl sulfonates, Carboxylic acids and polycarboxylic acids and their salts (soaps), for example polyacrylic acid salts with ammonia, amines and alkali metals, Polyvinyl carboxylic acids and their partial esters and / or salts, cellulose derivatives and polycondensed inorganic ones Acids and their salts, for example sodium hexametbaphosphate and lithium polysilicate.

To achieve sterically acting forces in the stabilization animal Emulsion can be one or more ionic surface-active

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I-iittel άΰν type mixed with electrostatic stabilization above and / or nonionic agents, for example fatty acid and fatty alcohol glycol ethers, polyethoxylated alkylphenols, polycarboxylic acid esters and ethers, for example fatty alcohol succinates, sorbitol esters and ethers, sorbitol alcohols, polyethers and ethers, sorbitol ethers, polyvinyl alcohols, sorbitan ethers, polyvinyl alcohols, sorbitan ethers, polyvinyl alcohols and distilled ethers and add efjter and cellulose derivatives, for example hydroxyethyl cellulose.

It has been found that a combination of one of the inner phase added, nonionic emulsifier with the correct KLb-V / ert (for example of the type: Aikylphenolpolyäthylenoxidaddukt) and a lower, the amount of anionic surface-active agents added to the outer phase Substance of the protective colloid type, for example a polyacrylate or a polyvinyl maleate to stabilize the actual emulsion is particularly z'Ackmäßig, for example, when suspending of pigments in the inner phase of emulsions of vegetable oils and their synthetic analogs or their derivatives acts satisfactorily and the article stability in the internal phase is not inferior Direction influenced. The aforementioned anionic component can also be used to set a suitable viscosity and for complex binding of Heavy metal ions act, which can otherwise destroy the electrostatic stabilization as impurities; but these functions can can also be perceived by separate components of a cationic, anionic or nonionic type, e.g. sodium tripolyphosphate.

To improve stability, especially when the suspension is in very dilute state is used, whereby due to large differences in the specific weight there may be a danger for layers, according to the invention, the oil phase can be one or more specifically

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Fish weight non-balancing agents, including light liquids such as aliphatic and aromatic carbon hydrides and heavy liquids such as halogenated carbon hydrides, e.g. ethylene dichloride, Add tris ~ 2,3-dibromopropyl phosphate and chlorinated paraffins. You can also use solid materials, for example light materials such as V / achs and microscopic hollow glass spheres (microballoons), and heavy substances such as Add solid chlorinated paraffin and antimony trioxide. These can be done at the same time serve as flameproofing agents.

Examples of pigments that can be used are: oxides and sparingly soluble Salts of alkaline earth metals and metals in the transition series, for example iron oxides, chromium oxides, zinc oxide, barium sulfate, titanium dioxide, calcium carbonate, aluminum and magnesium silicate; other oxides and basic materials, for example silicon dioxide, carbon black, aluminum powder and zinc dust, as well as organic compounds, e.g. Heliogen green, Phthalocyanine Blue, Benzidine Yellow, and Perylene Red. However, the type of pigment is not critical to the invention.

Finally, other protective substances can be added to the oil or water phase Add species that may also be in the form of finely divided solid particles, for example biocides such as fungicides, for example tetrachloroisophthalonitrile, copper-8-hydroxy-quinoline, Tributyl tin oxide and derivatives thereof; Preservatives such as sodium pyridinethione-1 and 2,2-dibromoglutarodinitrile; Insecticides like e.g. Lindane or Endosulfan, IR reflecting agents and special UV-absorbing agents, like the oil phase, also oil-soluble pigment binders Ttel can be added, for example oxidatively drying, if necessary modified oils. However, it has surprisingly been found showed that the need for UY ~ absorbing agents in the pigmented stains mentioned is very low, in that they

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but good penetration and distribution of the pigment in flutes Result in wood surfaces.

The water phase can be water-soluble or water-dispersible Binders, for example polyacrylate dispersions, styrene-butadiene-polymer dispersions or polyvinyl acetate dispersions are added. If you want, you can still get one Oxidation catalyst (siccative), which is Koniplexgebunden in such a form that the equilibrium concentration of the free catalyst in the outer phase is so small that the stabilization system of the emulsion is not worth mentioning is influenced, and optionally add a stabilizer and / or an antioxidant to stabilize the siccative.

The stable pigment suspensions produced according to the invention have the further advantage that they are well suited for achieving reproducible color nuances. When rubbed in different colors Pigments in the oil phase were previously observed to have a co-flocculation that was precise and reproducible Makes coloring difficult. It has been found that both when mixing ready-made pigment suspensions of the type mentioned and also when the pigments are rubbed in the oil phase by the process according to the invention Avoids co-flocculation and thus a desired one in a simple manner Color nuance can achieve.

The mixing ratio between the ingredients used can be vary within wide limits depending on the desired end product and, last but not least, the type of feston particles.

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The oil-Jn-V / ater emulsion can thus i to V ⁷ O Gcv: .-% oil-en Dial tone, but will generally contain about bi.s do J5o Gc \ ".-%.

For the production of, for example, a pigcieuti orten stain In Hegel one becomes first of all a paste of the following Z-U £: a ;;; nierj ~ rub out settlement:

1 to 7!) Parts by weight of pigment

o, l to Io "dispersing aid (pigment wetting agent)

5 bis / f5 "dispersant (stabilizer)

ο to l \ 5 "ctas specific weight compensating

Middle,

where the sum of the components is 100 parts by weight.

Used for 50 parts of this paste on the intestines

ο up to 6 ^ 0 weight percent pigment binder

Io bic 5o "emulsifier (stabilizer for the

Emulsion)

ο up to 5 "siccative and stabilizer for it ο bis io "biocides and other auxiliary substances.

This oil phase is emulsified in a water phase that

0.1 to 5o weight parts stabilizer that also has other functions

can exercise (calculated as active ingredient)

ο to ifoo "pigment binder, but at most

Ge \ ') .-% of the water phase,

ο bis Io "biocides and other auxiliary substances

as well as de-mineralized water for looo gev / ichtsteiien contain can.

The invention is illustrated in more detail by the following examples. EXAMPLE 1

Manufacture of a pigmented stain.

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ORIGINAL INSPECTED

A orangerute paste by reaming l \ o Gev / maybe share transparent red iron oxide (e.g., "VIi 188"> d. S. A of Siegle & Co. marketed, orange red hydrophilic pigment) was prepared by dispersing in a bead mill tcilen GewichtB-5 Dispergierhilfsrnittcl, (Pigraentbonotzer) for example "Disperbyk", which eats an electron neutral salt sold by Byk-Mallinckrodt, produced by reacting an alkyl olawin salt with a polycarboxylic acid, and 55 parts by weight of So.ia oil alkyd with an oil length of 65% ( sterically stabilizing dispersant for the pigment). The dispersion took place at ambient temperature to a particle size of at most 20 μm.

50 g of this paste are mixed with 2oo g of 100% (solvent-free) linseed oil alkyd with an oil length of about 80%, which acts as a binder, 12 g of nonylphenol dodecaethoxylate (eterically stabilizing deinonionic emulsifier), 1,2 cobalt naphthenate, at ambient temperature for about 10 minutes (G% co-siccative), 0.8 g of a 38% o-phenanthroline solution in butyl glycol "Activ 8" - sold by Vanderbilt Corp. (Stabilizer for siccative against hydrolysis) and 2 g of methyl ethyl ketoxime (volatile antioxidant that acts as an anti-skin agent) mixed.

The 266 g mixture thus obtained, which can be regarded as a thin oil paint, becomes approximately at ambient temperature For 10 minutes in a mixture of 21o g demineralized Water and 30 g of 15% strength polyvinyl maleic acid alkyl glycol ester ammonium salt (Thickner LIi ") dispersed, the anionic stabilizer int and continues to act as a complexing agent and thickener, soft initially for about 5 minutes with another 60 g

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ORIGINAL INSPECTED _ ^

demineralized has been mixed in water. This achieves a 566 g pigment dispersion, which has the character of an emulsion color, and to which, while stirring, 34 g of demineralized IVacrsor, to which biocides and other protective agents can be added. _t

The stain thus obtained (100 g) has a viscosity at 20 ° C of 12 cP, pH 7.8, specific gravity I, o83. It is inexpensive and easy to manufacture, has excellent penetration ability when applied to wooden surfaces and does not cause air pollution during use. It is stable while staying and shows no tendency to precipitate the pigment even after a storage period of 1 / f months. The stain has furthermore an excellent freeze-thaw stability. Thus become no changes in the product were observed after a standard sample, the 3 freezing processes to -18 ° C with intervening Includes thawing operations.

In the same way one has staining using pigments of other colors, for example "VN 088", (yellow iron oxide pigment) and "VN 288" (red iron oxide pigment), carbon black and phthalocyanine blue, and other dispersing aids, for example "Texaphor 963" »(electroneutral pigment wetting agent) and soy lecithin, and other dispersants, for example tall oil alkyds. There are excellent pickles from the same Quality achieved.

For comparison, identical stains have been produced, but using the dispersing aid peculiar to the invention omitted. In all cases, the pigments deposited after a short period of time.

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Kan also has the protective effect of several as mentioned above stains produced by treating wooden surfaces. Under accelerated test conditions with consideration of the weather the products mentioned have a surprisingly high degree of weather resistance and it has been found, inter alia, to employ common types of stains based on both alkyd solvents and based on acrylic dispersion under otherwise identical conditions Degree of pigmentation, binder concentration, etc /. surpass.

EXAMPLE 2

Manufacture of pigmented stain.

A black / hot paste of 15 parts by weight of carbon black ("Printex 300"), k parts by weight of bentonite (thickener, lo% in mineral turpentine), 1 part by weight of dispersing aid ("Disperbyk"), 35 parts by weight was obtained by dispersing in a bead mill linseed oil (dispersant) and l \ 5 parts by weight of mineral turpentine produced (the specific weight balancing agents).

50 g of this paste are produced in accordance with that in Example 1 Treated paste, and a stable stain with a specific weight of 1.03, pH 7> 8 and viscosity 12 cP was achieved. These Stain also has excellent penetration properties and is stable even when very diluted.

EXAMPLE 3

A polishing agent was made by rubbing in 1 part by weight of kieselguhr, 8 parts by weight of flavored turpentine, 1 part by weight of alkyd, o, l weight: steep linoleyltriaethylene diainine dioloate (dispersing aid), 0.5 parts by weight polyethylene glycol dioleate (PEG 400-

Dioleate) produced, which is then in 89.1+ weight parts V / ater with o, oo25 parts by weight polyacrylic acid ammonium salt "Acrysol ASE95" (anionic stabilizer) is emulsified. The obtained odorless

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ORIGINAL INSPECTED

Means v; ar when staying for a long time without a tendency to Precipitation stable.

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Claims (12)

P Λ ΐ ϋ N T A K £> P R U CHE 1. Process for the preparation of a stable suspension finely advantageous solid particles in the oil phase of an oil-in-water emulsion, for example a pigmented stain, a pigmented paint, an abrasive or a polishing agent, characterized in that the finely divided solid particles in an oil phase in the presence of one or more Dispersing agent that oleophi the surface of the particles ". know machon, as well as one or more sterically and / or electrostatically stabilizing dispersants are rubbed out to form a stabilized suspension, after which this in an aqueous medium in opposition to one or more emulsifiers of such a kind that it is determined by the mentioned dispersants and dispersing auxiliaries produced Do not affect the stability of the oil phase. 2. The method according to claim 1, characterized in » that as oleophilizing dispersant one or more surface-active agents selected from non-chemical agents, for example alkyl polyethoxylates, can be used and alkylaryl polyglycol ethers, ampholytic gowns such as e.g. Electronical salts of cation-active and anion-active Groups, for example salts of fatty amino acids with fatty acids or polycarboxylic acids; anion-active agents, e.g. Fet C alcohol sulfates, »Sulphimides, alkylarylsulphonates, in particular Alkylbenzene and naphthalenesulfoates, phosphate esters. Metal naphtha and metal salts of fatty acids; and cation-active 709852/1174 ORIGINAL INSPECTED Agents, for example, quaternuring ammonium compounds, Alkyliraid & zols & lzen and lecithin, and ; \ lr- stabilizing ;? Dispersing agent one; or more of the obc.nei'vähnLcn surface-active with one or more surface-active, soluble polymers of polar character are used, for example polymers of oxidized unsaturated fatty acids and their esters or xthor, partly polyincr.ated esters of polycarboxylic acids such as alkyds and styrene. Isocyanate and ciliconcino-iU.- fixed editions thereof, acrylwod.i.fixed and / or epoxidicrtc oils and resins, aldehyde condensation products with amines and / or phenols, as well as polyethers and polyvinyl derivatives. 3. The method according to claim 1 or R, characterized in that the oleophili.jiorcndeE dispersing aid is a compound with a hydrophobic group of catalytically active character, for example an amine; fall ^ i: o Form of an amine salt, especially with a hydrophobic anica. (Electron neutral salt) or an amine ester, for example Li; -a: .i thirj, and a sterically stabilizing surface-active polymer with a molecular weight of about 150 to 10000 is used as the dispersant. 4. The method according to claim 1, 2 or 3, characterized in that g e k e η η-records, that to stabilize the emulsion of the oil base a nonionic emulsifier and the water phase a smaller amount of an anionic surface active agent the protective colloid type adds. 5. Method according to claim 1 to h, characterized in that geke η η- notes that the oil phase continues to have an agent added which is the specific weight difference between the balances the inner and outer phase. 709852/1174 ORIGINAL INSPECTED 6. The method according to claim 1 to 5, characterized in that g e k e η η, that uses one or more pigments as finely divided particles will. 7. Ancestors according to claim 6, characterized in marked c Ji η e t, that an oil-soluble Pigrcent binder continues to be added to the oil phase will. 8. The method according to claim 7> characterized t, that all pigment binders are oxidatively drying, if necessary modified oil is used. 9. The method according to claim 6, characterized in that that in addition to the emulsion a water-soluble or water-dispersible one Pigment binder is added. 10. The method according to claim 9, characterized in that that an acrylic-based pigment binder is used. 11. The method according to any one of the preceding claims, characterized in that an oxidation catalyst (siccative ) is added which is complex-bound in such a form that the equilibrium concentration of the free catalyst in the outer phase is so low that the stabilization system of the emulsion is not significantly influenced by this. 12. Pigmented paint, characterized in that it is produced according to the method according to claims 1 to 11. IJ). Pigmented paint, characterized in that it is produced according to the process according to Claims 1 to 11. lif. Polishing or grinding media, characterized in that that they are produced by the process according to claims 1 to 5. 709852/1174 ORIGINAL INSPECTED