GB2078243A - Multicolour Coating Composition - Google Patents

Abstract

The composition is of the type in which a number of discrete colored globules of a size visible to the naked eye are dispered in an aqueous medium of a color different from that of the globules. The globules comprise a mixed organic complex reaction product resulting from both ionic and non-colloid reactions of two polyelectrolytes of opposite charges and a reactant which forms a complex with one of the polyelectrolytes and are of sufficient strength and fluidity as to not subdivide substantially when brushed or rolled on a desired substrate. The aqueous medium by the use of thickness or rheology modifiers, preferably of the associative type, is adjusted to have a viscosity profile that approaches Newtonian, with good resistance to brushing at high shear rates, and the composition leveling after application is complete. The polyelectrolytes may be ionic derivatives of synthetic resins or polysaccharides, and the complexing reactant may be a soluble boron compound or an organotitanium compound.

Description

SPECIFICATION Multicolor Coating Composition Background of the Invention Field of the Invention The present invention is an aqueous multicolor composition in which a number of discrete colored globules of a size visible to the naked eye are dispersed in an aqueous medium, with the globules and aqueous medium having such physical characteristics that the composition may be brushed or rolled onto a desired surface without substantial subdivision of the globules.

Description of the Prior Art Numerous multicolor coating compositions have been devised and used in the past that were satisfactory for spray application, but are not satisfactory for application by brush or roller. Inadequacy in this respect has generally been due to one or more of the following: (a) inadequate resistance of globules to breakdown on shear; (b) hard, gelatinous, or brittle consistencies of globules which give low surface drag and tendency to skid on smooth surfaces, (c) inadequate separation of globules which aggravates skidding tendencies. This often results from interchange between dispersed and continuous phases, making it difficult to retain required viscosity and flow characteristics in the continuous phase.

When aqueous dispersed globules are formed by the ionic interaction of first and second polyelectrolytes of substantial functionality and opposite charges, their physical characteristics are difficult to control. If the globules are sufficiently soft to have good surface drag, they tend to be unstable when applied by brush or roller. If they are hardened to a brittle consistency they have low surface drag, and tend to skid on a smooth substrate when the aqueous medium in which they are dispersed is applied thereto by a brush or roller.

Globules formed from the insolubilization of a polyelectrolyte by a non-colloidal reaction are unsatisfactory for application by brush or roller in that they have limited fluidity and tend to maintain their gel-like consistency in which they protrude outwardly from a layer of the composition of which they form a part, rather than blending into the layer to form a layer of substantially uniform thickness.

By "noncolloidal" reactions I mean those in which at least one of the reactants is noncolloidal in nature. For example, the reaction between galactomannoglycans such as guar gum or locust bean gum and water soluble boron and titanium compounds is noncolloidal because water soluble salts are not colloidal.

The term "ionic reaction" as used herein refers to one in which both reactants are ionic and opposite in charge. For example, reactions between cationic and anionic colloids are ionic.

It has been found surprisingly that if globules are formed that contain both ionic and non-colloidal reaction products that the globules have sufficient fluidity and strength as to be applied to a desired substrate by brush or roller without substantial sub-dividing even though ionic and non-colloidal reaction complexes are not alone satisfactory for this purpose.

The present invention is a multicolor coating composition in which the dispersed globules are a mixture of reaction products having interengaging lattice structures resulting from the concurrent interaction of first and second polyelectrolytes of opposite charges, and the non-colloidal reaction of one of the polyelectrolytes with a reactant such as a soluble boron compound, organic titanium compound or the like to which it is sensitive. The globules resulting from the concurrent ionic and noncolloidal reactions are fluid to semi-fluid in consistency, have such a high affinity for the liquid medium in which they are dispersed that they tend at all times to be enveloped therein, and are of such strength and deformability that they do not substantially subdivide when the composition is applied to a desired substrate by a brush or roller.

Although the globules of the present invention are defined by ionic reaction products and noncolloidal reaction products that individually are incapable of providing globules having physical characteristics that permit them to be applied satisfactorily to a desired substrate, the reaction products in combination cooperate synergistically to provide globules of fluid to semi-fluid consistency that have sufficient strength when dispersed in an aqueous medium of suitable viscosity to be brushed or rolled onto a desired substrate without substantially subdividing.

It is a major object of the present invention to overcome limitations of the prior art by utilizing a new and distinct concept in producing aqueous dispersions of macroscopic globules.

It is another object of the invention to produce aqueous dispersions of greater stability and globule strength than those provided by the prior art.

It is still another object of the invention to produce dispersions comprising a wider variety of film formers than those which are feasible for use by means of the prior art.

It is yet another object of the invention to produce dispersions useful as multicolor or texture coating compositions which are suitable for application by brush or roller as well as spray gun.

It is still another object to produce dispersions useful in applying coatings which have a more rapid drying rate and less water sensitivity than those provided by the prior art.

The shortcomings of prior art can be described more specifically according to the means of phase separation used.

U.S. Patents Nos. 3,458,328 and 3,725,089 disclose means of phase separation by "insolubilization" of hydrophilic colloids, the objective being to form "viscous, gelatinous globules rather than rigid gels or precipitates". It was recognized that the degree of gelatin should be minimized as far as possible, as by controlling the concentration of insolubilizing agent. With this insolubilizing system, however, there were distinct limitations on how much gel softening could be done without rendering the dispersion unstable. The best stable get structures did not approach the semi-fluid consistency which is attainable with the present dispersed particles.

With the exception of certain unique compositions employing immiscible fluid solutions of coating materials, dispersions containing particles of sufficient size to be readily visible were applied by spraying. The compositions of U.S. Patent No. 3,725,089 could also be applied by brushing because the particles were very small (below 25 microns). Without the addition of larger particles, however, they could not provide the color contrast which is the objective of the present invention.

If particles are of sufficient size to be readily visible and produce a desirable color contrast, dispersions of gel particles produced by "insolubilization" are not suitable for application by brush or roller coat. To be stable to brushing shear, they must have a pronounced gelatinous character. On application such gels tend to protrude from the surface, and to cover the substrate in a practical manner, require unusually thick and uneconomical films.

U.S. Patent No. 3,852,076 discloses means of "encapsulating" dispersed particles by use of a specific synthetic colloidal clay with a variety of hydrophilic colloids. This means of phase separation can produce particles of fair consistency and shear stability. As explained hereinafter, however, the dispersions are not capable of application by brush or roller, because of the adverse rheology induced ty the specified colloidal clay.

The deficiencies in the prior art methods of making dispersible globules of a size visible to the naked eye have been overcome by forming the material defining the same by concurrently occurring ionic and non-colloid reactions. The globules so formed have a desired shape and consistency, and the globules are compatible with rheological agents which provide satisfactory application properties.

Summary of the Invention The multicolor decorative coating composition of the present invention is defined by a number of discrete hydrated colored globules of sufficient size as to be visible to the naked eye that are dispersed in an aqueous medium of a color different from that of the globules. The globules are of sufficient strength and fluidity that they do not substantially subdivide by the shear force imposed thereon when they are brushed or rolled on to a desired substrate.

Each of the globules is defined by a mixture of reaction complexes that jointly cooperate to impart the desired strength and fluidity thereto. The first of the reaction complexes is that resulting from the ionic interaction of first and second polyelectrolytes of opposite overall charge. The second of the reaction complexes results from the non-colloid concurrent interaction of the first polyelectrolyte with a reactant such as a soluble boron or titanium compound to which it is sensitive. Although the ionic and non-colloid reactions may take place in the presence of colloidal clay, silica or a mixture thereof, the clay or silica is present only in an amount sufficient to maintain the formed globules in a hydrated condition, and not in an amount sufficient to substantially insolubilize either the first or second polyelectrolytes.

The polyelectrolytes used in forming globules as above described are those of very high molecular weight which produce viscous solutions at concentrations of less than 10%, and often at concentrations of 1-2%. These are well known in paint technology as well as many other fields, and are often used as thickeners, for aqueous compositions.

Other macromolecular polyelectrolytes which are useful as reactants are those which are high in molecular weight, but provide solutions of moderate viscosity at concentrations of about 1060%.

Some of these, for example, are the water thinnable oil modified polyester coatings. Others are polymeric surfactants, such as the naphthalene sulfonic acid condensates. Polyelectrolytes of this kind are often strongly reactive. Generally, however, it is preferable to use them in conjunction with high viscosity macromolecular colloids which help to maintain good hydration of the reaction product.

Anionic macromolecular polyelectrolytes include, without limitation thereto, sulfonated, sulfated, or carboxylated polymers such as sulfonated polystyrene, sulfonated polyvinyl toluene, sulfonated benzene or naphthalene formaldehyde condensates, sulfated cellulose, carboxylated cellulose, carboxylated vinyl polymers, carboxylated acrylic polymers, water soluble polyesters, maleinized oils, maleinized esters of styrene-allyl alcohol copolymers, etc. Carboxylated cellulosics which can be used include carboxyalkyl cellulosics such as carboxymethyl cellulose, and carboxyalkyl hydroxyalkyl cellulosics such as carboxymethyl hydroxypropyl cellulose.

Either linear or cross-linked polymers can be used. In many instances superior results are obtained by using more than one kind of anionic reactants, such as a combination of sulfonated and carboxylated polymers, or high viscosity and low viscosity polymers, or linear and cross-linked polymers.

Anionic colloids containing sulfonic or sulfate groups are typically more reactive than those containing carboxyl groups. When maximum globule strength is required, it is preferable that the anionic reactants should include a sulfonated colloid such as sulfonated polystyrene, exemplified by the Versatl polymers of National Starch. Among carboxyl containing polymers, the preferred types include carboxymethyl cellulose and carboxyl containing acrylic polymers such as the Acrysol (Registered Trade Mark) polymers of Rohm Er Haas.

Cationic macromolecular poiSyelectrolytes are preferably strong base polymers, as exemplified by quaternary ammonium compounds, rather than weak base polymers such as those comprising primary, secondary, or tertiary amine groups. In general the preferred cationic polymers comprise onium compounds. These are defined in Hackh's Chemical Dictionary (4th edition) as being of the type "RXHv.

An organic isolog of ammonium containing the element X in its highest positive valency . . .". They include, for example, quaternary ammonium, phosphonium, arsonium, and stibonium compounds, where X is pentavalent; ternary sulfonium, oxonium, and stannonium compounds, where X is tetravalent; and iodonium compounds, where X is trivalent. Quaternary ammonium compounds include those derived from heterocyclic based, such as pyridinium, quinolinium, piperidinium, and morpholinium compounds, as well as aliphatic types.

More specifically, the preferred cationic reactants are oxonium derivatives, such as quaternary ammonium derivatives of macromolecular colloid, including the derivatives of polysaccharides such as cellulose, starch, carrageenan, agar, and natural gums, and derivatives of synthetic polymers such as polyvinyl pyrrolidone, polyvinyl alcohol, epoxy and acrylic polymers. The cationic derivatives of cellulose are particularly advantageous, such as the Polymer JR resins of Union Carbide Corporation.

The activity of a polyelectrolyte with a strongly reactive non-colloidal reactant can be sufficiently great that the insoluble reaction complex formed and that defines the globules has such a tight knit intermolecular lattice structure that molecules of water are squeezed therefrom, and the reaction complex dehydrates extensively which is evidenced by the globules shriveling, collapsing or transforming to shreds. Such dehydration can be minimized by forming the globules of a mixture of reaction complexes, the first of the reaction complexes being that resulting from the interaction of oppositely charged ionic polyelectrolytes, and the second reaction complex being the result of a noncolloidal reaction between a polyelectrolyte and a reactant to which it is sensitive such as a soluble boron or tetanium compound.The first and second reaction complexes cooperate to provide a globule defining material that is strong and fluid to semi-fluid in consistency.

The ionic reaction complex and the non-colloidal reaction complex that define the globules of the present invention counteract their individual undesirable globule defining characteristics, and in combination cooperate to provide globules of such fluidity and strength that then brushed or rolled onto a substrate with the aqueous medium in which they are dispersed they do not tend to subdivide substantially nor project above the surface of the applied layer.

In the majority of instances the present invention will contain an aqueous component in addition to the ionic and non-colloidal reaction complexes that define the globules. This component can be characterized as the payload which defines the use of the composition. It is often advantageous to use in the continuous phase a substantially transparent coating material. On application this phase deposits a gloss or semi-gloss film which can partially or completely overlay an opaque film which is simultanebusly deposited by the discrete globules. Either or both phases may contain metallic particles, such as metallic powders, flakes or fibers, and various other particled material. Each phase can comprise various filler or extender components as well as pigments, defoamers, coalescing agents and the like, such as commonly used in coating applications.

In the majority of instances the present aqueous dispersions will contain an aqueous component in addition to the ionic and non-colloidal reactants necessary to produce the required phase separation.

This component can be characterized as a "payload" which defines the use of the composition.

A major application is in the production of multicolored or textured coatings, wherein the payload is. an aqueous film forming composition. For example, some of the globules may be colored differently from others and on application to a surface form a pointillistic design. Alternatively the globules may be colored differently from an aqueous film forming polymer contained in the continuous medium, and on application the composition may produce a mottled or striped appearance, depending on the method of application by brush, roller, or other type of tool. When varicolored coatings are not desired, unique textured coatings of a single color can be applied in a one-coat operation, where production of similar effects would normally require several coating operations.

It is often advantageous to use in the continuous phase a substantially transparent coating material. On application this phase can thus deposit a gloss or semi-gloss film which can partially or completely overlay an opaque film which is simultaneously deposited by the discrete globules. Unique color effects are obtained if the overlying film contains a transparent colorant. A special variation involves use of the continuous phase of light reflective elements such as glass beads or irregularly shaped particles which can be bound in place by the clear film forming material. Such compositions are useful as reflective paints in applications requiring high visibility.

Thickeners For application by brush or roller, the rheological characteristics of the dispersions are more critical than for application by such methods as spray or knife coating. Rheology of the dispersions is determined in part by the rheology of the continuous phase, and in part by other factors such as particle shape and consistency, and ratio of particle volume to volume of continuous phase.

Rheology of the-continuous phase is particularly important. If the continuous phase is too fluid, it provides inadequate resistance to brush or roller, and the color particles are dragged about by the applicator tool in irregular manner, independent of the continuous phase. If the continuous phase is too viscous, the color particles are more readily broken down by shear, and leveling of the film is also impaired.

The rheology required for the continuous phase is dependent in part on the shape and consistency of the particles. Relatively soft, flakelike particles can grip a surface more readily than harder, more three-dimensional particles. Insofar as relatively fluid type particles can be tolerated by the application system, it is not necessary to develop a high viscosity continuous phase in order to apply the coatings successfully.

For optimum commercialization and use by unskilled operators, it is desirable to produce dispersions which perform as far as possible in a manner similar to conventional latex paints. It is also preferable for the dispersions to be usable with a substantial range of particle shapes and consistencies rather than dependent on a specific type.

In formulation of conventional latex paints, it is customary to add a thickening or flow control agent which improves its rheological characteristics, enabling the paint to be applied more evenly to a surface, and after application to have sufficient flow properties to level and hide the substrate at an economical film thickness. Some degree of thixotropy is often favored in order to prevent sagging of the wet paint film.

Materials used for this purpose are water soluble hydrophilic colloids, often called protective colloids, thickeners, viscosity or flow control agents, which are effective when added to latex paints in small proportions, such as a few tenths of a percent, or up to 1 or 2 percent. Some of the materials commonly used as thickeners are hydroxyethyl cellulose, methyl cellulose, polyvinyl alcohol, starch, casein, sodium carboxymethyl cellulose, sodium and ammonium polyacrylate, sodium alginate.

Thickening agents of this kind are generally satisfactory in conventional latex paints, and it is surprising that they produce only marginal results in multicolor paints. In order to achieve satisfactory brush or roller resistance in the latter, it is necessary to develop relatively high viscosities at which iittle or no leveling can occur.

This surprising difference in behavior may result primarily from the macroscopic nature of multicolor dispersions. While conventional latex paints are also dispersions, the dispersed latex and pigment particles they contain are mostly on the order of 0.1-25 microns, which can develop high surface interactions. Rheologically these are found to perform more like one-phase systems than multicolor dispersions, in which the dispersed color entities are about 1 mm, or 1000 times as large.

It has now been found that a special type of rheology modifier is desirable to produce satisfactory application properties in multicolor coatings. These are commonly called associative thickeners, and are characterized by the fact that they tend to increase viscosity at high rates of shear (such as 5000- 35,000 reciprocal seconds) more than at low rates of shear. For example, they are capable of producing viscosities of 0.5-5 poises at shear rates of 10,000 reciprocal seconds, while permitting sufficient flow for leveling at very low rates of shear. This is done by incorporating the rheology modifier at concentrations of a few tenths of a percent to about 2%.

Thickeners or rheology modifiers of the associative type are water soluble polymers of low to moderately high molecular weight (up to several hundred thousand). The polymer molecule is characterized by having a relatively hydrophilic portion which keeps the polymer in solution, and two or more relatively hydrophobic portions which are capable of associating with polymer or pigment particles, or other polymer molecules.

With the associative type of thickener, viscosity increases are thought to arise from the formation of extensive networks of such associations, in which the polymer molecules are intimately associated with the whole volume of the composition. With conventional or non-associative thickeners the polymer molecules are thought to thicken primarily by association with water, and microscopically are often incompatible with other elements of the composition.

Associative rheology modifiers which are not thickeners are those which depress viscosity at low rates of shear, and in combination with conventional or associative thickeners serve to produce a more Newtonian viscosity profile. The preferred rheology modifiers for the present compositions are those which are also thickeners.

Associative rheology modifiers may be either ionic or nonionic. The art of making such materials is relatively new, and most of those currently available are anionic. A product which is preferred for its efficiency in muiticolor coatings is Rohm Er Haas Experimental Thickener QR-708, which is described as nonionic.

It is often desirable to use more than one thickener, one or both of which may have associative properties. In order to minimize the total amount of polyelectrolyte, it is helpful to use an anionic polyelectrolyte for particle formation which provides at least some of the associative characteristics needed for good application properties. An anionic associative thickener, Rohm 8 Haas Experimental Rheology Modifier E-1 684, is a preferred material for this purpose.

The amount of thickener required in a given composition is that necessary to produce a desirable high-shear viscosity, such as at 10,000 reciprocal seconds, while maintaining adequate leveling at very low rates of shear. It will be understood by those skilled in the art that the amount of thickener required is dependent in part on other elements in the composition, such as latex, pigments, surfactants, and coalescing agents. One of the desirable characteristics of associative thickeners is their ability to respond to surfactants which lower the low-shear viscosity, but have relatively little effect on high-shear viscosity, thus producing a more Newtonian viscosity profile.

It is generally desirable to add at least some of the associative thickener after formation of the color particles, since the total amount required may produce too high a viscosity for good particle formation if added before the dispersion process.

It has been found unexpectedly that application properties are improved if an addition of other paint components, particularly latex and pigments, is also made after dispersion of color particles is completed. Although not generally recognized heretofore, it is believed that substantial amounts of paint components in the continuous phase are entrapped during the process of particle formation. To provide the best response to associative thickeners, it is desirable for these to be at least partially replaced after equilibrium has been reached between particles and continuous phase.

To simplify the manufacturing process, one may simply add an additional amount of the initial continuous phase. If some hiding pigment, such as titanium dioxide, is to be used in the continuous phase, a portion of the particle base paint (before cationic colloid addition) may also be added at this point Relationship Between Thickeners and Dispersion Systems When thickeners are used to build high-shear viscosity in the continuous phase, it is important for the dispersed color particles to be able to withstand the increased shear forces. Materials which are useful in enhancing shear resistance are those which promote interior as well as surface reaction of the particles with the continuous phase.

In general these comprise the insolubilizing systems disclosed in U.S. Patents 3,458,328 and 3,725,089. By using the present ionic systems in combination with these, it is possible to balance interior vs. surface reactions, and thus overcome the disadvantages inherent in insolubilizing reactions alone.

For this purpose it is necessary to use a macromolecular polyelectrolyte which is capable of reacting ionically with a macromolecular polyelectrolyte of opposite charge, and also of complexing with a micromolecular reactant which further strengthens the reaction complex. The ionic reaction produce of polyelectrolytes is typically more fluid, but has less strength and shear resistance than the micromolecular reaction product. If used alone, the latter complex is typically too gelatinous or brittle to provide desired particle consistency. Those skilled in the art can easily determine the desired balance of components to produce the required particle consistency.

The preferred macromolecular polyelectrolytes are polysaccharides and their derivatives, particularly those derived from starch and cellulose, and the hemicelluloses obtained from the seeds and fruits of various plants. The hemicelluloses comprise locust bean gum, locust kernel gum, guar gum, flaxseed gum, psyllium seed gum, quince seed gum, and Iceland moss. Particularly valuable from a commercial standpoint are the galactomannan gums, guar and locust bean gums.

The hemicelluloses are advantageous for their ability to complex with boron compounds, and particularly water soluble borates, such as borax. The hemicelluloses also form complexes with a variety of other complexing agents including basic lead acetate, bases of other metal compounds such as those of the alkaline earth metals, salts providing polyvalent cations such as Al or Cu, tannins or tannic acid. Gelling agents such as these can be used in place of boron compounds, but generally require more care in use to obtain gels of desired consistency.

Organic titanates, such as triethanolamine titanate and the ammonium salt of titanium lactate, are capable of complexing to some degree with numerous polysaccharides or their derivatives. They are particularly active as reactants with the quaternary ammonium derivatives of polysaccharides, which are especially useful in the present invention.

For example, triethanolamine titanate forms strong complexes with: Polymer JR cationic cellulose derivative Jaguar C-1 3 cationic guar derivative Gendriv RW cationic guar derivative Celanese CMHPG carboxymethyl hydroxypropyl guar Jaguar A-40-F underivatized guar gum It is generally preferable to incorporate either one or both of the macromolecular and micromolecular reactants in the continuous phase. It is also possible to incorporate one or both of these in the same phase as the first polyelectrolyte with which they interact, but only to the extent that they enhance the strength of the resulting ionic complex in its reaction with the continuous phase. A macromolecular reactant which is present in the continuous phase should be substantially insensitive to the micromolecular reactant.

It is important in many instances to control particle consistency by use of two polyelectrolytes in the particle phase, both of which are capable of forming ionic reaction complexes, but only one of which is sensitive to the micromolecular reactant. It is then convenient to control particle consistency by varying the relative amounts of sensitive and non-sensitive polyelectrolytes. The two polyelectrolytes in the particle phase may carry the same charge. Alternatively they may carry an opposite charge, and cooperate to form a portion of the total reaction complex.

For example, if a water soluble borate is used to react with a borate-sensitive gum, it is preferable for part of the macromolecular polyelectrolyte to be non-borate sensitive. The relative proportion of polyelectrolytes which are borate-sensitive and non-borate sensitive can thus be used to effect the desired proportion of interior vs. surface reactivity. If the particle phase carries a net cationic charge, both borate-sensitive and non-borate sensitive gums may be cationic, or one of them may be anionic and used to the extent that it enhances the strength of the final ionic complex.

Stirring at 1000 RPM gave a disperson of white color particles of suitable size for multicolor coatings. Composition B could not be applied by brush or roller because of severe skidding tendencies.

Solutions of various thickeners (used successfully in Example I were added at concentrations appropriate for providing a suitable range of application viscosities. None of these were effective, however, in making the compositions applicable by brush or roller. Results are summarized in the following Table.

Table Concentration on Continuous Thickener Phase Result ThickenerXD7845.01 0.25% Very poor brush or roll.

(Dow Chem. Co.) Ditto 0.5% Particles string out and merge with light stirring Thickener XD7846.01 0.25% Particles soften. Very (Dow Chem. Co.) poor brush or roll Ditto 0.5% Particles string out and merge on stirring Rheolate 1 (NL Ind.) 1.0% Very poor brush or roll Ditto 1.4% Ditto Acrysol ASE-1 08 1.0% Ditto (Rohm Er Haas Co.) Ditto 1.4% Ditto Thickener LN (GAF Co.) 0.6% Ditto Ditto 1.0% Ditto Reten 425 (Hercules Inc.) 0.1% Ditto Ditto 1.14% Ditto The type of pre-reactant used in the dispersion base will determine in part the type of ionic colloids which are preferred in the continuous phase.For example, if a macromolecular polyelectrolyte is used as a reactant in a dispersion base, it may be desirable to use less or even no polyelectrolytes in 3 continuous phase which contains inorganic ionic colloids.

Preparation of Dispersions The dispersions are prepared by merely adding to one another the desired proportions of each phase, and stirring with moderate mechanical agitation to produce the desired globule size. Ordinary paddle type agitators are satisfactory, with stirring rates of about 100 to several hundred revolutions per minute, depending on the desired globule size. More rapid stirring reduces the average globule size.

The base which forms the globules can be added in several increments or all at once.

In preparing compositions designed to produce multicolor effects, such as multicolor coatings or glazes, it is generally convenient to prepare dispersions of each color separately, and mix these dispersions in desired proportions. It is also satisfactory to make multicolor dispersions directly by adding bases of different color successively to the dispersing medium, stirring after each addition to produce the desired discrete globules.

A slightly different procedure can be used if the final continuous medium is to be quite viscous, as in the production of dispersions for brush or roller application. Then it is often advantageous to form an initial dispersion in which the continuous medium is relatively low in viscosity, and contains a relatively high proportion of reactive ionic colloid. A second more viscous medium can then be added which may contain a lower proportion of reactive colloid, or even none at all. This minimizes the amount of stirring required in the presence of a viscous medium. In event a colored pigment or extender pigment is to be used in the continuous medium, it is convenient to add them in this second increment, minimizing the possible absorption of pigments by the discontinuous phase.

The phase relationships of the dispersions, may be either cation-in-anion, or anion-in-cation.

Cation-in-anion dispersions have the current advantage of a greater availability of a variety of anionic polymers which can be used as reactants and thickeners in the continuous medium. This permits more effective variation of the size and consistency of the dispersed globules. Generally this type of dispersion has also been found to permit a higher dispersion ratio of globules to continuous phase than anion-in-cation dispersions. By suitable choice of reactants, the ratio of dispersed to continuous phase can be as high as 4:1 or greater. Anion-in-cation dispersions are more suitable where dispersion ratios of 1:1 or lower are satisfactory, or where particularly fluid dispersed globules are desirable.

Pre-reaction of Dispersion Base When maximum globule size and strength are to be obtained, it is often desirable to increase the viscosity of the dispersion base (such as paint base) before dispersion, by adding to it a minor portion of reactive ionic colloid which is opposite in charge to that of the macromolecular polyelectrolyte it comprises. For example, if a point base is to contain a cationic macromolecular colloid, an appropriate agent for thickening it will be an anionic reactant, and preferably an anionic polyelectrolyte. The preferred reactants include polyelectrolytes designed to function as surfactants as well as the very high viscosity macromolecular colloids.In many instances a blend of different kinds of anionic reactants is more effective than a single reactant; for example, the anionic reactants may include one containing sulfonic groups, and others containing less reactive anions.

In preparing dispersions of paint bases, anionic polymeric surfactants are also advantageous in that they facilitate pigment dispersion and help to stabilize the latex against flocculation. They are preferably added during initial pigment dispersion, before addition of the cationic macromolecular colloid.

The desired quantity of reactive agent is that which thickens the dispersion base, but is sufficient to react with only part of the macromolecular polyelectrolyte of opposite charge. The appropriate amount is easily determined by experiment, as the use of too much reactant produces a dispersion of lower viscosity, rather than a uniform composition of higher viscosity than the starting material.

Compatibility of a reactive macromolecular agent with the dispersion base is enhanced if it contains a minor amount of nonionic groups, as well as the ionic groups which interact with the macromolecular polyelectrolyte of opposite charge. By pre-reacting with a reactive ionic agent in the dispersion base, as described herein, it is also convenient to introduce a second type of reactivity which can supplement or modify the ionic reactivity.

These factors are illustrated in Example I wherein a minor amount of carboxymethyl hydroxypropyl guar is added to the dispersion base. Compatibility of this reactive agent with the cationic cellulose is improved by the presence of hydroxypropyl groups. Carboxymethyl groups of the reactive agent cause it to complex with the cationic cellulose. The resulting cationic complex is then capable of further complexing with borate ions in the continuous phase to supplement and modify its reactivity with anionic polyelectrolytes.

Description of the Preferred Embodiments Examples of the multicolor coating composition of the present invention are as follows: Example I Blue-white coating compositions Payload-acrylic copolymer emulsion.

Composition A-Anionic dispersing medium Parts by Weight Water 11.64 Tetrasodium pyrophosphate, anhydrous 0.16 Synthetic hectorite clay, 8% colloidal dispersion in water (Laponite S, Laporte Industries, Ltd.) 7.5 Colloidal silica, 30% solids in water (Ludox AM, Du Pont de Nemours Er Co.) 2.2 Borax, 2% solution in water 3.1 Precipitated silica (Zeolex 80, J. M.Huber Corp.) 5.8 Silica (Imsil A-25, Illinois Minerals Co.) 15.6 Clay (ASP-400P, Minerals s Chemicals Div., Engelhard Minerals Er Chemicals Corp.) 1 5.6 Antifoam agent (Colloid 60, Colloids Inc.) 0.4 Acrylic polymer emulsion, 60% solids (Rhoplex AC-64, Rohm Er Haas Co.) 24.8 2,2,4-trimethyl-1 ,3-pentanediol monoisobutyrate 0.9 Ammonium hydroxide (28% ammonia) 0.8 Poly(methyi vinyl ether/maleic anhydride), neutralized partial nonionic ester, 8% solution in water (Thickener LN, GAF Corporation) 5.9 Water 5.6 100.0 Composition B--Cationic color base Parts by Weight Water 7.6 Anionic phosphate ester pigment dispersant, 25% active ingredients (Ulasperse 994-B, Ultra Adhesives, Inc.) 0.6 Polymeric pigment dispersant (Natrol 42, National Starch Er Chemical Corp.) 0.1 Titanium dioxide 12.7 Calcium carbonate 6.6 Acrylic polymer emulsion, 46.5% solids (Rhoplex B-60A, Rohm Er Haas Co.) 16.7 Antifoam agent (Colloid 60, Colloids, Inc.) 0.2 2,2,4-trimethyl-1 3-pentanediol monoisobutyrate 0.4 Ammonium hydroxide (28% ammonia) 0.2 Carboxymethyl hydroxypropyl guar, 1.5% solution in water (Celanese Polymer Specialties Co.) 6.8 Cationic cellulosic derivative, 2.5% solution in water (Polymer JR-30M, Union Carbide Corp.) 47.8 Ammonium hydroxide (28% ammonia) 0.3 100.0 After pigment dispersion with the polymer emulsion, anionic and cationic colloid solutions were added and mixed in the order indicated, followed by the second addition of ammonium hydroxide.

Composition C-White color base dispersion This was prepared by stirring together equal weights of Compositions A and B to produce a dispersion of white color particles. Stirring speeds up to 1 700 RPM were appropriate for producing particles having average size of about 1 mm. The particles were semi-fluid in consistency and much thinner in one dimension than in the other two dimensions.

Composition D-Blue color base dispersion This was prepared in the same way as Composition C, except the white color base was tinted before addition of anionic guar and cationic cellulose, by blending into it 0.4% by weight of a phthalo blue pigment dispersion (UCD4820Q, Universal Color Dispersions, Division of Bee Chemical Co.).

Composition E-Blue-white coating composition This was prepared by mixing white and blue dispersions at a weight ratio of: Composition C 75 Composition D 25 Composition E was readily sprayable to give a film with pleasing multicolor appearance. At this point it could not be brushed or rolled satisfactorily, as too much skidding of particles occurred to permit uniform coverage of the substrate.

Satisfactory application properties with either brush or roller were obtained in following compositions F, G, H, I by modification of composition E with the indicated thickeners.

Concentration Parts by on Continuous Weight Phase Composition F Composition E 100.0 Polymeric thickener XD7845.01, 7.5 0.58% 5% solution in water (Dow Chemical Co.) Water 7.5 Composition G Composition E 100.0 Polymeric thickener XD7846.01, 5.0 0.62% 8% solution in water (Dow Chemical Co.) Water 10.0 Composition H Composition E 100.0 Emulsion of polymeric thickener 3.75 0.68% containing acidic groups, 10% dispersion in water (Rheolate 1, Industrial Chemicals Div., NL Industries, Inc.) Ammonium hydroxide (28% ammonia) 0.5 Anionic acrylic polymer, 1.0 0.02% 1% solution in water (Reten 425, Hercules Inc.) Composition I Composition E 100.0 Emulsion of polymeric thickener 3.75 0.64% containing acidic groups, 10% dispersion in water Rheolate 1, Industrial Chemicals Div., NL Industries, Inc.) Emulsion of polymeric thickener 1.25 0.21% containing acidic groups, 1 0% dispersion in water (Acrysol ASE- 108, Rohm Er Haas Co.) Ammonium hydroxide (28% ammonia) 0.67 Water 3.3 In contrast to Example I which uses reactive ionic macromolecular colloids in both phases, the following Example II illustrátes the deficiencies of dispersions dependent on colloidal clay for phase separation.

Example II Composition A-Colloidal clay sol, 8% solids Parts by Weight This was prepared by stirring together for 1 hour Water 92.0 Tetrasodium pyrophosphate, anhydrous 0.8 Synthetic clay mineral (Barasym IBH, Industrial Chemicals Div., NL Industries, Inc.) 7.2 100.0 Where required, this was diluted with water to give a colloidal clay sol containing 5% solids.

Composition B-White coating composition Parts by Weight Water 3.26 Tetrasodium pyrophosphate, anhydrous 0.04 Hydroxyethyl cellulose, 3% solution in water (Cellosize QP-52M, Union Carbide Corp.) 27.5 Titanium dioxide 7.6 Acrylic polymer emulsion, 46.5% solids (Rhoplex B-60A, Rohm Er Haas Co.) 8.1 Antifoam agent (Colloid 60, Colloids Inc.) 0.05 After pigment dispersion was complete, addition was made of: Colloidal clay sol, 8% solids (Composition A) 7.75 This was stirred vigorously to uniformity, before addition of:Colloidal clay sol, 5% solids (from dilution of Composition A) 45.7 100.0 The use of dispersions with substantial high-shear viscosities enhances the value of systems using macromolecular polyelectrolytes in both phases. Since the desired rheology is that which is near Newtonian, dispersion systems dependent largely on colloidal clay are particularly undesirable.

The latter tend to produce a thixotropic rheology with poor leveling characteristics. Even more significant is the tendency for many thickeners to associate with colloidal clay to produce a slippery, pituitous consistency which does not allow the coating to grip the surface adequately. In some cases the interaction is sufficient to deactivate the colloidal clay and induce particle coalescence.

To produce coatings with good rheology, it is desirable to restrict colloidal clay content of the continuous phase to about 1 O/o or less. By use of other reactive systems for particle formation, the amount of clay which it is desirable to use is only that which prevents embrittlement and insures good hydration of the discrete particles.

As a portion of the reactive system, it is sometimes desirable to include colloidal silica. Although less effective than colloidal clay, it is generally more compatible with polymeric thickeners, and tends to act synergistically to increase the effect of colloidal clay. In absence of colloidal clay, colloidal silica tends to have an ambrittling effect on particle structure.

It was thought that application properties might be improved by addition to the continuous phase of a polymer emulsion or of non-hiding extender pigments such as those used in Example I.

Addition of Rhoplex AC-64 (8.5% solids on continuous phase) did not appreciable change application properties, either in the presence or absence of various thickeners.

Addition of the continuous phase pigment mixture used in Example I resulted in minor improvement in application properties if pigments were added after formation of the dispersed color particles, but behavior was far from acceptable. Addition of the same pigment mixture before formation of the color particles was detrimental to particle formation, resulting in either slow or rapid particle breakdown, depending on the colloidal clay concentration.

The phase separation system of Example II is not practical as a basis for formulating compositions for brush or roll application.

Example Ill Blue-white coating composition Payload-acrylic copolymer emulsion Composition A-Anionic dispersing medium Parts by Weight Water 5.7 Tetrasodium pyrophosphate, anhydrous 0.2 Colloidal silica, 30% solids in water (Ludox AM, Du Pont de Nemours Er Co.) 2.5 Borax, 2% solution in water 3.1 Synthetic hectorite clay, 8% colloidal dispersion in water (Laponite S.

Laporte Industries, Ltd.) 4.5 Water dispersible lecithin (Troykyd Lecithin WD, Troy Chemical Corp.) 0.8 Synthetic silica (Zeolex 80, J. M. Huber Corp.) 1.0 Mica 3.4 Calcium carbonate (Vicron 15-15, Pfizer Inc., Minerals, Pigments and Metals Div.) 12.3 Clay (ASP-400P, Minerals Er Chemicals Division, Engelhard Minerals Er Chemicals Corp.) 13.3 Di(phenylmercury)dodecenyl succinate, 10% mercury (PMDS-10, Troy Chemical Corp.) 0.1 Antifoam agent (Balab 737, Witco Chemical Corp., Organics Division) 0.2 Acrylic polymer emulsion, 46.5% solids (Rhoplex B-60A, Rohm Er Haas Co.) 43.0 Ethylene glycol monobutyl ether acetate 1.0 Ammonium hydroxide (28% ammonia) 0.4

Experimental rheology modifier,30.1 dispersion in water (E-1684, Rohm Er Haas Co.)) 1.3 Water ; Premix 2.35 Ammonium hydroxide (28% ammonia) 0.25 Water 4.6 100.0 Composition B-White color base Parts by Weight Water 17.3 Anionic phosphate ester pigment dispersant, 25% active ingredients (Ulasperse 994-B, Ultra Adhesives, Inc.) 1.3 Polymeric pigment dispersant (Natrol 42, National Starch Er Chemical Corp.) 0.4 Titanium dioxide 28.1 Calcium carbonate 14.6 Acrylic polymer emulsion, 46.5% solids (Rhoplex B-60A, Rohm Er Haas Co.) 36 7 Antifoam agent (Colloid 60, Colloids, Inc.) 0.4 Di=(phenylmercury) dodecenyl succinate, 1 0% mercury (PMDS-10, Troy Chemical Co.) 0.1 2,2,4-trimethyl-1 ,3-pentanediol monoisobutyrate 0.8 Ammonium hydroxide (28% ammonia) 0.3 100.0 Composition C-White cationic color base Parts by Weight Parts by Weight Composition B 47.0 Carboxymethyl hydroxypropyl guar, 2% solution in water (Celanese Polymer Specialties Co.) 5.0 Cationic guar derivative, 2.5% solution in water (Gendriv RW, Henkel Corp., Water Soluble Polymers Division) 28.0 Cationic cellulosic derivative, 2.5% solution in water (Polymer JR-30M, Union Carbide Corp.) 20.0 100.0 Composition D-White cationic color base dispersion This was prepared by stirring together Parts by Weight Parts by Weight Composition A 44.5 Composition C 55.5 to produce a dispersion of white color particles.

Composition E-Blue cationic color base dispersion This was prepared in the same way as Composition D, except the white color base was tinted before addition of anionic and cationic colloids by blending into it 2% by weight of a phthalo blue pigment dispersion (UCD 4820Q, Universal Color Dispersions, Division of Bee Chemical Co.).

Composition FRheology modifying solution Parts by Weight Rheology modifier QR-708, 34.3% solids in 60% propylene glycol, 40% water (Rohm Er Haas Co.) 29.1 Sodium dodecyl diphenyloxide disulfonate, 45% solution in water (Dowfax 2A1,Dow Chemical Co.) 3.3 Octylphenoxypolyethoxy ethanol, 70% solids in water (Triton X-405, Rohm Er Haas Co.) 2.2 Propylene glycol 28.0 Water 37.4 100.0 Composition G-Blue-white coating composition This was prepared by mixing the white and blue dispersions (compositions D and E) and thereafter adding other compositions with moderate stirring (about 700 RPM) in the order listed.

Parts by Weight Composition D 60.0 Composition E 20.2 Composition B 7.7 Anionic phosphate ester pigment dispersant, 25% active ingredients (Ulasperse 994-B, Ultra Adhesives, Inc.) 0.4 Composition F 5.6 Composition A 5.5 100.0 Example Ill could be applied easily by brush or roller to give a readily visible multicolored effect.

Example IV Blue-white coating composition This was prepared in the same way as Example Ill but in composition A (anionic dispersing medium) a different polyelectrolyte.

Polyacrylate solution, 10% solids in water (Poly-Tex 7551, Celanese Polymer Specialties Co.) was substituted for an equal amount of Rohm Er Haas Experimental Rheology Modifier E-1684. As a less associative polymer than E-1 684, this provided acceptable application results in combination with associative polymer QR-708. The performance was not as good, however, as when two associative polymers were used in conjunction with one another.

Brush and rool application was noticeably improved by the further addition to the composition of E-1 684, in the amount of 0.2% E-1684 solids on the weight of the continuous phase.

In Examples Ill and IV the ratio of borate-sensitive to borate-insensitive poiyelectrolyte is higher than in Example I. This produces somewhat more three-dimensional particles which permit better runoff of the continuous phase. Good run-off is desirable when the continuous phase contains a portion of hiding pigment, as in examples Ill, IV, which in sufficient thickness would tend to obscure the colored particles.

Claims (25)

Claims

1. A multicolor coating composition of the type in which an aqueous medium has a plurality of hydrated globules of a size visible to the naked eye dispersed, said globules and aqueous medium of different colors, said globules having sufficient strength and fluidity that they do not subdivide substantially due to the shear force imposed thereon when said composition is brushed or rolled onto a desired substrate to impart a decorative appearance thereto, said globules being defined by first and second reaction complexes that are formed concurrently, said first reaction complex resulting from the ionic interaction of a first polyelectrolyte with a second polyelectrolyte of opposite charge, said second reaction complex resulting from the non-colloidal reaction of said first polyelectrolyte with a reactant to which it is sensitive, with said first and second reaction complexes being present in said globules in such proportions as to impart said fluidity and strength thereto.

2. A multicolor coating composition as defined in Claim 1 which in addition includes a colloidal silicon containing material in said aqueous medium in an amount less than that required to insolubilize said first polyelectrolyte, said silicon containing material being present only in an amount to maintain said globules hydrated.

3. A multicolor coating composition as defined in Claim 1 that initially included first and second first polyelectrolytes the first of said first polyelectrolytes reacting ionically with said second polyelectrolyte to provide said first reaction complex, said first of said first polyelectrolytes not sensitive to said reactant, and said second reaction complex resulting from the non-colloidal reaction of said second of said first polyelectrolytes.

4. A multicolor coating composition as defined in Claim 3 in which said first reaction complex individually does not have sufficient strength as to be brushed or rolled onto said substrate without subdividing, and said second reaction complex having sufficient strength as to be brushed or rolled onto said substrate without subdividing but being of such a hard gel-like consistency as to have low surface drag and tend to slide when applied by brush or roller to said substrate, but said first and second complexes when formed concurrently so modifying the physical characteristics of one another that the globules defined thereby are of sufficient strength and fluidity as to be brushed or rolled onto said substrate without substantial subdivision thereof.

5. A multicolor coating composition as defined in Claim 1 in which said first polyelectrolyte is a borate sensitive water soluble polysaccharide and said reactant is one to which said polysaccharide is sensitive and interacts therewith to form said second reaction complex.

6. A multicolor coating composition as defined in Claim 1 in which the viscosity of said aqueous medium is such that the flow of said composition approaches that of being Newtonian when said composition is applied by a brush or roller to a desired substrate.

7. A multicolor coating composition as defined in Claim 1 in which said aqueous medium when said globules are dispersed therein contains said second polyelectrolyte, and said composition in addition containing in said aqueous medium a thickener that cooperates with said second polyelectrolyte to increase the viscosity of said aqueous medium and impart to said composition such rheological qualities that the flow thereof approaches Newtonian when applied by brush or roller to a desired substrate.

8. A multicolor coating composition as defined in Claim 1 in which said aqueous medium in which said globules are dispersed contains said second polyelectrolyte, and in addition a rheology determining agent in said aqueous medium that in cooperation with said second polyelectrolyte physically transforms said aqueous medium to the extent that said composition when applied to a desired substrate by brush or roller tends to flow thereon at a rate that approaches Newtonian.

9. A multicolor coating composition as defined in Claim 1 in which said aqueous medium in addition includes a first polymer, said first polymer being characterized by having a molecule that has a relatively hydrophilic portion that keeps said polymer in solution, and two or more hydrophobic portions that are capable of associating with other of said molecules of said polymer and in so doing impart such viscosity and rheological qualities that the flow of said composition approaches Newtonian when applied by brush or roller to a desired substrate.

10. A multicolor coating composition as defined in Claim 9 in which said first polymer is a thickener of the associative type.

11. A multicolor coating composition as defined in Claim 10 in which said aqueous medium in addition contains a second polymer that tends to increase the viscosity thereof but is of a nonassociative type.

12. A decorative coating composition of the type in which a plurality of discrete hydrated colored globules of a size visible to the naked eye are dispersed in an aqueous medium of a color different from that of said globules, said composition being characterized by said globules having sufficient strength and fluidity as to not substantially subdivide when brushed or rolled onto a desired substrate to impart a decorative appearance thereto, each of said globules being defined by a mixture of reaction complexes that jointly cooperate to impart said strength and fluidity thereto, the first of said reaction complexes being that resulting from an ionic first interaction of first and second polyelectrolytes of opposite charge, and the second of said reaction complexes resulting from a non-colloidal second interaction of said first polyelectrolyte with a reactant to which said second polyelectrolyte is not sensitive, said first and second interactions being effected concurrently.

13. A decorative coating composition as defined in Claim 1 2 that includes first and second first polyelectrolytes, the first of said first polyeiectrolytes reacting ionically with said second polyelectrolyte to form said first reaction complex and said second of said first polyelectrolytes reacting non-colloidally with said reactant to define said second reaction complex.

14. A coating composition as defined in Claim 12 in which said aqueous medium contains an inorganic material only in an amount to maintain hydration of said globules.

1 5. A coating composition as defined in Claim 14 in which said inorganic material is a colloidal silicon containing material.

1 6. A coating composition as defined in Claim 12 which in addition includes a rheology modifying agent in said aqueous medium in such amount that the flow of said composition approaches Newtonian flow when said composition is applied by brush or roller to a desired substrate.

1 7. A coating composition as defined in Claim 16 in which said rheology modifying agent is a thickener of the associative type.

1 8. A decorative coating composition that comprises an inner aqueous colored phase in the form of a plurality of discrete hydrated globules of a size visible to the naked eye that possess sufficient strength and fluidity as to be brushed onto a desired substrate without appreciable subdivision, said globules suspended in an outer aqueous phase of a color different from that of said inner phase, said outer phase containing colloidal clay only in an amount sufficient to maintain said globules hydrated, each of said globules defined by a plurality of reaction complexes that jointly cooperate to impart sufficient strength to said globules that they may be brushed onto said substrate, the first of said reaction complexes being that resulting from the ionic interaction of first and second polyelectrolytes of opposite charge, the first of said poiyelectrolytes being sensitive to a water soluble reactant and the second of said polyelectrolytes not being sensitive to said reactant, and the second of said reaction products being that which results from the interaction of said reactant and first polyelectrolyte.

1 9. A coating composition that comprises: a. a first colored aqueous phase containing at least one first polyelectrolyte that is sensitive to a water soluble reactant and is either anionic or cationic; b. a second aqueous phase containing said reactant, at least one second polyelectrolyte that is opposite in charge to that of said first polyelectrolyte and is not sensitive to said reactant, and colloidal clay, said first phase being insolubilized into a body comprising a plurality of reaction complexes by said second aqueous phase wiShiCh is of a color different from that of said first phase, said insolubiiized body being subdivided into a plurality of hydrated globules of sufficient size as to be visible to the naked eye and of such fluidity and strength as to be brushed onto a desired substrate without appreciable subdivision of said gloubules, the first of said reaction complexes being that which results from the ionic interaction of said first and second polyelectrolytes which in itself does not possess sufficient strength to withstand a brushing shear force, a second of said reaction complexes being that which results from the interaction of said first polyelectrolyte and said reactant, said second reaction complex augmenting the strength of said first reaction complex to the extent said globules may be brushed onto said substrate without appreciable subdivision, and said colloidal clay being present only in an amount sufficient to maintain said globules hydrated to the extent they may be brushed onto said substrate.

20. A coating composirion as defined in Claim 1 in which said first polyelectrolyte is selected from the group comprising water soluble polysaccharides and their derivatives.

21. A coating composition as defined in Claim 20 in which said first polyelectrolyte is selected from the group comprising cationic macromolecular quaternary ammonium compounds.

22. A method of making a coating composition that may be brushed onto a desired substrate to impart a decorative appearance thereto that comprises the steps of: a. preparing a first aqueous colored phase that contains at least one first polyelectrolyte that is borate sensitive and has an aggregate ionic charge that is either anionic or cationic; b. preparing a second aqueous phase that contains at least one second polyelectrolyte that is not borate sensitive, a soluble reactant to which said first polyelectrolyte is sensitive, and a colloidal silicon containing material in an amount insufficient to completely insolubilize said first polyelectrnlyte, said second aqueous phase having an ionic charge opposite to that of said first aqueous phase and a color different from that of said first aqueous phase;; c. sequentially adding said first aqueous phase to said second aqueous phase with stirring of the mixture thereof to provide an inner phase of a plurality of globules of a size visible to the naked eye suspended in an aqueous outer phase, said globules having a fluidity and strength as to permit said coating composition to be brushed onto said substrate without appreciable sub-division of said globules, with the material defining said globules being a mixture of a plurality of cooperating reaction complexes, the first of said reaction complexes being that resulting from the ionic interaction of said anionic and cationic first and second polyelectrolytes which in itself does not provide a reaction complex of sufficient strength as to provide globules that will withstand brushing shear forces without subdividing and the second of said reaction complexes being that resulting from the non-colloidal interaction of said reactant and first polyelectrolyte in said first aqueous phase, and said silicon containing material maintaining said globules sufficiently hydrated that they may be brushed onto said substrate without appreciable subdivision thereof.

23. A method of making a multi-color coating composition of the type that includes a plurality of hydrated globules of a size visible to the naked eye dispersed in an aqussi!a medium, said composition capable of being brushed or rolled onto a desired substrate without substaritial subdivision of said globules, said method including the steps of:: a. preparing a first aqueous phase of at least one first polyelectrolyte that has either an anionic or cationic charge and is non-colloidally reactive to a water soluble | reactant; b. preparing a second aqueous phase of a second polyelectrolyte of a charge opposite to that of said first polyelectrolyte and of a color different therefrom, and said second aqueous phase containing said reactant said second polyelectrolyte not sensitive to said reactant;; c. mixing said first and second phases to obtain a substantially water insoluble mixture of a plurality of reaction complexes, the first of said reaction complexes being that resulting from the ionic interaction of said first and second polyelectrolytes that in combination with a second reaction complex resulting from the non-colloidal reaction of said first polyelectrolyte with said reactant, said mixture of reaction complexes disposed in said aqueous medium which is the portions of said first and second aqueous phases that did not form said mixture of reaction complexes; d. Stirring said mixture of reaction complexes and aqueous medium to subdivide said mixture of reaction complexes into said globules, said globules having sufficient strength and fluidity as to not substantially subdivide when brushed or rolled onto a desired substrate; and e. adjusting the viscosity of said aqueous medium to that at which the same may be brushed onto a desired substrate with a Newtonian like flow.

24. A method as defined in Claim 23 in which said adjusting is accomplished by adding an organic polymer to said aqueous medium.

25. A method as defined in Claim 23 in which at least a portion of said organic polymer is added to said aqueous medium after the formation of said globules.