FR2514019A1 - Semi-solid water-based coating compsns. - contg. organo-metallic hydroxy cpd. to increase gel structure formation rate - Google Patents

Abstract

Known gelled coating compsns. capable of applicn. and flow on a solid substrate and consisting of (a) an H2O-reducible, film-forming polymer (I), (b) H2O, (c) an electrolyte (II), and (d) a colloidal gelling agent (III) (gelable by interaction with (II)) which gels the compsn. to a stable semisolid or solid (compsn. reducible to a coating applicn. viscosity on applicn. of small shearing force/rate; but does not recover (II)-(III) contributed gel structure) are improved by including one or more gel structure formation rate increasing cpds. (IV) (or hydrolysable in situ to (IV)) (or condensate). RxM(OH)y-x (IV) (Where M is B, Al, Si, Sn, Ti, Zr, V, Nb, Hf, or Ta; x is O or 1; y is valence of M; R is an organic moiety attached to M through a C-M bond). This is related to US4196107. Incorporation of (IV) into the compsn. decreases the time required for gelling without needing the applicn. of heat. In addn., pre-use tinting is facilitated. The compsns., when used as paints, provide excellent flow and levelling.

Description

 The invention relates to the field of coating compositions. A major criticism of the coating compositions that major @uressee @ux compos @@ conventional coating ions comes from their unpleasant handling and application conditions.

First of all, the coating composition must in particular be agitated for the redispersion of the solid materials, then at least part of the coating composition is transferred into a container suitable for an applicator with a roller or a pad. Splashes, drips or drips before and during the actual application of the coating composition to a support always constitute real dangers.

 Previous attempts have been made to provide "solid" coating compositions which can be applied in the form of sticks by manual or machine application, the shear force upon application thinning the coating composition. However, even in the best of these systems, the solid or semi-solid gelled composition was obtained by the use of thixotropic agents and, although the shear forces could momentarily provide a fluidized system, once the force of With the shear removed, the thixotropic agents present have once again returned the solid nature or gel structure to the system, thereby preventing desirable flow and tension from the coating compositions applied.

 In addition, the use of a rod-shaped product involves holding a heavy object in the hand up to the point of application and increases the fatigue of the arm.

 Unlike prior art systems, in the coating compositions of the invention, once the gel structure produced by the interaction of an electrolyte and a colloidal gelling agent is destroyed by the application of shear forces, there is little or no recovery of significant gel structure favored by the gelling system. Thus, the compositions of the invention act as conventional paints when applied to a support, providing excellent flow and tension.

 Pending Application No. 912,807, filed June 6, 1978 in the name of 3ames E. Jones et al., Describes compositions identical to those of the invention with respect to the presence of a compound increasing the rate of formation of the semi-solid composition. These semi-solid compositions described previously have excellent application and coating characteristics. However, as it is specified in said previous application, since the interaction of the colloid and the electrolyte frequently requires a significant period of rest at room temperature to obtain a gel structure which is stable in view of production parameters on an industrial scale, it is often desirable to accelerate the almost total interaction between the electrolyte and the colloid by application of heat for a sufficient time to substantially complete the colloid-electrolyte interaction.

Since this heating step is most conveniently carried out after filling the individual containers for marketing, mass production of such a product would require additional steps which are unusual and important to a conventional coating packaging system. The present invention avoids or reduces the need for such a heat treatment step without substantially modifying the other advantageous characteristics of the prior compositions described. The present invention also facilitates tinting before use (for example in retail stores) which could not easily be made with the heat treated composition.

The present invention relates to compositions which are "solid" before application and which, when applied to a support, flow and stretch in the same manner as conventional coating compositions. The coating compositions of the invention comprise a gelled coating composition able to be applied and to flow on a solid support comprising a) a water-dilutable polymer, b) water, c) an electrolyte, d) a colloidal gelling agent which can be gelled by interaction with the electrolyte, in an amount sufficient to gel the composition when it has interacted with said electrolyte, in order to form a stable semi-solid and to provide a composition which can be diluted to viscosity applying the coating after applying a relatively low shear force with a relatively low shear rate; said gelled coating composition, after having been sheared down to the application viscosity of the coating, not finding the gel structure produced by the colloidal gelling agent and e) an amount of a compound increasing the rate of formation of the gel structure, of formula - or is hydrolyzable in situ to effectively provide a compound of formula
Rx M (OH)
yx in which M is boron, aluminum, silicon, tin, titanium, zirconium, vanadium, niobium, hafnium or tantalum; x is 0 or 1; y is the valence of M, and R is an organic fraction attached to M through a carbon-M bond or else a condensation product or a combination of such compounds, said quantity being sufficient to reduce the time necessary for the formation of said gelled composition.

 Compositions comprising a), b), c) and d) which can be used in conjunction with e) above are described in pending application series No. 912.807, filed June 6, 1978 in the name of 3ames E. Jones and colt.

this request is mentioned in its entirety for reference and a person skilled in the art can refer to it, if necessary.

 The invention summarized above is described in more detail in the following.

 Generally, the coating compositions of the invention are conventional aqueous coating compositions containing, in addition to their usual constituents, suitable amounts of a gel-forming system which is a combination of an electrolyte, d colloidal gelling agent, gellable by interaction with said electrolyte and compound increasing the rate of formation of the gel. The conventional aqueous coating compositions used can be practically any of the available compositions containing, in the usual proportions, conventional materials such as, for example, water-dilutable film-forming resins, solubilizers and / or emulsifiers, variable amounts of organic solvents and co-solvents, pigments, fillers, diluents, wetting agents, viscosity adjusting agents, tension adjusting agents and the like.

 It should be noted that, since certain resins diluted with water and / or other conventional ingredients are electrolytes, the presence of these materials can fulfill the double function of an ingredient for a conventional coating composition, for example. example a film former and an electrolyte in the gel forming system.

 The water-dilutable film-forming polymers useful in the compositions of the invention include all polymers known for their effectiveness in such compositions to form an aqueous polymer system, for example a solution, a dispersion or an emulsion.

 The film-forming polymer includes - but is not limited to these - water-dilutable inorganic and organic polymers such as acrylic polymers, vinyl resins and chlorinated substituted vinyl resins, polyphosphorylonitriles, polyethers, saturated polyesters and unsaturated, polyurethanes and polyepoxides as well as natural resins or chemically modified natural resins. The resins which are addition polymers can be homopolymers or copolymers. Resins which are condensation polymers can be obtained from any number of condensable reactants. Appropriate functional groups can be incorporated into or grafted to the polymer chain. A mixture of more than one film-forming polymer can be used. The polymer used can provide thermoplastic or thermosetting systems which can, for example, cure by chemical means or by irradiation at room temperature or at elevated temperatures.

 It should be noted that the adjective "film-forming" defines the ability to form a film in the existing medium which may include solvents, co-solvents and / or plasticizers. Thus, polymers which are not, strictly speaking, film-forming agents in the absence, for example, of coalescing solvents and / or co-solvents are among the film-forming polymers capable of being used in the invention. It also represents conventional coating technology.

 The polymer is generally present in the amount normally used in coating compositions.

 Although not essential, the composition may contain one or more pigments, such as covering pigments, pigment thinners or pigment dyes. Examples of useful pigments are titanium dioxide, antimony oxide, zinc oxide, zirconium oxide, zinc sulfide and lithopone. As pigment diluents, mention may be made of silica, barytes, calcium carbonate, talc, magnesium silicate and aluminum silicate.

 In general, the pigment is used in an amount of 0 to 70% by weight of the total composition. The pigment may be present to provide volume pigment concentrations up to about 75 (i.e., 75% of the volume of the final dry film being pigment).

 The colloid gellable by an electrolyte used in the compositions of the invention can be practically any colloid, compatible with the coating composition, capable of being gelled by an electrolyte compatible with paint. Typically, these colloids are aqueous dispersions of non-agglomerated particles the size of the millimicron having a surface charge and which are stabilized by a counterion. These colloids can be anionic or cationic in nature.

 A particularly useful group of colloids is colloidal silicas, usually with high SiO2 / Na2O ratios in which the surface of the particle is partly composed of silanol groups which are partially ionized and stabilized in the presence of sodium as a counter ion. Similar colloids where the counterion is for example potassium ion, lithium, ammonium, substituted ammonium or quaternary ammonium are also useful. Examples of such colloids are commercially available under the names "Ludox", "Nalcoag" and "Nyacol".

 A number of aqueous colloidal silica soils are shown in Table I.

TABLEAU 1 2 3 4 5 64 7 8
Stabilizing counter ion Na Na Na Na Na Na Ammonium Na
Particle charge Negative Negative Negative Negative Negative Negative Negative Negative
Particle size, nm. 13-14 13-14 14-15 7-8 21-24 13-14 13-14 4
Specific area m2 / g 210-230 210-230 195-215 375-420 125-140 210-230 210-230 750
Silica (as
SiO2),% by weight 40 30 30 30 49.5 30 30 15 pH 9.71 9.81 8.41 9.91 8.91 9.01 9.61 10.4-10.7
Titratable alkali (as Na2O),% by weight 0.43 0.32 0.10 0.60 0.21 0.19 0.095 0.80
SiO / Na2O (by weight) 90 90 300 50 230 160 1206 19
Viscosity (cps.) 17.52 4.52 142 5.52 502 172 202 18 g / cm3 1.301 1.211 1.211 1.211 1.391 1.211 1.211 1.11 density 1.301 1.211 1.211 1.211 1.391 1.211 1.211 1.1041
Conductance (micromhos) 47303 - 15703 47303 - 22703 26303 125 C 225 C, using the Ostwald-Fenske pipette n 100 or 200, depending on the viscosity range.

320 C 4 surface modified with aluminate ions 7 sol containing 0.3% NH3 and 0.01% Na2O 5 sol containing 0.25% NH3 and 0.09% Na2O 820 C 6 SiO2 / NH3 (by weight) 9 Sol containing 0 , 2% NH3 and <0.01% Na2O.

TABLE I (continued) 9 10 11 12 13 14 15 16
Stabilizing counter ion Ammonium Na Na Na Na Na Ammonium Na
Particle charge Negative Negative Negative Negative Negative Negative Negative Negative
Particle size, nm. 5 8 15 13 20 60 20 8
Specific area m2 / g 600 375 200 190-270 120-176 40-60 150
Silica (as
SiO2),% by weight 14.5 30 40 30 50 50 40 30 pH 9.0 10.0 9.7 10.2 9.0 8.5 9.3 10.71
Titratable alkali (as Na2O),% by weight 0.017 0.65 0.40 0.40 0.35 0.25 <0.19 0.45
SiO2 / Na2O (by weight) 486 46 100 75 143 200 2006 67
Viscosity (cps.) 5 6 12 5 40 10 20 6 g / cm3 1.092 1.214 1.296 1.208 1.390 1.390 1.292 1.22 density 1.0928 1.214 1.2968 1.2088 1.3908 1.3908 1.2928 1.22 125 C 225 C, using the Ostwald-Fenske pipette n 100 or 200, depending on the viscosity range.

320 C 4 Surface modified by aluminate ions 5sol containing 0.25% NH3 and 0.09% Na2O 6SiO / NH3 (by weight) 820 C 7sol containing 0.3% NH3 and 0.01% Na2O 9Sol containing 0 , 2% NH3 and <0.1% Na2O.

TABLE I (continued) 17 18 19 20 21 22
Stabilizing counter ion Na Na Na Na Na
Particle charge Negative Negative Negative Negative Negative
Particle size, nm. 3-4 14 14 22 22 16-22
Specific area m2 / g - - - - - 135-190
Silica (as
SiO2),% by weight 15 30 40 50 40 34 pH 11 10.4 10.4 10 10 3.1
Titratable alkali (as Na2O),% by weight 0.75 0.35 0.48 0.48 - <0.05
SiO2 / Na2O (by weight) 20 86 83 104 -
Viscosity (cps.) 5 6 16 50 10 <20 g / cm3 1.1 1.21 1.30 1.4 1.30 1.230 density 1.1 1.21 1.30 1.4 1.30 1.2308 125 C 225 C, using the Ostwald-Fenske pipette n 100 or 200, depending on the viscosity range.

320 C 4 surface modified with aluminate ions 7 sol containing 0.3% NH3 and 0.01% Na2O 5 Sol containing 0.25% NH3 and 0.09% Na2O 820 C 6 SiO2 / NH3 (by weight) 9 Sol containing 0 , 2% NH3 and <0.1% Na2O.

An example of a cationic colloidal silica is one where part of the surface atoms are aluminum atoms. This allows the creation of a fixed positive charge. Such an aqueous colloidal silica stabilized by chloride ions is very stable in the pH range from 3.5 to 5.5. This aqueous colloidal silica comprises 26% of silica and 4% of alumina and is characterized by counter-ion stabilizer chloride particle charge Positive particle size, nm 13-15 specific area, mZ / g 200-220 silica (as Si02),% by weight /% by weight 26/4 of alumina pH (250C) 4.4
Chlorides (in the form of Nacl),% by weight 1.4 viscosity (250C), cps. 5.15 g / cm3 (250C) 1.23
Density (250C) 1.23
In addition to silica soils, other soils which are gelable by an electrolyte include As253 soils, Fe203 soils, A1203 soils, AgI soils, Su 203 soils and the like.

 An example of a useful colloidal alumina "(8aymal)" is a free flowing powder composed of aggregates of tiny boehmite alumina fibrils (AOOH).

The powder disperses in water, giving soils of final fibrils. The surface of the fibrils is modified by absorbed acetate ions. The powder has the following typical composition
Percent AlOOH 83.1 CH30OH 9.8 s04 1.7
Water 5.0
NH4 0.2
Na 0.07
Fe 0.02 Si02 0.02 and the following typical physical properties
Specific area 274 m2 / g
Pore volume 0.53 cm3 / g
Pore diameter 77 Angstroms
Apparent density
- loose 0.416 g / cm3
- packed 0.496 g / cm3
Absolute density (fibril) 2.28 g / cm3
Refractive index (fibril) 1,580 n25D
Oil absorption 147 (ASTM D-281-31)
White color pH - soil at 4% 3.8 (KC1 bridge /
calomel cell)
4.3 (without bridge)
Particle charge in positive soil
We can refer to the book "Colloid Chemistry",
A. Sheludko, 1st English edition, Elsevier Publishing
Company, Amsterdam 1966 and in particular in Chapter VII entitled "Stability of Lyophobic Sols" which deals, among other things, with the coagulation of colloids by electrolytes and the kinetics of rapid coagulation and where numerous examples of colloidal soils and d are given. electrolytes causing gelation.

 Examples of electrolytes which can be used in the gel-forming system of the invention are electrolytes capable of producing "rapid gelation" (see Sheludko, supra) of the particular colloidal sol employed.

The electrolyte is a dissociable salt in water which can be a mineral, organic or mixed salt. The salt can be a monofunctional or polyfunctional salt, or even a polymer salt.

Typical functional electrolytes are salts such as, for example, alkali metal salts of tripolyphosphoric acid and alkali metal salts of ethylenediaminotetraacetic acid. Polymeric salts such as sodium carboxymethyl hydroxyethyl cellulose and alkali metal salts of styrene-maleic anhydride copolymers are useful electrolytes. Many other electrolytes are cited as an example by Sheludko supra and are therefore not included here. Among other electrolytes which can also be used for the gelling of anionic colloidal silica soils are ethylenediaminotetraacetic acid, its mono-, di- , tri- and tetrasodium, its di (-triethylamine) salt as well as potassium tripolyphosphate, disodium phosphate, potassium salt of polyphosphoric anhydride ester, sodium polyacrylate, carboxylated ion exchange resins under the acid or neutral form, ion exchange resins based on sulfonic acid in their acid or neutral form, diethylenetriamine, sodium chloride and hydrochloric acid.

 Although it is not desired to be bound by any theory, it is believed that the addition of the additive of the present invention leads to the destabilization of the colloid, which causes faster gelation.

 The colloid and the electrolyte are used in a sufficient quantity one in relation to the other and with respect to the total system so that after a quasi-total interaction between the colloid and the electrolyte, a substantially stable gelled system is formed. which solidifies in the solid or semi-solid state and which can be reduced to an acceptable viscosity for painting by applying a relatively low shear force at a relatively low shear rate, such as l 'exercises for example a person using painting equipment such as for example a tampon applicator.

 Since the pigment particles as well as the polymer particles (for example the latex particles) are usually dispersed particles carrying a charge, they are capable of an interaction between the electrolyte and the colloidal gelling species. These interactions can influence the gelation mechanism. The amount of gelling agent and / or electrolyte may require adjustment to compensate for the presence of such interaction material.

In addition to the necessary or optional constituents described above, the compositions of the invention contain a component increasing the rate of formation of the gel structure, of formula - or is hydrolyzable in situ to effectively provide a compound of formula
RM (OH) (I)
yx in which M is boron, aluminum, silicon, tin, titanium, zirconium, vanadium, niobium, hafnium or tantalum, preferably boron, aluminum, silicon, titanium or zirconium; x is O to 1 yy is the valence of M and R is an organic fraction attached to M via a carbon-M bond as well as condensation products of these compounds including condensation products corresponding to the empirical formula
Rx MO (11)
x xy
2 in which R, M, x and y are as defined above, as well as partial condensation products of (I) / which intrinsically have a formula which can be defined as being in an intermediate state between the formulas (I) and (II) @; the amount of the compound in question is sufficient to reduce the time necessary for the formation of said gelled composition. The group R preferably has less than 20 carbon atoms and more preferably less than about 10 carbon atoms.

 The preferred compounds are silicon compounds, preferably organosilicon compounds having at least three hydroxyl or hydrolyzable groups attached to the silicon atom, said groups possibly being halogen, alkoxy, substituted alkoxy, aryloxy, substituted aryloxy, aralkoxy , substituted aralkoxy, alkyllamino, substituted alkyllamino, silylamino, substituted silylamino, mercapto and substituted mercapto.

 As suitable halogenated substituents, mention may be made of the chloro, bromo and iodo substituents. Examples of suitable groups are methoxy, ethoxy, propoxy, acetoxy and the like. Suitable substituted alkoxy groups are substituted alkoxy, chloro, bromo and iodo, where the alkoxy moiety belongs to the above groups. Examples of aryloxy, aralkoxy, substituted aryloxy and substituted aralkoxy groups are phenoxy, phenylethoxy, chlorophenylethoxy, and phenylchloroethoxy groups, respectively.

Suitable alkylamino and substituted alkylamino groups are methylamino or dimethylamino and chloromethylamino, respectively. Examples of substituted mercapto and mercapto groups are ethyl mercapto and chloroethyl mercapto groups, respectively. Among the silylamino and substituted silylamino groups are the secondary and tertiary amine groups having a silicon atom bonded to the amino nitrogen.

 A particularly preferred group of organosilicon compounds corresponds to the formula R n Si (OR 'in which n is O or 1, (OR') is -OH or a group hydrolyzable to -OH, for example an aliphatic hydrocarbon group having 10 or less and preferably 6 or less carbon atoms including methyl, ethyl, propyl, isopropyl, hexyl, 2-ethylhexyl, vinyl, 5-hexenyl and the like as well as phenyl and lower alkylphenyl groups and the like and R is an aliphatic hydrocarbon group or a hydrocarbyl group containing an ester, ether, amino or amido bond, preferably containing 10 or less carbon atoms or a phenyl group or preferably an aliphatic amino hydrocarbon group containing less than ten carbon atoms.

 Among others, gamma-aminopropyltriethoxysilane is an example of a preferred compound. When, in general, R 'is other. that hydrogen, at least one substituted amino R group is preferably present on the compound to provide a catalysis effect in internal hydrolysis.

Alternatively, compounds which can be used are those corresponding to the formulas
A1 (A) 3, Ti (A) 4, Zr <A) 4, or 8 (A) 3 and the like where A is -OH or an atom or an organic group hydrolyzable to form an -OH moiety. Examples of compounds which can be used are aluminum isopropylate, triethylborate, zirconium bytylate, titanium isopropylate and the like, as well as ethyl nioblum, ethyl vanadyl, ethyl tantalum, hafnium propylate, ethyl tin and the like.

 Within the meaning of the present description, the amount in (e) sufficient to reduce the time necessary for the formation of the gelled composition is the amount of such a compound and / or of a condensation product, which measurably reduces the time required to form a semi-solid or solid, gelled, stable coating composition which can be brought to an application viscosity of the coating after application of a relatively low shear force with a relatively low shear rate, which gelled composition, after having been sheared to the viscosity of application of the coating, practically does not recover the gel structure produced by the colloidal-electrolyte gelling agent, this quantity being less than that which produces an unstable gel and / or reducible by a non-shearing force.

 For convenience, these compounds are sometimes referred to as "gel state promoters".

 In some cases, in particular when the composition does not have a high pH and the gel state promoter contains hydrolyzable groups, it is possible, if desired, to add bases such as ammonia or amines to catalyze the hydrolysis reaction.

 The solid compositions of the invention can be formulated in many ways. A conventional coating composition can be prepared if desired and the gel generating system added thereafter. Alternatively, one, two or all three components, namely the colloid, the electrolyte and the gel state promoter can be introduced during the process of forming the coating composition. In this case, the final coating composition containing the gel-generating system can be introduced into a container suitable for providing a specific area compatible with the applicator to be used for the transfer of the coating composition from the container to the surface to be coated before significant gel formation. As a variant, the composition can be transformed into gel in the form of a plate which is then cut into a shape adapting to that of the final container.

As a tampon applicator is frequently used, the container typically has the shape of a relatively shallow bowl, although other types of containers may be used. In a preferred form, the surface of the container is sealed with a plastic film in contact with the surface of the paint.

 In a preferred embodiment, for example for commercial use, the coating formulation may be provided to provide a package containing the electrolyte and the gel state promoter. At the time of sale, the colloid (shades and / or color pigmentation, if applicable) can be added to quickly form the semi-solid coating compositions.

 As stated above, the constituents of the coating composition other than the gel generating system are present to fulfill the role of formulation of a conventional coating composition; in a preferred form, the compositions of the invention may, however, contain minor amounts of a high boiling organic solvent to retard or prevent the formation of cracks in the applied film. When the selected solvent is insoluble in water and not a true solvent for the binders which are present, the presence of the solvent in the system also serves to increase the covering power by creation of microvides as described in US Patents 3,669 .728 and 3.669.729. Since these unique gel generating systems act as an ideal matrix for finely dispersed solvent droplets, the stability of these droplets is improved. During extended storage periods, coalescence of solvent droplets can occur in conventional liquid paints.

This is avoided in the presence of an occluded gel. When subjected to a relatively low shear force with a relatively low shear rate, the viscosity of the coating compositions is reduced to that of a liquid paint. At this point, the stability of the droplet would be lowered to that of a liquid paint. However, since the duration of this liquefaction period is short, there is a significant improvement in the covering power compared to that mentioned in the two patents
US supra.

 When considering the use of a tampon applicator, the coating composition, in the absence of the gel generating system, is formulated so as to have a low viscosity value under high shear to reduce entrainment by l 'applicator.

 The stable "solid" coating compositions obtained range from semi-solid to consistent solid, all characterized in that they maintain themselves and resist flow in the absence of a applied shear force. The preferred solid coating compositions are strong enough to have a peak value, as defined below, of at least about 8. (Typically, the coating compositions have a penetrometer value as defined below, less than about 35 mm).

 The coating compositions of the invention are further characterized in that the viscosity induced by the gel generating system decreases upon application of reasonable shear forces, such as those applied by a man with a conventional applicator, to the point that the coating compositions have transfer properties suitable for the use of a paint applicator such as a pad applicator; as subsequent shear forces are applied during application of the coating composition, the coating compositions have application properties suitable for use with the applicator.

In general, the coating composition, after an almost total destruction of the gel structure caused by the colloidal gelling agent - electrolyte by reasonable shear forces, such as those applied by a man during the transfer and of the application, has a viscosity at 780 sec -l between approximately 0.2 Pa.s and approximately 1 Pa.s and preferably between approximately 0.3 Pa.s and approximately 0.7 Pa.s.

 Although the useful and optimal proportions of the various constituents of the compositions of the invention can vary within wide limits in part depending on the nature of the specific materials and their mutual interaction and that the particular proportions of a large part of the composition are governed to a significant degree by the selection within a formulation technology of a standard coating composition by generally relating the water-dilutable polymer, the colloid and the electrolyte to 100 parts by weight, the composition usually comprises between about 25 and about 99 parts and preferably between about 60 and about 95 parts by weight of the water-dilutable polymer, about 0.7 to about 60 and preferably about 1 to about 20 parts by weight of the colloid and about 0.1 to about 50 parts and preferably between about 2 and about 20 parts by weight of the electrolyte, the weight ratio of water to this system being e n generally between 9: 1 and about 1: 2

 The gel state promoter is generally present in the composition in an amount between approximately 1 part and approximately 100 parts by weight per 100 parts by weight of colloid and preferably in an amount between approximately 5 parts and approximately 50 parts by weight. weight per 100 parts by weight of colloid.

Although the description mentions the use
a single material to fulfill a function, it can
if necessary be insured in all cases by a combination
origin of two or more materials with the same
function.

A number of examples are given which
describe the invention. These examples should be considered
as illustrative and have no limiting character. Except
otherwise indicated, all percentages and parts in
the examples as well as throughout the description are
expressed by weight. All temperatures are except indica
opposite, degrees centigrade.

In the following examples,
preliminary assessments using an applicator
generally flat tampon type with rounded edges
to prevent the applicator from digging and collecting
coating composition over the edges of the applica
tor as it is pulled back and forth along
the surface of the semi-solid coating composition,
with sufficient pressure to cause rupture of the
dukel surface and the formation of a coating composition
with an appropriate transfer viscosity and a viscosity
suitable after application on a support.

In some of the examples, the strength of the gel and the
application viscosity of the coating composition have
have been characterized by a rheometer, namely a viscosi
RVake Rotovisco meter from Haake, Inc. using a
SVIIP sensor from O to 1000 rpm, a double measuring head
50/500, the tip being scale reading at a rate of
shear of about 15 sec 1 (or about 20 rpm) and the
end point at around 779 sec 1 (or around 1000 rpm).

(All Rotovisco viscometer values shown are
measurements made using the measuring head 500).

EXAMPLE I
Solid coating compositions have been
prepared using formulation and grinding techniques
conventional, from the following ingredients.

Ingredients Quantities
(parts in
weight)
Water 200.0
Associative thickener (30% solids) (TT-678 Rohm & Haas) 25.0
Polyphosphoric anhydride ester potassium salt (Strodex SEK-50-Dexter
Chemical) (50 X solids) 9.6
Sodium salt of a polymeric carboxylic acid (Tamol 731-Rohm & Haas) (25 X solids) 38.2
Nonylphenoxypolyethoxyethanol (Triton N-75 Rohm & Haas)) 6.4
Defoamer based on silica and mineral oil (Defoamer L445-Drew Chemical) 6.4
Phenylmercuric acetate (30% solution) 1.6
Ethylene glycol 63.7
Ethylene glycol phenyl ether 25.5
Anionic surfactant (Henkel International VP-535) 19.1
The above ingredients were mixed and then added with: diatomaceous earth (Celite 499 Johns-Manville) 67.5
SiO modified with calcium (HI-Sil 422) 30.0
Barium sulfate 159.2
The mixture was then dispersed with a Cowles dissolver. Then added hydroxyethylcellulose 4.0 aminomethylpropanol 1.0 O hydrocarbon solvent with high boiling point (Soltrol 200 from Phillips Petroleum) 84.4 premix with non-ionic surfactant (TX-45 Rohm & Haas) 2.4
The resulting mixture was dispersed for five minutes in a Cowles dissolver and transformed into a mixture of silica-based defoamer and mineral oil (Defoamer L-475) 15.9 TiO slurry (76% solids) 1074.3 (Titanox 41 01 slurry NL Industries) TiO slurry (62% solids) (ritanox 4131 slurry NL Industries) 860.0
Water 475.0 sodium salt of a copolymer of styrene maleic anhydride (Arco Chemical SMA-1000A, 100% theoretical neutralization) to 40% of solids 44.6 binder based on emulsion (Rohm & Haas AC 64) 60, 5% solids the solids are supposed to consist of 43% methyl methacrylate, 55% butyl acrylate and 2% methacrylic acid 1076.5
After mixing, colloidal silica was added (table 1 n 8 above) 270.6
To three separate portions of 780 parts of the above compositions, various additives were added and the tip as well as the end point of the composition were measured after 19 hours at room temperature and after heat treatment at 710C for 6 and 16 hours.

TABLE 2
Compo- Tip / end point sition Additives. 710C
7 p.m. at 6 a.m. 4 p.m.

 temper.

ambient
A 1.7 parts of ethylene diamino 22.5 / 9 5 22.5 / 24.4 / 10.0
tetrasodium tetraacetate (EDTA)
and 1.7 parts of gamma amino
propyltriethoxysilane
B 0.85 part of EDTA * 15.5 / 7
0.85 part of AT50
C 1.7 parts of gamma aminopropyl- 19.0 / 9.4 21.2 /
triethoxysilane
D witness 15.0 / 5 23.0 /
(no additives) * Tilcom AT 50: water-soluble chelate based on isopropyl titanate
and amino alcohols, 75% in isopropyl alcohol, 8.2% of Ti,
Titanium intermediates Limited.

In addition, after 4 p.m. at 71 C, samples
Lons of A, C and D were kept at 600C for two weeks and the peaks and endpoints were measured
A 22/6; C 23 / 7.2; D 23 / 7.2.

EXAMPLE 2
Using the basic composition of Example 1 (the formulation until the addition of colloidal silica), 9.9 parts of ethylene diamino tetraacetate tetrasodium and 9.9 parts of gamma aminopropyltriethoxysilane were used in addition. Portions of the resulting composition were added to 113 g containers and tip and end point determinations were made periodically. The results are summarized in Table 3.

TABLE 3
Hours - room temperature containers
113 g 1 2 4 6 24 temperature 20.5 * / 12.5 25.5 / 11.5 26.5 / 11.4 24.0 / 11.5 25.5 / 11.0 ambient 12.5 710C 23 .0 / 12.5 26.0 / 12.5 25.3 / 14.0 23.0 / 10-13 * Peak /
period
EXAMPLE 3
Two formulations of the same base composition of Example 1 were made except that colloidal silica was not added. The first formulation had an initial viscosity (Brookfield, axis n06 at 20 rpm) of 8000 cps; the second formulation had an initial viscosity of 9,500 cps. The first formulation was allowed to age for two weeks in a room heated to 600C. The second formulation was aged at room temperature for two weeks. At this point, the first formulation had a viscosity of 10,750 cps, while the second formulation had a viscosity of 10,500 cps.

 To each of the aged compositions, 400 parts of colloidal silica were then added (table l.

n 8), 9.9 parts of ethylenediaminotetraacetate tetrasodium and 9.9 parts of gamma aminopropyltriethoxysilane. Rotovisco tips and end points were then determined after 2 and 4 hours at room temperature.

2 hours 4 hours
Point point Point point
final final first formulation 21.0 9.9 22.5 10.0 second formulation 21.0 10.0 21.5 10.4
The semi-solid paint (4 hours at room temperature) was evaluated by two individuals (O = bad, 10 = excellent) with regard to transfer, entrainment and sagging (resistance to dripping).

transfer flow drainage first composition 9-10 sticky 9 sticky 10
8- 9 9 10 second composition 10 9-10 slightly 10
10 10 sticky
EXAMPLE 4
The basic compositions of Example 1 were used without the addition of colloidal silica. To show that the order of addition of the components of the gelling system is not critical, the following comparisons were made.

The following materials were added to separate 2.27 liter portions of the formulation and mixed in the order indicated
4-A 4-B 4-C 200 g of colloidal silica (table 1, nO 8) 5 g of EDTA 5 g of EDTA 5 g of ethylenediaminotetraacetate tetrasodium (EDTA) 5 g of GAPTS 5 g of GAPTS 5 g of gamma amino - 200 g of colloidal propyltriethoxysilane silica (GAPTS) (table 1, nO 8)
Formulations 4-A and 4-B formed a semi-solid gel structure within 2 to 3 minutes. Each addition had been stirred for about one minute.

 The 4-C formulation was placed in a warm room at 600C for two weeks. 200 g of colloidal silica - dale (Table 1, No. 8) were added to the 4-C formulation. In each case, the Rotovisco values were determined on each composition approximately 2 hours after the end of all the additions.

Peak End point 4-A 30.0 11.5 4-B 29.0 11.5 4-C 17.0 10.0 4-C (after two additional weeks
600C) 38.5 11.0
EXAMPLE 5
The following formulations have been made to demonstrate the effect of activating the gel state of various materials
TABLE 4
Ingredients Parts by weight
Ex n. 5A 5B 5C 5D 5E 5F colloidal silica (table 1, n 8) 160 160 160 160 160 160 ethylene diaminotetraacetate tetrasodium 3 3 3 3 3 3 emulsion-based binder (AC-490 Rohm & Haas) 80 80 80 80 80 80 gamma aminopropyltriethoxysilane 3 - - - - N-beta (aminoethyl) -gamma-amino- propyltriethoxysilane - 3 - - - 2N (CH2) 2NH (CH2) 2NH (CH2) 3 (CH30) 3si - - 3 - - aluminum isopropylate - - - 3 -
Zircomplex CC (Manchem Ltd.) (composed of aqueous ammonia organic zirconium, 15% zirconium) - - - - - 3 times until frost (minutes) 60 60 60 150 z 180 39
EXAMPLE 6
The following formulations have been produced (example n G being a control) to more fully demonstrate the activation effect of the gel state of various substances
Parts by weight
Ingredients Example n ABCDEFG binder based on emulsion (AC-33 Rohm & Haas) 40 40 40 40 40 40 40 colloidal silica (table 1, n 8) 80 80 80 80 80 80 80 ethylenediaminotetraacetate tetrasodium 1.5 1.5 1 , 1.5 1.5 1.5 1.5 1.5 triethyl borate 1.5 zirconium n-butoxide 1.5 1.5 bad vanadium ethylate mixture 1.5 niobium ethylate 1.5 gamma aminopropyltriethoxysilane 1.5 time to frost (hours) <17 (20 <0s75 (5 <3 <3,920
Various other ingredients described above and varying amounts of the ingredients listed above can be used in place of the example ingredients to achieve equivalent results. Likewise, the various example techniques can be changed in practice and be adapted in particular to the various semi-solid compositions cited as an example in pending application no. series 912.807 mentioned and cited for reference.

 The term "stable" is used throughout the description and claims to define the semi-solid or solid coating compositions of the invention.

The components of the gelling system are used so as to obtain the desired peak and end point values after substantially total interaction between the colloid and the electrolyte present. A certain shift of these values over time is typical, but the expression "stable" in the present description means that, even if these values shift moderately over time, the coating compositions of the invention have a commercial life. usable during which the semi-solid or solid product can be brought to acceptable transfer and application viscosities by application of a relatively low shear force with a relatively low shear rate, as exercised by a person using painting equipment, for example a tampon applicator, with an acceptable paint viscosity.

 The invention has been described above with reference to what is now considered to be its best embodiments. It is understood that, within the framework of the appended claims, the invention can be implemented other than that which is specifically described.

Claims (11)

 1. A gelled coating composition, capable of being applied and of spreading on a solid support, comprising:  a) a film-forming polymer dilutable with water,  b) water,  c) an electrolyte, and  d) a colloidal gelling agent, gellable by interaction with said electrolyte, in an amount sufficient to gel the composition, when it has substantially interacted with said electrolyte, in order to form a semi-solid or a stable solid and to provide a dilutable composition up to the viscosity of application of the coating after application of a relatively low shear force with a relatively low shear rate,  e) said gelled coating composition, after having been sheared to the application viscosity of the coating, not finding the substantial gel structure produced by the colloidal-electrolyte gelling agent, said composition being characterized in that it further contains an amount of at least one compound increasing the rate of formation of the gel structure of formula or is hydrolyzable in situ to effectively provide at least one compound of formula  R M (OH)  y-x in which M is boron, aluminum, silicon, tin, titanium, zirconium, vanadium, niobium, hafnium, tantalum; x is 0 or 1; there is the valence of M and R is an organic fraction attached to M through a carbon-M bond, or else a condensation product thereof or a combination thereof; said amount being sufficient to reduce the time necessary for the formation of said gelled composition.  2. A gelled coating composition capable of being applied and of spreading on a solid support comprising  a) a water-dilutable film-forming polymer which is an electrolyte,  b) water,  c) a colloidal gelling agent which can be gelled by interaction with said electrolyte, in an amount sufficient to gel the composition, when it has substantially interacted with said electrolyte, in order to form a semi-solid or a stable solid and to provide a composition which can be diluted up to '' to the application viscosity of the coating after application of a relatively low shear force with a relatively low shear rate,  d) said gelled coating composition, after having been sheared to the application viscosity of the coating, not finding the significant gel structure produced by the colloidal-electrolyte gelling agent, said composition being characterized in that 'it also contains a. amount of at least one compound increasing the rate of formation of the gel structure of formula - or is hydrolyzable in situ to effectively provide at least one compound of formula  RxM (OH)  y-x in which M is boron, aluminum, silicon, tin, titanium, zirconium, vanadium, niobium, hafnium or tantalum; x is 0 or 1; ffi is the valence of M and R is an organic fraction attached to M through a carbon-M bond or else a condensation product of these or one of their combinations; said amount being sufficient to reduce the time necessary for the formation of said gelled composition.  3. Composition according to one of claims 1 or 2, characterized in that M is boron, silicon, aluminum, titanium or zirconium.  4. Composition according to any one of claims 1 to 3, characterized in that the compound increasing the rate of formation of the semi-solid composition corresponds to the formula RnSi (OR) 4-n in which n = 0, 1 or 2 and (OR ') is -OH or a group hydrolyzable to -OH.  5. Method for forming a gelled coating composition, capable of being applied and of spreading on a solid support, said coating composition, after having been sheared to a viscosity of application of the coating, does not recover not the gel structure produced by the colloidal-electrolyte gelling agent, said process consisting in mixing with a preformed aqueous coating composition: an electrolyte and a colloidal gelling agent, gellable by interaction with said electrolyte in a sufficient amount, after substantial interaction with said electrolyte, to gel the composition in order to form a semi-solid or a stable solid and to provide a dilutable composition Up to a viscosity of application of the coating after application of a relatively low shear force with a relatively low shear rate, said process being characterized in that a quantity of quan is added to the composition, before the gel is formed tity of at least one compound increasing the rate of formation of the gel structure, of formula - or is hydrolyzable in situ to efficiently provide at least one compound of formula  RxM (OH)  y-x in which M is boron, aluminum, silicon, tin, titanium, zirconium, vanadium, niobium, hafnium or tantalum; x is 0 or 1; y is the valence of M and R is an organic fraction attached to M through a carbon-M bond or a condensation product thereof or a combination thereof; said amount being sufficient to reduce the time necessary for the formation of said gelled composition.  6. A method of forming a gelled coating composition capable of being applied and of spreading on a solid support, which coating composition, after having been sheared to a viscosity of application of the coating, not finding the gel structure produced by the colloidal-electrolyte gelling agent, said method consisting in mixing with a preformed aqueous coating composition containing an electrolyte: a colloidal gelling agent, gellable by interaction with said electrolyte in a sufficient amount, which interacts substantially with said electrolyte to gel the composition to form a semi-solid or a stable solid and to provide a composition which can be diluted up to a coating application viscosity after application of a relatively low shear force with a shear rate relatively low, said process being characterized in that a composition is added to the composition before the gel is formed. e amount of at least one compound increasing the rate of formation of the gel structure, of formula - or is hydrolyzable in situ to efficiently provide at least one compound of formula  R M (OH)  x y-x in which M is boron, aluminum, silicon, tin, titanium, zirconium, vanadium, niobium, hafnium or tantalum; x is O or 1; t is the valence of M and R is an organic fraction attached to M through a carbon-M bond or else a condensation product of these compounds or one of their combinations, said quantity being sufficient to reduce the time necessary for the formation of said gelled composition.  7. Method for forming a gelled coating composition capable of being applied and of spreading on a solid support, which coating composition, after having been sheared to a viscosity of application of the coating, does not find the gel structure produced by the colloidal-electrolyte gelling agent, said method consisting in mixing with an aqueous coating composition during the formulation of these ingredients: an electrolyte and a colloidal gelling agent gellable by interaction with said electrolyte in a sufficient amount, after substantial interaction with said electrolyte, to gel the composition in order to form a semi-solid or a stable solid and to provide a composition which can be diluted up to a viscosity of application of the coating after application of a force of relatively low shear with a relatively low shear rate, said method being characterized in that one adds to the composition , before the gel is formed, an amount of at least one compound increasing the rate of formation of the gel structure of formula - or is hydrolyzable in situ to efficiently provide at least one compound of formula  RXM (OH) y x  y-x in which M is boron, aluminum, silicon, tin, titanium, zirconium, vanadium, niobium, hafnium or tantalum; x is O or 1; y is the valence of M and R is an organic fraction attached to M through a carbon-M bond or else a condensation product of these compounds or one of their combinations, said quantity being sufficient to reduce the time necessary for the formation of said gelled composition.  8. A method of forming a gelled coating composition capable of being applied and of spreading on a solid support, which coating composition, after having been sheared to a viscosity of application of the coating, does not find the gel structure produced by the colloidal-electrolyte gelling agent, said method consisting in mixing an aqueous coating composition comprising a film-forming polymer electrolyte, during the formulation of these ingredients: a colloidal gelling agent, gellable by interaction with said sufficient electrolyte, after substantial interaction with said electrolyte, to gel the composition in order to form a semi-solid or a stable solid and to provide a composition which can be diluted up to a viscosity of application of the coating after application of a force relatively low shear with a relatively low shear rate, said method being characterized in that add to the composition, before gel formation, an amount of at least one compound increasing the rate of formation of the gel structure of formula - or is hydrolyzable in situ to efficiently provide at least one compound of formula RxM <OH) x in which M is boron, aluminum, silicon, tin, titanium, zirconium, vanadium, niobium, lthafinium or tantalum; x is O or 1; y is the valence of M and R is an organic fraction attached to M through a carbon-M bond, or else a condensation product of these compounds or one of their combinations; said amount being sufficient to reduce the time necessary for the formation of said gelled composition.  9. Method according to any one of claims 5 to 8, characterized in that M is boron, silicon, aluminum, titanium or zirconium.  10. Composition according to any one of claims 1 to 4, characterized in that the compound increasing the rate of formation of the semisolid composition is gamma aminopropyltriethoxysilane or ethyl silicate.  11. Method according to any one of claims 5 to 9, characterized in that the compound increasing the rate of formation of the semi-solid composition is gamma aminopropyltriethoxysilane or ethyl silicate.