FR2504932A1 - CONDENSED METAL PHOSPHATE-TYPE HARDENER COATED WITH REACTION PRODUCT OF METAL ALUMINATE AND / OR METAL BORATE AND SILICATE COMPOSITION THEREOF - Google Patents

Abstract

THE INVENTION CONCERNS A METALLIC PHOSPHATE CONDENSED INCLUDING A CORE OF METALLIC PHOSPHATE CONDENSED AND, ON THE CORE, A COATING CONSISTING OF A REACTION PRODUCT OF A METALLATE AND AN ACID, AS WELL AS PROCESSES FOR PREPARING THE METALLIC PHOSPHATE CONDENSED. COATED. IT CONCERNS AN AQUEOUS CURING COMPOSITION CONSISTING OF: A. A WATER SOLUBLE AND OR WATER DISPERSABLE SILICATE; B. A HARDENER OF CONDENSED METAL PHOSPHATE TYPE, THIS HARDENER CONSISTING OF A CORE OF CONDENSED METAL PHOSPHATE AND, ON THE CORE, A COATING CONSTITUTED BY A REACTION PRODUCT OF A METALLATE AND AN ACID; C. OF WATER. IT ALSO CONCERNS PROCESSES FOR PREPARING COMPOSITIONS ACCORDING TO THE INVENTION AND THEIR APPLICATION TO THE COATING OF SUBSTRATES.

Description

1 2504932

  Concerns about environmental pollution

  resulted in the technicians covering and residing

  developing grade curable compositions

  in organic solvents which are zero or at least substantially reduced

  In addition, the high cost and scarcity of by-products

  petroleum companies have made it desirable to develop

  curable conditions which are entirely, or at least

  - large part, based on inorganic components.

  Inorganic coating compositions based on alkali metal silicates and inorganic-type hardeners are, however, preferred. However, when mixing alkali metal salts and ph-type hardeners: inorganic, it tends to appear rapidly coagulation, solidification or other similar phenomenon,

  made of the strong reactivity between silicate and phospha-

  Thus, the compositions based on silicates of

  hulls and hardeners of the metal phosphates type

  dent to have relatively low longevities In addition,

  because of this high reactivity, the compositions of

  acidic alkali and hardener phosphate type contain-

  generally, unwanted particles or lumps.

  These particles or lumps are troublesome, for example, when

  spray application of compositions containing them.

  In addition, their presence in hardened coatings obtained at

  from such compositions is highly undesirable.

  US Pat. No. 3,930,876 discloses pretreatment

  using a silicate to a condensed phosphate hardener to form a slurry or paste The pretreated phosphate hardener slurry or paste is mixed with an aqueous solution of the modified silicate or silicate

  to prepare a coating or paint composition.

  The patent application FR 81 23 880 of 21 December 1981 in the name of the applicant describes a hardenable composition

  aqueous solution containing an alkali metal silicate and a

  aqueous pepper of the condensed metal phosphate type hardener with a base content sufficient to bring the pH of

  the hardener dispersion to more than 9.5 Such composites

  with the prescribed content in the base

  smooth, substantially free coatings

of lumps.

  The present invention relates to water-soluble and / or water-dispersible alkali metal-alkali silicate-based curable inorganic coating compositions which have long service lives.

  of the invention will emerge from the description of the invention

  tion. The present invention provides a coated condensed metal phosphate useful for curing metal silicates

  alkali dispersible in water and / or soluble in water.

  The coating of the condensed metal phosphate consists of a reaction product of a water-soluble metallate

  and / or dispersible in water and acid

  in water and / or dispersible in water is an alumina-

  This invention relates to a metal

  also a process for the preparation of the metal phosphate

that condensed coated.

  The present invention further provides a curable composition comprising a water soluble and / or water dispersible silicate and a phosphate hardener.

  condensed metal coated with a reaction product of

  water-soluble and / or water-dispersible and acid-soluble tallate The invention also provides a method of preparation

such a composition.

  In detail, the present invention relates to a coated condensed metal phosphate having a core of

  a condensed metal phosphate and, on this soul, a coating

  consisting of a reaction product of a water-soluble and / or water-dispersible metallate, which is preferably soluble in water, and of

  selected from a metal aluminate and a metal borate.

  The constituent acid may be the metal phosphate acid

  condensed acid itself Constitutive acid can also be

  an additional acid independently combined with phospha-

  metal and water-soluble and / or water-dispersible metallate The amount of the reaction product of aqueous metallate and acid present on the

3 25049 '

  condensed metal phosphate is from about 0.1 to about 50% and in practice from about 1 to about 15%, by weight based on the combined weight (or overall weight) of the metal phosphate

  condensed and of the aforementioned reaction product.

  The invention further provides a process for preparing coated condensed metal phosphate comprising:

  (A) the combination of an aqueous slurry of phospha-

condensed metal with

  (B) an aqueous solution and / or dispersion, preferably

  a solution of a metallate selected from an alumina-

  metal and a metal borate, the metallate being

  present in an amount sufficient to provide the phosphorus

  condensed metal pore a coating of about 0.1 to 50% and in practice about 1 to 15% by weight relative to the poic

  combined condensed metal phosphate and coating.

  Generally, the aqueous metalate is combined with the condensed metal phosphate slurry while the slurry H is about 4 to 10. For example, when

  combines an aqueous metal aluminate with the slurry a-

  condensed metal phosphate without the use of additional acid, the slurry can become

  clearly basic, as evidenced by the values of p H

  dyeing about 10 On the other hand, when combining an acid

  addition to the condensed metal phosphate slurry

  and aqueous metal aluminate, the pH of the suspension

  is in practice between 6 and 8

  In general, the combination of the aqueous slurry

  of the condensed metal phosphate and aqueous metalate maintaining the slurry at a temperature of about 25 to 950 C, preferably about 50 to 951 C and more preferably about

  at 950 C Special modes of preparing a phos-

  condensed metallic lighthé coated according to the invention, by the

  method according to the invention are described above.

  The present invention also provides an aqueous curable composition comprising: (A) about 10 to 45%, preferably about 10 to 32% and most preferably about 15 to 25% by weight of a water-soluble silicate and / or dispersible in water; (B) about 2 to 32%, preferably about 2 to 10 and,

  better, about 8 to 10% by weight of a phosphor-type hardener

  condensed metal lighthead, this phosphate type hardener

  condensed metal comprising a metal phosphate core

  condensed and, on the core, a coating consisting of a reaction product of a water-soluble and / or water-dispersible metallate and acid; and

  (C) water The metallate can be a metal aluminate

  metallic borate or a mixture thereof

  water soluble aluminate is preferred.

  The reaction product of the metalate and acid is

  between 0.1 and 50% and preferably between 1 and

  %, by weight based on the conjugate weight of the metal phosphate

  The rest of the aqueous curable composition is constituted by water and, optionally, by generally known pigments, fillers, additives or mixtures of these substances.

  amount of water present in the compositions according to

  can vary greatly depending on the intended use of a machine.

  In general, the aqueous phase of the compositions according to

  The invention has a water content of up to 90%,

  between 42% and 64%, and preferably between

  50 to 60% The water mentioned as constituent (C)

  above all water, of any origin,

  in the curable aqueous composition, for example

  the water quoted in (C) is understood to include water pre-

  alkali silicates generally known to be useful in

  in practice according to the present invention, as well as the water present in the aqueous dispersions of condensed metal phosphate typically carried out according to the present invention.

present invention.

  The fused metal phosphate core may be any condensed metal phosphate generally known for use in inorganic paints or silicate coating compositions. The fused metal phosphate may be prepared, for example, by dehydration.

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  from one or more orthophosphates to about 300 to 12001 C.

  For example, aluminum phosphate can be prepared

  evaporated to dryness of an aqueous solution

  30% by weight of Al (H 2 P 04) 3 and heating of the body

  at a temperature of about 400 to 500 ° C. Another example of a process for the preparation of condensed aluminum phosphate, described in US Pat. No. 3,943,231, consists in

  spray drying a relative solution or suspension

  dilution of an aluminum orthophosphate containing P 205 and A 1203 in the desired molar ratio in the final product at temperatures above 2501 C to ensure

  direct conversion to condensed aluminum phosphates

  DE 1 252 835 discloses a process for obtaining

  condensed aluminum phosphates according to which one evaporates

  that to dryness a solution of aluminum phosphate and subjecting the resulting body to a heat treatment in two stages at different temperatures Finally, methods of preferring condensed iron phosphates and condensed aluminum phosphates are described in the Bulletin of the

  Chemical Society of France, article 337, (1961), pages 2277-

  2282 and in the Bulletin of the Chemical Society of France,

  Article No. 221 (1962), pp. 1237-1243

  Condensed metal phosphates serving as a soul

  The present invention typically comprises the phosphors

  condensed aluminum phates Various condensed aluminum phosphates, as well as their methods of preparation, are described

  for example by Yvoire in the Bulletin of the Chilean Society

  France, (1961), article No. 337, pages 2277-2282 and in the Bulletin of the Chemical Society of France, (1962),

  Article No. 221, pages 1237-1243, where a list of

  Cyclic aluminum tetraphosphate (ie Form A

  Al (P 03) 3) and four long chain polyphosphates (as

  see forms B, C, D and E of Al (P 03) 3) As reported

  Yvoire, for example, these phosphates can be produced from

  luminium condensed by reacting P 205 and Al 203 in a molar ratio of from 4: 1 to 15: 1 US Patent 4,216,190

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  describes a process for the preparation of aluminum trimetaphosphate

  form B by addition of ammonium hydroxide con-

  centered with a solution of aluminum dihydrogen phosphate Al (H 2 PO 4) 3 to ensure the formation of a white precipitate which is converted directly to aluminum trimetaphosphate.

  form B, Al (P 03) 3, by a single time treatment.

high temperature.

  When it is a condensed aluminum phosphate that

  constitutes the soul according to the present invention, it is generally

  typically a linear condensed aluminum phosphate (ie one or more of the long-chain polyphosphates ie Al, B, C, D and E forms (P 03) 3) It is also possible to use according to the present invention a mixture of aluminum metaphosphate in form A with one or more

  long-chain aluminum polyphosphates (i.e.

  say the forms B, C, D and E of Al (P 03) 3) as the soul of the phos-

  condensed metallic lighthouse When a mixture containing aluminum metaphosphates of Form A and Form B is used as the core, the weight ratio of form B / form A aluminum metaphosphates is generally about 3: 5 to 4: 1 and of

preferably about 7: 3 to 4: 1.

  According to the present invention, the coating of the soul

  condensed metal phosphate consists of a

  reaction product of acid and a metal aluminate or

  metallic spleen soluble in water and / or dispersible in water It goes without saying that a mixture of aluminate and borate metal is to be considered as part of the

  The present invention can be any acid suitable for

  for the application of the coating on the phosphate core

  Condensed metal according to the invention

  condensed in a dispersion of metallic phosphate

  condensed, to render the dispersion acidic.

  appearing between the acid naturally present in such

  condensed metal phosphate dispersion and the metal

  aqueous solution, even without additional acid addition, serves as a pre-

  For example, according to a preferred embodiment, the phosphate dispersion is combined with the phosphate dispersion.

7 2504932

  condensed metal with aqueous metallic aluminate

  addition of any additional acid However, it is possible to combine

  add an acid or mixture of acids with the phos-

  condensed metal phate and aqueous metalate for

  Coating on condensed metal phosphate Examples of suitable back-up acids are:

  phosphoric, sulfuric, hydrochloric, hydrobromic, iodhy-

  nitric, perchloric, chloric, methane-sulfonic acid

  ethane-sulfonic, trichloroacetic and trifluoroacetic

  When using such an extra acid, it is the acid

phosphoric which is preferred.

  The metallate suitable for the purposes of the invention may be any soluble metallate or metal mixture

  in water and / or dispersible in water selected from among

  metallic minates and metal borates Aluminates

  metals, especially those soluble in water, are

  When metal borates are used according to the invention,

  Those soluble in water are preferred.

  Examples of suitable metal aluminates

  are sodium aluminate, potassium aluminate and a-

  Calcium luminate Sodium aluminate is used in practice. A solution of sodium aluminate can be prepared.

  type indicated for the implementation of the invention in dissol-

  water in enough sodium aluminate to obtain

  a solution of about 30 to 40% by weight of sodium aluminate

  It goes without saying that solutions with aluminum content

  metal paste greater or less than 30-40% by weight

  should be considered as falling within the scope of this

  Examples of suitable metal borates are sodium metaborate, potassium metaborate,

  sodium tetraborate and potassium tetraborate

  according to the invention, a metal borate is used,

  it is in practice sodium borate.

  Included within the scope of the invention are any fused metal phosphate, as well as any curable aqueous silicate compositions containing any condensed metal phosphate which has a fused metal phosphate core and, on the other hand,

8 2504932

  the soul, a coating consisting of a reaction product

  acid and a metalate which may be a metal aluminate

  metal borate or a mixture thereof, which

  regardless of how the coating is applied, we will describe

  certain typical modes of metal phosphate coating

condensed liquid.

  According to a first mode of operation for the coating

  condensed metal phosphate, a mixture of

  aqueous bond of condensed metal phosphate, an aluminate

  aqueous metal and an auxiliary acid such as

  described in order to maintain the pH of the slurry

  to about 4 and 10 and typically about 6 to 10 while maintaining the temperature of the slurry in the range of about 25 to 950 C, more

  50 to 950 C and usually 80 to 951 C Specifically, se-

  In this procedure, the metal aluminate is slowly added.

  However, it is also possible, without departing from the scope of the present invention, to

  the invention, add the aqueous metal phosphate slurry

  liquefied with aqueous metal aluminate Typically,

  the additional acid, such as those previously mentioned, is added slowly.

  cited above, to the condensed metal phosphate slurry

  during at least part of the addition of the aluminate

aqueous metal.

  We can certainly prepare the metal phosphate

  condensed coating using an aqueous slurry of phos-

  metal phase condensed at room temperature but,

  according to the first procedure, it is

  tially the aqueous slurry of metal phosphate con-

  at a temperature of from about 50 to about 950 ° C, and preferably from about 80 to 951 ° C, and the pH of the slurry is adjusted to about 4 to 10, and

  specifically 6 to 8, before combining the porridge with

  This metal p-amine can be condensed with the aqueous metal aluminate.

  place concurrently or not with the heating operation.

  In practice, the metal phosphate slurry is heated

  condensed during adjustment of the p H Adjustment

  The operation of the method as described above facilitates mixing.

  condensed metal phosphate with the aluminum aluminate

  than by increasing the fluidity of the metallic phosphate

that condensed aqueous.

  The initial adjustment of the pH of the phosphorus slurry

  metal pellet condensed according to the procedure described above.

  can be operated using an alkaline hydroxide, such as sodium hydroxide or potassium hydroxide, aqueous However,

  it is better to initially adjust the pH of the mixture.

  of condensed metal phosphate by the same use

  me of a metal aluminate, soluble in basic water.

  To the above-mentioned slurry of condensed metal phosphate, the aqueous metal aluminate is added slowly, partly at least at the same time as the makeup acid, so as to maintain the pH in the range of about typically from about 6 to 8, while maintaining a temperature of about 25 to 951 C, preferably about

  50 to 951 ° C and more preferably from about 80 to 950 ° C.

  metal luminate is determined by the percentage in

  weight of the reaction product to be deposited on the phosphate

  condensed metal; it is generally sufficient

  to provide on the condensed metal phosphate a coating of from about 0.1 to 50% and specifically from about 1 to 15% by weight based on the combined weight of the condensed metal phosphate and the coating.

  auxiliary acid normally added according to this procedure.

  is the one intended to maintain the p H in the inter-

  previously indicated valence It is believed that when using the makeup acid with the aqueous metal aluminate to coat the condensed metal phosphate, at least a portion, and probably a substantial portion, of the condensed metal phosphate coating results from the reaction. aluminate /

with the extra acid.

  Towards the end of the addition of the metal aluminate

  aqueous solution to aqueous metal phosphate slurry

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  condensed, the addition of acid may be

  so that the p H of the slurry after the addition of

  the metal aluminate is approximately 7.5 to 8.0

  If acid is added together with the alumina-

* until you have added all the metal aluminate, and if the pH is not then between 7.5 and 8.0

  approximately, one can possibly add a base, such as-

  aqueous alkaline hydroxide, to bring the pH into the

range from about 7.5 to 8.0.

  According to a second, preferred, procedure for

  condensed metal phosphate coating, we

  to slowly combine the aqueous metal aluminate, preferably in the form of a solution, with the aqueous metal phosphate slurry condensed so that the pH of the

  boiled water varies during the combination in an interval

  from about 4 to 10 No additional acid is added.

  with the aqueous slurry of condensed metal phosphate and

  aqueous metal aluminate according to this particular procedure.

  particular for the coating of condensed metallic phosphate

  The aqueous metal aluminate is combined with the kettle.

  aqueous solution of condensed metal phosphate maintaining the temperature of the slurry approximately between 25 and 951 ° C., preferably between 50 and 95 ° C. and preferably between 80 and 950 ° C. According to this procedure, it is believed that the coating of the condensed metal phosphate is partly at least the reaction product of the metal aluminate and the acid

  from the acidic condensed metal phosphate itself.

  As according to the first procedure previously described, the amount of metal aluminate used is determined

  the percentage by weight of the reaction product to be

  ser on condensed metal phosphate; it is generally sufficient to give on the condensed metal phosphate a coating at a rate of about 0.1 to

  % and specifically from about 1 to 15% by weight based on

  combined weight of condensed metal phosphate and

coating.

  It is possible to prepare the metallic phosphate

  condensed coating using an aqueous slurry of phos-

  metal phage condensed at room temperature, but typical

  According to this second procedure, the first step is to

  The aqueous metal phosphate slurry is condensed at a temperature of about 50 to 950 ° C and preferably

  about 80 to 950 ° C. As in the first mode of operation.

  re previously described, the p H of the

  condensed metal phosphate slurry at a

  4 to 10, and usually about 6 to 8, while initially bringing the slurry to a temperature within the above range.

  the condensed metal phosphate slurry can be o-

  aqueous alkaline hydroxide, or, preferably,

  the fact that a metal aluminate is used

soluble in basic water.

  According to a third procedure for the coating

  condensed metal phosphate, a combination of

  aqueous slurry of condensed metal phosphate, a borate

  aqueous metal and a make-up acid, as previously

  as indicated above, by the methods set out above in

  the description of the first procedure, except that

  an aqueous metal borate, specifically a metal

  aqueous sodium taborate with aqueous metal aluminate

according to the first operating mode.

  According to a fourth procedure for the coating

  condensed metal phosphate, one is satisfied with

  slowly combine an aqueous metal borate, preferably

  as a solution, with the aqueous slurry of

  condensed metal phosphate so that the pH of the mixture

  varies during the combination in the interval between

  From about 4 to 10, no additional acid is added to the aqueous slurry of condensed metal phosphate or

  aqueous metal borate, according to this particular procedure.

  The methods of combining the aqueous slurry

  condensed phosphate and aqueous metal borate se-

  In this mode of operation are set out in the description

  given above of the second mode of operation, except that

12 2504932

  a metallic borate metal aluminate

  than aqueous according to the second procedure.

  The condensed metal phosphate coated according to the invention is of interest as a silicate hardener in aqueous compositions according to the invention containing water-soluble and / or water-dispersible silicate, such as silicate-based cements and in particular of the

  Silicate-based coating compositions of such

  licates specifically include metal silicates

  water-soluble and / or water-dispersible, such as alkali metal silicates with a SiO 2: M molar ratio of approximately 2.0: 1.0 to 4.0: 1.0 and preferably between 3.3: 1.0 and 3.5: 1.0 M represents the alkali metal Preferably, silicates

  aqueous solutions include solutions or dispersions, preferably

  sodium and / or potassium silicate solutions,

  commonly called soluble glasses or orthosilicates Silicone

  Most preferably, the glass solids content of silicates of the compositions of the invention is approximately 10 to 45%, preferably 10 to 32%, by weight.

better, between 15 and 25%.

  Although the alkali metal silicates above

  are preferred, one can also use as a silicate

  of water-soluble and / or water-dispersible alkali metal silicates previously modified with an oxide or hydroxide of a metal such as Al, Ca, Mg, Zr,

  For example, V, Zn or Cs may be obtained.

  oxidized with hydroxide or hydroxide by mixing a solution

  aqueous solution of the appropriate metal oxide or metal hydroxide

  required with the aqueous silicate and heating the mixture with stirring.

  -1000 C for about 1 to 72 hours However, if the

  action is performed in a pressure vessel to a

  temperature exceeding 1000 C, the reaction time may be

  The amount of oxide or hydroxide can be

13 2504932

  be from 0.5 to 3.0 parts by weight per 100 parts by weight of the silicate (dry-solids recycled dry solids without water

crystallization).

  The amount (in solids) of the coated condensed metal phosphate hardener is

  curable aqueous positions according to the invention will

  approximately 2 to 32%, preferably 2 to 10%, and more preferably 8 to 10% by weight relative to the total weight of the composition.

  alkali metal silicate to metal phosphate solids

  that condensed is approximately included in the

  according to the invention, generally between 1.0: 1.0 and 10.6: 1.0, preferably between 1.7: 1.0 and

  , 6: 1.0 and more preferably between 1.9: 1.0 and 2.6: 1.0.

  The aqueous compositions can be prepared

  cissables of the invention by mixing the water-soluble and / or water-dispersible silicate with the hardener

  condensed metal phosphate type coated according to a

  for use, a water-soluble base is mixed with the aqueous dispersion of phosphate type hardener

  condensed before combining the hardener with the silicate.

  The water-soluble base is mixed with the dispersion a-

  of the condensed phosphate type hardener until the pH of the mixture is at least 9, preferably greater than 9.5, and more preferably at least 10.

  a composition according to the invention by mixing the dispersion

  aqueous solution of coated condensed phosphate and the water-soluble and / or water-dispersible silicate, while the pH of the condensed phosphate dispersion is

  appropriate value as indicated above Examples

  bases that can be used to identify the p H of the dis-

  aqueous persion, condensed phosphate are:

  alkali metals, such as sodium hydroxides,

  of potassium and lithiu 1 ,: hydroxydes iamm ,, niiim qua

  ternary such as hydra \: s'> tetraethyl-arum arum

  and tetraethanolammonium; Ammonia, amines, such

  triethylamine and 3- (diethylamino) -propan-1

  ol; tertiary sulfonyl hydroxides, such as

14 2504932

  trimethylsulfonium and triethylsulfonium hydroxides;

  quaternary phosphonium hydroxides, such as hydro-

  tetramethylphosphonium and tetraethylphosphonium oxides;

  organosilanolates, such as γ-aminopropylsilantriola-

  tripotassium, N - (, '- aminoethyl) aminopropyl silane

  tripotassium triolate, dimethylsilandiolate dipotassi-

  that, potassium trimethylsilanolate, dimethylsilandiolate

  of bis-tetramethylammonium, bis-dimethylsilandiolate

  tetraethylammonium, and tetraethyltrimethylsilanolate

  ammonia and mixtures thereof. Among the above-mentioned bases, the

  preferred are the alkali metal hydroxides, the hydroxides

  quaternary ammonium, ammonia and amines.

  Alkali metal hydroxides are particularly preferred.

  When using a database like those immediately

  above in a composition according to the invention, the percentage of this base present in the comiposition is approximately, in general, from 0.2 to 0.8% and

  preferably from 0.2 to 0.5%, by weight relative to the total weight of

  As previously stated, the base is mixed with the aqueous dispersion of hardener type

  condensed phosphate coated before mixing this hardener a-

  with water-soluble or water-dispersible silicate.

  As indicated above, the com: 1-itions of

  aqueous coating of the invention containing silicate

  in water and / or water-dispersible and phospha-

  Coated Condense Metallic may also contain pigments

  substances, fillers, additives or mixtures of these

  Examples of suitable pigments are: titanium dioxide, iron oxide red, iron oxide, manganese black and carbon black.

  also use mixtures of pigments A particular pigment

  The most preferred is titanium dioxide coated with alumina sold under the designation R-900 by the Pont de Nemours & Company Company. Optionally, pigments to be used

  in the coating compositions according to the invention can

  Also be coated with the reaction product of metal-

  water soluble and / or water dispersible and

  either separately or concurrently with phosphate

2504932

  Condensed metal Coating compositions

  such coated pigments would appear to have a long

  gévité (for example 8 days or more) still greater than that of coating compositions containing silicate, coated metal phosphate coated according to the invention,

and uncoated pigment.

  Aqueous coating compositions according to

  with water-soluble silicate and / or

Mtal 1 toque

  persistant in water, and coated condensed phosphatel have

  typically longevities of at least 8 hours, preferably reaching 24 hours and exceeding for some hours compositions "longevity" of a coating composition,

  the time during which a coating composition is

  aqueous solution according to the invention containing silicate

  It is substantially water-free and / or water-dispersible and the coated condensed metal phosphate remains substantially free of "lumps" and sprayable to a cured coating substantially free of lumps. The cured coatings prepared from compositions according to the present invention. invention resist

  at high temperatures, water, detergents and fis-

  suration. Among the fillers that can be used in the curable aqueous compositions according to the invention are the inert fillers and / or reinforcing fillers generally known to those skilled in the art. Examples of such fillers are: silica, mica, clay, Sand, glass fibers and steel fibers The fillers may be incorporated at any stage of the formulation of the compositions according to the invention. Among the additives which can be used in the curable aqueous compositions according to the invention are the generally known additives such as colorants. anti-foam additives, anti-blocking agents, preservatives, fluidity adjusting agents, surfactants, thickeners, fungicides and

  anti-mold agents These various additives may be

  at any stage of the formulation of the compositions se-

the invention.

16 2504932

  When pigments, fillers and / or additives are incorporated

  mentioned above to a composition according to the invention, it is possible

  use them in terms of volumetric percentages of solids

  ranging in general up to 80%, and specifically

  between about 32 and 80% and preferably between and about 60% by volume relative to the total volume of

  solids present in the composition.

  Curable aqueous compositions according to the invention

  find a variety of applications, for example in

  silicate-based cements and in particular in

  Silicate-based coating compositions are particularly

  lently indicated as coating compositions when

  that we want resistance to high temperatures,

  water and detergents can be applied to a large

  variety of substrates or substrates, inter alia, for example

  on wood, metal, glass, wall panels,

  such compositions of coatings are

  particularly interesting in certain materials or

  as a substitute for porcelain,

  hardening at moderate temperature The application of

  The coating compositions may be carried out by any known method, for example by soaking with a soaked, rolled,

  flow, on the rake, by spraying and by methods

  Analogs The techniques and spraying equipment generally known to those skilled in the art can be adopted. The compositions can be cured according to the invention.

  moderate or high temperature It is possible to carry out the drying at 1 '-

  air at ambient atmospheric temperature, but compositions

  so hardened coatings do not stand as well at 1 '-

  water, detergents and cracking than those hardened to

  moderate or elevated temperature In a general way

  Silicate-based coating positions according to the invention containing coated condensed metal phosphate can cure in relatively short times at high temperatures.

  not exceeding 100 O C or, normally, 200 OCs to

  sea smooth and durable coatings, substantially free

  lumps, resistant to heat, water and detergents.

  For example, such a coating composition having a wet film thickness of about

17 204932

  152 Am on a steel substrate can normally, a-

  by air drying, form by hardening a coating-

  lasting dryness of about 76 k Lm in about 60 minutes

  or less at about 220 C or less.

  The following examples illustrate the invention. Quantities and percentages are indicated by weight, except

otherwise stated.

  As used to qualify the result of a survey

  given, the word "positive" means that at the end of the

  sai, the coating shows no signs of deterioration

tion.

EXAMPLE 1

  (Preparation of a coated aluminum metaphosphate) (a) An aqueous slurry is prepared from 3009

  HB hardener sold by the Pennwalt Company (containing

  80% by weight of aluminum metaphosphate in B form

  and about 20% by weight of aluminum metaphosphate under

  A), 75 g of aluminum metaphosphate in A form and

  600 ml of water These bodies are mixed for about 16 hours.

  in a ball mill to obtain a slurry at 37.5% by weight solids and at pH 2.4 to 250 C.

  (b) 475 g of the mixture are heated to 90.degree.

  prepared according to (a) immediately above

  enough aqueous solution at 50% by weight of hydroxide

  sodium to bring the pH between 6 and 8.

  A 42.5% by weight aqueous solution of sodium aluminate is then added dropwise to the slurry.

  sodium and an aqueous solution containing 96% by weight of sulfuric acid

  by stirring the slurry and keeping the temperature between 85 and 950 C The simultaneous addition, drop by drop, of

  solutions of sodium aluminate and sulfuric acid is o-

  to maintain the pH of the slurry between 6 and 8.

  A total of 22.8 ml of the solution was used during the addition.

  42.5% sodium aluminate.

  The pH of the slurry is then adjusted to between 7.5 and 8. The slurry is then filtered and washed with water until

  that there is no detectable sulfate ions in the pre-

  cipitation with an aqueous solution of barium chloride.

18 2504932

  The solid product is dried at 120 ° C. and 189.5 g are obtained.

dry aluminum phosphate coated.

EXAMPLE 2

  (Preparation of a curable coating composition and a cured coating)

  (a) A hardener of the metaphosphate type is

  aluminum by mixing the components indicated in

Table 1 below.

TABLE 1

  Coated Parts by weight Aluminum metaphosphate / according to Example 1 165.7 Water 266.9 50% aqueous solution of KTP Pl 20.9 Strodex PK-902 3.6 Strodex SEK-503 6.5 Foamaster VL 4 2 , 3 Attagel 405 14.7 Micromica C-10006 94.4 Minusil-107 20.9 Pigment 8 143.6

  1 solution with 50% potassium tripolyphosphate.

  2 Surface active agent, specialty of Dexter Chemicals Corp. 90% solids including potassium salts of organophosphates. 3 Surface Agent, specialty of Dexter Chemicals Corp,

  at 50% solids comprising potassium salts of

  ganophosphates. 4 Defoamer sold by Diamond Shamrock Corp. Clay additive sold by Englehard Minerals Corp. 6 Mica sold by English Mica Corp.

19 2504932

  7 Charge silica sold by PGS Corp. Black Shepherd No. 1 sold by Shepherd Chemical Co. The mixture was then adjusted to 10.5 with 12.7 parts by weight of a 50% by weight aqueous solution of potassium hydroxide. resulting is a hardener of the metaphosphate type here called 2 A.

  (b) A hard coating composition is prepared

  soluble at 46.5% solids, here called 2 C, by mixing

  components shown in Table 2 below.

TABLE 2

  Composition 2 C (parts by weight) Hardener 2 A 731.9 Water 78.8 Aqueous sodium silicate 1 698.7 Aqueous potassium silicate 2 349.4 1 A 37.9% solids; molar ratio Si O 2 / Na 20 = 3.40

  2 At 38.8% solids; molar ratio Si O 2 / K 20 = 3.30.

  The curable composition 2 C remains liquid and

  sprayable even after two days.

(c) The curable coating composition 2 C is sprayed on several steel panels two days after the preparation of this composition The wet films are substantially free of lumps and have a thickness of about 152 μm. air dry

  at room temperature, and then, by hardening,

  at 2200 C for about 1 hour, in durable coatings

  substantially lump-free, approximately

76, m thick.

  The hardened coatings carried by the

  panels to the tests below, with the results indicated.

  Cross-hatching the coating of a panel and applying adhesive tape to the surface

2504932

  striped coating When the adhesive tape is quickly detached

  of the panel, the coating remains intact, which reveals

  its excellent adhesion to the panel.

  After heating at 538 ° C. for one hour, the coating of another panel showed no sign of deterioration. We strip the coating of a panel and place the

  panel in a humid atmosphere cabinet with 100% humidity

  condensing temperature, at 37.8 C, according to ASTH D 1735-60 T, as described in Cardener's Paint Testing Manual

  and Sward, (1962) The coating gives no sign of

  after 1000 hours of residence in the cupboard

  TURE. A panel is placed in a 56.8 l detergent tank containing a 74 C La detergent formulation.

  detergent formulation contains 505 g of tetrapyrophospha-

  tetrahydrate, 107.7 g of anhydrous sodium sulphate

  39.7 g of sodium metasilicate, 5.7 g of

  anhydrous sodium, 113.4 g of sodium alkylarylsulfonate (yen

  by the Fisher Scientific Company under the designation S-198) and a sufficient amount of water to supplement to

  56.8 1 After 500 hours of residence in the reservoir

  the coating shows no evidence of deterioration

  tion. A panel is placed in salt spray at% by weight of salt, according to ASTM B 117, described in US Pat.

  Gardener and Sward's Paint Testing Manual (1962).

  does not show signs of deterioration after 1000

  hours of stay at 35 C in salt spray.

  Another board is immersed in water

  at 93 C After 48 hours in the water, the

  water shows no signs of deterioration.

  Example 3 below illustrates the following

  the invention, on aluminum metaphosphate, of a

  coating even more so than in Example 1, and the use of

  the use of phosphoric acid instead of sulfuric acid.

21 2304932

EXAMPLE 3

  (Preparation of coated aluminum metaphosphate) (a) An aqueous slurry was prepared from 280 g of HB hardener, 70 g of aluminum metaphosphate in A form and 400 ml of water, by blending the components with ball mill for 4 hours After the mixing is complete, an additional 100 ml of water is added to the mixture to obtain a slurry of 41.1% by weight of solids and

a p H of 2.7.

  (b) Each of two separate portions of

  425 g of the mixture prepared according to (a) immediately

  3 S and 3 S 'respectively, at 90 ° C. and with stirring. To each portion, then, enough aqueous solution containing 50% by weight of sodium hydroxide is added to bring the

p H in the range of 6 to 8.

  By shaking the 3S portion and keeping its temperature

  at a temperature of 900 ° C. + 40 ° C., 6.7 g of aqueous 42.5% by weight of sodium aluminate and 85% of aqueous solution are added dropwise thereto simultaneously. % by weight of phosphoric acid The pH is maintained between 6 and 8 during the dropwise addition. The addition of phosphoric acid is stopped immediately before that of sodium aluminate, and the remaining number of drops of phosphoric acid is added. sodium aluminate to adjust the pH to 7.5 Then the

  portion 3 S The resulting composition, here called 3 A,

  holds 32.6% by weight of solids and, once reduced to 20 C,

a p H of 6.8.

  Portion 3 S 'is treated in the same manner as Portion 3 S above, except that 17.0 g (11.0 ml) of 42.5% by weight aqueous solution of sodium aluminate is used. The resulting composition, referred to herein as A ', contains 31.1 wt% solids and, when reduced to 200 ° C, a pH of 6.3.

- 22 2504932

EXAMPLE 4

  (Preparation of two hardened coating compositions

  and from them two hardened coatings)

  (a) Two hardeners of the metaphosphate type are

  aluminum phate, here called 4 A and 4 A 'respectively, in

  mixing the components indicated in Table 3 below.

below.

TABLE 3

  Hardener 4 A Hardener 4 A '(parts in (parts by weight) weight)

Aluminum metaphosphate

  clad 3 A according to example 3 (b) 531.8 -

Aluminum metaphosphate

  3 'according to Example 3 (b) 519.1 A 50% aqueous solution of

KTPP * 10.5 10.5

  Strodex PK-90 * 7.3 7.3 Foamaster VL * 2.3 2.3 Attagel 40 * 14.7 14.7 Micromica C-1000 * 47.2 47.2 Minusil-10 * 20.9 20.9 Pigment of the TiO 2 type 110.6 110.6 * according to Example 2 (a) ** pigment of the titanium dioxide type coated with alumina sold under the designation R-900 by the Du Pont de Nemours & Company

  (b) The hardener 4 A is mixed with 2.28 parts

  by weight of aqueous solution containing 50% by weight of hydro-

  potassium hydroxide until a pH of 10.4% is obtained.

  then a curable coating composition

  holding 44.2% by weight of solids, here called 4 C, in

23 2504932

  components as shown in Table 4 below.

  under. Similarly, the hardener 4 A 'is mixed with 3.8 parts by weight of 50% by weight aqueous solution of potassium hydroxide until a

  After 10.5 hours, a hardened composition is prepared.

  43.9% by weight of solids, here called 4 C ', in terms of

  the components shown in Table 4 below.

under.

TABLE 4

  Composition 4 C Composition 4 C '(parts in (parts by weight) weight)

Hardener 4 A 747.6 -

Hardener 4 A '736.4 Water 32.1 32.1

Aqueous solution of silica

sodium salt * 698.7 698.7

Aqueous solution of silica

  Potassium * 349.4 349.4 Micromica C-3000 ** 47.2 47.2 * According to Example 2 (b) * Mica sold by English Mica Corp. (c) Several steel panels, collectively called PCs, are sprayed with the coating composition 4C shortly after its preparation until a thickness is obtained.

  wetted film of about 152 μm.

  the wet ones are substantially free of lumps.

  Several steel panels are sprayed,

  24 C, coating composition 4 C, twenty-four hours after its preparation, until a wet film thickness of about 152 is obtained.

24 2504932

  152 km Wet films are substantially free

of lumps.

  Several steel panels are sprayed,

  so-called PC ', the coating composition 4 C', shortly after its preparation, until a thickness is obtained

  wet film of about 152 μm.

  wet cules are substantially free of lumps.

  The air-dried compositions are allowed to air-dry.

  garment carried by all PC boards, P 24 C and PC ', then they are cured for about 1 hour

  at 2200 C in smooth coatings, substantially free from

  males, of a thickness of about 76 per cent.

  from each group to tests of exposure to

  their, at an atmosphere with 100% humidity of condensation,

  detergent and fog with 5% salt, as well as

  mersion in water, as described in Example 2 (c).

  These tests are carried out as in Example 2 (c) except

  formal contrary indication The results are indicated in

Table 5 below.

TABLE 5

TEST PC P 24 C PC '

  1 hour at 5380 C positive positive positive 1000 hours under positive 100% positive positive atmosphere

of moisture from

densification at 37.81 C

250 hours in

Detergent

  gent to 740 C positive positive positive 500 hours in fog to 5% salt to 351C positive positive positive 24 hours in water to 930C positive positive positive

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  A comparison of the above results obtained on

  panels of the PC and P 24 C groups indicate that the composi-

  considered coating, sprayed even 24 hours a-

  by its preparation, gives by hardening a durable coating free of lumps, just like the same composition

  sprayed shortly after preparation.

  The following example 5 illustrates the preparation according to

  the invention, without addition of acid, of aluminum metaphosphate

coated minium.

EXAMPLE 5

  (Preparation of coated aluminum metaphosphate) (a) An aqueous slurry was prepared from 600 g of HB hardener sold by Pennwalt Company (containing

  about 80% by weight of aluminum metaphosphate under

  me B and about 20% by weight of aluminum metaphosphate

  in the form of A), 150 g of aluminum metaphosphate

  Me A and 1000 ml of water are kneaded these bodies during

  16 hours in a ball mill to obtain a

  45.2% by weight solids having at room temperature

biante a pH of about 2.3.

  (b) To 1517 g of the slurry prepared according to (a)

  As above, 525.7 grams of Brown Shepherd No. 20 (a pigment sold by the Shepherd Chemical Company) was mixed to form

a pigmented slurry.

  (c) 2042.7 g of the pigmented slurry are then heated

  according to (b) immediately above by adding by

  intermittence of the distilled water.

  Termite of distilled water when a total of 1 ml of water was added and the temperature of the pigmented slurry

  to about 85% C, then 8.1 ml of

  aqueous solution containing 50% by weight potassium hydroxide

  bring the pH of the pigmented slurry to about 6, leaving

  At a temperature of about 90.degree. C., 314.7 g of aqueous sodium aluminate solution (41.1% by weight of sodium aluminate) are slowly added dropwise to the pigmented slurry, with stirring.

26 2504932

  this and maintaining the temperature between 85 and 95 C.

  Once the addition of the aqueous sodium aluminate solution has been completed, the pigmented slurry is stirred and allowed to return to room temperature. The resulting composition, referred to herein as 5A, contains aluminum meta-phosphate. coated, has a solids content of

58.7% and a p H of 7.2.

EXAMPLE 6

  (Preparation of a curable coating composition and, from it, of a cured coating)

  (a) A hardener of the metaphosphate type is

  aluminum, here called 6 A, by mixing the components

  shown in Table 6 below.

TABLE 6

  Hardener 6 A (parts by weight) Composition 5A according to Example (c) 451, 9 Water 68.1 Aqueous solution at 50%

KTPP * 20.0

  Strodex PK-90 * 3.5 Strodex SEK-50 * 6.2 256, Foamaster VL * 2.3 Attagel 40 * 14.0 Micromica C-1000 * 45.0 Minusil-10 * 20.0

* According to Example 2 (a).

  (b) 300 parts by weight of hardener 6 A are mixed with enough 50% by weight aqueous solution of potassium hydroxide to bring the weight of the hardener 6 A

at around 9.5.

  A curable coating composition with a solids content of 46% by weight, referred to as 6 C, is then prepared.

  mixing the components indicated in Table 7 below.

below.

TABLE 7

  Composition 6 C (parts by weight) Hardener according to Example 6 (b) 300 Water 20.8 Aqueous solution of sodium silicate * 257.6 Aqueous solution of potassium silicate * 128.8 Micromica C-3000 * 21.6 * According to Example 2 (b) ** Mica sold by English Mica Corp. (c) Spray on a steel panel, up to

  obtaining a film thickness in the wet state of

  152 Ap viron, the coating composition 6 C shortly after its preparation The wet film is substantially free

of lumps.

  The coating composition is allowed to dry at

  air and then cured at 220% C

  for one hour in a smooth coating, substantially free of lumps having a thickness of about 76 Am.

EXAMPLE 7

  (Preparation of a coated aluminum metaphosphate).

  (a) An aqueous slurry is prepared containing

  24.3% by weight of HB hardener, 6.2% by weight of metaphosphate

  aluminum pte form A, 23.0% by weight of Brown

  Shepherd No. 20 and 45.8% by weight of water by kneading

  ball milled for about 16 hours.

  (b) An aqueous solution of metaborate is prepared

28 2504932

  of sodium by dissolving 50 g of sodium metaborate

  Na 2 8204 8H 20 in 100 ml of water 750 g of the mixture are

  binds according to (a) immediately above at a temperature of

  at 900 ° C. Then enough of the solution is added to the slurry.

  The aqueous solution of sodium metaborate is then added dropwise to the slurry in the aqueous solution of sodium metaborate and an aqueous solution of wt. phosphoric acid, in a time of about

  15 minutes, stirring the porridge and keeping the temperature

  at about 850 ° C. The addition is carried out by simultaneous drip, so as to keep the pH of the slurry approximately between 6 and 8. The addition of phosphoric acid is stopped just before the addition of the sodium metaborate. , and the remaining drops of sodium metaborate are added to

  adjust the pH to 7.5. A total of 12.2 g of

  85% by weight of phosphoric acid in the course of

  simultaneous addition 509

  sodium taborate during the described operations of initial adjustment of p H and simultaneous dropwise addition The resulting composition, here called 7 A, contains 51.6% by weight.

  weight of solids and, after cooling to approximately

220 C, a p H of 7.1.

EXAMPLE 8

  (Preparation of a curable coating composition and, from it, of a cured coating)

  (a) A hardener of the metaphosphate type is

  aluminum lighthouse, here called 8 A, by mixing

  listed in Table 8 below.

29 2504931

TABLE 8

  8A Hardener (parts by weight) 7A coated aluminum metaphosphate according to Example 7 (b) 264.0 50% aqueous solution

KTPP * 9.2

  Strodex PK-90 * 7.3 Strodex SEK-50 * 2.8 Foamaster VL * 1.1 Minusil-10 * 9.2 Micromica C-100 * 41.8

* According to Example 2 (a).

  (b) 8A hardener is mixed with 10.2 parts by weight of 50% by weight aqueous solution of hydroxide

  of potassium until a pH of 9.8 is obtained.

  a curable coating composition, here called 8 C, by mixing the components shown in Table 9 below.

TABLE 9

  Composition 8 C (parts by weight) Hardener 8 A according to Example 8 (b) 339.9 Water 10.9 Aqueous solution of sodium silicate 247.2 Micromica C30002 10.2 Attagel 403 6.8

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  According to Example 2 (b) 2 According to Example 4 (b)

3 According to Example 2 (a).

  (c) Spray on several steel panels,

  collectively called PC 0, until a thick

  of about 152)> m, in the wet state

  coating position 8 C shortly after its preparation.

  moist acids contain some lumps

  the size decreases considerably during air drying. After letting the dandruff dry in the air at

  ambient temperature, the reaction compositions are

  clothing, by curing for approximately 1 hour at 2200 C,

  in coatings with a thickness of about 76 .mu.m,

  a small number of small lumps that could be

  more exactly, call small grains.

  Several steel panels are sprayed, collected

  called PC 24, until a wet film thickness of about 152 μm was obtained, the coating composition 8 C about 24 hours after its preparation.

  wet films are substantially free of lumps.

  These coating compositions are allowed to air-dry at room temperature and then cured.

  for about 1 hour at 2200 C in coatings sensitive-

  lump-free with a thickness of about 76 m.

  Panels from each group are tested

  from exposure to heat, an atmosphere with 100% moisture

  condensation, detergent and 5% fog

  of salt, as well as immersion in water, described in the ex-

  Example 2 (c) These tests are carried out as in Example 2 (c), unless otherwise stated formally.

  shown in Table 10 below.

31 2504932

TABLE 10

PC TEST PC 24

1 hour at 5380 C positive positive

575 hours under atmospheric

100% moisture content

condensation tee at

37.80 C

  Detergent tank deterioration at deterioration at

  at 740 C end of 150 hours last 150 hours

about 5% salt at 5% salt deterioration at

  at 350 C 350 hours after 350 hours

  about 24 hours in positive positive boiling water

  The results above indicate that this composi-

  coating, even 24 hours after its preparation.

  paration, gives by hardening a reasonable coating-

  durable, substantially free of lumps.

  Example 9 below illustrates the implementation according to the invention of a soluble metal aluminate in

  water and not dispersible in water.

EXAMPLE 9

  (Preparation of a coated aluminum metaphosphate)

  (a) 200 g of alumina are ground by ball mill

  substantially insoluble calcium, Ca A 1204, with sufficient

  of water to obtain a paste with 30.5% solids.

  An aqueous slurry was prepared containing 24.3% by weight of HB hardener, 6.2% by weight of aluminum metaphosphate in Form A, 23.7% by weight of Brown Shepherd No. 20 and 45.8% by weight of water by grinding the components in

  a ball mill for about 16 hours.

  750 g of the aqueous slurry are placed in a beaker.

  expensive steel equipped with an air motor attached to a blade to

32 2504932

  The slurry was stirred and heated to a temperature of about 60 ° C., to which was added 2 ml of a 50% by weight aqueous solution. of potassium hydroxide so as to increase the fluidity of the slurry. The slurry is then heated to a temperature of 850.degree.

  which begins to add the aluminum aluminate paste

  The calcium aluminate paste is added to the slurry in 10 minutes while maintaining the pH between 7.

  and 8 by simultaneous addition of a small amount of

  85% by weight of phosphoric acid.

  the addition of calcium aluminate paste and phosphoric acid

  Once complete, the total amount of calcium aluminate paste added to the slurry was 63.9 g, the total solution of 85% by weight of phosphoric acid added was 2.7 g and the pH was about 850. It is 7.6 We continue to shake the

  boiled while being allowed to come back to about the

  The resulting composition containing coated aluminum metaphosphate is here called 9 A.

EXAMPLE 10

  (Preparation of a curable coating composition and, from it, of a cured coating)

  (a) A hardener of the metaphosphate type is

  aluminum, here called OA, mixing the components

  shown in Table 11 below.

33 250493:

TABLE 11

  Hardener 10 A (parts by weight) Aluminum metaphosphate coated 9 A, according to Example 9 (b) 233.1 Water 25.0 Strodex PK-90 * 1.6 Strodex SEK-50 * 2.8 Foamaster VL * 1.1 Minusil-10 * 9.2 Micromica C-1000 * 41.8

* According to Example 2 (a).

  (b) IOA hardener is mixed with 6.3 parts by weight of 50 wt.% aqueous solution of potassium hydroxide to bring the pH to 9.8. A coating composition, here called 10 c, is then prepared. by mixing

  components shown in Table 12 below.

TABLE 12

  Composition 10 C (parts by weight) Hardener OA according to Example (b) 320.9 = Water 1 0.0 Aqueous solution of sodium silicate * 247.2 Aqueous solution of potassium silicate * 123.6 Micromica C -3000 ** 10.2 Attagel 40 ** 9.1

* According to Example 2 (b).

*** According to Example 4 (b)

*** According to Example 2 (a>.

  Several steel panels are sprayed, collected

  0 PC composition, until a wet film thickness of about 152 .mu.m is obtained, the composition 1 OC shortly after its preparation. The wet films are smooth and substantially free of lumps. The films are allowed to dry at room temperature. at room temperature, and then cured at about 2200 C for about one hour in durable, substantially free coatings.

  of lumps, approximately 76 μm thick.

  Several steel panels are sprayed, collected

  called PC 60 +, the coating composition l OC, 60 hours after its preparation is allowed the film to dry

  air at room temperature, then transform them by

  curing at 2200 C for about 1 hour in coatings

  durable, substantially free of lumps, approximate

63.5 MN thick.

  Panels from each group are tested

  from exposure to heat, an atmosphere with 100% moisture

  condensation, detergent, 5% salt and water immersion mist as described in Example 2 (c) These tests were carried out as in Example 2 (c), except where indicated formal Test results are indicated

in Table 13 below.

2d 04932

TABLE 13

  TEST o PC PC 60 + 1 hour at 5380 C positive positive

575 hours under atmospheric

  100% condensation moisture at 37.80 C Positive positive 575 hours Positive tank Deterioration at 740 C About 575 hours in fog at 5% Salt at 350 C Positive 24 hours in positive positive boiling water A comparison of the above results for

  panels of the O PC and PC 60 + groups indicate that this

  coating containing hardener prepared with the aid of

  of calcium aluminate dispersible in water, sprayed with

  even 60 hours after its preparation, gives hardening

  a durable, lump-free coating, just like

  the same composition pulverized in short time after its

repair.

36 2504932

Claims (14)

  1 Coated metal phosphate condensate, characterized   in that the coating of the condensed metallic phosphate   It comprises an acid reaction product and a metallate selected from a metal aluminate and / or a metal borate. 2 Condensed metal phosphate coated according to   claim 1, characterized in that the reaction product   is present at about 0.1 to 50% by weight based on the combined weight of the condensed metal phosphate and the reaction product.   3 Condensed metal phosphate coated according to one   Claims 1 or 2, characterized in that the phosphate   condensed metal is formed of a mixture of metaphosphate   of condensed aluminum in B form and of aluminum metaphosphate condensed minium in form A.   4 Condensed metal phosphate coated according to   claim 3, characterized in that the ratio by weight of   condensed aluminum metaphosphate form B / form A of melange   Ge is approximately between 3: 5 and 4: 1.   Process for the preparation of metallic phosphate   coated condensate according to any one of claims 1   at 4, characterized in that it comprises   (A) the combination of an aqueous slurry of phosphorus condensed metallic phate with   (B) an aqueous metallate which is a metal aluminate   metal borate or a mixture thereof, the metal   tallate being present in an amount sufficient to give the condensed metal phosphate a coating of about   0.1 to 50% by weight relative to the combined weight of phospha-   condensed metal and coating, with the maintenance of   slurry in the range of about 4 to 10.   Process according to Claim 5, characterized   in that the slurry is maintained at a temperature of viron 50 to 951 C.   Method according to one of claims 5 or 6,   characterized by maintaining the p H of the slurry between 37 2504932   About 6 and 8 during the combination of the porridge with the aqueous metallate.   A curable aqueous composition, characterized in that it comprises water, water-soluble and / or water-dispersible silicate, and metal phosphate.   condensed coated according to any one of the claims 1 to 4.   9 Composition according to claim 8, characterized   in that the metalate is soluble in water.   Composition according to claim 8, characterized   in that the metalate is dispersible in water.   11 Composition according to any one of the   8 to 10, characterized in that the metal phosphate   The coated condensed liquid is present in the composition   about 2 to 32% solids, by weight relative to total weight of the composition.   12 Composition according to any one of the   8 to 11, characterized in that the silicate is a   alkali metal salt with a SiO 2: M 20 molar ratio of   2.0: 1.0 to 4.0: 1.0, where M is an alkali metal;   in that the silicate is present in the composition   its about 10 to 32% solids by weight compared to   total weight of the composition; in that the metal phosphate   The coated condensed liquid is present in the composition   its about 2 to 10% solids by weight relative to the total weight of the composition; and in that the reaction product is present in an amount of about 1 to 15% by weight relative to   the combined weight of condensed metal phosphate and reaction duit.   13 Composition according to any one of the   8 to 12, characterized in that the metal phosphate   that the coated condensate is in the form of an aqueous dispersion, the aqueous dispersion containing a water-soluble base in an amount such that the pH of the aqueous dispersion is at least 9.   Application of the Cured Water Composition   according to any one of claims 8 to 13 in the clothing of a substrate.