FR2508475A1 - FORMULATIONS OF RICH ZINC PAINTS USING THE MANGANO-MANGANIC OXIDE PIGMENT - Google Patents

Abstract

A. THE INVENTION RELATES TO A PAINT ESSENTIALLY CONTAINING A RESIN AS A BINDER, A SOLVENT AND A COLORING PIGMENT. B. A MIXTURE OF ZINC AND MANGANO-MANGANIC OXIDE MNO POWDER FROM THE FUMES FROM THE MANUFACTURE OF FERROMANGANESE AND WHICH ARE OBTAINED DIRECTLY IN PARTICULATE FINES, IS USED AS A COLORING PIGMENT. C. MANGANO-MANGANIC OXIDE ALLOWS AN ADVANTAGEOUS REPLACE, IN SOME CASES, OF IRON OXIDES BY SIGNIFICANTLY IMPROVING THE CORROSION RESISTANCE OF PAINTS.

Description

Formulations of zinc-rich paints and using

  the manganic-manganic oxide pigment ".

  The invention relates to paints rich in zinc More specifically, it relates to paints

  rich in zinc containing the pigment manganese-manganese oxide

  smoke, which greatly improves the resistance

  corrosion of these paints.

  Zinc-rich paints are

  killed with a binder containing zinc powder.

  zinc concentration in a solvent-free binder is generally greater than 75% by weight when

  used as a unique pigment These paints are prepa-

  by mixing the zinc powder, together with

  other possible pigments, with a binder-resin a sol-

  and other ingredients known as

  The other possible pigments are intended to increase the corrosion resistance, and to produce a distinctive and pleasant color, when added to paint formulations, alone

  or in combination with other pigments In addition, pigments

  must be stable in order to maintain their

  color for an extended period.

  Another important requirement is that the pigments consist of very fine particles,

  less than 10 microns, for example

  Particle growth strengthens the ability of pigments to

  be easily dispersed in the paint during

  cation, allows a regular distribution of the paint

  in a thin layer when applied to an over-

  face, without any scratches or other imperfections, and

  thus, a uniform protection against corrosion.

  This last condition becomes very important in

  the cases where the paint is applied by conventional means

by brush or roller.

  In a current application, there is described a solvent-based paint formulation which uses an improved dye pigment consisting of the manganomanganic oxide (Mn 304) smoke or a material containing this oxide as the main constituent. discovered that Mn 304 smoke, when used as a coloring pigment, has a deep reddish-brown color, which is analogous to the brown coloration produced by synthetic iron oxide pigments, for example yellow iron oxides The Mn 304 has a particle size of about 10 microns which makes it suitable for uniform distribution throughout the composition. invention is prepared in the most advantageous manner by

  to pass a current of oxygen in a mass of ferro-man

  molten ganesis or on the surface of this mass Common ferro-manganese, produced in a blast furnace or in an electrometallurgical furnace, and other similar at temperatures of about 12000 C or more may contain up to 6 % and more carbon

  usually reduces this carbon content, for example

  about 1.5% oxygen or a mixture of oxygen and air in the melted ferro-manganese mass or

  its surface This operation takes place in a separate crucible

  which contains a mass of ferro-manganese melt freshly cast from an electric furnace whose

  temperature is about 10,000 C or more and preferably

13000 C or more.

  A process for reducing the carbon content of molten ferro-manganese is described in US Pat.

  U.S. No. 3,305,352 published on February 21, 1967, the disclosure of which

  The description is incorporated herein by reference.

  recommended process for producing mangano-manganese oxide

  that of smoke which is the subject of the invention, ferromanganese is cast from the electric furnace in which it was produced, in a treatment vessel such as a ladle or an oven, at a temperature of

  13000 C or more Preferably all schools are

  and then oxygen is blown off the surface of the molten ferro-manganese mass by an appropriate means such as one or more

  oxygen blowing maintained at approximately 25 mm above

  above the surface, so as to direct one or more

  Oxygen flow at a pressure of 7.750 kg / cm 2 to ensure good contact with this surface. Oxygen flow is approximately 1.8 to 2.25 kg per min for a mass of 225 kg of melt. , in a pocket of

  cm high and 5 D cm inside diameter

  may be multiplied to bring it to the desired scale. The lost gases thus produced contain

  very finely divided particles of manganese-manganese oxide

  spherical shape, which can easily be

  from lost gases by means of

current recovery.

  If desired, the mangano-manganic oxide

  of smoke according to the invention can be obtained as

  product of the specific process described in the U S patent

  NO 3 305 352 reduction of the ferro-

  In this case, the molten mass of ferro-manganese

  ganesis should be at a temperature of about 12500 C, and

  the oxygen will be blown on top at a sufficient speed

  to heat the bath to a temperature of 17,000 C before the carbon content of the molten metal

  was reduced to 1.50% of C The blowing of oxy-

  gene will continue until the temperature of the bath has

  ringworm about 1750 ° C as described in the patent.

  The mangano-manganic oxide smoke is recovered from the gases

lost in the usual way.

  The terms of Mn 304 smoke and oxide man-

  gano-manganic smoke used in the description of

  the invention and in the claims apply here

  finely divided spherical particles recovered from the fumes formed by the blowing of oxygen on the

  ferro-manganese in fusion as described above

  above. For this purpose, the invention provides an improved dye pigment for solvent-based paints,

  consisting of the manganomanganese oxide (Mn 304) of

  or a material containing the manganic manganese oxide smoke as the main constituent, and zinc powder The term "zinc powder" refers here to very fine particles of zinc, of average size between 2 and 40 microns The zinc-Mn 304 pigment may be used in the paint formulation together with a resin binder, solvent and other ingredients such as pigment thinners, suspending agents, etc. Smoke zinc-Mn 304 pigment can constitute 74 to 96% by weight of the total composition of the paint, on a solvent-free basis A preferred order of magnitude is

from 80 to 92% by weight.

  The invention is based on the observation that the manganic-manganic smoke oxide or a material which contains this manganic-manganic smoke oxide as the main constituent, in the finely divided or milled state, used as a coloring pigment in a paint

  solvent-based, high in zinc, produced on

  metal ports, coatings that exhibit

  corrosion resistance superior to that of the coating

  The corrosion protection provided by the paint formulation is a function of the ratio of manganomanganic oxide to zinc.

  When used as a color pigment

  mn 304 smoke has a reddish-brown color

  which is similar to the brown color produced by

  conventional synthetic iron oxide pigments,

  see red, yellow or brown iron oxide pigments, but however easy to distinguish from this brown color pigment Mn 3 o 4 may also be produced with

  a particle size that approximates the

  This last factor is very important in the preparation of solvent-based paints,

  for various reasons, namely that the fineness of the

  ticles strengthens the suspension properties and allows

  the pigment to be evenly distributed in the composition

  Generally, the Mn 304 smoke pigment should have a particle size such that about 98% of the particles are smaller than 10 microns in size. As indicated, the dye pigment used

  in the invention may be man-made oxide

  gano-manganic material or a material containing manganous oxide

  manganese smoke as the main component, ie

  in a proportion greater than 60% by weight. Such a material may be the fumigated mangano-manganic oxide mentioned above, which is obtained as a by-product

  the oxidation reaction of manganese at high temperatures

  erage in electro-metallurgical furnaces, during

  of ferro-manganese production.

  The manganic-manganic oxide of smoke pro-

  as described above and intended for the

  of the invention, has the following characteristics:

  vantes: Chemical formula: essentially Mn 304 Generally,

  it contains 96 to 98% by weight of mangano-manganese oxide

  that, the rest being a mixture comprising the oxides of calcium, magnesium, potassium and silicon, with less

  1% by weight of free metal manganese.

  Chemical analysis: (% by weight): 65.27 Mn; 2.03 Fe; 0.029 to 1; 0.28 Si; 0, 17 C; 0.040 P; 0.045 As; 0.46 Ca;

  1.43 Mg; 0.072 K; 0.023 Cr; and 0.002 Pb.

Bulk density: 720 1440 g / l.

  Humidity: 0.22% (1 hour at 107 ° C).

  Particle size: 98% less than about 10

  microns (99% have to pass through 325 mail Tyler sieve-

the).

  H: 9-13 (Mn 304 at 50% in H 2 O, distilled).

shape: spherical.

Density: 4.6 to 4.75 g / cm 3

  Thermal stability: no effect up to 6000 C.

  The current coating technology insists

  on the use of very fine colored pigments

  in order to enhance the coloring efficiency (

  see covering) suspension properties and homogeneity

  It has been discovered that the smoke Mn 304, when used as a coloring pigment according to the invention,

  have a particle size such as 98%

  particle size is less than 10 microns

  Mn 304 smoke obtained in electro-metallurgical furnaces

  by conventional methods, as described above,

  may contain from 1 to 20% of particles having a

  As a result, it may be desirable or even necessary in some cases to remove these large diameter particles from Mn 304 from

  This can be done for example by means of

  conventional sorting, or by shock processes

  such as ball milling. Manganese oxide

  The manganic smoke sorted or ground so that 98% of the particles are less than 10 microns, can be dispersed easily in the paint formulation, using a shear apparatus, such as the "Cowles Dissolver". The paint formulations containing smoke Mn 304 having particles of this order of magnitude generally apply to the surface to be treated without apparent scratches or scratches.

other imperfections.

  Solvent-based paint formulation

  according to the invention can be prepared using the most

  commercially available zinc powders, such as zinc powder, "Zinc dust L-15" produced by Federated Metals This material is of a size

  average particle size of about 5 microns.

  The paint formulations based on

  Zinc-rich pigment containing Mn 304 smoke coloring pigment according to the invention are composed in the following manner. Composition Ingredients Preferred Characteristics% by weight% by weight A Binder resin 4 25 8 20 B Zinc powder 43 90 47 68 C Pigment Mn 304 smoke 3 -38 20 36

D Other pigments, including

taken diluents from pig-

  Etc, fillers, etc. O 35 1 15 E Pigment suspending agent O -5 0.5 3 D Solvent * *

  * Depending on the desired application viscosity.

  Solvent-based paint formulation

  using a Mn 304 dye of smoke according to the invention.

  Alternatively, it can be prepared by known conventional methods. For example, the paint formulation can be prepared by mixing the resin binder with the smoke Mn 304, the zinc powder, the other pigments and pigment suspending agents, and the solvent. A medium shear apparatus can be used for this purpose, such as the U Cowles Dissolver "This apparatus is constituted

  by a vertical axis, having at its end

  a sawtooth propeller When rotating, this propeller gives the mixture of fluids and

  of pigments at a high speed, which creates conditions

  Other devices, such as a ball mill, may also be used, such as

  this will be obvious to specialists.

  The binder used in the paint formulation according to the invention may be one of the known conventional resins generally used for this purpose in the paint industry. Generally, the binder is chosen from one of the following four groups: ) Reactive binders such as epoxy resins derived from bisphenol A and epichlorohydrin, which are cured with polyamines such as polyaminoamides,

  diethylenetriamine, triethylenetetramine or amine

  coal tar; (2) air-drying binders such as those derived from the reaction of diglycidyl ether of bisphenol A and vegetable oil fatty acids; (3) solvent-soluble binders which cure by evaporation, such as bisphenol A polyhydroxyether derived from bisphenol A and epichlorohydrin (Phenoxy PKHH); and

  (4) binders traditionally used in systems

  moisture-hardening membranes, such as silicates from

  prepared by hydrolysis or polymerization of tetra-

ethyl silicate, alcohol and glycol.

  Polyaminoamide hardened epoxy resins

  of, usable as binder, are sold under the trade name Epon 1001 CX 75 (Shell Chemical); which is a condensation product of epichlorohydrin and bisphenol A This resin has an equivalent epoxy weight

  450-550 g per gram of epoxide equivalent (ASTM D-

  1652); it has a solids content of 75% in the methylisobutylketone / xylene mixture, in the ratio of 65:35. Suitable hardeners which can be used with this resin are marketed under the tradename Versamide 415 (General Mills) These hardeners are resins polyaminoamide reactive fatty acid based vegetable oils They have an amine value of 230-246 mg KOH equivalent relative to the nitrogen base content in a sample of 1 g and a viscosity of about 31 -38 poises at 75 C Epoxy resin binders

  ester, which can be used in oxidative drying systems.

  in the air, are marketed under the brand name Epotuf

  38-403 (Reichhold Chemical) Polymeric ethyl silicate

  risé is a good example of a suitable binder for a system

  Moisture-curing Soluble binders in soil

  and drying by evaporation of the solvent are the

  Polyhydroxy ethers derived from bisphenol A and epichlorophyll

  marketed by Union Carbide under the name of

"Phenoxy resins".

  Other suitable solvent-soluble binders that can be used in paint formulations are, for example, high molecular weight epoxy resins, alkyd resins, polyesters, chlorinated rubber, and vinyl chloride-acetate copolymers. vinyl, with or without hydroxyl function

or carboxyl.

  The mixture of manganic manganic oxide smoke and zinc powder pigment, can be used in the paint formulation according to the invention, alone or in combination with conventional coloring pigments, pigment diluents, fillers and inhibitors of For example, the Mn 304 smoke pigment can be used in conjunction with conventional TiO 2 pigments, as well as with various types of iron oxide pigments, for example red or yellow iron oxides. also be used, as

  talc, white clays (aluminum silicate

  The talc sold under the brand name Nytal 300 (RT Vanderbilt) is a good pigment extender for use in the paint formulation. In addition, other corrosion inhibiting pigments such as zinc chromate, example, can be used

in the paint formulation.

  An agent of sus-

  pigment board Suspension agents for the formation of

  painting are marketed under the brand Benton 27 (NL Industries) and are organic derivatives

  hydrated aluminum silicate and magnesium; the Kele-

  F (Spencer Kellog), that is, lecithin; and

Nuosperse (Tenneco Chemical Co).

  The solvent used in the paint formulation according to the invention can be part of the solvents

  or solvent mixtures commonly used in paints

  Solvent-based solvents Suitable solvents and solvent mixtures include ketones such as methyl isobutyl ketone (MIBK), aromatic solvents, and the like.

  and mixtures of ketones with aromatic solvents.

  Suitable aromatic solvents are, for example,

  xylene and toluene Another aromatic solvent used

  Sand is SC-100 (Exxon), which is based on diethyl benzene. Other common solvents that can be used are cellosolve (ethylene glycol mono-ethyl ether) and cellosolve acetate (ethylene glycol monoethyl ether-acetate), which are Two brands of Union Carbide Corp. Cellosolve acetate is particularly recommended for use as a solvent in systems employing phenoxy resins, as described above. In the case where the solvent-soluble binder is an alkyd resin, products are generally used. Likewise, when the binder is a chlorinated rubber, xylene such as toluene are good solvents. Other suitable solvents for these binders are ketones and / or ketone mixtures. paint formulation a mixture containing a third of xylene, a third of

MIBK and a third of cellosolve.

  The paint formulations according to the invention

  may also include various ingredients

  widely used in solvent-based paints.

  Thus various additives can be used to improve

  the film-forming properties of the film

  Among the commercially available products for this purpose, there is Beetle 216-8 (American Cyanamide) which is a urea resin in 60% solution in butanol / xylene; and the ethyl alcohol that is recommended

  for use with Benton 27 suspending agent.

  A viscosity control agent such as kieselguhr

  can also be used in the formulation of paints

  ture, for example the Celite, a mark of Johns Manville.

  Other ingredients which can be used as agents which avoid the formation of gases or water sensors are marketed under the trademark Syloid ZN-1 (W R Grace), which is a gel

  Silica Anti-skin agents are also used

  such as Ex-Kin N 12 (Tenneco Chemical Company).

  The invention will be better understood by means of

examples below.

Example 1

  A paint formulation based on

  was prepared by mixing 120 g Phenoxy PKHH (Union Carbide Corp); 30 g of Phenolic BKR-2620 (Union Carbide Corp); 1.1 g suspension agent, namely MPA-60 (NL Industries); 1.1 g of suspending agent, namely Silanoc 101 (Cabot Corp) which is a silane-treated pyrogenic silica; and 179 g of zinc powder, namely Zinc Dust L 15 (Federated Metals) Phenoxy PKHH and Phenolic BKR 2620 were dissolved in cellosolve acetate (Union Carbide), due to 21% solids. has been vigorously

  waved in a "Cowles Dissolver" for a sufficient time

  to ensure that all ingredients have been uni-

  formally dispersed in the paint formulation The solids content of the paint formulation was set at 84% by weight, or 48% by volume. This paint formulation was used as a reference in a

series of tests.

  The paint formulation thus prepared has been applied to several rolled steel specimens &

  cold, measuring approximately 100 x 150 mmn The application

  that was subjected to a heat treatment at 176 C during

  minutes The thickness of the coating film was measured

  the average thickness was evaluated to 0.017 mm

  The specimens were subjected to a salt spray corrosion test in accordance with ASTM B 117-73 and were classified in accordance with

  indicated in the ASTM standards (D 714-56, D 610-68).

Example 2

  Solvent-based paint formulation prepared with the same ingredients as in Example 1, except that instead of 179 g of zinc powder, 118 g of smoke Mn 304 was used. The solids content of this paint formulation was set at 78% by weight, ie 48% by volume. The paint formulations were applied to cold rolled steel specimens, as described in Example 1, with a layer thickness average of 0.015 mm The test pieces were subjected to the same salt spray corrosion test, and classified according to the mames

ASTM requirements.

Example 3

  A solvent-based paint formulation

  was prepared with the same ingredients as in the example

  2, except that here an increased amount of

  Mn 304 pigment, namely 147.5 g.

  The composition had a solids content of 83% by weight, 56% by volume. The formulation was applied to similar cold-rolled steel specimens, as described in Example 1, and the average layer thickness. was set at 0.017 mm The test pieces

  have been subjected to my 9 spraying corrosion tests.

  saline, and classified according to the same ASTM

Example 4

  A paint formulation based on

  It was prepared with the same ingredients as in Example 3, except that an increased amount of Mn 304 smoke was used here, ie 162 g. The paint formulation had a solids content of about 83%. weight,

  56% by volume The paint formulation was

  pleated on cold-rolled steel specimens,

  the manner described in Example 1, and the thickness of

  The average specimen was evaluated at 0.0196 mm. The specimens were then subjected to the same m 9 corrosion tests.

  saline spray, and classified according to the

ASTM records.

Example 5

  A paint formulation based on

  was prepared with the same ingredients as in Example 2, except that here a greater amount of Mn 304 smoke pigment was used, namely 177 g.

  84% by weight, ie 58% by volume.

  lation was applied to stainless steel test-pieces

  The test specimens were subjected to the same salt spray corrosion tests, as described in Example 1, and the average layer thickness was evaluated to 0.196 mm.

* classified according to the same ASTM requirements.

Example 6

  A paint formulation based on

  was prepared with the same ingredients as in

  example 1, except that here a

  zinc powder, 89.5 g, together with 59 g of Mn 304 smoke, The paint formulation had a solids content of 82% by weight, 48% by volume. The volume ratio of the Mn 304 to the zinc powder was 1: 1 The formulation was applied

  on cold rolled steel specimens,

  described in Example 1, and the layer thickness was evaluated to 0.017 mm. The specimens were then subjected to the same sputter corrosion tests.

  saline, and classified according to the same ASTM requirements.

Example 7

  A solvent-based paint formulation

  was prepared with the same ingredients as in the example

  6, except that here a smaller amount of Mn 304 of smoke, namely 39 g, was used in common with one more

  large quantity, 119 g of zinc powder The volume ratio

  In this case, the concentration of Mn 304 from smoke to zinc powder was 1: 2.

  in solids of 83% by weight, ie 48% by volume.

  The paint formulation was applied to

  cold-rolled steel vices, as described in

  example 1, and the average layer thickness was

  The specimens were then subjected to the same salt spray corrosion tests,

  and classified according to the same ASTM requirements.

  The results of the salt spray corrosion tests of Examples 1-7 are summarized in Table I below. Ln r% r (OC> Ln Cu LL e OT E t, t 7 ea 09 C 09 Z OOT 09 E 09 Z 09 C 09 E 09 E 09 Z OOT 09 E 09 Z OOT 09 E 09 Z el Il tocukl 1% q, the Ows awe aws there he

6 TI -'GE

  he He, his 6 th, or Tz ap aapnala DUTZ op Gapnod he 41,

"VOEUW

  a) E) ci E) c w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w w

(1148-9

IE 3-9

C 140-9

  he Il ail f 1 T 8.ldwox l 09 ú 09 Z le il OUTZ op gapnod kio las we LL a -P ^ Il 6 LI 1 geiiiiiiiiii B 1 Uawb Ta seaub Ta '4 W t (99 znetl) -409-4 % e nd, ega -4 ugui ST 6 op 94 T, 4 uvtlo t., Oc IDUTZ BP G Xpnod eu-es no From Al Roçpm; The results of Table I show that the paint formulation of Example 2, containing 48% by volume of smoke Mn 304 pigment, exhibits equivalent corrosion resistance. to that of formulations containing the same% by volume of zinc powder, up to 260 hours of testing It is well known that paint formulations containing zinc powder as a corrosion inhibiting pigment are well known for their good performance.

  under saline spraying conditions, and that is why

  what these paint formulations were primarily used for

  mainly as references It is also seen that, when

  that the amount of smoke Mn 304 is increased beyond 118 g or 48% by volume, the corrosion resistance of

  the wording does not increase but on the contrary, the efficiency

  quoted pigment as a corrosion inhibitor decreases strongly

  Lastly, Table I shows that we obtain

  results higher than those of the reference example,

  that the smoke Mn 304 is combined with the zinc powder, and that this improvement is valid for the entire duration of the test, ie 360 hours The effectiveness of the smoke Mn 304

  as a corrosion inhibitor in a paint formulation

  In most cases, zinc-rich

  volume port Mn 3 04-Zinc The best results are

  obtained when this ratio is about 1: 1 by volume.

  Phenoxy coatings, with manganomanganic oxide and zinc pigments, shown in Table I, were examined under a scanning electron microscope to compare coating surfaces to

  to determine the protection mechanism of these systems.

  After exposure to a 100 hour salt spray, the zinc particles of Example 1 coated with crystalline corrosion products, which have a tendency to clog the pores of the coating, and thus protect the substrate. of Example 2, on the other hand, appeared to be eroding nevertheless, its

  corrosion are probably capable of producing a coating

  passively on the surface of the steel.

  The protective action of the combination of

  Mn 304 of smoke and zinc is apparently due to the

  one or more new compounds, during the ex-

  salt spray position Crystal products

  The formation of corrosion during the course of corrosion is different from that which is formed either by zinc or by the Mn 304 of smoke during saline spraying. The formulation of these new products is likely to reduce the rate of penetration of the corrosive salt by their closing effect Hexagonal plates have been

clearly visible.

Claims (11)

REPRESENTATIVES) Paint formulation essentially containing a binder-resin, a coloring pigment and a solvent, having improved corrosion resistance, a formulation characterized by containing fine zinc particles and a pigment dye consisting of fine particles of mangano-manganic oxide smoke.   2) Paint formulation according to the   cation 1, characterized in that the manganomanganic oxide coloring pigment is smoke Mn 304, having the following characteristics: (a) Chemical composition with a content greater than 96% by weight of manganomanganese oxide, the remainder being consisting of a mixture of oxides of calcium, magnesium, potassium and silicon, with less than 1% by weight of free metal manganese, and (b) a thickness   particles such as 98% of the particles have a less than 10 microns.   A paint formulation characterized in that it consists of about 4 to 25% by weight of resin binder; about 43 to 90% by weight of zinc powder; about 3 to 38% by weight of Mn 304 smoke pigment; O to   about 35% by weight of other possible pigments, including   took diluents of pigments and fillers; from 0 to 5% by weight of a pigment suspension agent; the rest   consisting of a solvent in the appropriate proportion   required to obtain the necessary application viscosity.   ) Painting formulation according to the   cation 3, characterized in that it contains about 8 to 20% by weight of a resin binder.   ) Painting formulation according to the   cation 3, characterized in that it contains from 47 to 68% by weight of zinc powder.   ) Painting formulation according to the   cation 3, characterized in that it contains from 20 to 36% by weight of Mn 304.   7) Paint formulation according to the   cation 3, characterized in that it contains about 1 to% by weight of other possible pigments, including diluents and pigment fillers.   8) Formulation of paint according to the   cation 3, characterized in that it contains about 0.5   at 3% by weight of a pigment suspension agent.   9) Formulation of paint according to the   cation 3, characterized in that the binder is an epoxy resin derived from bisphenol A and epichlorohydrin which is cured with polyamines belonging to the group of polyaminoamides, diethylene triaminek triethylene   tetramine and coal tar amines.   10) Paint formulation according to the   cation 3, characterized in that the binder is a resin   drying in air, obtained by the reaction of the digly ether   of bisphenol A and fatty acids of vegetable oils the.   11) Painting formulation according to the   cation 3, characterized in that the binder is a solvent-soluble resin consisting of polyhydroxyether of   bisphenol A, bisphenol A derivative and epichlorohydrin.   12) Painting formulation according to the   cation 3, characterized in that the resin binder is a dealcoyl silicate prepared by hydrolysis or polymerization   tetraethyl silicate, alcohol and glycol.   13) Paint formulation according to the   cation 3, characterized in that the solvent is selected from   ketones, aromatic solvents and mixtures of keto and aromatic solvents.   14) Formulation of paint according to the   cation 3, characterized in that it further comprises a   additive for improving the film-forming ability   of a urea resin or ethyl alcohol lic.   ) Painting formulation according to the   cation 3, characterized in that it further comprises a viscosity adjusting agent.   16) Painting formulation according to the   cation 3, characterized in that it further comprises an agent suppressing the formation of gas or a water-sensing agent.