BE485449A - - Google Patents

Description

       

    <Desc / Clms Page number 1>
 



  Materials and method for protecting surfaces.



   The invention relates to materials for the protection of surfaces, and especially those which serve to protect surfaces against seawater and underwater organisms, those which are intermittently exposed to the action of seawater. sea and air, those which are permanently exposed to the action of air and the processes for preparing these materials.



   In general, the object of the invention is to provide coatings or coatings which are easy, convenient and quick to prepare, the elements of which can be obtained easily and are relatively inexpensive and which can be applied to surfaces. in a rapid, economical and efficient manner, and simple and inexpensive methods of preparing such coatings or plasters.



   Other subjects of the invention are as follows:

  <Desc / Clms Page number 2>

 a preservative coating which is substantially impermeable to seawater; a preservative plaster, the exposed surface of which is constantly toxic, which disappears by erosion due to its dissolution and / or its disintegration under the rubbing attack of the water in relative movement, at least as rapidly as the surface toxicity is removed by washing, so that a toxic surface remains permanently uncovered; coating of which the rate of erosion and the rate of leaching of the surface are in such a ratio that a surface of total toxicity remains permanently uncovered, but which, in general, does not destroy itself more quickly than it is necessary for it to maintain its toxicity;

   coating whose rate of washing from the surface is sufficient to maintain the necessary toxicity, but which is low enough for the necessary erosion rate to allow the coating to resist wear normally and give it wear resistance much greater than that of currently known plasters, all of which are attacked by organisms, and a permanently toxic layer, the minimum erosion period of which is three to five years and whose erosion rate is less than a quarter of a millimeter per year; a general formula for the preparation of a preservative coating and the manufacture of which can be directed so as to obtain erosion rates determined according to the needs corresponding to different leaching rates of various toxic compounds;

   a coating, one of the constituents of which consists of a partial polymer, the degree of polymerization of which can be adjusted during one or more operations in the manufacture of the coating; and a method of making this coating which allows the use of a large excess of catalyst;

  <Desc / Clms Page number 3>

 preservative coatings, of the above type, which can be applied hot or cold;

   coatings of this nature which do not char when hot applied, hot applied coatings containing a plasticizer which, while performing its usual function, also lowers the viscosity of the molten coating and makes it homogeneous before and after its application, from which it follows that once the coating has been applied, none of its constituents collects on the surface and that, consequently, the toxicity of its surface remains unaltered; hot-applied plasters, the softening temperature of which is chosen so that they do not soften, do not flow and retain their protective properties when these plasters or the materials to which they are applied are exposed to direct sunlight. 'summer;

   a process for making a cold-applied protective coating which is imparted to the desired toughness by incorporating therein relatively low proportions of curing agents consisting of very large molecule compounds; a coating for a surface exposed to the intermittent action of sea water and air for periods of varying durations; a durable coating, having adhesion and surface protection properties / and a coating, for the interior surface of a tank, the properties of which are not affected by the speed of entry and exit of the tank. 'sea water; seawater pipes in which no submarine organisms settle;

   an inert and impermeable to humidity coating, whether the surface to which it is applied is permanently exposed to the action of water, intermittently to the action of water and air, or permanently to the action of the air; a coating serving as a screen between a protective layer against fouling and the surface it is to protect.

  <Desc / Clms Page number 4>

 



   Other objects of the invention are, or obvious, or will appear later.



   Accordingly, the invention relates to the processes, the products produced and the substances having the characteristics, properties and relationships between their elements, which will be given by way of example in the following description of the processes, products and substances in question. question.



   All the coatings according to the invention are based on the presence of a certain fundamental constituent, the nature of which is variable, and the choice of the other constituents depends on the nature of the plaster that is desired to be obtained and on its mode of application. .



  The plasters can therefore be classified according to their mode of application and the use for which they are intended, namely: molten protective plasters, to be applied hot, anti-corrosive or protective plasters, melted, to be applied to hot, cold-applied preservative plasters and anti-corrosive or primer plasters, cold-applied. Since the basic constituent of all plasters is part of the group of chemicals known as materials plastics, they are sometimes called for abbreviation hot plastics and cold plastics.



   In general, all coatings can be considered to consist of the following substances classified according to their function
 EMI4.1
 
 <tb> Painting
 <tb>
 <tb> Vehicle <SEP> Pigments
 <tb>
 <tb> Solvent <SEP> Matrix <SEP> Toxic <SEP> Reinforcers <SEP> Others <SEP> (by <SEP> this <SEP>
 <tb> emple <SEP> agents
 <tb> Resin <SEP> Plasticizer <SEP> Agent <SEP> of <SEP> hardened <SEP> of inertia, <SEP> and
 <tb> safely.
 <tb>
 



   The hot melt coatings do not contain a solvent in the ordinary sense of this term and hence the vehicle becomes identical to the matrix and the two terms are synonymous.

  <Desc / Clms Page number 5>

 



  The choice of pigments depends on the use for which the coating is intended. The pigment in protective paints is obviously largely toxic material. That of anticorrosive plasters may contain inertia agents. In other cases, it may only serve as a dye. Strengtheners, which are generally substances intended to give body to the paint or impart other properties to it, can be incorporated into various plasters.



   Each of the two main categories of coatings or coatings forming the subject of the invention will be studied separately.



   Condom coatings.



   Although many different theories have been proposed to explain the mode of action of preservative coatings, it will suffice to refer to certain modern theories to explain the mode of action of protective coatings according to the invention. It is believed that fouling by underwater organisms is prevented by the presence on the coated surface of a solution which is toxic to organisms in that it prevents them from attaching to the surface, to some extent. way which does not seem to be perfectly known.

   The coating must therefore contain a toxic material soluble in seawater and retained in the binder or matrix of the coating, so as to be able to dissolve continuously during the useful life that must have. painting, at a speed at least as high as that which is necessary (and which will be indicated later) for the coating to retain its protective properties. According to some theories, this result can be obtained in several ways. The binder or matrix may be substantially insoluble in seawater, but must contain a sufficient proportion of toxic material so that all particles of this material remain in continuous contact.

   This type of Insoluble matrix paint works by allowing each particle to undergo the action

  <Desc / Clms Page number 6>

 seawater as soon as that above it has been dissolved and removed. A second type of paint layer in which the proportion of toxic material required may be lower, is sufficiently permeable to sea water to allow it to penetrate deeply into the paint and dissolve the toxic material, and to allow the dissolved toxic material to diffuse to the surface to exert its protective action. A third type of paint, which is especially the subject of the invention, is that whose matrix is soluble in sea water and whose action consists in a simultaneous loss of the matrix and of the toxic material.



   A review and compendium of the progress made in this field can be found in two articles entitled Action of anti-fouling paints "one of which has the subtitle" Maintenance of the leaching rate of anti-fouling paints formulated with insoluble, waterproof matrices "was published, pages 806-810, volume 38, n. 8, of the Journal" Industrial Engineering Chemistry "August 1946, and the other with the subtitle" Maintenance of the leaching rate of antifouling paints formulated with soluble matrices " was published, pages 931-956, vol. 38, n. 9, of the Journal "Industrial and Engineering Chemistry", September 1946.



   It is believed that the action of protective paints depends on the persistence on the plaster surface of a solution of toxic material in sufficient concentration to prevent underwater organisms from attaching themselves to it during the life of the paint. This solution is maintained by a substantially continuous dissolution of the toxic material of the paint, by the action of sea water. This action may be generally referred to as leaching, and its rate is determined. ends up being the overall rate of release of toxic material per unit area of paint per unit time. The benchmark for protective coatings is

  <Desc / Clms Page number 7>

 based on the toxicity of copper and hence it is convenient to compare the leaching rates with those of metallic copper.



  It has been considered that an average solution of 7-10 micrograms of copper per cm2 per day is sufficient to prevent fouling. A method of determining the rate at which copper leaches from protective paints is described in an article entitled Evaluation of antifouling paints by leaching rate determinations ", pages 456-460, volume 37, n. 5, of the Journal" Industrial and Engineering. Chemistry ", May 1945.



  When copper compounds, such as copper oxide are employed, their rate of leaching necessary to maintain the protective state must be chosen so as to release the minimum necessary quantity of copper and the rate of release. leaching is thus expressed, for example, in micrograms of copper per cm 2 per day. When other toxic materials are employed, their minimum leaching rate necessary to maintain the protective state is determined by their toxicity to submarine fouling organisms relative to that of copper. For example, it has been found that mercury is about 5 times more effective than copper in preventing fouling and, therefore, must be released at a rate of 2 micrograms per cm2 per day to prevent fouling. clogging.



   The tests carried out to date to prepare protective coatings have only given partially satisfactory results, because these coatings are toxic only for a fraction of their useful life, or their maximum useful life is too short. . For example, the composition of some earlier paints is chosen so as to make them permeable to water, which allows the element toxic to underwater organisms to wash off. But this also results in a weakening of the coating due to the action of water in the entire mass of the paint, which, as a result, disappears by friction or

  <Desc / Clms Page number 8>

 mechanically after a short time, and even before the paint is gone, sea water can reach and corrode the metal below the plaster.

   All waterproof protective paints are generally hard and brittle and will not erode away. They retain their toxicity only until the toxic element from their original surface has been leached out, and they are so brittle that considerable portions of the layer split, chip and / or break off. This exfoliation was recommended in United States Patent No. 1,421,914 of July 4, 1922, but it has been found, in practice, that it is not possible to regulate it, and that it is not. not uniform over the entire surface.

   At certain points, the paint inevitably loosens up to the metal it covers and it immediately results in organisms attaching to it and water and corrosion spreading below the surrounding surfaces of which the paint is so. destined to disappear completely.



   On the contrary, the protective coatings according to the invention are toxic throughout their useful life, and, since they are not fragile while they are exposed to the action of sea water, they do not crack. not. However, they are strong enough that their useful life is at least one year for 0.25 mm thick. In addition, you can give the layer the thickness you want.



   The toxic material of the coatings according to the invention washes off the surface. These layers are not industrucible when they are subjected to the action of seawater, but undergo chemical and / or mechanical erosion at a rate the ratio of which to that of the leaching of their surface is such that at no time is this leaching insufficient to prevent fouling.



  A sufficient toxic surface to prevent fouling is thus permanently provided.

  <Desc / Clms Page number 9>

 



   A resinous component which achieves just the desired rate of chemical and mechanical erosion is incorporated into the layer. According to an important characteristic of the invention, it is possible not only to adjust this regulating property of the erosion of the constituent, for any toxic material at will, but also to vary it to take account of the leaching rates of the components. different toxic materials.



   It has been found that, although some erosion is necessary to maintain the desired toxicity, the rate of erosion is so low that the plasters can withstand for several years without appreciable fouling occurring and without causing any significant fouling. 'they need to be replaced. The economy and the enormous advantages of these plasters over the best plasters currently known (which last from four to nine months) are immediately evident when one considers the expense of dry-docking and drying. removal of shells and old paint, the expense of material and labor for the application of a new coat and the loss which results from the immobilization of the vessel in dry dock.

   Perhaps even more important is the loss of speed of the ship whose hull is covered with shells, as well as the expense which results from the extra fuel required to keep it at normal speed.



   The amount of fuel to be consumed to reach a given speed is much greater when the ship is fouled.



   Likewise, fouling often limits the maximum speed that can be achieved, to a value significantly lower than the maximum construction speed, regardless of the amount of fuel consumed.



   The toxicity of the prior coatings during their relatively short toxic duration is variable and reaches a maximum for a very short time. On the contrary, that of the following plasters

  <Desc / Clms Page number 10>

 the invention is substantially constant throughout their useful life. In general, it is ensured that they disappear by erosion only at a rate just sufficient for their toxicity to have the minimum value necessary to maintain their protective action.



   When the plasters according to the invention have been exposed for a certain time to the action of sea water, they become covered with a thick layer of silt, more dense and of a more muddy nature than that which is has been found so far on previous entries. This thick sludge contains a higher copper content. It appears that the concentration of copper ions is related to the inability of underwater organisms to cause hardening of the binding materials which they secrete and that, therefore, they cannot attach strongly and are washed away by the relative movement of water.



   The protective coatings according to the invention can be applied hot or cold. As already stated, the toxic material support element of a hot-apply molten coating, generally referred to as a "vehicle", does not contain a solvent in the ordinary sense and consists of reality by the melted matrix. If the coating is to be applied cold, this support may contain a solvent or thinner and, in this case, the vehicle can be said to consist of this solvent and the matrix, or the vehicle may not contain solvent. and, in this case, the cold matrix, which must necessarily be sufficiently fluid so that the application can take place by any method chosen in advance, constitutes the vehicle.

   These liquid cold matrix coatings probably dry or harden by polymerization and / or oxidation of the liquid matrix, and not by evaporation of a solvent diluent. As has already been said, the dies of hot melt coatings and cold coatings contain cha-. some basic constituent, polymer or condensate,

  <Desc / Clms Page number 11>

 which may be identical in all the plasters but which preferably contains the same substances, in slightly different proportions, which have reacted under slightly different conditions.



   An examination of the nature of protective paints and the functions performed by their various elements, based on the foregoing considerations, will help to make the invention easier to understand. Protective paints include a film forming phase in which pigments which contain toxic materials are dispersed or suspended.



  The constituents must be such that, on drying or hardening, they form a film adhering to the surface to be covered and sufficiently flexible, compact and durable to resist destruction by mechanical forces. This film can be defined as being amorphous, resinous and possessing a certain degree of elasticity and plasticity. If its mode of action as a protective coating is based on the principle of disintegration by exfoliation and / or by dissolution in seawater, its duration must obviously be regulated to determine the rate of disintegration. Some constituents of protective paints can perform more than one function in the same paint and can be used for different purposes in different paints.



  However, it is convenient to define a constituent by its main function in the special paint under consideration.



   Since the elements of the matrix must form by drying, hardening or solidification of the paint, the film or homogeneous continuous matrix in which the pigments are coated, these elements must generally comprise a resin.



   Matrix.



   Resins:
We used natural resins, such as resin

  <Desc / Clms Page number 12>

 pine or shellac, as well as various processed natural resins, and synthetic resins. According to the invention certain novel synthetic resins or plastics prepared by reacting known substances in a novel manner, as well as synthetic resins modified with pine resin or other carbon-forming agents are employed. pine resin-like films. Most natural resins are acidic in nature and this property is advantageous in protective paints because it promotes solubility in seawater which is slightly alkaline.



   Plasticizers:
A plasticizer is a substance added to paint to form a softer film. In addition, a plasticizer can be used in hot melt paints to make them more fluid and to make the melt easier to apply.



   Curing Agents:
A curing agent is a substance added to a paint to increase the toughness and resistance to mechanical erosion of the paint film and thereby help to increase the life of the film. It can also be used to raise the softening temperature of a film and to stabilize the latter by improving its homogeneity and promoting the maintenance of a colloidal suspension. Curing agents are compounds with very large molecules, such as vinyl resins, ethyl cellulose, chlorinated rubber, cyclized synthetic rubber and other synthetic polymers.,
Solvent.



   The nature of the solvent in cold applied paints is determined to a large extent by that of the matrix elements. Commonly used solvents are ketones, alcohols, gasoline of tar naphtha, gasolines of petroleum and terebenthine.

  <Desc / Clms Page number 13>

 



   Pigments.



   The pigments of protective paints give them the toxic properties necessary for the protective action, give body to the coating and, consequently, maintain the desired thickness by adjusting the speed of application and give it strength and color. wanted. Inert pigments, commonly referred to as boosters, are sometimes added to aid in the suspension of heavier pigments and to prevent deposits from forming during storage.



   Protective plastic coatings to be applied hot.



   If we analyze the plastic protective coatings to be applied hot, which are the subject of the invention, based on the foregoing considerations and apply to coatings in general, and on the description which has just been given the constituents of protective paints, the "resin" of heat-applied plastic protective coatings includes what may be called a resin, but which is probably best defined as a partial polymer, that is to say a material which has not been completely polymerized but which has remained in an intermediate state of polymerization.

   Since the "resin" of the plaster can be regarded by itself as a resin and that, besides the resin referred to as the partial polymer, it can include pine resin or other substance which may be considered. Also called resin, the partial polymer will be referred to hereinafter, for clarity, by the word "polymer" or, where appropriate, "condensate", although it may itself be a reaction. - sine. The polymer is a condensation polymer of phenol or a homolog thereof with an aHyde, and for this reason it is often referred to as a phenoplast.

   The following phenols can be advantageously used:
Hydroxybenzene
Para substituted phenols such as p-tert-amyl phenol p-tert-butyl phenol

  <Desc / Clms Page number 14>

 
Cresol The following aldehydes can be advantageously used:
Formaldehyde Benzaldehyde Acetaldehyde.



  The resin further contains the film-forming compound which can be:
Pine resin
Abietic acid
Hydrogenated pine resin (found commercially as staybelite)
Acid "Petrex" (synthetic resinous polybasic acid of terpene, the main element of which is 3-isopropy1-6-methyl-3,6-endo-ethylene) (see the book "The technology of plastics and resins" by Mason in Manning, Van Nostrand,
1945)
Yacca gum
Pine resin-phenol (mixture of substituted isomeric phenols prepared by the reaction of pine resin with phenol in the presence of a boron fluoride catalyst) It is therefore seen that the film-forming compound prin - cipale is resinous in nature and must be acidic to the point of dissolving in seawater which is slightly alkaline (pH = approx. 8.1).

   Any resinous, acidic film-forming compound can probably be employed, provided that its solubility in seawater is of the same order of magnitude as that of pine resin and is compatible with others. constituents of paint.



   Plasticizers.



   Plasticizers serve two functions in hot applied melt coatings, as already indicated: they make the final film flexible and increase the fluidity or decrease the viscosity of the melted paint. A large number of plasticizers are available from which the following can advantageously be chosen:

  <Desc / Clms Page number 15>

 
Waxes or wax-like substances, such as animal and vegetable waxes, for example beeswax and sugar cane wax *; mineral waxes, such as paraffin and ceresin; micro-crystalline waxes; synthetic waxes, such as terphenyl, hydrogenated waxes and chlorinated waxes; fatty acids; metallic soaps; chemical plasticizers, such as esters and sulfonamides;

   natural plasticizers, such as vegetable oils and pine oils.



  Curing agents.



   The hardening agent added to a hot melt paint can perform certain functions, in addition to its ordinary function, which is to increase the resistance of the paint film to the erosive action of sea water. It can have the advantageous effect of raising the melting or softening point of the paint without undesirably increasing its viscosity. It tends to prevent the plastic flow of paint on the side of a ship in dry dock under the action of a bright sun and similar deformation of the paint under the shearing action of the high speed water.



  Substances of the following categories can be advantageously used:
Addition elastomeric plastics such as vinyl chloride, vinyl acetate, polyvinyl butyral, and copolymer of vinyl chloride and vinyl acetate,
Cellulosic plastics such as benzyl cellulose, ethyl cellulose, cellulose acetate, propionate and acetobutyrate;

  <Desc / Clms Page number 16>

 
Rubber and rubber substitutes, as well as their derivatives, such as natural rubber, chlorinated natural rubber, Buna.S, cyclized rubber and "thiocol".



  Toxic materials.



   The toxic material can be selected from the known substances available and suitable for this purpose, such as those which form dense metal ions, for example copper, copper compounds, such as cuprous oxide and verdigris, mercury compounds, such as mercuric oxide, and organic toxicants, such as DDT.



   The following examples indicate the composition of various products to be preferably chosen and their methods of preparation according to the invention. Unless otherwise indicated, the word "parts" refers to the stated proportions by weight and parts by weight of all of the listed elements relating to the hydrated, or solution, form of the constituents.



  Example 1 -
The polymer of this example is referred to as Liquid Phenolic Condensate 4A.
 EMI16.1
 
 <tb>



  Parts <SEP> Month <SEP> Report
 <tb> in <SEP> weight <SEP> @ <SEP> molar
 <tb>
 <tb> Phenol <SEP> (hydroxybenzene) ...... <SEP> 290 <SEP> 3.08 <SEP> 1.25
 <tb>
 <tb> Acetate <SEP> of <SEP> lead <SEP> (hydrated) ... <SEP> 130 <SEP> 0.34 <SEP> 0.14
 <tb>
 <tb> Solution <SEP> of <SEP> formaldehyde .... <SEP> 200 <SEP> 2.47 <SEP> 1
 <tb>
 
Lead acetate is of the normal commercial grade known as lead sugar and is hydrated as indicated by its formula Pb (C2H3O2) 2.3H2O. The formaldehyde used is in all the examples an aqueous solution at 37% by weight.



  The phenol and formaldehyde are reacted in the presence of lead acetate as a catalyst in any known manner, for example by a continuous flow process, at low speed.

  <Desc / Clms Page number 17>

 closely analogous to those described in United States Patent Nos. 1,660,403 of February 28, 1928 and 1,473,347 of November 6, 1923 and in British Patent No. 230,861 of March 16, 1925. Since the reflux process is the most common, its detailed description is given below. In this process, the phenol, lead acetate and the formaldehyde solution are introduced into a varnish kettle with a reflux condenser.



  The boiler is heated slowly until the temperature reaches about 65 C. Then the heating is carefully regulated due to the exothermic nature of the reaction, to prevent extremely violent boiling when the temperature is about to reach. reflux range from 99 to 100 C.



  Reflux is continued until almost all of the formaldehyde has combined. This point can be determined by noting that the odor of formaldehyde has substantially disappeared or by the hydroxylamine hydrochloride test described in the book A Laboratory Manual of Plastic and Synthetic Resins "by GF d'Alolio, edited by John Wiley & Son. This test shows that the free formaldehyde content at this time is about 1/20 mol per liter. Experience indicates that this time is usually reached after about 45 minutes.



  A very small proportion of lead acetate acting as a catalyst is sufficient to produce the reaction. But a relatively large amount is added in this operation so that it acts as a shock absorber throughout the formation of the compound.



  It is found that it is relatively not advantageous to add the excess of catalyst when the reaction is already advanced. The product prepared by this process is one of the variants to be preferably adopted of this fundamental constituent which exists in all the coatings targeted by the invention. Another variant giving good results and prepared in the same way is designated as follows and has the following composition:

  <Desc / Clms Page number 18>

 EXAMPLE 2. Liquid phenolic condensate 4B.
 EMI18.1
 
 <tb>



  Parts <SEP> Month <SEP> Report
 <tb> @ <SEP> @ <SEP> molar
 <tb>
 <tb> Phenol <SEP> (hydroxybenzene) <SEP> 290 <SEP> 3.08 <SEP> 1.25
 <tb>
 <tb> Acetate <SEP> of <SEP> lead <SEP> (hydrated) ..... <SEP> 33 <SEP> 0.09 <SEP> 0.04
 <tb>
 <tb> Solution <SEP> of <SEP> formaldehyde <SEP> 200 <SEP> 2.47 <SEP> 1
 <tb>
 Molar ratio.



   Although the molar ratio between phenol and aldehyde is 1.25: in the compositions, preferably chosen, which precede, it can be varied between wide limits provided that it does not become less than unity , to ensure that the final coating thus obtained adheres satisfactorily to a surface and melts without charring at the application temperature. A molar ratio lowered to 0.7 results in a coating which chars on prolonged heating at the application temperature.

   If one chooses, by way of example, the condensate 4B of Example 2 and if one varies the proportion of formaldehyde while maintaining constant that of the other elements, it is noted that the proportion of formaldehyde (anhydrous) less than that which is most suitable for the condensate 4B up to a minimum value of 1.3 parts per 10 parts of phenol and, which can vary above the preferred proportion, up to at a maximum value of 3.2 parts per 10 parts of phenol.

   In other words, the molar ratio between phenol and formaldehyde can vary from 2.5 to 1, as indicated;
 EMI18.2
 
 <tb> Parties
 <tb>
 <tb> Phenol <SEP> ........................ <SEP> 60
 <tb>
 <tb> Acetate <SEP> of <SEP> lead <SEP> (hydrated) ..... <SEP> 6.75
 <tb>
 <tb> Solution <SEP> of <SEP> formaldehyde <SEP> 20.6- (from <SEP> preference <SEP> 41.4) -
 <tb> 51.7
 <tb>
 Phenols
It is also possible to obtain, by different phenols,

  <Desc / Clms Page number 19>

 suitable polymers as indicated by the following examples, in which a ratio between phenol and formaldehyde equal to unity is adopted, only by way of example. The reaction proceeds in principle in the same way as in the previous examples.



  EXAMPLE 3.-
 EMI19.1
 
 <tb> Parties <SEP> in <SEP> weight
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> p-tert-amyl <SEP> phenol <SEP> ................... <SEP> 164
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Acetate <SEP> of <SEP> lead <SEP> (hydrated) <SEP> ........... <SEP> 60
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Solution <SEP> of <SEP> formaldehyde <SEP> ............. <SEP> 81
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> EXAMPLE <SEP> 4.-
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Hydroxybenzene <SEP> ....................... <SEP> 47
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Cresol <SEP> ............................... <SEP> 54
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Acetate <SEP> of <SEP> lead <SEP> (hydrated) ........... <SEP> 13.5
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Solution <SEP> of <SEP> formaldehyde ............. <SEP> 81
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> EXAMPLE <SEP> 5.

    <SEP> - <SEP>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> p-tert-butyl <SEP> phenol <SEP> ................... <SEP> 150
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Acetate <SEP> of <SEP> lead <SEP> (hydrated) ............ <SEP> 60
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Solution <SEP> of <SEP> formaldehyde .............. <SEP> 81
 <tb>
 
Mixtures of phenols are also satisfactory.



  Aldehydes
The following examples show changes in the aldehyde used to prepare the polymer, choosing for explanatory purposes only a ratio of phenol to aldehyde equal to unity. The process is generally the same as for formaldehyde, but the reaction temperature obviously varies with the various compositions.



  EXAMPLE 6.-
 EMI19.2
 
 <tb> Parties <SEP> Month
 <tb>
 <tb> Phenol <SEP> ............................ <SEP> 94 <SEP> 1
 <tb>
 <tb> Acetate <SEP> of <SEP> lead <SEP> (hydrated) <SEP> 53 <SEP> 0.14
 <tb>
 <tb> Acetaldehyde ...................... <SEP> 44 <SEP> 1
 <tb>
 <tb> EXAMPLE <SEP> 7.-
 <tb>
 <tb> Phenol <SEP> ............................ <SEP> 94 <SEP> 1
 <tb>
 <tb> Acetate <SEP> of <SEP> lead <SEP> (hydrated) <SEP> 53 <SEP> 0.14
 <tb>
 <tb> Benzaldehyde <SEP> ...................... <SEP> 106
 <tb>
 

  <Desc / Clms Page number 20>

 
Mixtures of aldehydes are also satisfactory.



   The following example relates to a preparation using a mixture of phenols and a mixture of aldehydes.



  EXAMPLE 7a. -
 EMI20.1
 
 <tb> Parties
 <tb>
 <tb> Hydroxybenzene <SEP> 47
 <tb>
 <tb> Cresol <SEP> 54
 <tb>
 <tb> Acetate <SEP> of <SEP> lead <SEP> (hydrated) <SEP> ................. <SEP> 60
 <tb>
 <tb> Benzaldehyde <SEP> 53
 <tb>
 <tb> Solution <SEP> of <SEP> formaldehyde <SEP> 41
 <tb>
 Catalysts.



   When lead acetate is used as a catalyst, its proportion can vary between 0.01 and 0.2 mol per mol of formaldehyde. The proportion per mol of formaldehyde is about 0.14 in the condensate 4A and about 0.04 in the condensate 4B which are those which are preferably adopted. The possible variations in the proportion of the catalyst are indicated in the following examples.



  EXAMPLE 8. -
 EMI20.2
 
 <tb> Parties <SEP> Month
 <tb>
 <tb> Phenol <SEP> ........................... <SEP> 94 <SEP> 1
 <tb>
 <tb> Litharge <SEP> ......................... <SEP> 4.5 <SEP> - <SEP> 20 <SEP> 0.02 <SEP> - <SEP> 0.09
 <tb>
 <tb> Solution <SEP> of <SEP> formaldehyde <SEP> 81 <SEP> 1
 <tb>
 EXAMPLE 9. -
 EMI20.3
 
 <tb> Phenol <SEP> ........................... <SEP> 94 <SEP> 1
 <tb>
 <tb> Acetate <SEP> copper (hydrated) <SEP> 4- <SEP> 18 <SEP> 0.02 <SEP> - <SEP> 0.09
 <tb>
 <tb> Solution <SEP> of <SEP> formaldehyde <SEP> 81 <SEP> 1
 <tb>
 EXAMPLE 10.-
 EMI20.4
 
 <tb> Phenol <SEP> ........................... <SEP> 94 <SEP> 1
 <tb>
 <tb> Salicylate <SEP> of <SEP> lead ..............

    <SEP> 4.8 <SEP> - <SEP> 28.9 <SEP> 0.01 <SEP> - <SEP> 0.06
 <tb>
 <tb> Solution <SEP> of <SEP> formaldehyde <SEP> 81 <SEP> 1
 <tb>
 

  <Desc / Clms Page number 21>

   Resin.



   To form "the resin", which is the main element of the matrix, the liquid phenolic condensate is mixed with the main resin-like film-forming substance. As already stated, this resinous film-forming or resin-like substance may be pine resin or some other substance having similar properties. The two varieties of resin to be preferably adopted are prepared from the condensates of Examples 1 and 2, as follows.



  EXAMPLE 11 Resin 4A.
 EMI21.1
 
 <tb>



  Parts <SEP> in <SEP> weight
 <tb>
 <tb> Condensate <SEP> phenolic <SEP> liquid <SEP> 4A <SEP> 128
 <tb>
 <tb> Resin <SEP> of <SEP> pin ......................... <SEP> 360
 <tb>
 <tb> EXAMPLE <SEP> 12. <SEP> - <SEP> Resin <SEP> 4B.
 <tb>
 <tb>



  Condensate <SEP> phenolic <SEP> liquid <SEP> 4B <SEP> 108
 <tb>
 <tb> Resin <SEP> of <SEP> pin <SEP> ........................ <SEP> 260
 <tb>
 
The liquid phenolic condensate is mixed with the pine resin which may be in the molten or solid state. The mixture is stirred and the temperature is allowed to rise to 135-163 C, but preferably about 149 C. Although this method is preferable and most convenient, the condensate can be heated and re-heated. pine sine in separate containers and mix them while hot, provided that at no time does the condensate temperature exceed that specified for the mixture. It is assumed that during this heating operation the condensate of the formaldehyde of the phenol continues to polymerize in part by dehydration.



  As is known, whatever the method applied, the heating of the condensate takes place at a constant rate, just sufficient to avoid the formation of an extremely abundant foam. For example, 30 to 45 minutes are required to bring to a temperature of 149 C a mixture of about 23.6 kg of a con-

  <Desc / Clms Page number 22>

 Hot phenol formaldehyde densate (at about 100 C) with about 78.8 kg of hot pine resin (at about 100 C). The mixture is allowed to cool and, when cooled, takes the form of a solid thermoplastic resin. When this resin is a phenol formaldehyde (hydroxybenzene), its acid number is about 130.

   The pH value of a suspension in distilled water of a complete protective coating, described below, prepared with this resin, is about 4 to 7 and thus fulfills the previously indicated condition of the acidic nature of the matri - these protective coatings of the soluble matrix type. Neither the acidity index nor the aforementioned pH values are used as a criterion in the preparation of the protective coatings according to the invention, but should only be considered as recognized characteristics of the products in question.



   Prolonged heating, such as results, for example, from the reheating required for the application of protective coatings containing this resin and which may last for six hours, does not appreciably modify the nature and properties of the product, provided that the maximum temperatures specified are not exceeded.



   The pine resin can be replaced, as the film-forming agent in the preceding examples, weight for weight, in part or in whole, by any of the following compounds:
Yacca gum
Petrex Acid "
Abietic acid
Hydrogenated pine resin ("Staybelite") or
Phenol resin or mixtures of two or more of these compounds. The following example shows the composition of type 4B resins containing various film forming agents.

  <Desc / Clms Page number 23>

 



  EXAMPLE 13.-
 EMI23.1
 
 <tb> Parties
 <tb>
 <tb> Phenol <SEP> ................................. <SEP> 60
 <tb>
 <tb> Acetate <SEP> of <SEP> lead ....................... <SEP> 6.75
 <tb>
 <tb> Solution <SEP> of <SEP> formaldehyde <SEP> 41.4
 <tb>
 <tb> A <SEP> of <SEP> compounds Following <SEP> <SEP>:
 <tb> Yacca Gum
 <tb> Acid <SEP> Petrex
 <tb> Acid <SEP> abietic <SEP> 360
 <tb> "Staybelite"
 <tb> Resin <SEP> of <SEP> pin-phenol
 <tb>
 
The next step in forming the matrix is to mix the resin with a plasticizer, also known, when it comes to hot melt plasters, as flux, since it serves to increase fluidity. of the melt. (In certain particular cases indicated below, the resin can also constitute the matrix on its own).

   The plasticizer and the resin are mixed and the temperature raised sufficiently to obtain a homogeneous mixture and a colloidal state. Preferably the temperature is about 149 ° C. The compounds serving as plasticizers are chosen, as is evident, from the thousands of plasticizers known to be fluid but not decomposing at the maximum temperature. preparation or application of the particular coating in which they are incorporated.



   To complete the preparation of a protective coating, a toxic material should be added. This is generally done by spraying the toxic material into the molten resin and plasticizer mixture which is stirred to cause the necessary wetting of the toxic material.

   In the case of cuprous oxide, this operation is carried out very easily at a temperature of about 149 ° C., while it is preferably carried out at lower temperatures with mercuric oxide which decomposes at high temperatures. . Various satisfactory compositions of products containing different film-forming agents, plasticizers, toxic materials and fillers or

  <Desc / Clms Page number 24>

 enhancers, are indicated in the following examples: EXAMPLE 14 - Paraffin with a melting point of 47 to 54 C.
 EMI24.1
 
 <tb>



  Parts
 <tb>
 <tb> Resin <SEP> 4B ................................ <SEP> 163
 <tb>
 <tb> Paraffin <SEP> ................................ <SEP> 99
 <tb>
 <tb> Oxide <SEP> copper ........................... <SEP> 116
 <tb>
 <tb> Silicate <SEP> of <SEP> magnesium <SEP> 30
 <tb>
 EXAMPLE 15. Paraffin with a melting point of
55 to 90 C.
 EMI24.2
 
 <tb>



  Resin <SEP> 4B <SEP> ................................ <SEP> 163
 <tb>
 <tb> Paraffin <SEP> ................................ <SEP> 99
 <tb>
 <tb> Oxide <SEP> copper ........................... <SEP> 177 <SEP> - <SEP> 750
 <tb>
 EXAMPLE 16.-
 EMI24.3
 
 <tb> Resin <SEP> 4B <SEP> ................................ <SEP> 163
 <tb>
 <tb> Naphthalene <SEP> chlorinated <SEP> ("Halowax") <SEP> ............ <SEP> 18 <SEP> - <SEP> 99 <SEP>
 <tb>
 <tb> Oxide <SEP> copper <SEP> ........................... <SEP> 177 <SEP> - <SEP> 600
 <tb>
 EXAMPLE 17.-
 EMI24.4
 
 <tb> Resin <SEP> 4B <SEP> ................................ <SEP> 163
 <tb>
 <tb> A <SEP> of <SEP> compounds <SEP> following:

  
 <tb> Terphenyl <SEP> ("Santowax")
 <tb> Wax <SEP> of <SEP> cane <SEP> to <SEP> sugar
 <tb> Wax Bee <SEP> <SEP> 18 <SEP> - <SEP> 99
 <tb> Acid <SEP> stearic
 <tb>
 <tb> Oxide <SEP> copper <SEP> ........................... <SEP> 300 <SEP> - <SEP> 750
 <tb>
 EXAMPLE 18.-
 EMI24.5
 
 <tb> Resin <SEP> 4B <SEP> ................................. <SEP> 163
 <tb>
 <tb> A <SEP> of <SEP> compounds <SEP> following:

  
 <tb> Linoleate <SEP> of <SEP> manganese
 <tb> Oleate <SEP> of <SEP> lead <SEP> 18 <SEP> - <SEP> 70
 <tb> Oleate <SEP> of <SEP> copper
 <tb>
 <tb> Oxide <SEP> copper ............................ <SEP> 116 <SEP> - <SEP> 300
 <tb>
 EXAMPLE 19.-
 EMI24.6
 
 <tb> Resin <SEP> 4A ................................. <SEP> 165
 <tb>
 <tb> Toluene <SEP> ethyl <SEP> sulfonamide <SEP> 9 <SEP> - <SEP> 29
 <tb>
 <tb> Oxide <SEP> copper ........................... <SEP> 116 <SEP> - <SEP> 177
 <tb>
 

  <Desc / Clms Page number 25>

 EXAMPLE 20. -
 EMI25.1
 
 <tb> Resin <SEP> 4A <SEP> ............................. <SEP> 163
 <tb>
 <tb> Oil <SEP> of <SEP> Tonga <SEP> ......................... <SEP> 43
 <tb>
 <tb> Oxide <SEP> copper <SEP> 99
 <tb>
 <tb> Green <SEP> of <SEP> gray <SEP> ...........................

    <SEP> 34
 <tb>
 <tb> Oxide <SEP> mercuric ....................... <SEP> 34
 <tb>
 EXAMPLE 21. -
 EMI25.2
 
 <tb> Resin <SEP> 4A .............................. <SEP> 163
 <tb>
 <tb> Paraffin <SEP> (Point <SEP> of <SEP> fusion <SEP> 47 <SEP> to <SEP> 54 C) <SEP> ... <SEP> 99
 <tb>
 <tb> Oxide <SEP> copper <SEP> 99
 <tb>
 <tb> Green <SEP> of <SEP> gray ........................... <SEP> 34
 <tb>
 <tb> Oxide <SEP> mercuric <SEP> ....................... <SEP> 34
 <tb>
 
A procedure to be preferably adopted for products such as those of Examples 19 and 20, containing mercuric oxide, consists in melting together the resin and the paraffin by raising the temperature to about 149 ° C. Then, while maintaining When the temperature is at this value, the cuprous oxide and the verdigris are sprayed into the mixture which is stirred to obtain a satisfactory dispersion.

   The heating is then interrupted and the temperature is allowed to drop to about 138 C; at this time, mercuric oxide is sprayed into the mixture which is continued to stir until a homogeneous product is obtained. If desired, this product, still liquid, can be passed through a colloid mill to further improve the dispersion of the pigments in the mixture.



   Various plasticizers can be incorporated into a product of the same composition to take advantage of the particular advantages of each of them. For example, paraffin tends to cause a melted coating to acquire low viscosity or high fluidity during its application, while metallic soaps, such as manganese linoleate, are particularly advantageous in. what they give plasticity to the film

  <Desc / Clms Page number 26>

 applied when dry. The following compositions are given by way of example.



  EXAMPLE 22.-
 EMI26.1
 
 <tb> Parties
 <tb>
 <tb> Resin <SEP> 4B <SEP> .................................. <SEP> 163
 <tb>
 <tb> Paraffin <SEP> (47-54 C) <SEP> ........................ <SEP> 40-85
 <tb>
 <tb> Linoleate <SEP> of <SEP> manganese .................... <SEP> 59-14
 <tb>
 <tb> Oxide <SEP> copper ............................. <SEP> 116-177
 <tb>
 EXAMPLE 23.-
 EMI26.2
 
 <tb> Resin <SEP> 4B <SEP> 163
 <tb>
 <tb> Paraffin <SEP> (47-54 C) <SEP> ........................ <SEP> 49.5
 <tb>
 <tb> Palmitate <SEP> of <SEP> copper ........................ <SEP> 17.5
 <tb>
 <tb> Oxide <SEP> copper <SEP> 116
 <tb>
   EXAMPLE 240-
 EMI26.3
 
 <tb> Resin <SEP> 4B .................................. <SEP> 163
 <tb>
 <tb> Paraffin <SEP> (47-54 C) <SEP> ........................

    <SEP> 49.5
 <tb>
 <tb> Oleate <SEP> of <SEP> lead <SEP> ............................ <SEP> 20
 <tb>
 <tb> Oxide <SEP> copper <SEP> ............................. <SEP> 116
 <tb>
 EXAMPLE 25. -
 EMI26.4
 
 <tb> Resin <SEP> 4B .................................. <SEP> 163
 <tb>
 <tb>
 <tb> Paraffin <SEP> (47-54 C) <SEP> ........................ <SEP> 90.5
 <tb>
 <tb> Acid <SEP> stearic <SEP> ............................ <SEP> 9-49
 <tb>
 <tb>
 <tb>
 <tb> Oxide <SEP> copper <SEP> ............................. <SEP> 116
 <tb>
 <tb> Silicate <SEP> of <SEP> magnesium <SEP> ...................... <SEP> 30
 <tb>
 EXAMPLE 26.-
 EMI26.5
 
 <tb> Resin <SEP> of <SEP> type <SEP> 4B <SEP> to <SEP> base <SEP> of <SEP> eraser <SEP> Yacca (ex.13) <SEP> 163
 <tb>
 <tb> Phosphate <SEP> of <SEP> tricresyle <SEP> ....................

    <SEP> 103
 <tb>
 <tb> Oxide <SEP> copper <SEP> ............................. <SEP> 177
 <tb>
 EXAMPLE 27.-
 EMI26.6
 
 <tb> Resin <SEP> of <SEP> type <SEP> 4B <SEP> to <SEP> base <SEP> of acid <SEP> "Petrex" <SEP> (ex.13) <SEP> 163
 <tb>
 <tb> Terphenyl <SEP> ("Santowax") <SEP> ..................... <SEP> 99
 <tb>
 <tb> Oxide <SEP> copper <SEP> ............................. <SEP> 177
 <tb>
 

  <Desc / Clms Page number 27>

 EXAMPLE 28.-
 EMI27.1
 
 <tb> Parties
 <tb>
 <tb> Resin <SEP> of <SEP> type <SEP> 4B <SEP> to <SEP> base <SEP> of <SEP> resin <SEP> phenol (ex.13) <SEP> 163
 <tb>
 <tb> Acid <SEP> oleic <SEP> ................................. <SEP> 16
 <tb>
 <tb> Oxide <SEP> copper <SEP> 177
 <tb>
 EXAMPLE 29 - Type 4B resin with one of the following compounds:

   
 EMI27.2
 
 <tb> Resin <SEP> of <SEP> pin
 <tb>
 <tb>
 <tb> "Staybelite" <SEP> 163
 <tb>
 <tb> Acid <SEP> abietic
 <tb>
 <tb>
 <tb>
 <tb> Paraffin <SEP> (47-54 C) <SEP> .......................... <SEP> 99
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Oxide <SEP> copper <SEP> ................................ <SEP> 177-750
 <tb>
 Curing agents.



   Curing agents, which must of course be of the type which will not decompose at the high temperatures of preparation and application of the plasters, can be added to the hot plastic compositions, although, as the preceding examples indicate, they are not. not essential for the preparation of satisfactory plasters. It is believed that, in addition to their primary function, curing agents help to keep plastic coatings hot in a suspended or colloidal state. Preferably, but not necessarily, the curing agent is generally mixed with the resin before adding the plasticizer. If the plasticizer is liquid, it may be convenient to first dissolve the curing agent in this plasticizer by heating and then mix this solution with the resin.

   Examples of compositions containing these curing agents are given below.
 EMI27.3
 
 <tb>



  EXAMPLE <SEP> 30.- <SEP> Parties
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Resin <SEP> 4B <SEP> 163
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Paraffin <SEP> (47-540C) <SEP> ........................... <SEP> 75
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Terphenyl <SEP> ("Santowax") <SEP> ........................ <SEP> 24
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Benzyl <SEP> or <SEP> ethyl <SEP> cellulose <SEP> ..................... <SEP> 2-4
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Oxide <SEP> copper <SEP> 116-177
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Silicate <SEP> of <SEP> magnesium <SEP> ......................... <SEP> 30
 <tb>
 

  <Desc / Clms Page number 28>

 EXAMPLE 31.- Parties
 EMI28.1
 
 <tb> Resin <SEP> 4A <SEP> ................................. <SEP> 163
 <tb>
 <tb> Paraffin <SEP> (47-54 C) <SEP> .......................

    <SEP> 38
 <tb>
 <tb> Wax Bee <SEP> <SEP> ............................ <SEP> 30
 <tb>
 <tb> Ethyl <SEP> cellulose <SEP> ........................... <SEP> 30
 <tb>
 <tb> Oxide <SEP> copper <SEP> ............................ <SEP> 99
 <tb>
 <tb> Green <SEP> of <SEP> gray <SEP> .............................. <SEP> 34
 <tb>
 <tb> Oxide <SEP> mercuric <SEP> .......................... <SEP> 34
 <tb>
 EXAMPLE 32.-
 EMI28.2
 
 <tb> Resin <SEP> 4B ................................. <SEP> 163
 <tb>
 <tb> Paraffin <SEP> (47-54 C) <SEP> ....................... <SEP> 99
 <tb>
 <tb> Wax Bee <SEP> <SEP> ............................ <SEP> 30
 <tb>
 <tb> Ethyl <SEP> cellulose ........................... <SEP> 30
 <tb>
 <tb> Oxide <SEP> copper ............................ <SEP> 177
 <tb>
 EXAMPLE 33.-
 EMI28.3
 
 <tb> Resin <SEP> 4B <SEP> .................................

    <SEP> 163
 <tb>
 <tb> Paraffin <SEP> (47-54 C) <SEP> ....................... <SEP> 75
 <tb>
 <tb> Terphenyl <SEP> ("Santowax") <SEP> .................... <SEP> 24
 <tb>
 <tb> Polyvinyl <SEP> butyral <SEP> or <SEP> acetate <SEP> of <SEP> polyvinyl. <SEP> 2-14
 <tb>
 <tb> Oxide <SEP> copper <SEP> ............................ <SEP> 177-300
 <tb>
 EXAMPLE 34.-
 EMI28.4
 
 <tb> Resin <SEP> 4B ................................. <SEP> 163
 <tb>
 <tb> Wax Bee <SEP> <SEP> ............................ <SEP> 24
 <tb>
 <tb> Copolymer <SEP> of <SEP> chloride <SEP> and <SEP> acetate <SEP> of <SEP> vinyl <SEP> 2-14
 <tb>
 <tb> Oxide <SEP> copper ............................ <SEP> 177-300
 <tb>
 
Satisfactory protective compositions can be prepared without the incorporation of a curing agent therein, as shown in the following examples:

   
 EMI28.5
 
 <tb> EXAMPLE <SEP> 35.- <SEP> Parties
 <tb>
 <tb> Resin <SEP> 4B <SEP> ................................. <SEP> 163
 <tb>
 <tb> Paraffin <SEP> (47-54 C) <SEP> ....................... <SEP> 99
 <tb>
 <tb> Oxide <SEP> copper <SEP> ............................ <SEP> 116
 <tb>
 <tb> Green <SEP> of <SEP> gray <SEP> .............................. <SEP> 34
 <tb>
 

  <Desc / Clms Page number 29>

 
 EMI29.1
 
 <tb> EXAMPLE <SEP> 36.- <SEP> Parties
 <tb>
 <tb> Resin <SEP> 4B <SEP> 163
 <tb>
 <tb> Paraffin <SEP> (47-540C) <SEP> .......................... <SEP> 99
 <tb>
 <tb> Oxide <SEP> copper ............................... <SEP> 177
 <tb>
 
It is also possible to prepare satisfactory protective compositions, the matrix of which is formed by the resin alone, as in the following example, and which are suitable for special modes of application such as immersion.



  EXAMPLE 37.-
 EMI29.2
 
 <tb> Resin <SEP> 4B <SEP> 163
 <tb>
 <tb> Oxide <SEP> copper ............................... <SEP> 116
 <tb>
 <tb> Silicate <SEP> of <SEP> magnesium ........................ <SEP> 30
 <tb>
 
Hot melted protective coatings can be applied to a hull immediately or they can be allowed to cool for later application after reheating to give them the necessary fluidity for the chosen application mode. These hot plasters acquire the fluidity necessary for spray application at a temperature of about 149 ° C. They are normally applied by pressure spray in thicknesses of 0.5 to 0.75 mm. The protective action of these 0.5 mm thick plasters persists for at least two seasons.

   A season in the waters of the northern hemisphere is. from about April to about October and, in the southern hemisphere, from October to April. Two seasons are normally considered to span 18 months.



  Summary of the characteristics of plastic protective coatings for hot application.



   The nature of the elements and the processes for preparing the protective coatings to be applied hot, which form the subject of the invention, are summarized below. The coatings contain a polymer or condensate prepared by reacting a phenol or a mixture of phenols with an aldehyde or a mixture of aldehyde, in

  <Desc / Clms Page number 30>

 the presence of an acid catalyst which exerts a neutralizing action in the range of pH values from 3.6 to 6, the ratio of phenol to aldehyde being at least unity.

   The polymers or condensates of the group in question are prepared by reflux until the odor of aldehyde, phenol (hydroxybenzene) and formaldehyde has disappeared, in the presence of a lead acetate catalyst, the molar ratio between phenol and formaldehyde being between 1 and 2.5 and the proportion of lead acetate being between 0.01 and 0.2 per mol of formaldehyde.



   The preferably chosen examples of compounds of this group use: 1. Condensate 4B: 1.25 mol of phenol, 1 mol of formaldehyde and approximately
0.04 mol of lead acetate and 2. Condensate 4A: 1.25 mol of phenol, 1 mol of formaldehyde and approximately
0.14 mol of lead acetate.



   The polymer or condensate is combined with a film-forming substance, to obtain a resin. Resins of the desired group are prepared by mixing one part of the polymer or condensate with 1.5 to 7 parts of the film-forming substance. A first preferred resin of this group (resin 4B) is obtained by mixing a part of the condensate 4B with 3.33 parts of pine resin, and a second resin of this same group (resin 4A) by mixing a part of the condensate 4A with 2.81 parts of pine resin.



   To form a matrix, 100 parts of resin are mixed with 5 to 70 parts of plasticizer which may be a single plasticizer or a mixture of different plasticizers. The most advantageous matrix consists of 163 parts of resin 4B and 99 parts of paraffin. Although the presence of curing agents is not essential for the preparation of matrices

  <Desc / Clms Page number 31>

 To be successful, an advantageous group of such matrices contains a proportion of curing agents of between 0.5 and 13% by weight of the matrix.



   The abovementioned matrices are given protective properties against fouling by adding a toxic material, preferably in proportions of 0.4 to 3 parts of toxic material per part of matrix, and thus completing the preparation of the protective coating. hot-apply plastic. A particularly advantageous coating is obtained by adding to the aforementioned matrix a proportion of cuprous oxide of about 0.44 part per part of the matrix.



   Protective coatings to be applied cold.



   A coating which can be applied at atmospheric temperature is said to be cold coated. Those which are described in the first place are applied in the state of cold solutions and it is necessary, for this purpose, that the degree of partial polymerization of the polymer is in general different from that of thermoplastic hot coatings. The most preferred embodiments of the cold plasters may contain the same constituents as those of the hot plasters, but the method of preparation varies slightly, as shown by the following examples.



  EXAMPLE 38 Polymer known as Phenolic Condensate @ n. 2 (hereinafter referred to as Phenolic n. 2)
 EMI31.1
 
 <tb> Parties <SEP> Report
 <tb> in <SEP> weight <SEP> molar
 <tb>
 <tb> Phenol <SEP> ...................... <SEP> 281 <SEP> 0.94
 <tb>
 <tb> Acetate <SEP> of <SEP> lead <SEP> hydrated <SEP> 169 <SEP> 0.14
 <tb>
 <tb> Solution <SEP> of <SEP> formaldehyde .... <SEP> 258 <SEP> 1
 <tb>
 
The phenol, lead acetate and formaldehyde solution are reacted by one of the methods given in connection with heat coatings, but preferably as described below. The reaction can be carried out conveniently in

  <Desc / Clms Page number 32>

 a varnish boiler with removable reflux condenser.

   The elements are introduced into the boiler and heated at a moderate rate and when the temperature reaches about 93 ° C, the heating is reduced to a minimum, as the exothermic nature of the reaction continues to raise the temperature of the mixture. until the reflux temperature is reached, which is close to 99 to 100 C. The reflux is continued until the bad smell of formaldehyde has disappeared and, at this time, the hydrochloride test d The hydroxylamide described above indicates that the formaldehyde content does not exceed about 1/20 mol per liter. This generally lasts about 45 minutes with the weight equivalents indicated in the previous example, but it can be observed that the time required does not vary appreciably when the size of the load is varied.

   It may further be noted that when the bad smell of formaldehyde has disappeared, the pH of the mixture is about 4, but the pH measurement is generally not used as an indication and one is usually content with the. indication given by the smell. The reflux condenser was then dismantled and the mixture continued to be heated with stirring to cause it to dehydrate. Heating is continued until the temperature preferably reaches about 104-107 ° C., but does not exceed 107 ° C., this heating generally lasting 30 minutes. If the phenolic condensate is to be stored, the heating is stopped as soon as the desired temperature is reached and the product is allowed to cool.

   The liquid phenolic condensate thus obtained is a variant preferably to be chosen of the basic constituent used to prepare the cold plasters according to the invention. The highest temperature reached by the condensate determines its characteristics in the final product. As will be seen later, suitable variants of the final product can be obtained by raising the temperature of the condensate to a maximum value of 149 C.

  <Desc / Clms Page number 33>

 



   Another advantageous embodiment prepared in a manner analogous to that of Example 38 is as follows: EXAMPLE 39 Phenolic n. 2A.
 EMI33.1
 
 <tb>



  Parts <SEP> Month
 <tb>
 <tb> Phenol <SEP> ......................... <SEP> 281 <SEP> 0.94
 <tb>
 <tb> Acetate <SEP> of <SEP> lead <SEP> (hydrated) <SEP> 42 <SEP> 0.94
 <tb>
 <tb> Solution <SEP> of <SEP> formaldehyde <SEP> 258 <SEP> 1
 <tb>
 <tb> Report <SEP> molar.
 <tb>
 



   The molar ratio between phenol and formaldehyde is preferably at least equal to approximately 1, that is to say between 0.9 and 1, but it may be between 0.5 and 2.



  Phenols.



   As has been said in connection with hot plastic protective coatings, hydroxybenzene can be replaced in whole or in part by many other phenols. In Example 1, cresol satisfactorily replaced phenol mole for mole and a polymer or condensation product was obtained having a pH equal to 3.85. Likewise, the hydroxybenzene of Example 38 was satisfactorily replaced by p-tert. amyl phenol mol for mol.



  Aldehydes.



   As has been said in connection with hot plastic protective coatings, various aldehydes can replace all or part of the formaldehyde of Example 38. Good results have been obtained by replacing in this example, mol for mol, the formaldehyde by benzaldehyde and acetaldehyde.



  Catalyst.



   The proportion of lead acetate serving as a catalyst may vary between 0.01 and 0.2 mol per mol of formaldehyde. But, in practice, this proportion is respectively 0.14 mol and 0.04 mol of lead acetate in the condensates of preferred, phenolic n .2 and phenolic n .2A, given that

  <Desc / Clms Page number 34>

 this proportion allows the reaction to reach the desired point after a relatively short time of about 45 minutes.



  Certain other catalysts have given satisfactory results with the proportions indicated per mol of formaldehyde in compositions containing only, by way of example, hydroxybenzene and formaldehyde in molar proportions equal to unity.
 EMI34.1
 
 <tb>



  Month
 <tb>
 <tb>
 <tb> Salicylate <SEP> of <SEP> lead <SEP> 0.01 <SEP> - <SEP> 0.06
 <tb>
 <tb>
 <tb> Acetate <SEP> cupric <SEP> ................... <SEP> 0.02 <SEP> - <SEP> 0.09
 <tb>
 <tb>
 <tb> Litharge <SEP> 0.02 <SEP> - <SEP> 0.09
 <tb>
 
The catalyst should facilitate the reaction of phenol and formaldehyde by controlling it to prevent it from proceeding too quickly and to prevent the polymer from becoming infusible. The catalyst should exert a neutralizing action in the range of pH values from about 3.6 to about 6.



   After the preparation of the polymer or phenolic condensate, the next step in the preparation of the cold protective coating may differ, for convenience, from the analogous process applied to the preparation of the molten, hot protective coatings.



  Instead of storing the resin as a separate product, it is used immediately prepared for the preparation of a so-called "intermediate product" which is easier to store and handle later; show the following examples: EXAMPLE 40. - Intermediate phenolic product n. 143.
 EMI34.2
 
 <tb>



  Parts <SEP> Composition
 <tb>
 <tb> Phenolic <SEP> n. 2 <SEP> ................. <SEP> 300 <SEP> 111.2 <SEP> kgs
 <tb>
 <tb> Resin <SEP> of <SEP> pin <SEP> ................... <SEP> 600 <SEP> 222.4 <SEP> kgs
 <tb>
 <tb> Gasoline <SEP> of <SEP> naphtha <SEP> of <SEP> tar <SEP> or
 <tb> xylol <SEP> of <SEP> petroleum <SEP> 180 <SEP> 77.6 <SEP> liters
 <tb>
 
To prepare the resin, the phenolic condensate No. 2 and the pine resin are mixed. This can be done / 1 by heating the compounds, separately or together, taking care

  <Desc / Clms Page number 35>

 that the condensate never reaches a temperature exceeding 149 C.



  Of course, it is necessary, in order to obtain a satisfactory mixture, that the resin be melted during this operation. Since the resin melts at about 100 ° C, this means that, if the method chosen is to heat the elements together, the temperature of the mixture is between this melting point of about 100 ° C and the upper limit of 149 ° C. .

   Obviously, it is possible to add the resin to the phenol-formaldehyde polymer as soon as reflux is complete, and then to heat the mixture of polymer and resin to dehydrate this polymer to any temperature chosen within the allowable range. , or to add the resin as soon as the above operation of dehydrating the polymer is completed at 107 ° C. Under these conditions, it would be unnecessary to prepare and store the phenolic condensate n. 2 or the like as a separate product. The preferred process at the plant to save heat energy is to combine the molten resin with the condensate, this condensate being at room temperature.

   The criterion for the temperature of the molten resin in this preferred factory operation is that the entire charge remains molten throughout the duration of the mixing operation to be sure that all of the resin is suitable. - finely mixed. When the charges to be treated at the plant are 180 to 225 kg of resin, it is found that a resin temperature of about 115 ° C. is sufficient to maintain it in the molten state during the mixing operation. For smaller fillers containing about 4.5 kg of resin, it has been found that a temperature of about 135 ° C has been found to be satisfactory. In the preferred industrial operation the two components are mixed by stirring them slowly enough to prevent excessive bubbling and boiling.

   As soon as the mixing is complete, the resin is ready to be diluted with a quantity of naphtha, tar or petroleum xylol gasoline sufficient to maintain.

  <Desc / Clms Page number 36>

 the product is liquid at room temperature. But, due to the relatively low boiling point of the solvent, the resin should be allowed to cool to a temperature of about 82 ° C before adding the solvent to prevent excessive loss of solvent by evaporation. The resin is still sufficiently melted at this temperature so that it is easy to dilute with the solvent. If it is desired to speed up the operation, the boiler in which the operation is carried out can be cooled externally with a sprinkler device to bring the resin to the temperature which is suitable for its dilution.



   It will be noted that, when, in this operation, the phenolic condensate n. 2 is replaced by various condensates, although satisfactory plasters can be prepared using condensates whose ratio between phenol and formaldehyde is very close to 0.7, the maximum temperature being close to the upper limit of 149 C, provided that the condensate is not maintained at this temperature for more than 30 minutes, it is however better to regulate the preparation of the plasters containing condensates with molar ratio also low, so as never to exceed a maximum condensate temperature of 135 C.



   If, in Example 40, the phenolic n .2A is replaced by the phenolic n .2, another intermediate product known as the intermediate phenolic n .143A "is obtained.



   By varying the proportion of the pine resin from 1 to 15 parts per 3 parts of the condensate, obviously keeping the temperature between the limits indicated, a series of resins can be prepared, the consistency of which varies between that of a liquid and that of a solid. A series of intermediates can be prepared by adding to the members of the resin series a sufficient amount of solvent to facilitate application by any selected method. The quantity of solvent required in each of these particular cases,

  <Desc / Clms Page number 37>

 In general varies inversely with the proportion of condensate, since the condensate itself is a liquid and, together with the solvent, serves to facilitate the application of the plaster.



   The amount of solvent may be zero, and in this case the resin and the intermediate product are the same. For example, with a proportion of 3 parts of condensate n. 2 and 1 part of resin, a coating is obtained which is suitable for application with a brush without the need to add a solvent thereto. Some other of these variations, prepared without solvent, are not liquid at room temperature and therefore would normally require a solvent in order to be easily applied by brush or spray like ordinary cold plasters, and they constitute semi-solid hybrid products which can be applied neither as a true cold plaster nor as a true hot melt plaster, but only by special processes, for example with a trowel or a broom.

   The curing of these hybrid products is effected by a drying operation analogous to that of ordinary cold paints and not by solidification from the melt state, as in the case of true hot melt plasters. These hybrid products are applied by light heating instead of high temperature heating, as with true hot melt paints.



  Film-forming agents.



   The resin substitutes as a film forming agent which give satisfactory results in the cold protective coatings of the invention are the same as those discussed above. hot protective coatings, namely:
Hydrogenated resin ("Staybelite")
Abietic acid
Petrex acid
Yacca gum
Pine-phenol resin

  <Desc / Clms Page number 38>

 
Each of these compounds or their mixtures can replace pine resin, in whole or in part. The film forming agent should be characterized by a solubility in sea water on the order of that of pine resin.

   Since the seawater solubility of the final layer matrix is influenced by that of the film forming agent, the proportions of the toxic material must be varied accordingly to maintain the protective properties against. fouling.



   To complete the preparation of the cold protective paint, toxic material and, in general, ordinary plasticizers and hardeners must be added to the intermediate. An excellent quality protective plastic paint is obtained by giving it the following composition:

   EXAMPLE 41. - (143 E.)
 EMI38.1
 
 <tb> Parties
 <tb>
 <tb>
 <tb>
 <tb> Product <SEP> phenolic <SEP> intermediate <SEP> n .143 <SEP> 540
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Oxide <SEP> copper ........................ <SEP> 360
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Phosphate <SEP> of <SEP> tricresyle <SEP> 60
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Rubber <SEP> chlorinated <SEP> ..................... <SEP> 8
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Gasoline <SEP> of <SEP> naphtha <SEP> of <SEP> tar <SEP> or <SEP> xylol <SEP> of <SEP> petroleum <SEP> 32
 <tb>
 
To make mixing easier, the curing agent, i.e. chlorinated rubber, is preferably dissolved first in gasoline of tar naphtha or petroleum xylol and then add the tricresyl phosphate plasticizer.

   Then all the components, i.e. the intermediate, the dissolved curing agent and plasticizer and the toxic material are mixed in the manner known in the art, preferably by means of a mill. colloid or ball mill. If desired, the plasticizer can be mixed with the pine resin before combining it with the # 2 phenolic to form the intermediate.

  <Desc / Clms Page number 39>

 



   As has already been said, the coatings prepared according to the invention may contain coloring pigments. It is also possible to use, in order to color them, coloring materials which do not chemically combine with the pine resin and which, in the case of hot plastic coatings, do not destroy the homogeneity of the mass. The following example is that of a cold coating colored with a black pigment.
 EMI39.1
 
 <tb>



  EXAMPLE <SEP> 42.- <SEP> Parties
 <tb>
 <tb>
 <tb>
 <tb> Product <SEP> phenolic <SEP> intermediate <SEP> n. 14 <SEP> 540
 <tb>
 <tb>
 <tb>
 <tb> Oxide <SEP> copper <SEP> ........................ <SEP> 300
 <tb>
 <tb>
 <tb>
 <tb> Phosphate <SEP> of <SEP> tricresyle <SEP> 60
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Rubber <SEP> chlorinated ..................... <SEP> 8
 <tb>
 <tb>
 <tb>
 <tb> Gasoline <SEP> of <SEP> naphtha <SEP> of <SEP> tar <SEP> 102
 <tb>
 <tb> Black <SEP> of <SEP> smoke <SEP> ......................... <SEP> 80
 <tb>
 
Although, as already stated, cold protective paints usually contain plasticizers and curing agents, satisfactory paints can be prepared consisting of the intermediate and the toxic material or the intermediate, the plasticizer. and toxic material.

   Below are given examples of coatings suitable for protecting surfaces exposed to seawater moving at moderate speeds and whose mechanical erosion is not appreciable.
 EMI39.2
 
 <tb>



  EXAMPLE <SEP> 43.- <SEP> Parties
 <tb>
 <tb> Product <SEP> phenolic <SEP> intermediate <SEP> n .143 <SEP> 54
 <tb>
 <tb> Oxide <SEP> copper <SEP> ........................ <SEP> 36
 <tb>
 <tb> EXAMPLE <SEP> 44.-
 <tb>
 <tb> Product <SEP> phenolic <SEP> intermediate <SEP> n .143 <SEP> 95
 <tb>
 <tb> DDT <SEP> .................................... <SEP> 5
 <tb>
 
An example of a coating composed of an intermediate, a plasticizer and a toxic material is as follows: EXAMPLE 45.-
 EMI39.3
 
 <tb> Product <SEP> phenolic <SEP> intermediate <SEP> n .143 <SEP> 54
 <tb>
 <tb> Phosphate <SEP> of <SEP> tricresyle <SEP> 6
 <tb>
 <tb> Oxide <SEP> copper ........................ <SEP> 36
 <tb>
 <tb>
 

  <Desc / Clms Page number 40>

 Solvents.



   As also noted above, these coatings can contain various solvents. Since the primary condition is only that the solvent is capable of dissolving the resin (polymer plus film-forming substance), it is obvious to those skilled in the art that a large number of solvents are available. For example, in general, all the common solvents for varnishes and lacquers can be used.



  The proportion of solvent added in addition to the minimum amount which is necessary to dissolve the various solids of the plasters is not critical and can easily be varied, as is known, to make the preparation easier. application of the final coat by brush or by sprinkling.



  Some special examples of solvents which have been tried with success are listed below.



  Hydrocarbons such as:
Gasoline
Petroleum essences
Dipentene
Xylene
Toluene
Benzene
Lamp oil Nitro-substituted hydrocarbons such as:
Nitroethane
Nitromethane
1-nitropropane
2-nitropropane Alcohols such as alcohols:
Ethylic
Methyl
Butyl
Isopropyl Esters such as:
Amyl acetate
Butyl acetate
Ethyl acetate Ketones such as:
Acetone
Methyl ethyl ketone

  <Desc / Clms Page number 41>

 Halogenated aliphatic hydrocarbons such as:
Methylene dichloride
Ethylene dichloride
Ethylene tetrachloride
Good results have also been obtained with various combinations of solvents such as: 1. Acetone 70% - Hexane 30% 2. Ethylene glycol monoethyl ether 18% - Turpentine 59% -
Mineral spirits 23% 3. Turpentine 70% - Oil of naphtha 30% 4.

   Mono ethyl ether of ethylene glycol 30% - Turpentine 70%.



   An advantageous variant of the phenolic intermediate prepared with mixtures of solvents is indicated by the following example: EXAMPLE 46 - Phenolic intermediate no. 143 B.
 EMI41.1
 
 <tb>



  Parts <SEP> Composition
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Phenolic <SEP> n. 2 <SEP> 300 <SEP> 111.2 <SEP> kgs
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Resin <SEP> of <SEP> pin <SEP> 600 <SEP> 222.4 <SEP> kgs
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Gasoline <SEP> of <SEP> naphtha <SEP> of <SEP> tar <SEP> 118 <SEP> 50.3 <SEP> liters
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Alcohol Ethyl <SEP> <SEP> 31 <SEP> 13.6 <SEP> liters
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Alcohol <SEP> butyl Secondary <SEP> <SEP> 31 <SEP> 13.6 <SEP> liters
 <tb>
 If the coating contains a curing agent, the solvent should be chosen so that this agent is soluble therein, as is known in the art of paint preparation.



  Conversely, if for economic reasons, for example, a specific solvent is chosen, it suffices to choose from among the many curing agents available an agent soluble in the chosen solvent.



  Plasticizers.



   As explained above, there are many classes of compounds available, each of which contains many elements which can serve as plasticizers in protective coatings. In fact, it is estimated that there are over 20,000 different substances known as plasticizers. Many of these substances have been found suitable for protective coatings

  <Desc / Clms Page number 42>

 cold forming the subject of the invention. Some examples which have given good results are listed below.



  Chemical plasticizers.



  1. Diphenylchlorinated (polychlorinated diphenyl) 2. Hydrogenated methyl abietate 3. Butoxy ethyl stearate 4. Diethoxy ethyl phthalate 5. Dimethoxy ethyl phthalate
6. Methoxy ethyl oleate 7. Bis- (diethylene glycol monoethyl ether) phthalate 8. Di-2-ethyl hexyl phthalate 9. Butyl benzene sulfonamide 10. Toluene sulfonamides (mixture of ortho and para) 11. D glycolate Ethyl phthalyl ethyl 12. Dibutoxy ethyl phthalate 13. Methoxy ethyl acetyl ricinoleate 14. Butyl phthalyl butyl glycolate 15. Dibutyl phthalate 16. Methyl abietate.



   Other plasticizers.



   1. Camphor
2. Cocoa butter
3. Sheep tallow
4. Acetylated castor oil
5. Pine oil
6. Heavy linseed oil
7. Raw linseed oil
8. Soybean oil fractionated fatty acids consisting of
Oleic acid 30%
Linoleic acid - 56%
Linolenic acid - 10%
Saturated acid - 4%

  <Desc / Clms Page number 43>

 
9. Alkyd resin (60% solids), Navy Dept.Spec.52
R.13 (of May 1, 1944) 10. Varnish of Navy Dept.Spec. 52 V 12 C rigging of June 15, 1945.



  11. Soft resins of coumarone and indene.



   The proportion of plasticizer depends on the nature of the plasticizer chosen. If this proportion is too high in a coating which must contain it, the cold plastic paint thus obtained is too soft and snakes or sinks when tested on the hull of a ship moving at high speed in the water. 'Hot water. On the other hand, if the proportion of plasticizer is insufficient, a fragile film is obtained which flakes or cracks. Satisfactory coatings are obtained with the following composition, when replacing, weight for weight, the tricresyl phosphate which is most often used by compounds chosen from the preceding lists and whose properties are similar to those of tricresyl phosphate, such as methyl abietate and chlorinated diphenyl.

   This composition (Example 47) provides a paint of the type of Example 41.
 EMI43.1
 
 <tb>



  EXAMPLE <SEP> 47 <SEP> - <SEP>
 <tb>
 <tb> Parties
 <tb>
 <tb>
 <tb>
 <tb> Product <SEP> phenolic <SEP> intermediate <SEP> n .143 <SEP> 540
 <tb>
 <tb>
 <tb>
 <tb> Oxide <SEP> copper <SEP> ........................ <SEP> 360
 <tb>
 <tb>
 <tb>
 <tb> Plasticizer <SEP> ........................... <SEP> 20-120
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Rubber <SEP> chlorinated <SEP> ..................... <SEP> 8
 <tb>
 <tb>
 <tb>
 <tb> Gasoline <SEP> of <SEP> naphtha <SEP> of <SEP> tar <SEP> 32
 <tb>
 <tb>
 <tb>
 <tb> Agents <SEP> of <SEP> hardening.
 <tb>
 



   The curing agents to be incorporated into the cold protective coatings are chosen from the large number of agents available belonging to the above-mentioned categories with careful consideration of their solubility in any given solvent chosen in advance. Since the curing agent not only renders the coatings wear resistant but also decreases the solubility of the matrix, its range is determined.

  <Desc / Clms Page number 44>

 portion for any given fixed ratio of toxic material to matrix so that it does not make the solubility of the matrix less than that at which the rate of paint washout becomes less than the minimum of about 10 micrograms per cm2 per day, which is necessary to ensure decassing.

   On the other hand, if the proportion of the curing agent is determined only by the resistance which one wishes to impart to the film, it is necessary to add a quantity of toxic material sufficient to assure a leaching rate. minimum appropriate. The examples in the following series show various compositions containing curing agents of different categories.



  EXAMPLE 48 Vinyl copolymer.
 EMI44.1
 
 <tb>



  Parts
 <tb>
 <tb>
 <tb>
 <tb> Product <SEP> phenolic <SEP> intermediate <SEP> (solvent <SEP> toluene) <SEP> 540
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Oxide <SEP> copper <SEP> ............................. <SEP> 360-720
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Phosphate <SEP> of <SEP> tricresyle <SEP> 60
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Vinylite <SEP> VYHH (Copolymer <SEP> of <SEP> chloride <SEP> and <SEP> acetate
 <tb>
 <tb>
 <tb> from <SEP> vinyl) <SEP> 2-50
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Methyl <SEP> ethyl <SEP> ketone <SEP> ....................... <SEP> 16-160
 <tb>
 EXAMPLE 49 Vinyl Polymer.
 EMI44.2
 
 <tb>



  Product <SEP> phenolic <SEP> intermediate <SEP> (solvent <SEP> gasoline
 <tb> from <SEP> naphtha-alcohol <SEP> ethyl-monoethyl <SEP> ether
 ethylene <tb> <SEP> glycol) <SEP> 540
 <tb>
 <tb> Oxide <SEP> copper <SEP> ............................... <SEP> 360
 <tb>
 <tb> Phosphate <SEP> of <SEP> tricresyle <SEP> ...................... <SEP> 60
 <tb>
 <tb> Polyvinyl <SEP> butyral <SEP> (vinylite <SEP> XYSG) ............. <SEP> 2-10
 <tb>
 <tb> Monoethyl <SEP> ether Ethylene <SEP> <SEP> glycol ............. <SEP> 19-95
 <tb>
 EXAMPLE 50.-
 EMI44.3
 
 <tb> Product <SEP> phenolic <SEP> intermediate <SEP> n .143 ....... <SEP> 540
 <tb>
 <tb> Oxide <SEP> copper ............................... <SEP> 360
 <tb>
 <tb> Oil <SEP> of <SEP> castor <SEP> acetylated <SEP> ...................... <SEP> 60
 <tb>
 <tb> Polyvinyl <SEP> butyral <SEP> ............................

    <SEP> 8
 <tb> Alcohol <SEP> butyl <SEP> ........................... <SEP> 89
 <tb>
 

  <Desc / Clms Page number 45>

 Cellulosic plastics.
 EMI45.1
 
 <tb>



  EXAMPLE <SEP> 51. <SEP> - <SEP> Parties
 <tb>
 <tb> Product <SEP> phenolic <SEP> intermediate <SEP> n .143 ....... <SEP> 540
 <tb>
 <tb>
 <tb> Oxide <SEP> copper <SEP> ............................... <SEP> 360
 <tb>
 <tb>
 <tb> Abietate <SEP> of <SEP> methyl <SEP> hydrogenated <SEP> 60
 <tb>
 <tb>
 <tb> Benzyl <SEP> or <SEP> ethyl <SEP> cellulose <SEP> 8
 <tb>
 <tb>
 <tb> 25% <SEP> of alcohol Ethyl <SEP> <SEP> + 75% <SEP> of <SEP> xylol <SEP> 63
 <tb>
 EXAMPLE 52.-
 EMI45.2
 
 <tb> Product <SEP> phenolic <SEP> intermediate <SEP> n .143 ....... <SEP> 540
 <tb>
 <tb> Oxide <SEP> copper <SEP> 360
 <tb>
 <tb> Aceto <SEP> propionate <SEP> of <SEP> cellulose <SEP> 0.8-4
 <tb>
 <tb> Diphenyl <SEP> chlorinated <SEP> (polychlorodiphenyl) <SEP> ....... <SEP> 60
 <tb>
 <tb> Acetone <SEP> ......................................

    <SEP> 35-57
 <tb>
 <tb> Alcohol <SEP> ethyl ............................. <SEP> 4-7
 <tb>
 EXAMPLE 53. -
 EMI45.3
 
 <tb> Product <SEP> phenolic <SEP> intermediate <SEP> n .143 ....... <SEP> 540
 <tb>
 <tb> Oxide <SEP> copper <SEP> ............................... <SEP> 360
 <tb>
 <tb> Aceto <SEP> butyrate <SEP> of <SEP> cellulose <SEP> .................. <SEP> 0.8-2
 <tb>
 <tb> Diphenyl <SEP> chlorinated <SEP> (polychlorodiphenyl) ........ <SEP> 60
 <tb>
 <tb> Acetone <SEP> 29-35
 <tb>
 <tb> Alcohol Ethyl <SEP> <SEP> ............................. <SEP> 3-5
 <tb>
 
Rubber and rubber derivatives.



  EXAMPLE 54.-
 EMI45.4
 
 <tb> Product <SEP> phenolic <SEP> intermediate <SEP> n .143 ........ <SEP> 540
 <tb>
 <tb>
 <tb>
 <tb> Oxide <SEP> copper <SEP> ................................ <SEP> 360-540
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Phosphate <SEP> of <SEP> tricresyle <SEP> 60
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Rubber <SEP> natural <SEP> ............................ <SEP> 0.8-4
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Gasoline <SEP> 20-100
 <tb>
 EXAMPLE 55.-
 EMI45.5
 
 <tb> Product <SEP> phenolic <SEP> intermediate <SEP> n .143 ........ <SEP> 540
 <tb>
 <tb> Oxide <SEP> copper <SEP> ................................ <SEP> 360
 <tb>
 <tb> Phosphate <SEP> of <SEP> tricresyle <SEP> ....................... <SEP> 60-120
 <tb>
 <tb> Rubber <SEP> chlorinated <SEP> .............................

    <SEP> 8-25
 <tb>
 <tb> Gasoline <SEP> of <SEP> naphtha <SEP> of <SEP> tar <SEP> 32-200
 <tb>
 

  <Desc / Clms Page number 46>

 
 EMI46.1
 
 <tb> EXAMPLE¯56¯- <SEP> Parties
 <tb>
 <tb> Product <SEP> phenolic <SEP> intermediate <SEP> n .143 <SEP> 540
 <tb>
 <tb> Oxide <SEP> copper <SEP> ........................ <SEP> 360
 <tb>
 <tb> Phosphate <SEP> of <SEP> tricresyle <SEP> 60
 <tb>
 <tb> Buna <SEP> S <SEP> chlorinated <SEP> ......................... <SEP> 8-25
 <tb>
 <tb> Gasoline <SEP> of <SEP> naphtha <SEP> of <SEP> tar <SEP> ......... <SEP> 32-200
 <tb>
 EXAMPLE 57 -
 EMI46.2
 
 <tb> Product <SEP> phenolic <SEP> intermediate <SEP> n .143 <SEP> 540
 <tb>
 <tb> Oxydecuivreux
 <tb> Oxide <SEP> copper <SEP> ........................ <SEP> 360
 <tb> Diphenyl <SEP> chlorinated <SEP> (polychlorinated diphenyl). <SEP> 60
 <tb>
 <tb> Rubber <SEP> cyclized <SEP> ("Pliolite") ........

    <SEP> 4-8
 <tb>
 <tb> Gasoline <SEP> of <SEP> naphtha <SEP> of <SEP> tar <SEP> 32
 <tb>
 Summary of the characteristics of plastic protective plasters to be applied cold.



   In summary, the cold protective coatings which are the subject of the invention contain a polymer or condensate prepared by reacting a phenol or a mixture of phenols with an aldehyde or a mixture of aldehydes in the presence of a catalyst. Preferably, the phenol and formaldehyde are refluxed until the odor of formaldehyde is gone, in the presence of a lead acetate catalyst. The molar ratio between phenol and formaldehyde can vary between 0.5 and 2 and the molar ratio between catalyst and formaldehyde can vary between 0.01 and 0.2. The preferably chosen molar ratio between phenol and formaldehyde is about 1 (for example between 0.9 and 1), and, in a preferably chosen embodiment of condensate, this molar ratio is equal to 0.94.

   In this embodiment, the proportion of the lead acetate catalyst is 0.14 mol per mol of formaldehyde. After reflux, the condensate is continued to be heated to dehydrate it to a temperature of up to 149 ° C. and preferably the temperature does not exceed 115 ° C.

  <Desc / Clms Page number 47>

 



   The polymer or condensate is mixed with a film forming agent to prepare a resin in the proportion of one to 15 parts of this agent per 3 parts of the polymer. The weight ratio of the film forming agent to the polymer of a preferably selected resin is 2 and the resin serves as the film forming agent. Although some of these resins can be used alone as matrices, it is generally advantageous to add one or more other substances, as will be seen later.



   An intermediate product can be prepared by adding a solvent to the resin in varying proportions starting from zero, in an amount necessary to make the final coating sufficiently fluid, depending on the intended application process. An advantageous intermediate product is prepared with approximately 5 parts by weight of the aforementioned resin per part by weight of an organic solvent, ie 4.28 kg of resin per liter of solvent. Although some of these intermediates may serve as a vehicle alone, it is generally advantageous to add thereto a plasticizer and, optionally, a curing agent.



   The plasticizer is usually mixed with the intermediate in proportions of 27 parts of the intermediate to 1 to 6 parts of the plasticizer. A preferred mixture consists of 27 parts of the above intermediate and 3 parts of a plasticizer, preferably tricresyl phosphate. Likewise, although some of these mixtures can serve as vehicles alone, it is preferable to add a curing agent thereto.



   Usually, a curing agent is added to the mixture of the intermediate and plasticizer to form a matrix carrier with a curing agent of 0.1% to 10%. An advantageous vehicle consists of 600 parts of the above mixture of the intermediate product and the plas-

  <Desc / Clms Page number 48>

 Tifier combined with 8 parts of the curing agent, preferably the chlorinated rubber dissolved in 32 parts of the organic solvent. It can thus be seen that the matrix of this vehicle contains approximately 1.5% of the curing agent.

   Note that, since it is more convenient to mix the curing agent with the rest of the vehicle by dissolving it first in a solvent, this addition of solvent should be taken into account in determining the ratio. between solvent and matrix or the percentage of solids contained in the vehicle.



   Considered from the general point of view of the composition of a coating, the proportions of the elements of the cold protective coatings can be indicated as follows: 100 parts of the resin contain from 4 to 27 parts of plasticizer. The preferably selected embodiment contains 100 parts of the above resin with 13.3 parts of the tricresyl phosphate plasticizer. The proportion of solvent varies from zero to about 0.58 liters per kg of matrix, this proportion in the most advantageous embodiment being about 0.27 liters per kg. matrix.



   In order to give the cold protective coatings the proper hardening effect, the usual toxic materials are added. For example, cuprous oxide can be added in a proportion of about 0.5 to 1.5 parts per part of matrix, while with DDT a coating is obtained which exerts a protective action against certain kinds of matrix. Underwater organisms, in proportions not exceeding about 0.07 parts per part of matrix. In a preferably selected embodiment, the proportion of cuprous oxide is about 0.74 part per part of matrix.



   The plasters described above applied with the usual thickness: on a surface exposed to the action of sea water,

  <Desc / Clms Page number 49>

 have the effect of permanently maintaining a minimum reaction with sea water whereby the copper salt is leached at a constant rate sufficient to prevent underwater organisms from permanently adhering at least for two successive fouling seasons . The average copper salt leaching rate is 12 mg / 1000 cm2 / day. It is constant at 2mmgs near either side of the mean. The minimum duration of the plaster measured during operation is three to five years per millimeter of thickness. The aforementioned protective coatings are generally applied over a suitable underwater basecoat.

   They prevent fouling not only when applied to the hulls of ships, but also to the interior surface of saltwater pipes.



   Anti-corrosive.



   To protect a surface against corrosion, it is essential to remove all moisture. This can be achieved, in some cases, by applying certain metals, such as zinc, to the surface by galvanizing or electroplating. These layers and the like are said to be of the metallic type.



   The removal of moisture for other layers, normally paints, depends on the nature of the vehicle or the film-forming substances.



   The film of these other layers must not only suppress moisture, but also resist influences (variations in temperature and action of the sun's rays) which may destroy or damage the film. In other words, the useful life and behavior of each type of these "other layers" are expressed, first, by their moisture removal power and, second, by their resistance to moisture. effects of other factors that compromise the impermeability of the diaper.

   Since in principle all "other" layers generally contain a le, \

  <Desc / Clms Page number 50>

 pigment and carrier, true protection has long been provided more by the ability of the carrier or film-forming substance to keep the film intact at all times, than by the specific power of the elements of the pigment to prevent corrosion.



   A category of these other layers known in the prior art is that of bituminous enamels, applied in the form of hot melt paints. It has been found by experience that a very high temperature is necessary for the application of these bituminous emaus which, even at this high temperature, are very viscous and set free gases, which gives rise to adhesion. insufficient and porosity of the final film.



   Anti-corrosive hot melt plasters or sealants.



   The anti-corrosive or molten stopping coatings, hot, according to the invention, have the properties of being impermeable to water or humidity, of resisting influences (variations in temperature and the action of sunlight. ) which have the effect of damaging or breaking ordinary plaster and resisting erosion. These coatings are thermoplastic, non-volatile and, in general, not very viscous. They provide complete protection against oxidation for a period of at least twice as long as the coatings previously used for this purpose and do not have the disadvantages of the latter from the point of view of their application, such as fumes, and others.



   Accordingly, they are particularly advantageous for the protection of surfaces exposed to the intermittent action of air and water, including the case where water flows along the surface at a relatively high speed. An example of a surface subject to these extreme influences is that of submarine ballast tanks, in which seawater flows at very high speed when being filled or emptied for

  <Desc / Clms Page number 51>

 cause the vessel to submerge or emerge.

   Hot melt anticorrosive coatings are quite similar to the hot melt protective coatings described above, except that the toxic material is replaced by more or less common pigments. They do not need to contain any of the elements previously known to be anti-corrosive. The expression "stop coating" is used to designate these coatings, because they form a kind of barrier between the surface to be protected and seawater, air or other corrosive element surrounding. It is obvious that the plasters used for this purpose must in principle be insoluble in seawater. The hot-melted barrier plasters according to the invention contain a variant of the basic constituent which is treated so as to give it the desired insolubility.

   They are generally applied by spraying, but can also be applied by brush or other means and the following example shows a typical composition of a hot melt sealant.
 EMI51.1
 
 <tb>



  EXAMPLE <SEP> 58.- <SEP> Parties
 <tb>
 <tb> Resin <SEP> 4A <SEP> or <SEP> 4B <SEP> .......................... <SEP> 226
 <tb>
 <tb> Pigment <SEP> of <SEP> dioxide <SEP> of <SEP> titanium-sulfate <SEP> of
 <tb> barium <SEP> ("Titanox" <SEP> B ") <SEP> 61
 <tb>
 <tb> Silicate <SEP> of <SEP> magnesium <SEP> 38
 <tb>
 <tb> Terphenyl <SEP> ("Santowax") <SEP> 63
 <tb>
 <tb> Abietate <SEP> of <SEP> methyl <SEP> hydrogenated ("Hercolyn") .. <SEP> 12
 <tb>
 
The titanium barium pigment is slowly added to the molten resin at about 149 ° C. with stirring to achieve satisfactory dispersion.

   Then the magnesium silicate is added; the temperature is raised to 177 ° C., the terphenyl is added at this temperature which is suitable for the melting of this compound, the temperature is further raised to 193 ° C., the temperature at which the whole of the mixture is perfectly fluid, then the mixture is added. methyl hydrogen abietate, the most convenient way being to mix the liquid plasticizer with the molten product. We then still raise

  <Desc / Clms Page number 52>

 the temperature at 205 C, which is the application temperature of the coating, and is maintained at this value until the foam collapses (about 5 to 10 minutes) to remove the volatile constituents which would otherwise be liable to release later and be harmful during subsequent application inside, for example, tanks.

   The product thus obtained is then preferably passed through a colloid mill to ensure satisfactory mixing and allowed to cool and solidify to facilitate storage. Although the product can be prepared by combining the elements in any way, as long as the final temperature of 205 C is reached, preference is given to the order of succession given, as it is by this. proceed that one achieves most easily the intimate mixture of all the elements. To prepare the coating for its application with a spray gun, it suffices to melt it again and bring it back to the temperature of 205 C at which its viscosity allows it to be easily applied. Once solidified, the layer is homogeneous and non-porous, adheres perfectly and is impermeable to moisture.

   According to the formula indicated, one of the elements consists of resin 4A or 4B, since these resins are easy to prepare in large quantities and to store for use as a raw material in the preparation of products. protective coatings against fouling and anti-corrosives. However, it should be understood that the coating can be prepared starting from the reaction of the phenol and the aldehyde and operating continuously by dehydration up to the final temperature.



   Although operating at a final temperature of 205 C, a plaster of satisfactory quality is obtained, others can be obtained which also give satisfaction by varying the final temperature of the condensate between 149 and more than 205 C and, hence, its degree of polymerization. If we heat the condensate

  <Desc / Clms Page number 53>

 alone, the temperature of 260 C is the limit temperature for obtaining satisfactory plasters, while if the condensate is first combined with a film forming agent, to prepare the resin, and if the condensate is first combined with a film forming agent. '' the resin is then heated,

   the final limit temperature is 360 C. An example of a plaster prepared in the lower temperature range consists of a simple product of high viscosity which can be applied with a brush and prepared by dehydrating the resin at 177 C and then mixing it. mixing with a liquid plasticizer, such as hydrogenated methyl alcohol.



   The addition of a high melting point type plasticizer, such as terphenyl, to the resin in the formula of Example 58 has the effect of raising the melting point or dripping point of the resin. die enough so that the final plaster can be used under ordinary conditions. If it is to be used under conditions where the ambient temperature is abnormally high, the drainage or softening temperature of the layers can be further increased by the addition of a curing agent. An advantageous, high softening or high drainage stopper can be prepared by adding a small amount of a curing agent to the elements of Example 58.

   This coating does not meander at the high temperature prevailing in the tanks of a submarine in a dry dock exposed to the rays of the summer sun. The following formula is an example.
 EMI53.1
 
 <tb>



  EXAMPLE <SEP> 59. <SEP> - <SEP> Parties
 <tb>
 <tb>
 <tb> Resin <SEP> 4B <SEP> ................................ <SEP> 358
 <tb>
 <tb>
 <tb> Polyvinyl <SEP> butyral <SEP> ("Vinylite" <SEP> XYNC) <SEP> 6
 <tb>
 <tb>
 <tb> Pigment <SEP> of <SEP> titanium-barium <SEP> ................. <SEP> 92
 <tb>
 <tb>
 <tb> Silicate <SEP> of <SEP> magnesium .................... <SEP> 56
 <tb>
 <tb>
 <tb> Terphenyl <SEP> ("Santowax") <SEP> ................... <SEP> 95
 <tb>
 <tb>
 <tb> Abietate <SEP> of <SEP> methyl <SEP> hydrogenated <SEP> ("hercolyn") ..

    <SEP> 17
 <tb>
 

  <Desc / Clms Page number 54>

 
Preferably, but not necessarily, the polyvinyl butyral is first added to the molten resin at 149 C, then the pigments and the terphenyl at 177 C, the hydrogenated methyl abietate at 193 C, then the temperature is raised to 205 C and the product is preferably passed through a colloid mill.



   Titanium pigments, for example titanium dioxide, titanium-barium pigment and titanium-calcium pigment, wet easily and give the coatings a light color which makes them advantageous inside tanks and other containers. by increasing their illumination. Black paints are advantageous in camouflage applications, for example in the superstructure of submarines.

   Two advantageous formulas are given by the following examples:
 EMI54.1
 
 <tb> .EXAMPLE <SEP> 60.- <SEP> Parties
 <tb>
 <tb> Resin <SEP> 4A <SEP> or <SEP> 4B <SEP> .......................... <SEP> 296
 <tb>
 <tb>
 <tb>
 <tb> Pigment <SEP> of <SEP> titanium-barium ................. <SEP> 80
 <tb>
 <tb>
 <tb> Silicate <SEP> of <SEP> magnesium .................... <SEP> 17
 <tb>
 <tb> Black <SEP> of <SEP> smoke ............................ <SEP> 20
 <tb>
 <tb>
 <tb>
 <tb> Terphenyl ("Santowax") <SEP> .................... <SEP> 82
 <tb>
 <tb>
 <tb> Abietate <SEP> of <SEP> methyl <SEP> hydrogenated ("Hercolyn") .. <SEP> 15
 <tb>
    EXAMPLE 61.-
 EMI54.2
 
 <tb> Resin <SEP> 4B <SEP> ................................ <SEP> 373
 <tb>
 <tb> Pigment Oxide <SEP> <SEP> of <SEP> iron <SEP> black <SEP> 50
 <tb>
 <tb> Silicate <SEP> of <SEP> magnesium ....................

    <SEP> 100
 <tb>
 <tb> Terphenyl <SEP> ("Santowax") <SEP> ................... <SEP> 99
 <tb>
 <tb> Abietate <SEP> of <SEP> methyl <SEP> hydrogenated <SEP> ("Hercolyn"). <SEP> 18
 <tb>
 <tb> Polyvinyl <SEP> butyral <SEP> ("Vinylite" <SEP> XYNC) <SEP> 16
 <tb>
 
The above examples are given only as an indication because the preparation process, the nature and the proportions of the elements can be varied. Stop plasters are easy to produce from pre-prepared 4A or 4B resins, but can also be prepared by a conventional operation.

  <Desc / Clms Page number 55>

 continues starting with the reaction of phenol and aldehyde.



  The variations shown in connection with the choice of phenol, aldehyde, catalyst and film forming agents in the preparation of hot melt protective coatings are also suitable for hot melt sealants. The plasticizer can be a single substance or several substances used together. In general, the plasticizer can constitute from 5 to 60% of the matrix, depending on the special characteristics of the plasticizer chosen. The required proportion of liquid plasticizers is generally only 5 to 15% of the matrix, since their action is more accentuated. Each of the plasticizers forming part of the following formula was used separately and made it possible to obtain satisfactory layers.
 EMI55.1
 
 <tb>



  EXAMPLE <SEP> 62.- <SEP> Parties
 <tb>
 <tb> Resin <SEP> 4A <SEP> .............................. <SEP> 66.7
 <tb>
 <tb> Pigment <SEP> of <SEP> titanium-barium <SEP> 34.7
 <tb>
 <tb> Plasticizer <SEP> liquid .................... <SEP> 3.5 <SEP> - <SEP> 12 <SEP>
 <tb>
 <tb> Enumeration <SEP> of <SEP> plasticizers <SEP> liquids:

  
 <tb>
 
Ethyl toluene sulfonamide
Chinese wood oil
Oiticica Oil
Raw linseed oil
Dehydrated Castor Oil
Tricresyl phosphate
Polychlorodiphenyl
Hydrogenated methyl abietate
Crude Tonga Oil
Dioctyl phthalate
Pine oil
Butyl benzene sulfonamide
Oleic acid
Methyl phthalyl ethyl glycolate
Mineral oil
Talloil
Pine tar
Coal tar
Linseed oil, thick
Ortho cresyl para toluene sulfonate
Carbitol phthalate
More specifically, particularly satisfactory coatings were prepared with 6.6 parts of each of the first seven liquid plasticizers, separately.

  <Desc / Clms Page number 56>

 



   Semi-solid and solid plasticizers can be used in amounts of 10 to 60% of the matrix. In Example 62, these plasticizers would replace the liquid plasticizer in amounts of 7.5 to 100 parts instead of 3.5 to 12 parts.



   List of semi-solid and solid plasticizers:
Stearic acid
Palmitic acid
Terphenyl
Manganese linoleate
Lead oleate
Camphor
Cocoa butter
Lanolin
Paraffin
Micro crystalline waxes
Beeswax
Carnauba wax
Chlorinated Naphthalene
Montane wax
Ceresin wax
Sheep tallow Summary of the characteristics of anti-corrosive coatings for hot application.



   In summary, it is seen that all the varieties of resins which can be used in the hot plastic protective coatings described above are also suitable for hot anti-corrosive coatings, the final dehydration temperature of the resin reaching 360 C.



   The proportion of plasticizer is 11 to 150 parts per 100 parts of resin. In preferred embodiments, this proportion is about 31 parts of plasticizer per 100 parts of resin. These embodiments contain a curing agent in an amount of about 1.2% of the matrix.



  The proportion of pigment can vary between 0 and 14% by volume of the total applied layer. Sealants are generally applied with a spray gun or brush, in a thickness of about 4 to 6 mm and preferably over a base coat.



   Cold anti-corrosive plasters, or basecoats.



   Cold anti-corrosive coatings, or primer coats, are generally applied directly to the surface to be protected.

  <Desc / Clms Page number 57>

   ger which can be metal, wood or other material. The object of the primer is to form a layer which adheres satisfactorily to the surface and to which the next layer satisfactorily adheres. When applying the anti-corrosive plaster when cold as a primer on a metal surface liable to fouling, it also acts as a barrier layer between the metal surface and the protective layer. fouling. This solution is advantageous, since the protective coatings often contain substances which exert a corrosive action on the steel.

   The cold anti-corrosive coatings or basecoats forming the subject of the invention contain variants of the same fundamental constituent common to all the other coatings described above.



  This constituent makes the coating waterproof. Preferably, it contains the resin 4B, plasticizers, pigments, and a sufficient quantity of solvent to obtain a relatively fluid product which penetrates into all the smallest irregularities of the surface to be protected. In general, all the constituents, except the resin, have been incorporated in the anticorrosive paints earlier, but by replacing the earlier resins with 4B resin, one obtains truly anticorrosive coatings, while that the previous plasters, which generally contain natural resins, deteriorate after a relatively short time. Examples of these endings are given below.
 EMI57.1
 
 <tb>



  EXAMPLE <SEP> 63. <SEP> - <SEP> Parties
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Resin <SEP> 4B .............................. <SEP> 314
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Gasoline <SEP> of <SEP> naphtha <SEP> of <SEP> tar ........... <SEP> 314
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Tar ................................ <SEP> 37
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> A <SEP> of <SEP> compounds Following <SEP> <SEP>:

  
 <tb>
 <tb>
 <tb>
 <tb> Linoleate <SEP> of <SEP> manganese
 <tb>
 <tb>
 <tb>
 <tb> Linoleate <SEP> of <SEP> lead
 <tb>
 <tb>
 <tb>
 <tb> Acid <SEP> bold <SEP> of oil <SEP> of <SEP> lin <SEP> 103
 <tb>
 <tb>
 <tb>
 <tb> Oleate <SEP> of <SEP> lead
 <tb>
 <tb>
 <tb>
 <tb> Oxide <SEP> of <SEP> zinc <SEP> .......................... <SEP> 184
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Yellow <SEP> of <SEP> chrome <SEP> ........................ <SEP> 92
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>, -Silice <SEP> 92
 <tb>
 

  <Desc / Clms Page number 58>

 
Other variants containing resin 4B have the following composition:

   
 EMI58.1
 
 <tb> EXAMPLE <SEP> 64. <SEP> - <SEP> Parties
 <tb>
 <tb> Resin <SEP> 4B ............................. <SEP> 314
 <tb>
 <tb>
 <tb> Gasoline <SEP> of <SEP> naphtha <SEP> of <SEP> tar <SEP> 314
 <tb>
 <tb>
 <tb> Polychloro <SEP> diphenyl <SEP> (Arocler <SEP> 1248) .... <SEP> 37
 <tb>
 <tb>
 <tb> Linoleate <SEP> of <SEP> lead <SEP> 103
 <tb>
 <tb>
 <tb> Oxide <SEP> of <SEP> zinc ......................... <SEP> 184
 <tb>
 <tb>
 <tb> Yellow <SEP> of <SEP> chrome ....................... <SEP> 92
 <tb>
 <tb>
 <tb> Silica <SEP> ................................ <SEP> 92
 <tb>
 EXAMPLE 65. -
 EMI58.2
 
 <tb> Resin <SEP> 4B ............................. <SEP> 145
 <tb>
 <tb> Gasoline <SEP> of <SEP> naphtha <SEP> of <SEP> tar <SEP> 380
 <tb>
 <tb> Tar <SEP> ............................... <SEP> 47
 <tb>
 <tb> Linoleate <SEP> of <SEP> manganese ................

    <SEP> 129
 <tb>
 <tb> Oxide <SEP> of <SEP> zinc <SEP> ......................... <SEP> 186
 <tb>
 <tb> Red <SEP> of <SEP> Venice ....................... <SEP> 93
 <tb>
 <tb> Silica ................................ <SEP> 92
 <tb>
 EXAMPLE 66. -
 EMI58.3
 
 <tb> Resin <SEP> 4B ............................. <SEP> 314
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Xylol <SEP> of <SEP> petroleum <SEP> 275
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Phosphate <SEP> of <SEP> tricresyle <SEP> 20
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Acids <SEP> bold <SEP> of oil <SEP> of <SEP> lin ............ <SEP> 75
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Minium <SEP> ................................

    <SEP> 184
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Chromate <SEP> of <SEP> zinc <SEP> 92
 <tb>
 <tb>
 <tb>
 <tb>
 <tb>
 <tb> Silicate <SEP> of <SEP> magnesium <SEP> 92
 <tb>
 
Although resin 4B has been specified in the foregoing examples, it should be understood that all the variations concerning the choice and the proportions of phenols, aldehydes, catalysts, film-forming substances, plasticizers, hardening agents, etc., indicated in connection with cold protective plasters, also suitable for cold anticorrosive plasters.


    

Claims (1)

CLAIMS 1) Polymer for use in protective layers, characterized in that it is prepared by reacting with reflux, until the odor of formaldehyde disappears, an aqueous mixture containing phenol and formaldehyde , wherein the molar ratio between phenol and formaldehyde is between 2.5 and 1 and a catalyst and a neutralizing agent. 2) Polymer according to claim 1, characterized in that the catalyst and the neutralizing agent are chosen from compounds of the group formed by lead acetate, cupric acetate, litharge and lead salicylate. 3) Polymer according to claim 1, characterized by a molar ratio of 0.01 to 0.2 mol of catalyst and neutralizing agent per mol of formaldehyde. 4) Resin for use in protective layers, characterized in that it is prepared by mixing 108 to 128 parts of the polymer according to claims 1, 2 or 3 with 360 parts of a film-forming agent . 5) Resin according to claim 4, characterized in that the film-forming agent is chosen from the compounds of the group formed by pine resin, yacca gum, pretrex acid ", hydrogenated pine resin, abietic acid, pine resin phenol, and mixtures thereof. 6) Resin according to claim 4, characterized in that the temperature of the polymer at least has been raised to 135-163 C to polymerize and partially dehydrate it. 7) Product preservative against fouling, characterized in that it comprises a toxic material against fouling and a synthetic resin matrix. <Desc / Clms Page number 60> 8) Product according to claim 7, characterized in that the matrix is obtained by forming an intimate mixture containing 70 parts of a plasticizer with 100 parts of the aforementioned resin. 9) Product according to claim 7; in that the toxic material contains 116 parts of cuprous oxide and the matrix is obtained by intimately mixing 99 parts of paraffin with 163 parts of the aforementioned resin. 10) Product preservative against fouling, characterized in that it contains a toxicant against fouling and a vehicle, which consists of a solvent and a matrix. 11) Product according to claim 10, characterized in that the solvent and the matrix are combined in proportions of approximately 27.1 liters of solvent per 100 kg of matrix. 12) Product according to claim 11, characterized in that the matrix consists of 450 parts of the resin according to claims 4, 5 or 6, 60 parts of tricresyl phosphate and 8 parts of chlorinated rubber. 13) Anti-corrosive product, characterized in that it consists of 226 parts of the aforementioned resin, 61 parts of a titanium-barium pigment, 38 parts of magnesium salicylate, 63 parts of terphenyl, and 12 parts of hydrogenated methyl abietate. 14) Product according to claim 13, characterized in that the temperature of at least the polymer of the resin has been raised to about 205 C to polymerize and further dehydrate the polymer.