DE2321555A1 - Protective and insulating coatings and paints - contg hydrated or hydratable and resinous components - Google Patents

Abstract

Coatings comprise mainly hydratable (hydraulic) cement worked-up with solns. of resins, pref. synthetic resins such as unsatd. polyesters, pref. at elevated temps. and in presence of pigments. Homogenisation of the ingredients results in formation of highly viscous, adhesive, usually thixotropic spreadable reaction prods. adapted, after evaporation of solvents and after hardening, to chemically bind the environmental humidity and thereby hydrate the cement in the compsn. whereby any pores are effectively sealed. Used as anti-corrosive paints, for water-proofing flame-protection, thermal and acoustic insulation, tank and furnace linings, mfr. of building elements, and coatings for paper and cardboard.

Description

Protective paints and coatings, of hydrated or Hydratable substances.

Rust protection coatings whose mode of action not only on firmly adhering Paint films are based but are already supplemented by chemical effects known That applies to everyone; for use of oxidative pigments for passivation Such chemical measures and fosfating chemical measures, for example, can does not prevent swelling in the course of weathering, which is when it is dry Weather conditions have been declining and due to this over time Frequent changes in condition make the protective film cracked and / or brittle, something in general is subsumed as "aging" of the protective film. Under-rusting of the film is the most intolerable Follow this so impossible penetration of atmospheric moisture up to According to the present invention, this can be achieved by using a previously unknown chemical compound, or a group of these compounds. It deals are compounds, first of all hydratable (hydraulic) cements, portland cement (calcium silica) Cement) and / or bauxite cement together with solutions of resins, mostly synthetic resins The same minor valences @ r are required for the formation of these new compounds responsible for the hydration of the powdery Cement effect in concrete elements of great strength, but with an in the favorable Meaning crucial difference. This is based on the fact that this new connection occurs primarily as a highly viscous, thixotropic, exceptionally adhesive solution that is stable when stored under the exclusion of air and can be kept practically indefinitely after this very easy to paint coating material has been applied and through Subsequent evaporation of the resin solvent takes place the first phase of the film curing, which, on the surface, in the It takes minutes, followed by drying, which takes about 24 hours may require.

Another particularly characteristic of the new protective coating The post-curing phase only occurs during the course of weathering. superficial release of resin there hydration of the center at least in a partial way, for a bed-clay-like hardening of the surface and because of the associated, fine increase in volume at the same time blocking all, including the possible microscopic pores This way occurs contrary to the familiar in the course of the long-term protective effect through the new protective coating a gradual, positive aftermath.

The aforementioned significantly increased is effectively supported Protective effect also due to the pronounced thixotropic nature and high viability of the new protective coating material, especially in relation to very rusty surfaces with their mostly pointed, numerous bumps. When twisting known, less adhesive paint materials the film thickness at these peaks disproportionately thin compared to the rust valleys the inevitable thermal expansion stresses on the film form this uneven film thickness creates an additional factor of uncertainty for durability the protective effect.

In contrast, because of the exceptional adhesiveness and thixotropy of the new protective coating material in the state of application, the protective film gets also at the said grate tips practically the same thickness as in the grate areas the exceptional durability of the new protective coating also plays a role Developing a role in relation to the strength of reinforcement iron in structural engineering Concrete elements is known. Something very similar also plays on the inside of the new anti-rust coating.

Certain advantageous characteristics of the new Protective coating , practically almost all of them, also have an effect on water-proofing-tm2.chenden when it is used Impregnation and superficial consolidation of porous materials. This applies to in primarily its use for the production of roofing felt, through the one for the outside certain coating with it, the on porous gray board directly after their Fabrication in the cardboard factory itself has to be carried out a significant saving compared to painting, for example with tar asphalt The most valuable advantage of this, however, is the aforementioned through Subsequent gradual superficial hydration caused by humidity and rain the cement component. In this way, contrary to the familiar, the watertightness leaves in the course of time not after, but is increasingly secured, so that deviating from the usual one or two layers of this roofing material mostly serve their purpose.

When it is completely dry, the total amount of cement is with the pigmentation, i.e. the non-flammable portion usually over 80% in order not to be able to de-fluff the underside of the cardboard, it is expediently preserved a protective coating based on hydrated, amorphous, adhesive ferrofosfate Flame retardancy is based on two complementary factors properties of said hydrated ferrofosate, firstly, from the heat-reducing effect of the said water of hydration, which releases endothermic water vapors when exposed to a flame and at least temporarily pushes back combustion air. The same applies to such Ferro-phosphate additives for the raw materials of the gray board.

This protective effect is increased by the transition of the bivalent Iron component of Fermfosfats in the trivalent Borm, whereby the neighboring Air is deprived of sufficient oxygen to prevent inflammation but at most to carbonizations.

In order to increase the water resistance of the cardboard underside, your said flame-retardant paint additions of 10-15% of the top-side paint added, whereby the flame retardant effect is practically not damaged.

The mutually useful complement of the two protective coating materials mentioned goes well beyond what has been said above, including the Production of the protective coating material containing ferrofosfate in the following Implementation and application examples are explained in detail0 Execution examples.

1. Anti-corrosive protective coating material.-In a heated mixer or kneader. the following raw materials are mixed together: 50 kg xylene, 240kg normal hydratable, white cement (calcium silicate cement), 35 kg iron oxide red pigment and 40 kg of an unsaturated polyester. With the complete dissolution of the polyester granules the homogenization of the mixture is finished.

This is followed by heating to 60-70 ° until the viscosity is constant Depending on the mixing intensity, this usually takes 20-30 minutes0For many purposes for film thicknesses of several centimeters the coating material is ready for manual Paint, which takes into account the pronounced thixotropic nature of the paint For thinner film thicknesses, or for spray technology, use thinner with 5-1OXylene or with other common benzene derivatives Painting, a separate topcoat is often unnecessary where it is not on special shine arrives.

2. Flame-retardant and waterproof cardboard, mainly for roofing purposes.-In 270 kg of technical iron vitriol (FeSO4.7H2 @ boiled together with 340kg granulated 18% superfosfat, so long until the superfoss granules have completely disintegrated and the resulting mixture from ferrefosfate and plaster of paris appears to be completely honed to neutralize the When the reaction pulp is still acidic, powdered hydrate is sieved in with constant mixing until the PH 5.5 -6.5 is constantly maintained.

The said reaction slurry serves firstly as an additive to the conventional, "Substance", the starting materials to be produced for the present case Gray board from 250-300g / m2 and this addition is measured at 10-15% on the dry substance of said cardboard starting materials 4 is used for the roofing felt underside the spreadable pulp containing ferrous sulfate for cold or warm application Impregnation and coating of the porous and therefore absorbent cardboard, whereby 10-15% of the protective coating according to the example must be mixed in beforehand to increase it the water resistance.

The protective coating material is used for waterproofing the roofing felt top used according to Example 1, pigmented with 4-6% aluminum powder pigment instead the said iron oxide pigmentation. From this non-flammable, waterproof Cardboard is usually used for roofing purposes with 1 or 2 layers.

Example 3.-Thermally insulating, non-flammable waterproof, insulating, self-supporting panels for use as structural elements for partition walls Rough ceilings and roof structures. Porous cardboard material and corrugated cardboard, consisting of one corrugated layer and only one smooth layer (liner).

The adhesive for insulating, flame-retardant bonding of two such layers with the cardboard side against each other is prepared as follows 10 kg of the polyol component for polyurethane foam are in a 35 kg of the flame-retardant adhesive according to Example 2, plus 5 kg of Na2S.9H20 in the form of a hot-saturated solution. After the above-mentioned homogenizer has taken place Components are added 14 kg of N for conventional polyurethane foam usual \ poly-isocyanate component and re-generation.

This mixture becomes one of the two layers of cardboard mentioned coated so that the grooves are almost completely filled. The second layer of corrugated cardboard with the groove side down is placed on the coated layer in such a way that the grooves on both sides come to rest. The foaming of the coating material achieved by heating from below and / or by infrared radiation from above for a few minutes temperatures up to 50 ° within the said double layer approximately The foam height and pore structure of the foam are through Rating the addition of fluorotrichloromethane (CCl3F) can be regulated.

Example 4. Self-supporting panels according to Example 3 of increased compressive strength Flame-retardant and insulating adhesive is produced as follows: I @ In a jacketed mixer for heating or cooling will make 70kg more hydrated, technical Iron vitriol (FeSO4.7H20) plus 8kg water melted at 50-600 and through Sift in the hydrated lime while mixing continuously, adjusted to pH 4 12 kg of Na2S.9H20 are stirred in and the mixture becomes completely homogenized kept with stirring at 60-70 °. The mixture is then brought to room temperature cooled down and homogenized again with 20kg of said poly-isocyanate component this mixture in the fresh state is the corrugated cardboard coating according to the example 3 and left to store for 24-36 hours after coating has taken place what time the solidification of the coating material as a result of said chemical reaction between the iron vitriol and the poly-isocyanate component to a large extent The subsequent treatment on a drying section near 400 leads mainly to the escape of moisture water and thus for the formation of porosity for the insulation effect, furthermore for further solidification and developing said compressive strength. For the exterior painting of the elements genass examples 3 and 4 are best suited to suitably pigmented protective coatings based on resin-zemeate according to Example 1. For increased strength requirements can 2 or more layers are often connected to one another, usually by riveting or screw connection.

With regard to the potentially extraordinarily large scope of the Possible uses of the present invention, including the associated The above exemplary embodiments can only be used for combinations and modifications Show characteristics of the scope.

As for the modifications of Example 1 in particular, so is the replacement of said calcium silicate cement and / or bauxite cement with burnt Plaster of paris (CaSO4. 1 / @ H2O) is an advantage, just mix it up with the aforementioned time, especially when it comes to disposal there is no difference in the way of processing. The said advantage arises from the acid resistance of calcium sulphate, which are required in such industrial plants can, where acid vapors occur, not only for construction elements made of iron and or concrete, for concrete foundations, concrete vats, and the like with the protective coating according to example 1 can be provided but also for interior painting of concrete tanks or iron tanks, for the latter purpose rit 2 or 3 coats in as a rule, depending on the nature and acidity of the liquids to be filled Multiple coats usually also apply to the use of the first two protective coats based on Portland cement or bauxite cement in the context of concrete or asphalt road construction for the purpose of waterproofing the road surface and for protection against frost damage Particularly good adhesion to concrete roads is also due, among other things, to the high cement content of the new paints, which results in a similar coefficient of expansion like the road surface itself, in addition to the high cement content conditional durability against abrasion. For the attachment of street signs According to the invention, particularly resin-free suspensions are suitable for the said protective coating of aluminum pigments in resin solvents, their adherence to the superficial Dissolution of the narcotic content of the underlying resinous protective coating is based Scaly pigment particles are practically only on their underside glued, so that the almost resin-free surface is practically metallic has a reflective effect after abrasion the street sign rises above the aluminum Due to its high content of white cement, it is still good from gray cement ahODie Renewing the aforementioned old minium paint is particularly time-saving, because after application only the solvent has to be evaporated, which is normally im Is the case within a few minutes.

What the particularly good adhesive strength of the new protective coating As far as asphalt road surfaces are concerned, it is based in particular on the superficial ones Dissolution of the asphalt by the paint solvent, such as xylene, because of the aforementioned The almost white color of the said new protective coating can be used for it directly In some cases, the aforementioned aluminum top coats are saved from the need to attach D-route signs or they can also be attached directly to the asphalt, where they come from the the same reasons as previously explained. The application of said new, Aluminum painting is not limited to what has been predicted, but among other things also on roofing material made from originally waterproofed according to claim 1 porous cardboard produced in a manner known per se from old cellulose-containing material.

In use of the new, anti-corrosive protective coating material, on a case-by-case basis with particularly smooth top coats also in shipbuilding can be used for antifouling purposes also paraformal dehydration can be used in addition, preferably in highly polymerized form and conveniently together with for this purpose well known metal compound additives.

As for the flame-proofing coating material according to Example 2, so it can also be used as a single or multiple top coat of flame-insulating nature For load-bearing or structurally loaded steel structures are used Everything in multi-storey warehouses or buildings of a similar character dte flame-retardant ferrofosfate according to Example 2 are additionally used, where it is about impregnation and / or coating of starting materials, mainly in the context of paper, cardboard and corrugated cardboard products, including the production of panels that can contain cellulose and / or wood pulp a special way of working, additional effects can be achieved for this purpose is the neutralization phase according to Example 2 as the final phase of the preparation of the To classify starting materials together with the said additives, normally by means of the well-known "Dutch" or pulpers for quick mix. ' Before the said A considerable part of the Perrofosfate is still in dissolved form in the neutralization Conditions and this proportion precipitated in the said "Stoif" of the hydrated ferrofosfate together with that obtained by rutalization with falcon hydrate down, CaS04.2H20 can with the said classification of the neutralization be particularly effective as the final phase of the raw material preparation; because on in this way the said precipitation takes place in a firmly adhering manner on the fibers and as a bonding agent between the pasers, mainly significantly increasing Strength of the cardboard is achieved, in addition to the flame retardancy The same applies to the flame retardant gypsum VeP processing of textile fibers are mineral fibers.

Further modifications according to the invention according to Example: 2-4 relate to Use of secondary and / or tertiary calcium fosfate (raw fosfate) instead of the said primary calcium phosphate, which is particularly advantageous with simultaneous Replacement of the aforementioned ZeS04.7H20 with the well-known strong sulfuric acid and therefore raw fossil revealing, so far very annoying @ wastewater from TiO2 industries and from comparable ones Pickling wastewater from steel industries, rendering them harmless if doing so The primary purpose for the said implementation is namely transfer into wastewater water-insoluble material that can be used outdoors without any concerns about groundwater protection can be stored, so MnO2 supplements for formation can also be used in the implementation of hydrolysed ferric sulphates: eight are used, which are used for the digestion of raw fossil fuels are cheaper than ferrous sulfateOIn any case, the product can be because of its biological assimilable iron and possibly manganese fosfate as artificial fertilizers can be used in large-scale, continuous process management until the practical neutralization, the said boiling in open stirring vessels Then, until the implementation is practically sufficient it may be advantageous to carry out the process in autoclaves or groups thereof, preferably in the temperature range of 140-180 °.

With regard to Examples 2, 3 and 4, an anti-flame-proof adhesive is used often the poly-isocyanate-containing adhesive according to Example 4 into consideration, wherein said hydrated ferrous sulfate is often at least partially replaced by FeSO4.7H2O As described in example 4 for flame-retardant corrugated cardboard The mixtures described in Example 3/4 can be used from normal temperature to hot or heated surfaces are painted on, and only then to be foamed in situ.

This applies to areas of any design and location, including vertical surfaces and doing this can be done in a much more practical way than before in industry, often also during operation, thermal and / or acoustic insulation generated in situ.

This primarily applies to furnace systems such as steel furnaces, blast furnaces, Glass furnaces, ceramic furnaces and furnaces of the chemical industry, pertochemistry, distillation plants, Reactors of all kinds and the like.

Overheating of the flameproof foam in the aforementioned applications lead in a first stage to larbonization of the organic portion in the immediate vicinity Close to the overheated areas, even if the overheating goes so far that eventually only the inorganic skeleton remains from the decomposition products of iron sulphate, so its porosity and insulation effect can affect the outside of the insulation remain intact, at least for the DeilO In a middle phase of said foam decomposition A carbonaceous inorganic skeleton, sometimes containing iron oxide, is formed this carbon is highly active and, above all, the said iron oxy-containing Skeleton is catalytically effective, the method according to Example 3-4 in an well-known systems of the activated carbon industry for the production of special types activated charcoal. In economic terms, the leaching phase can be used and the drying phase of the washed-out coal is also omitted Foaming methods, which are known per se for flammable foam, can according to the foregoing also activated charcoal moldings can be obtained, in particular for Gas catalytic purposes and for the filtration of liquids.

Claims (9)

Claims 1. Protective painting and coating materials, mainly for anti-corrosive purposes, and / or waterproofing purposes and / or for flame protection and / or for insulation purposes of a thermal or acoustic nature, especially for the construction sector and for construction material of all kinds, characterized in that it concerns anti-corrosive protective coatings, which are also used for waterproofing Porous material can serve in the manufacture of two main starting materials are hydratable (hydraulic) cements that, together with Solutions of resins, preferably synthetic resins such as unsaturated polyesters, are processed are mostly at elevated temperatures, usually together with pigments, whereby through the homogenization of the said main starting materials, chemical compounds are formed from them in the form of highly viscous, exceptionally adhesive, mostly thixotropic, paintable reaction products, their paint films, which after Evaporation of the solvent and after the film has hardened the ability to have surrounding Moisture hydrates cement and thus chemically binds pore-blocking, especially in the area of the painted surface 2. Protective paint materials for anti-corrosive purposes according to claim 1, characterized by at least partially Replacement of said types of cement with incompletely hydrated, hydratable ones Calcium sulphate preferably CaSO4.½H2O, mainly to protect against acid dehydration and or acidic liquids in relation to masonry or concrete construction of all kinds, including of interior painting of concrete tanks or steel tanks for absorption weak, respectively vinegar acidic liquids, also valid for many types of piping. 3. Protective coatings for anti-corrosive purposes according to claims 1-2, characterized by adding paraformaldehydes, preferably in highly polymerized form for Antifouling purposes, preferably together with metal compound additives well known for this purpose. 4. Topcoats for protective coatings according to claims 1-2, characterized through resin-free suspensions of aluminum pigments in resin solvents, their Adhesion to the superficial dissolution of the resin content of the underlying Resin-containing protective coating is based, for the purpose of forming a practically metallic reflective , almost resin-free surface, especially for roofing material made according to requirement 1 waterproofed, originally porous cardboard or for traffic signs for according to Concrete roads or asphalt cups made waterproof and frost-proof. 5. Flameproof paints according to claim I, characterized in that they contain hydrated, amorrhous, sticky ferrous phosphates, made in aqueous Media by heating or boiling of hydrated ferrous sulfates, such as BeS04.7H20 together with natural or artificial fosfat, such as rawfosfat, superfosfat and Or ammonium phosphate, followed by a neutralization stage for achieving approximately PH6- 7.6 and occasionally, for increased water resistance, of additives from Products according to claims 1-2 and or as single or multiple top coats flame-combing nature, mainly for load-bearing or loaded Steel structures. 6. Flame retardant or flame retardant insulating materials and from them existing paint or coating materials according to paint @, characterized by Addition of poly-urethane foam components of a known type or just their poly-isocyanates Component, in some cases together with reducing agents such as sulfides to avoid premature Oxidation of the products. @. Application of flame retardant or flame retardant materials according to claim 5 and additionally by products according to claim 1-2, characterized through their application in industries dealing with flammable fibers as additives for impregnation and / or coating of raw materials, mainly under the paper, cardboard and corrugated cardboard products, including production of panels containing cellulose and / or wood, mainly under classification the said neutralization as the final phase of the preparation of the starting materials together with the said additives, this for the purpose of increased adhesion of the the hydrated, tacky to deposit said fibers Ferrofosfate, and from CaSO4.2H2O. @. Flame retardant, insulating paint and coating materials according to claims 5-7, characterized in that for the mixture with said Poly-isocyanate component and the reducing agent such as sulfide according to claim 6, paints according to claim 4 are replaced in whole or in part by hydrated ferrous sulfates, the application of the mixture product from normal temperature for its foaming is to be strung on hot or heatable, in some cases also vertical surfaces, Concerning mainly thermal and acoustic insulation in industrial plants, including Furnaces such as steel furnaces, blast furnaces, glass furnaces, ceramic furnaces and chemical furnaces Industry 9. Hydrated, amorphous, ferrofosfate-containing substances according to claim 5, characterized in that marked that the ferrous sulfate raw materials are sulfuric acid, ferrous sulfate-containing Waste water from the TiO2 industry or similarly composed steel pickling waste water be used, together, for the boiling, with the said raw tosfaten and that these bioassimilable, hydrated, produced with the elimination of harmful waste water Ferrofosfate can also be used as an artificial fertilizer. @@. Hydrated, amorphous, ferrofosfate-containing substances emass claim 9, characterized in that said boiling down to the area of neutralization the free sulfuric acid of the said wastewater in open mixing vessels is then in preferably continuously operating autoclaves or autoclave groups, preferably in the temperature range from 140-1800. 11.Verfahr'en according to claim 1 and 5-10, characterized in that organic substances, which accordingly with hydrated, amorphous, ferrous sulfates and / or Ferrofosfates have been processed, in particular the said flame-retardant Foams converted into material containing activated carbon through thermal decomposition or molded bodies containing activated carbon by way of foaming in appropriate form.