Classifications

• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
  • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
  • C04B28/04—Portland cements
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
  • C04B26/02—Macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
  • C09D1/06—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances cement
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/16—Antifouling paints; Underwater paints
  • C09D5/1687—Use of special additives
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
  • C04B2111/00034—Physico-chemical characteristics of the mixtures
  • C04B2111/0012—Thixotropic mixtures
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
  • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
  • C04B2111/00482—Coating or impregnation materials
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
  • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
  • C04B2111/00482—Coating or impregnation materials
  • C04B2111/00508—Cement paints
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
  • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
  • C04B2111/00482—Coating or impregnation materials
  • C04B2111/00525—Coating or impregnation materials for metallic surfaces
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
  • Y02W30/00—Technologies for solid waste management
  • Y02W30/50—Reuse, recycling or recovery technologies
  • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

• the present invention relates to paint or coating compositions, methods for painting or coating surfaces and the use of particular compositions for painting or coating particular structures.
• European Patent Application No. 79 104321.9 and the corresponding International Patent Application No. PCT/DK79/00047 discloses particular materials showing extremely valuable properties with respect to dense and durable structure and excellent shapeability in uncured state.
• these materials will be designated materials containing a "densified matrix”. This term designates any coherent binder matrix disclosed in the above-mentioned patent applications. All of these binder matrices comprise
• the particles A or the coherent structure formed therefrom being homogeneously distributed in the void volume between the particles B,
• the dense packing being substantially a packing corresponding to the one obtainable by gentle mechanical influence on a system of geometrically equally shaped large particles in which locking su rface forces do not have any significant effect.
• additional bodies which have at least one dimension which is at least one order of magnitude larger than the particles A may be embedded in the matrix .
• Such additional are termed "bodies C" in I nternational Patent Application NO. PCT/DK79/00047 and comprise a wide variety of bodies, including particles such as sand or stone and fibers such as, e. g . , glass fibers, steel fibers , and plastics fibers .
• a material comprising the densified matrix designates any material having the densified matrix as a binder matrix and optionally containing bodies C as defined above.
• the particles B are preferably Portland cement particles
• the particles A are preferably ultrafine silica particles ("silica dust") having a specific surface area of about 50,000 - 2,000,000 cm 2 /g, preferably about 250,000 cm 2 /g
• preferred silica particles are described in detail in the said patent applications and comprise, e. g. , particles by growth from liquid or preferably vapou r phase such as particles formed as a byproduct in the production of ferrosilicium or silicium metal in electrical furnaces .
• articles comprising the densified matrix may be made from an easily flowable composite material of an extremely low liquid content by shaping in a low stress field .
• composite material designates any composite material which, on cu ring, forms a material comprising the densified matrix .
• composite materials are described in great detail in the above-mentioned patent applications .
• the composite material containing Portland cement particles as particles B comprises an extremely high amount of a dispersing agent, typically a concrete superplasticizer, and examples of useful concrete superplasticizers are given in the above-mentioned patent applications .
• Methods and materials for producing, casting and fu rther treating the densified matrix as disclosed in the above-mentioned patent applications are also useful for producing the densified matrix in the context of the present application.
• the densified matrix is utilized as protective coating for application on particular surfaces to be protected, in particular steel surfaces.
• the density of the matrix with its inherent mechanical properties is utilized.
• the particles B preferably comprise cement particles, in particular Portland cement particles, or at least a major proportion of cement particles, in particular Portland cement particles, thereby resulting in a paint which has the well-known rust-prevention properties of cement-containing paints.
• Surfaces which are suitably protected by means of such paint are, e.g., steel surfaces in ballast tanks, cargo holds, cofferdams, and other surfaces, especially on ship hulls or other marine structures, particularly in or on ships, or offshore structures, where rust prevention or resistance to other kinds of corrosion is to be obtained, including bridge undersides, the interior of offshore legs, ship cabins; ship decks and aircraft landing areas on ships or other constructions.
• Other structures which are protected by means of the paints or surface coatings comprising the densified matrix are drinking water tanks, underseals for containers, and jacketing for pipelines, etc.
• ship structures such as cabin walls which are to be supplied with a superimposed insulating layer such as a layer of Rockwool® are typical surfaces being treated with the paints or surface coatings comprising the dense matrix.
• the present invention is not restricted to the use of the materials comprising the densified matrix in or on marine or offshore structures; also the painting or coating of other structu res, including industrial piants, containers, buildings, etc. is within the scope of the present invention .
• the composite material When used as a paint or su rface coating for application on the above-mentioned surfaces or similar su rfaces, the composite material is preferably adapted to obtain - optimum adhesion to the surface to be painted or protected, ordinarily a steel surface, and is suitably modified to fu rther enhance its adhesion to the surface and to improve the application properties of the paint and the flexibility and resistance against cracking of the final paint layer. According to the invention, this modification is performed by addition of additives of organic or inorganic character. Important additives are organic or inorganic binders, thixotropic agents, co-solvents, defoamers, dispersing agents, pigments, and plasticizers .
• the composite material' or paint of the invention comprises - in addition to the components resulting in the formation of a densified matrix comprising particles A, B, and optionally C - an organic binder.
• the organic binder is suitably incorporated as a water-based emulsion such as an acrylic emulsion , polyvinylacetate emulsion, polyvinylidene chloride emulsion , acryl-styrene emulsion, styrene-butadiene emulsion, polyvinyl chloride emulsion, wax emulsion, polyethylene derivative emulsion, polyvinylidene-butadiene emulsion , or vinyiacryl emulsion .
• uch emulsions are incorporated in an amount of typically 5 - 60% by weight, preferably, to obtain maximum flexibility, 20 - 40% by weight, calculated on the dry matter content of the emulsion and the total dry matter content of the composition; a water-based emulsion such
• thixotropic agents for improvement of the flowing properties of the paint, permitting the obtainment of thicker layers of the paint applied .
• the thixotropic agents are typically added in an amount of 0.5 - 10% by weight, preferably 1 - 5% by weight, calculated on thixotropic agent dry matter and the total dry matter of the paint.
• Typical thixotropic agents are
• Mineral thixotropic agents including silicas bentonites and attapulgites vegetable thixotropic agents, including cellulose, starch, dextrin, alginates, castor oil derivatives natural gums, thixotropic agents of animal origin, including gelatine, glue, casein, synthetic thixotropic agents, including synthetic cellulose derivatives including starch acetate, polyvinyl alcohols, polyvinylpyrrolidone, polyvinylether derivatives, polyacrylamides, polyurethanes.
• vegetable thixotropic agents including cellulose, starch, dextrin, alginates, castor oil derivatives natural gums, thixotropic agents of animal origin, including gelatine, glue, casein, synthetic thixotropic agents, including synthetic cellulose derivatives including starch acetate, polyvinyl alcohols, polyvinylpyrrolidone, polyvinylether derivatives, polyacrylamides, polyurethanes.
• an interesting embodiment of the invention comprises incorporating a "co-solvent" in the form of a water-miscible organic solvent in an amount of 1 - 5% by weight, calculated on the dry matter of the paint.
• co-solvents are glycolethers, e.g. ethoxyethanol, butoxyethanol (also termed “butylglycol"), glycoletheracetates, e.g.
• diethyleneglycolmonobutylether acetate also termed “butyldiglycol acetate”
• esters of carboxylic acids such as 2,2,4-trimethyl-1,3-pentanediol-monoisobutyrate ("Texanol” from Eastman Kodak, USA).
• Texanol 2,2,4-trimethyl-1,3-pentanediol-monoisobutyrate
• These co-solvents exert their effect when the water originally present in the composite material gradually reacts , thus leaving a gradually increasing concentration of the solvent in the remaining liquid phase.
• the solvent thus gradually concentrated tends to migrate in the composite material and swell and coalesce the particles of emulsified binder, which tends to improve the flowing and film-forming properties of the paint and to result in a film which is substantially free of any pores .
• binders which are of the emulsion type as exemplified above, it is also possible to use binders of the types which are soluble in water/alcohol mixtu res and incorporate alcohol in the water phase of the paint. Such combination can be used to secure a relatively fast drying of the paint surface as the alcohol evaporates, thereby securing that the water present beneath the dried su rface is prevented from evaporating and is thus retained for the desired reaction with the inorganic binder.
• Binders soluble in water/alcohol mixtures and contemplated for this purpose are, e. g . , al kyds, allylethers, acrylics, and styrene-maleic acid polymers . Such binders are used in the same amount as stated above for binders in emulsified form.
• the paint incorporates small amounts , e. g . 0.01 - 5% by weight, calculated on the total dry matter content of the paint, of defoaming agents such as silicone-containing defoamers, e. g . , "Tegopren K 133" from Goldschmidt, Essen, Federal Republic of Germany, or silicone-free defoaming agents, e.g . , fatty acid derivatives such as "Bevaloid 688" or "Bevaloid 581 B” from “Bevaloid Ltd. , Yorkshire, England, or “Nopco NXZ” or “Nopco 8034” from Diamond Shamrock Corporation , Wilmington, Delaware, U . S . A.
• the defoaming agents prevent the incorporation of air during the formulation , mixing and application of the paint, thus avoiding air voids in the dry coating .
• compositions used for the pu rpose of the present invention will usually have a liquid : powder ratio in the range of about 0.20 - 0.45 or even 0.50 by weight, in particular in the range of 0.23 - 0.40, especially 0.27 - 0.38 by weight.
• the binder content thereof is considered as pertaini ng to the powder and will normal ly be in the size range defined for particles A .
• the paint incorporating the densified matrix is prevented from prematu re cu ring or setting by using, instead of the water in the usual embodiment of the composite material disclosed in the above-mentioned patent application , a water-miscible liquid such as a glycol , e. g . , ethylene glycol or propylene glycol .
• a water-miscible liquid such as a glycol , e. g . , ethylene glycol or propylene glycol .
• the paint is formulated as an antifouling paint for application of ship hulls , offshore structu res , or other marine structu res .
• antifouling agents are incorporated in the paint.
• the antifouling agents may be in the form of pa rticles (normally of the size corresponding to pa rticles B) such as cuprous oxide or zinc oxide, or they may be in the form of liquid antifouling agents .
• Particularly interesting antifouling agents are tin compounds of the general formula R 3 SnX wherein each R is a hydrocarbon group such as phenyl , benzyl, propyl, butyl, pentyl, octyl, or nonyl and X is an acid residue of a mineral or organic acid such as chloride, flou ride or acetate, or X is the acid residue of a polymeric acid such as polyacrylic acid .
• Examples of such tin compounds are triphenyltin chloride, triphenyltin fluoride, tributyltin fluoride, or tributyltin chloride.
• tributyltin oxide As an example of a liquid antifouling agent may be mentioned tributyltin oxide.
• the antifouling paint according to the invention may also be formulated with a content of a herbicide such as Diuron or antimicrobial enzymes such as protease, esterase, or cellulas
• the paint of the present invention is useful not on ly for normal application methods such as ai rless or ai r spraying , brushing, or rolling, but also for application under water or in the splash zone by brushing, by means of brooms, by means of rollers, or by spraying .
• a pre-treatment of the surface on which the paint of the invention is to be applied in order to increase the adhesion of the paint to the surface and enhance the protective efficiency of the paint.
• suitable pre-treatments are: Treatment with acids such as sulphu ric acid or phosphoric acid, treatment with bacteria such as sulfate-reducing and iron-oxidizing bacteria, dry or wet blasting with sand or grit, mechanical cleaning of the su rface, such as scraping, hammering, or high pressure washing.
• the paint of the invention is suitably composed in such a manner that it has a substantially light colour so that it is easier to visually asses what surfaces have been treated .
• This may be obtained by incorporating pigments as part of particles B, e.g . , zinc oxide or titanium dioxide, or by using particles A which are of a light colou r, such as white silica particles derived from the production of silicium and/or ferrosilicium in electrical fu rnaces .
• composition of the invention may be prepared in almost any desi red colou r.
• white cement and tinting pastes red, green , blue and black samples have been prepared .
• pigments of a plate-shaped character such as mica or asbestine, aluminum, micaceous iron oxide, or fibers, including asbestos, ch rysotil, graphite, basalt, polyethylene, cellulosic fibers, etc. may be incorporated as bodies C.
• the composite material constituting the paint or coating composition of the present invention is prepared from particles A, particles B , a liquid, a surface-active dispersing agent and optionally additional bodies C in the same manner as disclosed in the above-mentioned patent applications .
• amou nt of particles B substantially corresponds to dense packing thereof in the composite material with homogeneously packed or preferably densely packed partic A in the voids between the particles B and that the amount of liquid substantially corresponds to the amount necessary to fill the voids between particles A and B , and fu rther, that the amount of dispersing agent is sufficient to impa rt, to the composite material , a fluid to plastic consistency in a low stress field of less than 5 kg/cm2, preferably less than 100 g/cm 2 .
• the additional constituents incorporated in accordance with most aspects of the present invention are incorporated by methods adapted in accordance with the character of the particular constituent.
• the binder is a binder in the form of an emulsion
• the emulsion per se is used as part of or as the whole liquid constituent for preparing the composite material .
• the additional components are added in powder form, these are suitably either mixed with the dry constituents before addition of liquid, or are incorporated du ring the mixing, after the liquid or part of the liquid has been added, or they may be added in a form where they are dissolved or dispersed in liquid .
• the liquid will normally be water, but it will be understood that it is also within the scope of the invention to use glycol or a glycol/water mixture as the liquid in order to obtain retardation of the cu ring of the inorganic binder, and it is also within the scope of the invention to incorporate, e. g . , alcohol or another organic solvent in order to coalesce or dissolve an incorporated organic binder in accordance with the principles discussed above.
• the dry constituents thereof may be mixed in any desired manner.
• the particles B typically Portland cement
• the particles B may be mixed with the pa rticles A, and the resulting mixture may be admixed with any added dry constituents such as particles C and/or binder, thixotropic agent, or defoamer, or the particles A may be mixed with any other dry constituents to be added, such as binder, thixotropic agent, or de foamer, and thereafter mixed with the particles B and optionally particles C.
• the particles B comprise, e. g .
• Portland cement an interesting mixing sequence is to mix all other constituents than the Portland cement, including particles A, added binder (when the binder is not constituted by the pa rticles A) , optionaly thixotropic agents and defoamers, and optional pa rticles C and liquid, optionally including coalescing agent or a glycol , and then to add the cement to this mixtu re at the application site, preferably immediately before the application of the paint.
• care must be taken to obtain a homogeneous mixture showing the essential characteristics of the materials resulting in the densified matrix, of the above-mentioned patent applications .
• Fig. 1 illustrates the size distribution of Portland cement, silica, and acrylic emulsion, respectively,
• Fig. 2 illustrates the packing density of compositions with varying cement/silica ratios with 15 parts by weight of acrylic emulsion and without acrylic emulsion ("Acronal" S 702 from BASF) , respectively.
• Example A The products were prepared in the same manner as in Example A, the cement and the silica being dry mixed before addition of the emulsion.
• the emulsion was added in varying amounts. In all cases, excellent paint properties with respect to viscosity, pot life and film formation (when curing at 100% relative humidity) were obtained, such as appears from Table 2.
• Example 2 Three compositions of the same type as described in Example 1 were prepared, with varying amount of silica. The compositions were pre pared in the same manner as described in Example 1 . The the proportions of ingredients and the results obtained appear from Table 3.
• No. cizer 1 lids ratio Krebs Units g g g g g
• compositions of the invention were applied on steel panels by means of a conventional spray technique, using a pistol G FG-50 from DeVill Biss, nozzle 0.030" .
• the ingredients and their relative ratios, etc. appear from Table 4 in which "Sa 3" and "St 3" indicate the degree of cleanness of the steel according to Swedish Standard No. S IS 055900-1967.
• the panels with the compositions were immersed in sea water for 3 months at Kyndby, Denmark. The results of this test appear from Table 4.
• Other application methods which have been tested in practice and found to be suitable are pressu re pot application using a PQM 5499 equipment from DeVill Biss , nozzle 0.064", or hoppergun application , using an equipment from Joe, Sweden .
• a number of fiber-containing compositions of the invention were made in the same manner as described in Example 2; the fibers were added together with the water.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Ceramic Engineering (AREA)
• Inorganic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Structural Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Paints Or Removers (AREA)

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• 1982
  • 1982-02-08 WO PCT/DK1982/000012 patent/WO1982002709A1/en unknown
  • 1982-02-08 EP EP82900501A patent/EP0071622A1/de not_active Withdrawn

Non-Patent Citations (1)

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