WO2024094900A1 - Système de revêtement antistatique - Google Patents

Système de revêtement antistatique Download PDF

Info

Publication number
WO2024094900A1
WO2024094900A1 PCT/EP2023/080890 EP2023080890W WO2024094900A1 WO 2024094900 A1 WO2024094900 A1 WO 2024094900A1 EP 2023080890 W EP2023080890 W EP 2023080890W WO 2024094900 A1 WO2024094900 A1 WO 2024094900A1
Authority
WO
WIPO (PCT)
Prior art keywords
coating
coating system
isocyanate
mdi
carbodiimide
Prior art date
Application number
PCT/EP2023/080890
Other languages
English (en)
Inventor
Christian Bruchertseifer
Dirk SEEGER
Burkhard Walther
Original Assignee
Sika Technology Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sika Technology Ag filed Critical Sika Technology Ag
Publication of WO2024094900A1 publication Critical patent/WO2024094900A1/fr

Links

Classifications

    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/302—Water
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/04—Antistatic

Definitions

  • the invention relates to anti-static coating systems, to coatings prepared from such systems to uses of such coating systems, and to coating methods.
  • anti-static means that electrostatic discharge is reduced, dampened or otherwise inhibited.
  • Antic-static properties are in particular desirable in the context of handling flammable substances to avoid that electrostatic charges ignite such flammable substances.
  • coating systems such as epoxide systems and polyurethane systems fail to provide coatings which are sufficiently anti-static.
  • the known coating systems often lead to coatings which have inferior adhesion and are thus prone to delamination. This is in particular a problem when a coating formed from such coating systems shall act as a diffusion barrier to protect a substrate on which they are formed.
  • a coating formed from such coating systems shall act as a diffusion barrier to protect a substrate on which they are formed.
  • another diffusion barrier layer is required in order to provide antic-static properties and also diffusion barrier properties to a substrate, especially to a concrete substrate.
  • Subject of the invention is a coating system, comprising: a part (A) comprising at least one polyol bearing two or more hydroxy groups, and a part (B) comprising at least one isocyanate bearing two or more isocyanate groups and comprising carbon nanotubes, wherein parts (A) and (B) are physically separated from each other, and wherein a coating produced by mixing parts (A) and (B) has an electrical resistance of ⁇ 80 kQ, measured according to DIN EN 61340- 4-1 :2016-04, and a bond strength of > 1.5 MPa, measured according to DIN EN 1542:1999-07.
  • a polyol is to be understood in the usual skilled manner, i.e., as an organic compound bearing, or having, two or more hydroxy groups (> 2 OH groups). It is preferred that the polyol is selected from 1 ,2-ethanediol or ethylene glycol, 1 ,2-propanediol or 1 ,2- propylene glycol, 1 ,3-propanediol or 1 ,3-propylene glycol, 1 ,4-butanediol or 1 ,4-butylene glycol, 1 ,6-hexanediol or 1 ,6-hexamethylene glycol, 2-methyl-1 ,3-propanediol, 2,2- dimethyl-1 ,3-propanediol or neopentyl glycol, 1 ,4-bis(hydroxymethyl)cyclohexane or cyclohexanedimethanol, 1 ,2,3-propanetriol or g
  • polystyrene resin Particularly preferred is 1 ,4-butanediol.
  • the polyol is selected from polyether polyols, especially polymer-analogous polyether polyols, which regularly bear two or more hydroxy groups (> 2 OH groups), i.e., which have a functionality of > 2. It is also contemplated that a preferred polyol is selected from polyols having a polyester backbone or a polybutadiene backbone, which polyols again regularly bear two or more hydroxy groups (> 2 OH groups).
  • the isocyanate bearing 2 or more isocyanate groups is selected from tolylene 2,4-diisocyanate (also known as toluene 2,4-diisocyanate), tolylene 2,6-diisocyanate (toluene 2,6-diisocyanate), a mixture of these isomers (TDI), diphenyl methane 4,4'- diisocyanate, diphenylmethane-2,4'-diisocyanate or diphenylmethane-2,2'-diisocyanate, a mixture of these isomers (MDI), phenylene-1 ,3-diisocyanate or phenylene-1 ,4-diisocyanate, 2,3,5,6-tetramethyl-1 ,4-diisocyanatobenzene, naphthalene-1 ,5-diisocyanate (NDI), 3,3'- dimethyl-4,4'-diisocyanato
  • p-TMXDI p-tetramethylxylylene-1 ,4-diisocyanate
  • MDI diphenylmethane- 2,4'-diisocyanate
  • MDI diphenylmethane-2,2'-diisocyanate
  • MDI a mixture of these isomers
  • MDI the following isomers or regioisomers of MDI are employed and form part of the mixture in which technical grade MDI normally occurs:
  • Polymeric isocyanates according to the invention can be represented by the following general formula:
  • a carbon nanotube is to be understood in the usual skilled manner.
  • a carbon nanotube having a single-wall is also referred to as a single-wall carbon nanotube (SWCNT).
  • SWCNT single-wall carbon nanotube
  • Such a single-wall carbon nanotube is an allotrope of carbon and can for example be seen as an intermediate between a fullerene cage and flat graphene, with diameters typically in the range of a nanometer.
  • a single-wall carbon nanotube can be idealized as a cut-out from a two-dimensional hexagonal lattice of carbon atoms rolled up along one of the Bravais lattice vectors of the hexagonal lattice to form a hollow cylinder.
  • a multi-wall carbon nanotube is made of nested single-wall carbon nanotubes weakly bound together by van-der-Waals interactions in a tree ring-like structure. Multi-wall carbon nanotubes encompass double-wall and triple-wall carbon nanotubes.
  • parts (A) and (B) are physically separated from each other, i.e., there is no physical contact between them. Accordingly, part (A) and part (B) may be placed in two separate containers, e.g. part (A) is in a first container and part (B) is in a second container.
  • the coating system according to the present invention may thus also be termed a two-component system, or a kit of parts, comprising parts (A) and (B).
  • the physical separation of parts (A) and (B) may be achieved by storing parts (A) and (B) in two different containers, or in two different compartments of one container.
  • the physical separation may in particular be such that no reaction between the at least one polyol comprised by part (A) and the at least one isocyanate comprised by part (B) can occur.
  • the coating systems according to the present invention may thus also be referred to as polyurethane coating systems.
  • the end of those reactions can for example be determined by measuring the temperature of the mixture of parts (A) and (B). As soon as no change of temperature - in an otherwise isothermic environment - of the mixture of parts (A) and (B) can be observed anymore, the coating has formed. A coating is regularly formed within 24 h. Once the coating has formed, its properties can be determined according to protocols established in the art.
  • the electrical resistance is measured according to DIN EN 61340-4-1 :2016- 04, “Standard test methods for specific applications - Electrical resistance of floor coverings and installed floors”.
  • the bond strength is measured according to DIN EN 1542:1999-07, “Products and systems for the protection and repair of concrete structures - Test methods - Measurement of bond strength by pull-off’.
  • a coating formed from the coating system according to the present invention Due to its low electrical resistance, a coating formed from the coating system according to the present invention has improved anti-static properties. Further, due to its high bond strength, a coating formed from the coating system according to the present invention has an improved adhesion to a substrate and in particular has an improved adhesion to a concrete substrate. Additionally, the coating system according to the present invention can do away with the requirement of an additional diffusion barrier layer. Without wishing to be bound to theory, it is assumed that the improved anti-static properties and the simultaneously improved bond strength are at least partly brought about by an orientation of the carbon nanotubes and/or an agglomeration thereof at the surface of the coating (surface effect).
  • carbon nanotubes can be distributed more uniformly in the coating system according to the present invention, more specifically in part (B) thereof. Further, the carbon nanotubes can be incorporated into the coating system according to the present invention and more specifically into part (B) thereof without experiencing a disadvantageously increased viscosity, i.e., the carbon nanotubes can be incorporated at reduced processing viscosity. It is preferred for the coating system according to the present invention that the electrical resistance is ⁇ 20 kQ, more preferably ⁇ 10 kQ. With such a particularly low electrical resistance, a coating formed from the coating system can have particularly improved antistatic properties. However, reducing the electrical resistance to almost zero would potentially require the addition of excessive and hence uneconomic amounts of carbon nanotubes.
  • the electrical resistance is > 0.1 kQ, more preferably > 1 kQ. Accordingly, it is particularly preferred for the coating system according to the present invention that the electrical resistance is in the range of > 0.1 kQ to ⁇ 80 kQ, more preferably in the range of > 0.1 kQ to ⁇ 20 kQ. and still more preferably in the range of > 1 kQ to ⁇ 10 kQ.
  • the bond strength is > 3.0 MPa. With such a particularly high bond strength, a coating formed from the coating system can have a particularly improved adhesion to substrates.
  • an almost unlimited increase of the bond strength would potentially require the use of specifically designed and hence costly and uneconomic polyols in part(A) and/or isocyanates in parts (B). Therefore, it is preferred for the coating system according to the present invention that the bond strength is ⁇ 10.0 MPa, more preferably ⁇ 5.0 MPa. Accordingly, it is particularly preferred for the coating system according to the present invention that the bond strength is in the range of > 1.5 MPa to ⁇ 10.0 MPa and still more preferably in the range of > 3.0 MPa to ⁇ 5.0 MPa.
  • the at least one isocyanate is a carbodiimide-modified isocyanate.
  • Carbodiimide-modified isocyanate with loss of carbon dioxide, usually under catalysis (e.g. catalyzed by a phosphine oxide of general formula R1R2R3PO with substituents R1R2R3 being independently selected from the group consisting of alkyl and aryl, wherein said substituents can be the same or different or two substituents can form a ring), as is well-known in the art; this leaves a carbodiimide unit in the backbone and two free terminal isocyanate groups, i.e. one isocyanate group at either end of the respective isocyanate compound obtained, as is shown by the general formula for a carbodiimide-modified isocyanate above.
  • catalysis e.g. catalyzed by a phosphine oxide of general formula R1R2R3PO with substituents R1R2R3 being independently selected from the group consisting of alkyl and aryl, wherein said substituents can be the
  • R represents symmetrical or asymmetrical substitution patterns at the two phenylene rings in ortho- or para-position (with a small to negligible proportion of substitution in meta-position), as is shown by the formulas for diphenyl methane 4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate and diphenylmethane-2,2'- diisocyanate, all of which are depicted hereinbefore.
  • the electrical resistance can be further lowered and hence the anti-static properties can be further improved.
  • the improved electrical resistance is at least partly brought about by delocalized ⁇ -electrons in the carbodiimide- unit of the carbodiimide-modified isocyanate.
  • the carbodiimide-modified isocyanate is used in part (B) together with a fatty acid ester-based plasticizer, i.e., that part (B) comprises a fatty acid ester-based plasticizer, which can lead to even further improved anti-static properties of the resulting coating.
  • polymeric aromatic isocyanate in admixture or blended with monomeric and/or carbodiimide-modified aromatic isocyanate.
  • polymeric aromatic isocyanate by increasing the proportion of polymeric aromatic isocyanate of the overall content of aromatic isocyanates, the effect of decreasing the electrical resistance is less pronounced or reduced. This is because the presence of a monomeric and/or carbodiimide-modified aromatic isocyanate in a part (B) composition lowers the electrical resistance of a coating obtained by using such part (B) composition more than the presence of a polymeric aromatic isocyanate.
  • the polymeric isocyanate is used in part (B) together with a fatty acid ester-based plasticizer, i.e., that part (B) comprises a fatty acid ester-based plasticizer, which can lead to even further improved anti-static properties of the resulting coating. It is further preferred that the polymeric isocyanate is used in part (B) togetherwith a quaternary ammonium salt, i.e., that part (B) comprises a quaternary ammonium salt, which can also lead to even further improved anti-static properties of the resulting coating.
  • the at least one isocyanate is a monomeric isocyanate.
  • the carbon nanotubes can be even more uniformly distributed in part (B) of the coating system and can be distributed at reduced processing viscosity.
  • the monomeric isocyanate is used in part (B) together with a fatty acid ester- based plasticizer, i.e., that part (B) comprises a fatty acid ester-based plasticizer, which can lead to even further improved anti-static properties of the resulting coating.
  • the monomeric isocyanate is used in part (B) together with a quaternary ammonium salt, i.e., that part (B) comprises a quaternary ammonium salt, which can also lead to even further improved anti-static properties of the resulting coating.
  • the improved anti-static properties and the simultaneously improved bond strength observed when using a monomeric isocyanate in part (B) of an inventive coating system are at least partly brought about by an improved dispersion of the carbon nanotubes in part (B) of the system and by a subsequent orientation of the carbon nanotubes and/or an agglomeration thereof at the surface of the coating formed from the coating system, i.e., by a subsequent surface effect of the previously dispersed carbon nanotubes.
  • the coating system according to the present invention does not comprise a fatty acid ester-based plasticizer and does more preferably not comprise any plasticizer.
  • the absence of a fatty acid ester-based plasticizer and in particular the absence of any plasticizer in such a coating system avoids an undesired increase of the electrical resistance.
  • the at least one isocyanate is an aromatic isocyanate.
  • the electrical resistance can be further lowered and hence the anti-static properties can be further improved.
  • the improved electrical resistance is at least partly brought about by delocalized n- electrons in the aromatic unit of the aromatic isocyanate.
  • aromatic isocyanates are often less expensive than aliphatic isocyanates so that the use of an aromatic isocyanate can improve the cost efficiency of the coating system according to the present invention.
  • the aromatic isocyanate is MDI, more preferably carbodiimide-modified MDI and/or monomeric MDI.
  • part (B) comprises two different isocyanates.
  • the carbon nanotubes can be even more uniformly distributed in part (B) of the coating system and can be distributed at a reduced processing viscosity.
  • the two different isocyanates are two different aromatic isocyanates.
  • the two different isocyanates are one monomeric aromatic isocyanate and one carbodiimide-modified aromatic isocyanate.
  • the carbon nanotubes can be even more uniformly distributed in part (B) of the coating system and can be distributed at a reduced processing viscosity.
  • the monomeric aromatic isocyanate allows for a better distribution of the carbon nanotubes and a reduced processing viscosity.
  • the electrical resistance can be further lowered and hence the anti-static properties can be further improved.
  • the improved electrical resistance is at least partly brought about by delocalized n- electrons in the aromatic units of the two aromatic isocyanates, in particular by the aromatic units in the monomeric aromatic isocyanate and carbodiimide-modified aromatic isocyanate which is hence assumed to particularly contribute to lowering the electrical resistance.
  • part (B) comprises monomeric aromatic isocyanate, preferably monomeric MDI or TDI, more preferably monomeric MDI.
  • monomeric aromatic isocyanate preferably monomeric MDI or TDI, more preferably monomeric MDI.
  • part (B) comprises carbodiimide-modified aromatic isocyanate, preferably carbodiimide-modified MDI or TDI, more preferably carbodiimide-modified MDI.
  • carbodiimide-modified aromatic isocyanate preferably carbodiimide-modified MDI or TDI, more preferably carbodiimide-modified MDI.
  • part (B) comprises monomeric aromatic isocyanate and carbodiimide-modified aromatic isocyanate, preferably monomeric MDI and carbodiimide-modified MDI or monomeric TDI and carbodiimide-modified TDI, more preferably monomeric MDI and carbodiimide-modified MDI.
  • monomeric MDI and carbodiimide-modified MDI or monomeric TDI and carbodiimide-modified TDI more preferably monomeric MDI and carbodiimide-modified MDI.
  • part (B) comprises carbodiimide-modified aromatic isocyanate and polymeric aromatic isocyanate, preferably carbodiimide-modified MDI and polymeric MDI or carbodiimide-modified TDI and polymeric TDI, more preferably carbodiimide-modified MDI and polymeric MDI.
  • part (B) comprises monomeric aromatic isocyanate and polymeric aromatic isocyanate, preferably monomeric MDI and polymeric MDI or monomeric TDI and polymeric TDI, more preferably monomeric MDI and polymeric MDI.
  • part (B) comprises carbodiimide-modified aromatic isocyanate, preferably carbodiimide-modified MDI or TDI, more preferably carbodiimide-modified MDI, and a plasticizer, preferably a fatty acid ester-based plasticizer.
  • a composition comprised by part (B) further improved workability, e.g. reduced viscosity can be achieved.
  • part (B) comprises polymeric aromatic isocyanate, preferably polymeric MDI orTDI, more preferably polymeric MDI, and a plasticizer, preferably a fatty acid ester-based plasticizer.
  • a plasticizer preferably a fatty acid ester-based plasticizer.
  • part (B) comprises monomeric aromatic isocyanate, preferably monomeric MDI or TDI, more preferably monomeric MDI, and a plasticizer, preferably a fatty acid ester-based plasticizer.
  • a plasticizer preferably a fatty acid ester-based plasticizer.
  • part (B) comprises carbodiimide-modified aromatic isocyanate, preferably carbodiimide-modified MDI or TDI, more preferably carbodiimide-modified MDI, and a quaternary ammonium salt.
  • carbodiimide-modified aromatic isocyanate preferably carbodiimide-modified MDI or TDI, more preferably carbodiimide-modified MDI, and a quaternary ammonium salt.
  • part (B) comprises polymeric aromatic isocyanate, preferably polymeric MDI orTDI, more preferably polymeric MDI, and a quaternary ammonium salt.
  • polymeric aromatic isocyanate preferably polymeric MDI orTDI, more preferably polymeric MDI, and a quaternary ammonium salt.
  • part (B) comprises monomeric aromatic isocyanate, preferably monomeric MDI or TDI, more preferably monomeric MDI, and a quaternary ammonium salt.
  • the carbon nanotubes are single-wall carbon nanotubes.
  • the dispersibility of single-wall carbon nanotubes in part (B) is usually better than the dispersibility of multi-wall carbon nanotubes, leading to a better distribution of the carbon nanotubes in part (B).
  • multi-wall carbon nanotubes usually increase the processing viscosity of the carbon nanotubes in part (B) so that single-wall carbon nanotubes are also preferred from the viewpoint of a reduced processing viscosity.
  • part (A) comprises Ca(OH) 2 , preferably > 20 wt.% Ca(OH) 2 based on the total weight of part (A).
  • part (A) and part (B) of the coating system according to the present invention are mixed to form a coating, part (A) and part (B) react with each other.
  • the at least one polyol in part (A) and the at least one isocyanate in part (B) react with each other to form polyurethane.
  • Produced CO 2 can lead to an undesired foaming of the coating, but the Ca(OH) 2 acts as a CO 2 -scavenger and reacts with the CO 2 to yield CaCO 3 and H 2 O.
  • the Ca(OH) 2 preferably comprised by part (A) can prevent an undesired foaming of the coating. This effect is particularly pronounced when the Ca(OH) 2 is more preferably comprised by part (A) in an amount of > 20 wt.%, wherein the weight percentage is calculated based on the total weight of part (A).
  • part (A) comprises particles of at least one basic metal compound independently selected from the group consisting of basic metal oxide compounds and basic metal hydroxide compounds, and at least one chelating agent comprising at least two functional groups capable of binding to a cation of said metal.
  • the basic metal compound is preferably selected from calcium oxide, magnesium oxide, calcium hydroxide and magnesium hydroxide, more preferably from calcium oxide and calcium hydroxide, and is most preferably calcium oxide.
  • the presence of the basic metal compound prevents the formation of bubbles or blisters in a coating from the coating composition according to the present invention, particularly on the surface of the coating, by capturing or quenching CO 2 which may be generated by the reaction of isocyanate compounds with water as described above.
  • the chelating agent is preferably selected from amino acids, particularly naturally occurring amino acids, more preferably proteinogenic amino acids, polyphosphonic acids including diphosphonic acids, triphosphonic acids, tetraphosphonic acids and pentaphosphonic acids, phosphoric acids, phosphonic acids, sulfonic acids including monosulfonic acids having at least one further functional group selected from the group consisting of amino and hydroxy, disulfonic acids and polysulfonic acids, superplasticizers, carboxylic esters, carboxylic anhydrides, polyhydroxy carboxylic acids, carboxylic acids, polycarboxylic acids, such as e.g.
  • dicarboxylic acids dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids and polycarboxylic acids, bidentate chelating agents, such as e.g. acetylacetone (acac), ethylenediamine (en), oxalate (ox), tartrate (tart), dimethylglyoxime (dmg), 8-hydroxychinoline (oxin), 2,2’- bipyridine (bpy), 1 ,10-phenanthroline (phen), dimercaptosuccinic acid (DMSA) and 1 ,2- bis(diphenylphosphino)ethane, tridentate chelating agents, such as e.g.
  • bidentate chelating agents such as e.g. acetylacetone (acac), ethylenediamine (en), oxalate (ox), tartrate (tart), dimethylglyoxime (dmg), 8-hydroxychinoline (oxin), 2,2’
  • 2-(2- aminoethylamino)ethanol AEEA
  • diethylenetriamine dien
  • iminodiacetate ida
  • citrate cit
  • tetradentate chelating agents such as e.g. triethylenetetramine (trien, TETA), triaminotriethylamin (tren), nitrilotriacetate (nta), bis(salicylidene)ethylenediamine (salen), pentadentate chelating agents, such as e.g. ethylenediaminetriacetate (ted), hexadentate chelating agents, such as e.g.
  • EDTA ethylenediaminetetraacetate
  • octadentate chelating agents such as e.g. diethylenetriaminepentaacetate (DTPA) and 1 ,4,7,10-tetraazacyclododecane-1 ,4,7,10-tetraacetate (DOTA)
  • decadentate chelating agents such as e.g. triethylenetetraminehexaacetate (TTHA).
  • part (A) is an aqueous emulsion, i.e., an emulsion of the at least one polyol in water.
  • the at least one polyol comprised by part (A) can be stored in a safe manner, and its concentration can be easily adjusted as needed.
  • additional components of part (A) for example a CO 2 -scavenger like Ca(OH) 2 , can be easily dispersed in part (A).
  • part (A) comprises a source of chemically bound water to take part in a urea-forming reaction.
  • chemically bound water means water that is bound in crystalline form, for example in ettringite, calcium silicate hydrate, aluminium hydroxide, zeolites, and the like. These materials may also be used in combination with each other and/or in combination with CO 2 scavengers, more preferred in combination with Ca(OH) 2 .
  • Preferred for the composition of part (B) is a content of aliphatic isocyanate(s) in the range of from 0% to 100% by weight, based on the total weight of part (B) (corresponding to a range of from 0% to 70% by weight, based on the total weight of the coating system) and/or a content of aromatic isocyanate(s) in the range of from 0% to 80% by weight, based on the total weight of part (B) (corresponding to a range of from 0% to 60% by weight, based on the total weight of the coating system).
  • the aromatic isocyanate(s) in part (B) it is preferred to have a content of carbodiimide modified aromatic isocyanate(s) in the range of from 0% to 90% by weight, based on the total weight of part (B) (corresponding to a range of from 0% to 60% by weight, based on the total weight of the coating system), a content of polymeric aromatic isocyanate(s) in the range of from 0% to 75% by weight, based on the total weight of part (B) (corresponding to a range of from 0% to 50% by weight, based on the total weight of the coating system), and/or a content of monomeric aromatic isocyanate(s) in the range of from 0% to 90% by weight, based on the total weight of part (B) (corresponding to a range of from 0% to 60% by weight, based on the total weight of the coating system).
  • the aforementioned weight percentage ranges apply particularly to those coating systems and/or compositions of part (B) in which the aromatic isocyanate is MDI, particularly polymeric MDI, carbodiimide-modified MDI and/or monomeric MDI, preferably carbodiimide-modified MDI and/or monomeric MDI.
  • the aforementioned weight percentage ranges also apply particularly to those coating systems and/or compositions of part (B) in which the aromatic isocyanate is TDI, particularly polymeric TDI, carbodiimide-modified TDI and/or monomeric TDI, preferably carbodiimide- modified TDI and/or monomeric TDI.
  • the coating system does not comprise an amine compound.
  • An amine compound (especially a primary amine having an -NH 2 group and/or a secondary amine having a -NHR group with R being a hydrocarbon group such as alkyl, alkenyl and alkynyl) may interfere in the reaction between the at least one polyol comprised by part (A) and the at least one isocyanate comprised by part (B) and may in particular react itself with the isocyanate comprised by part (B). Such an interference may reduce the bond strength of the formed coating.
  • it is preferred that no amine compound (or amine) is present in the coating system according to the present invention.
  • the coating system does not comprise an epoxy compound.
  • An epoxy compound may interfere in the reaction between the at least one polyol comprised by part (A) and the at least one isocyanate comprised by part (B) and may in particular react itself with the polyol comprised by part (A). Such an interference may reduce the bond strength of the formed coating. Hence, it is preferred that no epoxy compound is present in the coating system according to the present invention.
  • Subject of the invention is also a coating prepared from a coating system according to the present invention by mixing parts (A) and (B).
  • the preferred embodiments of the coating system described herein including the claims are likewise preferred for this coating in an analogous manner. Due to its low electrical resistance, such a coating can have improved anti-static properties, and due to its high bond strength, such a coating can have an improved adhesion to a substrate, in particular to a concrete substrate.
  • Subject of the invention is also the use of a coating system according to the present invention for coating a substrate.
  • the substrate is preferably a concrete substrate.
  • the preferred embodiments of the coating system described herein including the claims are likewise preferred for the inventive use in an analogous manner.
  • the use according to the present invention yields a coated substrate, or a substrate having a coating. Due to the high bond strength of the coating, the adhesion between the substrate and the coating can be improved. Further, due to low electrical resistance of the coating, the substrate may advantageously be used in environments requiring anti-static properties, especially where flammable substances are present. Additionally, due to the simultaneously low electrical resistance and high bond strength of the coating, no further coating layer such as a diffusion barrier layer needs to be applied.
  • the coating system according to the present invention can thus be used for instance for flooring, coating a wall or ceiling, creating a (waterproof) membrane, coating truck beds and loading areas in vessels such as cars, trucks, railway wagons and carriages, and marine vessels such as ferries and ships, and aircraft.
  • a coating method comprising the steps of
  • step (iii) applying the mixture obtained in step (ii) onto the substrate.
  • the substrate is preferably concrete, e.g. a concrete slab or concrete surface.
  • the preferred embodiments of the coating system described herein including the claims are likewise preferred for the inventive coating method in an analogous manner.
  • the coating method according to the present invention provides a coating which has improved anti-static properties as well as improved adhesion to a substrate, in particular to a concrete substrate. Additionally, because of its simultaneously improved anti-static properties and adhesion to a substrate, the coated substrate obtained by the coating method according to the present invention does not require an additional diffusion barrier layer.
  • part (B) of the coating system is regularly prepared by mixing the at least one isocyanate and the carbon nanotubes. It has been found that in the coating method according to the present invention, the carbon nanotubes are distributed more uniformly in part (B). Further, the carbon nanotubes are incorporated into part (B) at a reduced processing viscosity.
  • the electrical resistance is measured according to DIN EN 61340-4-1 :2016-04. More specifically, a copper strip is glued in the middle of an approx. 0.24 m 2 (40 x 60 cm 2 ) Pavatex panel so that it overlaps approx. 5 cm inwards and outwards. Afterwards, MasterTop P 687 WAS conductive varnish (consumption 24 g per panel) is rolled on in a criss-cross pattern. After drying overnight at room temperature, the leakage resistance of the panel can be measured which shall be ⁇ 10 kQ. The Pavatex panel prepared in this way is sealed all around with a pre-laying tape so that no material can leak out.
  • Parts (A) and (B) of the to-be-tested coating system are weighed out with the appropriate mixing ratio and are homogenized well with a wooden spatula.
  • the resulting mixture is applied evenly to the conductive varnish by means of a toothed squeegee.
  • the specimen is then cured on a horizontal surface for 24 h at room temperature.
  • the electrical resistance is then measured using a Unilap ISO as an appropriate testing device. The defined standard conditions for this measurement are 23°C and 50 ⁇ 10% humidity.
  • the measured resistance value is read on the display of the measuring device and is then documented. Twenty (20) measurements are taken at different points per sample plate so that an average value can be determined from this. The thereby determined electrical resistance is reported in Ohm (Q). However, if the determined value exceeds 2.999 GQ, the discharge capacity is too low and is assessed as a faulty measurement.
  • the bond strength is measured according to DIN EN 1542:1999-07. More specifically, the surface of a concrete panel of 40x40 cm is blasted to be fat-free, dry and smooth. Thereafterthe surface of the concrete panel is coated with a coating prepared from the exemplified coating systems by mixing parts (A) and (B) thereof. On top thereof, MasterSeal M 790AS is applied in an amount of 0.8 kg/m 2 as a body coat. Four annular grooves are formed in the coated concrete panel using drilling heads each having a diameter of 5 cm. Four threaded punches are glued to the annular grooves using a two- component epoxy resin as an adhesive. The thereby produced specimen is allowed to dry for seven days (at standard climate, 23°C, 50% relative humidity).
  • a testing device (Freundl F 20+5 Easy DM 20200-20kN) is screwed onto the threads of the punches.
  • the motor of the testing device is started, and the device pulls the punches off from the coated concrete panel at a defined force of 6 kN. From the given diameter of the punches and the force at complete pull-off of the punches, the bond strength is determined and is reported in N/mm 2 or MPa.
  • the following composition was used to produce a part (B) of an inventive coating system:
  • the isocyanates Lupranat MM 103 and Lupranat M 20 R were mixed in a mixer (dissolver) under nitrogen atmosphere and then stirred for 5 min at approx. 500 rpm.
  • the carbon nanotubes Tuball Matrix 202 were added and the composition was stirred for another 5 min at 700 rpm.
  • the carbon nanotubes were uniformly dispersed in the composition by stirring at approx. 2000 rpm until a paste-like consistency was obtained (obtained after 5 min).
  • the stirring speed was then increased to 3000 rpm, and the stirring was continued for another 10 to 15 min.
  • the electrical resistance of the resulting coating was determined as described herein and was found to be 9.8 kQ (9,800 Ohm).
  • the bond strength (sometimes also referred to as adhesive strength or pull-off strength) of the resulting coating was determined as described herein and was found to be 3.5 MPa (N/mm 2 ).
  • Example 1 demonstrates that the combined use of a carbodiimide-modified MDI and a polymeric MDI in part (B) of an inventive coating system simultaneously leads to an improved electrical resistance and an improved bond strength.
  • composition was used to produce a part (B) of an inventive coating system:
  • the part (B) was produced in the same manner as in Example 1 except for using Lupranat Ml instead of Lupranat MM 103. Thereafter a coating was prepared and the electrical resistance thereof was determined also in the same manner as in Example 1. As a result, an electrical resistance of 16 kQ (16,000 Ohm) was determined. Further, the bond strength of the resulting coating was determined as described herein and was found to be 3.3 MPa (N/mm 2 ).
  • Example 2 demonstrates that the use of a monomeric MDI in part (B) of an inventive coating system simultaneously leads to an improved electrical resistance and an improved bond strength.
  • composition was used to produce a part (A) of a comparative coating system:
  • a polyol-containing standard part (A) of a MasterSeal P770 two-component polyurethane system (“P 770 PT A”) was added to a mixer and was stirred at approx. 600 rpm. Thereafter, Tuball Matrix 202, 10% in Disflamoll DPK, was added as carbon nanotubes and mixed into part (A) at approx. 700 rpm. Next, the carbon nanotubes were dispersed at approx. 2000 rpm. The rotational speed was increased during the dispersing process to 3000 rpm, and it was dispersed for in total approx. 30 min until a gel-like consistency is achieved.
  • Part (A) showed decomposition and was inhomogeneous.
  • the electrical resistance of the resulting coating was determined as described herein and was found to be > 2,999 GQ (> 2.9*10 12 Ohm).
  • the bond strength of the resulting coating was determined as described herein and was found to be 3.5 MPa (N/mm 2 ).
  • composition was used to produce a part (A) of a comparative coating system:
  • the part (A) was prepared in the same manner as in Comparative Example 1 except for using Tuball Matrix 202, 5% in Novares LA 700, as carbon nanotubes.
  • the produced part (A) showed decomposition and was inhomogeneous.
  • a coating was prepared in the same manner as in Comparative Example 1 , and the electrical resistance was also determined in the same manner as in Comparative Example 1. As a result, an electrical resistance of > 2,999 GQ (> 2.9*10 12 Ohm) was determined. Further, the bond strength of the resulting coating was determined as described herein and was found to be 3.1 MPa (N/mm 2 ). Like in Comparative Example 1 , it was also tried to stabilize and to homogenize the produced part (A) by adding 1 wt.% Byk P 104 S as a dispersing additive. However, no improvement was achieved.
  • compositions were used to produce a respective part (B) of an inventive coating system:
  • Part (B) was prepared in a manner analogous to Example 1 .
  • Mseal P 770 PTA Standard was applied in an amount of 0.25 to 0.4 kg/m 2
  • the electrical resistance of the resulting coating was determined as described herein after 7 d.
  • the determined electrical resistances are summarized in the following table:
  • Lupranat M 20 R used in Comparative Example 3 is a polymeric MDI and Lupranat MM 103 used in Comparative Example 4 is a carbodiimide-modified MDI.
  • Lupranat Ml used in Example 3 is a monomeric MDI (2,4'MDI and 4,4'MDI in a weight ratio of 50/50).
  • Tuball Matrix 202 as used in Comparative Examples 3 and 4 and also in Example 3 is composed of single-wall carbon nanotubes (SCNT). From the determined electrical resistances, it is seen that the use of a monomeric MDI in part (B) of an inventive coating composition leads to particularly improved antistatic properties of the resulting coating.
  • compositions were used to produce a respective part (B) of an inventive coating system:
  • Part (B) was prepared in a manner analogous to Example 1 .
  • Mseal P 770 PTA Standard was applied in an amount of 0.25 to 0.4 kg/m 2
  • the electrical resistance of the resulting coating was determined as described herein after 7 d.
  • the determined electrical resistances are summarized in the following table:
  • the material Oxfilm 351 additionally used in these (Comparative) Examples is a fatty acid ester-based plasticizer. It is seen that the use of such a plasticizer lowered the electrical resistance for the composition containing a monomeric MDI in part (B) as well as for the composition containing a carbodiimide- modified MDI in part (B). While the plasticizer slightly increased the electrical resistance of the composition containing a monomeric MDI in part (B), the same trend as previously is observed, namely that the electrical resistance drops in the order polymeric MDI > carbodiimide-modified MDI ⁇ monomeric MDI as a component of part (B).
  • compositions were used to produce a respective part (B) of an inventive coating system:
  • Part (B) was prepared in a manner analogous to Example 1 .
  • Mseal P 770 PTA Standard was applied in an amount of 0.25 to 0.4 kg/m 2
  • the material EFKA IO 6783 additionally used in these (Comparative) Examples is composed of a liquid quaternary ammonium salt which acts as a conductive additive and lowers the electrical resistance in all cases.
  • the electrical resistance is particularly lowered when a carbodiimide modified MDI or a monomeric MDI is used as an isocyanate component in part (B) of the respective coating system.
  • the electrical resistance drops in the order polymeric MDI > carbodiimide-modified MDI ⁇ monomeric MDI as a component of part (B).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne un système de revêtement qui comprend une partie (A) comprenant au moins un polyol portant au moins deux groupes hydroxy, et une partie (B) comprenant au moins un isocyanate portant au moins deux groupes isocyanate et comprenant des nanotubes de carbone, les parties (A) et (B) étant physiquement séparées l'une de l'autre, et un revêtement produit par mélange des parties (A) et (B) ayant une résistance électrique ≤ 80 kΩ, mesurée selon la norme DIN EN 61340-4-1:2016-04, et une résistance de liaison ≥ 1,5 MPa, mesurée selon la norme DIN EN 1542:1999-07.
PCT/EP2023/080890 2022-11-04 2023-11-06 Système de revêtement antistatique WO2024094900A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP22205635.0 2022-11-04
EP22205635 2022-11-04

Publications (1)

Publication Number Publication Date
WO2024094900A1 true WO2024094900A1 (fr) 2024-05-10

Family

ID=84245884

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2023/080890 WO2024094900A1 (fr) 2022-11-04 2023-11-06 Système de revêtement antistatique

Country Status (1)

Country Link
WO (1) WO2024094900A1 (fr)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110147675A1 (en) * 2008-08-20 2011-06-23 Bayer Materialscience Ag Antistatic or electronically conductive polyurethanes, and method for the production thereof
CN108219658A (zh) 2017-12-28 2018-06-29 姜菊芳 一种耐腐蚀聚氨酯涂料及其制备方法
CN108559050A (zh) * 2018-05-11 2018-09-21 美瑞新材料股份有限公司 一种抗静电、导电热塑性聚氨酯弹性体及其制备方法
EP3670470A1 (fr) 2018-12-17 2020-06-24 STO SE & Co. KGaA Composition de revêtement pour revêtement de sol
CN111808464A (zh) 2020-07-30 2020-10-23 绵阳惠利环氧工程有限公司 一种防静电耐磨地坪涂料及其制备方法
CN112852269A (zh) 2021-01-14 2021-05-28 青岛爱尔家佳新材料股份有限公司 一种用于石油石化行业抗静电聚脲涂料及其制备方法
US20220056277A1 (en) 2020-08-21 2022-02-24 Sumitomo Rubber Industries, Ltd. Highly antistatic coating floor material and coating floor
WO2022049070A1 (fr) 2020-09-01 2022-03-10 Sika Technology Ag Revêtement de résine époxyde électroconducteur et sol à dissipation électrostatique
WO2022049071A1 (fr) 2020-09-01 2022-03-10 Sika Technology Ag Revêtement de résine époxy transparent conducteur de l'électricité et plancher dissipatif électrostatique

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110147675A1 (en) * 2008-08-20 2011-06-23 Bayer Materialscience Ag Antistatic or electronically conductive polyurethanes, and method for the production thereof
EP2315810B1 (fr) 2008-08-20 2013-10-02 Bayer Intellectual Property GmbH Polyuréthanes antistatiques ou électroconducteurs et procédé de production
CN108219658A (zh) 2017-12-28 2018-06-29 姜菊芳 一种耐腐蚀聚氨酯涂料及其制备方法
CN108559050A (zh) * 2018-05-11 2018-09-21 美瑞新材料股份有限公司 一种抗静电、导电热塑性聚氨酯弹性体及其制备方法
EP3670470A1 (fr) 2018-12-17 2020-06-24 STO SE & Co. KGaA Composition de revêtement pour revêtement de sol
CN111808464A (zh) 2020-07-30 2020-10-23 绵阳惠利环氧工程有限公司 一种防静电耐磨地坪涂料及其制备方法
US20220056277A1 (en) 2020-08-21 2022-02-24 Sumitomo Rubber Industries, Ltd. Highly antistatic coating floor material and coating floor
WO2022049070A1 (fr) 2020-09-01 2022-03-10 Sika Technology Ag Revêtement de résine époxyde électroconducteur et sol à dissipation électrostatique
WO2022049071A1 (fr) 2020-09-01 2022-03-10 Sika Technology Ag Revêtement de résine époxy transparent conducteur de l'électricité et plancher dissipatif électrostatique
CN112852269A (zh) 2021-01-14 2021-05-28 青岛爱尔家佳新材料股份有限公司 一种用于石油石化行业抗静电聚脲涂料及其制备方法

Similar Documents

Publication Publication Date Title
US20160024310A1 (en) Pocess for providing metallic substrates with corrosion resistance
KR102469487B1 (ko) 수성 코팅
JP4850522B2 (ja) 硬化型樹脂組成物用表面処理炭酸カルシウム填料、及び該填料を含有してなる硬化型樹脂組成物
US4582891A (en) Process for inhibiting corrosion of polyurethane coating
JP5400005B2 (ja) エポキシ樹脂組成物及びそれを含む塗料組成物
EP2368945A2 (fr) Revêtements résistants à la corrosion
Koh et al. Self-anticorrosion performance efficiency of renewable dimer-acid-based polyol microcapsules containing corrosion inhibitors with two triazole groups
Attaei et al. Smart epoxy coating modified with isophorone diisocyanate microcapsules and cerium organophosphate for multilevel corrosion protection of carbon steel
Koh et al. Microencapsulation of the triazole derivative for self-healing anticorrosion coatings
SE446100B (sv) Malningssystem pa basis av fuktighetsherdande polyisocyanat-forpolymer och anvendning derav for beskickning av stalytor
US4555536A (en) Anti-corrosive coating composition
BR112014001986B1 (pt) pigmentos revestidos com liga de alumínio e revestimentos resistentes à corrosão
JP2006257142A (ja) 二液硬化型水性被覆組成物及び基材
WO2024094900A1 (fr) Système de revêtement antistatique
US5393567A (en) Powder mixture for making an undercoating agent for steel surfaces
KR101969646B1 (ko) 중방식 도장용 도료 키트
JPH1036481A (ja) 一液湿気硬化型ウレタン組成物及び接着剤
JP2019112626A (ja) 防食性に優れた水性塗料組成物
KR101317645B1 (ko) 트리아졸계 화합물 함유 폴리우레탄 마이크로캡슐 방청제, 이의 제조방법 및 이를 포함하는 방청성이 우수한 다층 도막
RU2177019C2 (ru) Антикоррозионная лакокрасочная композиция
Shirke et al. Enhancement of physico-chemical and anti-corrosive properties of tung oil based polyurethane coating via modification using anhydrides and inorganic acid
JP5767670B2 (ja) プライマー組成物及び被覆鋼材
RU2537001C2 (ru) Однослойный антикоррозионный лакокрасочный материал на основе эпоксидного связующего с углеродными нанотрубками
JP2005306892A (ja) 水性防水材組成物
RU2169165C1 (ru) Антикоррозионная лакокрасочная композиция

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23802191

Country of ref document: EP

Kind code of ref document: A1