WO2009141438A2 - Novel fast curing ultra high solids low voc coating system for aggressive corrosive environments - Google Patents

Novel fast curing ultra high solids low voc coating system for aggressive corrosive environments Download PDF

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Publication number
WO2009141438A2
WO2009141438A2 PCT/EP2009/056248 EP2009056248W WO2009141438A2 WO 2009141438 A2 WO2009141438 A2 WO 2009141438A2 EP 2009056248 W EP2009056248 W EP 2009056248W WO 2009141438 A2 WO2009141438 A2 WO 2009141438A2
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WO
WIPO (PCT)
Prior art keywords
epoxy
coat
composition
primer
primer composition
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PCT/EP2009/056248
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French (fr)
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WO2009141438A3 (en
Inventor
Karl-Johan Hansen
Søren Mørch NYSTEEN
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Hempel A/S
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Application filed by Hempel A/S filed Critical Hempel A/S
Priority to KR1020107029049A priority Critical patent/KR101694425B1/en
Priority to CN2009801269648A priority patent/CN102089347B/en
Priority to BRPI0913054-3A priority patent/BRPI0913054B1/en
Priority to EP09749928A priority patent/EP2283056B1/en
Priority to ES09749928T priority patent/ES2394149T3/en
Priority to PL09749928T priority patent/PL2283056T3/en
Priority to DK09749928.9T priority patent/DK2283056T3/en
Publication of WO2009141438A2 publication Critical patent/WO2009141438A2/en
Publication of WO2009141438A3 publication Critical patent/WO2009141438A3/en

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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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins

Definitions

  • the present invention relates to novel fast curing coating systems consisting of an epoxy primer and a polyurea top-coat.
  • the coating systems have improved drying time and low VOC and still maintain excellent rust creep resistance.
  • the present invention provides improved drying time and low VOC by using an ultra high solid polyurea top-coat on top of an epoxy primer.
  • the coating systems of the present invention are non-thermosetting compositions.
  • Epoxy coatings are used mainly as part of an anti -corrosive coating system on steel substrates due to outstanding corrosion and chemical resistance.
  • Epoxy coating compositions are typically one or two-component products. If the product is two-component, component one normally consists of an epoxy base and component two consists of a curing agent. If the epoxy is a zinc epoxy, the zinc will normally be present in the base composition.
  • Zinc epoxies are superior to standard epoxies concerning anticorrosive properties due to their function as a sacrificial anode applied directly on top of the clean steel surface. When the coating layer is damaged the zinc will protect the damage by a galvanic process. The function is similar to that of galvanized steel.
  • Epoxies can be used as a primer, i.e. first coating layer in a multiple coat system with subsequent layers of suitable generic types of coatings, or as an intermediate coat with subsequent suitable coats e.g. polyurethane or polyurea, or as a top-coat.
  • suitable generic types of coatings e.g. polyurethane or polyurea
  • top-coat e.g. epoxy paints
  • epoxy paints can also be used as one-coat systems.
  • Polyurea is the general term used for coatings based on amines reacted with iso-cyanates or poly-isocyanates.
  • the polymerization reaction between amine and isocyanates is in general extremely fast.
  • Both aromatic and aliphatic isocyanates are used in polyurea coatings. However, it is only aliphatic iso-cyanates that give acceptable outdoor durability.
  • Poly aspartic acid esters are a special type of polyurea binder where an amine is pre-reacted with di-ethyl maleate. The amine functionality is by this pre-reaction becoming partly sterically hindered. The reaction speed is dependent on the amine used.
  • Poly aspartic esters are available in different reaction speed from fast to slow reaction polymers.
  • Polyurea top-coats based on poly aspartic acid esters are well known to give excellent outdoor durability with excellent gloss and color stability.
  • Poly aspartic esters can be designed to give fast cure at ambient condition and with the partly sterical hindrance of the amine the reaction speed gives a reasonable pot-life to be handled in either two-component application equipment or standard airless spray equipment.
  • Epoxy and polyurea paint systems are normally used where superior corrosion protection and fast process time is needed.
  • Such paint systems are designed to be used in aggressive corrosive environments like off-shore platforms, windmill towers, steel chimneys, power stations, steel bridges, cranes etc. in costal, off-shore, or industrial environments, but also tidal zone areas where fast salt water resistance is required.
  • Corrosive environments are rated according to ISO 12944 on a scale from C2 to C5 with C2 being mildly corrosive and C5 being an aggressively corrosive environment.
  • the curing process starts on the surface of the coating.
  • the soft uncured part of the coating will not have sufficient strength to "carry” the stress built up during curing and defects will develop on the surface leading to subsequent loss of adhesion, cohesion and corrosion problems.
  • VOC Volatile Organic Compound
  • the present invention provides a high solids coating system consisting of an epoxy primer and a top-coat, enabling faster processing time and low VOC.
  • the present invention relates to coating system according to claim 1.
  • the present invention also provides a coated structure carrying such a coating system, cf. claim 9, and a method for the establishment of a coated structure, cf. claim 10.
  • the present invention also provides a zinc epoxy primer composition, cf. claim 12, and an epoxy primer composition, cf. claim 14.
  • the present invention relates to a coating system consisting of:
  • a first layer of a primer composition comprising an epoxy-based binder system, said primer composition having a volume solids % of at least 82 %;
  • a second layer of top-coat composition comprising a polyurea-based binder system, said top-coat composition having a volume solids % of at least 82 %.
  • coating system is intended to mean the combination of the first and second layers in wet form when applied to the surface of a substrate. It should be understood that the second layer is applied subsequent to the first layer so as to be in direct contact with said first layer. It should further be understood that one or more layers of other coating compositions may be applied to the surface of the substrate prior to the application of the first layer, although such other coating layer are generally not necessary or desirable. Moreover, it should be understood that one or more layers of other coating compositions may be applied subsequent to the application of the second layer, although such other coating layer are generally not necessary or desirable.
  • the coating system consists of the above-defined first and second layers, where the first layer is in direct contact with the surface of the substrate and where the second layer is the outermost layer.
  • the coating systems disclosed herein are designed to cure at ambient temperatures (i.e. typically the temperature at the location at which the coating system is applied, e.g. in paint shops or outdoor where the temperature will depend on the general climate at the geographical location), e.g. at temperatures of 0-50 0 C (either in cold or in very hot regions of the world), such as 5-30 0 C, in particular about 15-25 0 C, such as around 20 0 C.
  • the coating system disclosed herein is of the non-thermosetting type.
  • other coating systems are of the thermosetting type, which require heating of the substrate with the coating to temperature of several hundred degrees Celsius. Such conditions are of course in practise inapplicable with the types of substrates for which the present coating systems are designed.
  • a particular feature of the coating system of the invention is the very high volume solids % ("VS%") and thereby the low content of volatile organic compounds (VOC).
  • the primer composition has a volume solids % of at least 82 %, such as at least 84 %, e.g. at least 85 %.
  • the top-coat composition has a volume solids % of at least 82 %, such as at least 84 %, e.g. at least 85 %.
  • the weighed average volume solids % of the coating system is at least 84 %, such as at least 85 %, e.g. at least 86 %.
  • the volume solids (expressed in %) is often referred to as "VS%".
  • VS% is determined according to ISO 3233 with the modification that drying is carried out at 23 0 C and 50 % relative humidity for 7 days instead of drying at higher temperatures.
  • weighed average volume solids % refers to average of volume solid percentages taking into account that the primer composition and the top-coat composition may not be applied with the same wet film thicknesses. If the primer composition having a VS% of 90 % is applied in a thickness of 200 ⁇ m and a top-coat composition having a VS% of 84 % is applied in a thickness of 100 ⁇ m, the weighed average volume solids % will be 88 %.
  • VOC very low content renders it possible to establish a fast curing coating system which has a very short "dry-to-handle” time, i.e. preferably a "dry-to-handle” time which is less than 11 hours at 20 0 C.
  • the "dry-to-handle” time is less than 9 hours at 20 0 C, or even less than 7 hours at 20 0 C.
  • the "dry-to-handle” time is conveniently determined as described in the Examples section.
  • VOC Volatile Organic Compound
  • the coatings system of the present invention has very low VOC emission compared to the coatings systems as presented in Table 5.
  • VOC can be determined by various methods e.g. ISO 11890 or EPA method 24.
  • the first layer of the primer composition comprises an epoxy-based binder system.
  • the primer composition may further include other constituents as it is described further below.
  • the primer composition may include anticorrosive constituents and/or fibres.
  • epoxy-based binder system should be construed as the combination of one or more epoxy resins, one or more curing agents and any reactive epoxy diluents.
  • the epoxy-based binder system is one of the most important constituents of the primer composition, in particular with respect to the anticorrosive properties.
  • the epoxy-based binder system comprises one or more epoxy resins selected from aromatic or non-aromatic epoxy resins (e.g. hydrogenated epoxy resins), containing more than one epoxy group per molecule, which is placed internally, terminally, or on a cyclic structure, together with one or more suitable curing agents to act as cross-linking agents.
  • suitable curing agents to act as cross-linking agents.
  • Combinations with reactive diluents from the classes of functional glycidyl ethers or esters of aliphatic, cyclo aliphatic or aromatic compounds can be included in order to reduce viscosity and for improved application and physical properties.
  • the binder system can also include reactive acrylic modifiers such as acrylate monomers and oligomers comprising at least two alpha, beta unsaturated carbonyl groups, reacting with the one or more curing agents via a Michael- type addition reaction.
  • Suitable epoxy-based binder systems are believed to include epoxy and modified epoxy resins selected from bisphenol A, bisphenol F, Novolac epoxies, non-aromatic hydrogenated epoxies, cyclo aliphatic epoxies, glycidyl esters and epoxy functional acrylics or any combinations hereof.
  • Epikote 862 Ex Resolution Performance Products (The Netherlands), bisphenol F type DEN 438-X 80, ex Dow Chemical Company (USA), epoxy novolac Epikote 154, ex Resolution Performance Products (The Netherlands), epoxy novolac DYD-128, ex Dalian Qihua Chemicals, China, bisphenol A type Epikote 872-X-75, ex. Hexion (former Resolution performance products, Netherlands), bisphenol A/ epichlorohydrin resin reacted with dimer fatty acids.
  • the epoxy-based binder system can comprise one or more reactive epoxy diluents.
  • suitable commercially available reactive epoxy diluents are:
  • the epoxy primer composition can comprise one or more epoxy accelerators.
  • the epoxy-based binder system comprises one or more curing agents selected from compounds or polymers comprising at least two reactive hydrogen atoms linked to nitrogen.
  • Suitable curing agents are believed to include amines or amino functional polymers selected from aliphatic amines and polyamines ⁇ e.g. cyclo-aliphatic amines and polyamines), polyamido amines, polyoxy alkylene amines ⁇ e.g. polyoxy alkylene diamines), aminated polyalkoxy ethers ⁇ e.g. those sold commercially as "Jeffamines”), alkylene amines ⁇ e.g. alkylene diamines), aralkyl amines, aromatic amines, Mannich bases ⁇ e.g. those sold commercially as "phenalkamines”), amino functional silicones or silanes, and including epoxy adducts and derivatives thereof.
  • amines or amino functional polymers selected from aliphatic amines and polyamines ⁇ e.g. cyclo-aliphatic amines and polyamines), polyamido amines, polyoxy alkylene amines ⁇ e.g.
  • Adeka Hardener Ex Adeka Corporation (Japan), Mannich base CeTePox 1490 H, ex CTP Chemicals and Technologies for Polymers (Germany), polyoxyalkylene amine
  • Epoxy hardener MXDA Ex Mitsubishi Gas Chemical Company Inc (USA), aralkyl amine
  • Preferred epoxy-based binder systems comprises a) one or more epoxy resins selected from bisphenol A, bisphenol F and Novolac; and b) one or more curing agents selected from Mannich Bases, polyamido amines, polyoxy alkylene amines, alkylene amines, aralkyl amines, polyamines, and adducts and derivatives thereof.
  • the epoxy resin has an epoxy equivalent weight of 100-2000, such as 100-1500 e.g. 150-1000 such as 150-700.
  • Especially preferred epoxy-based binder systems comprises one or more bisphenol A epoxy resins having an epoxy equivalent weight of 150-700 and one or more polyamine or adducts and derivatives thereof.
  • Preferred epoxy-based binder systems are ambient curing binder systems.
  • the total amount of epoxy-based binder system is in the range of 15-80 %, such as 35-80 %, e.g. 40-75 % by solids volume of the primer composition. In one particularly interesting embodiment, the total amount is in the range of 45-55 % by solids volume. Without being bound to any particular theory, it is believed that the selection of the ratio between the hydrogen equivalents of the one or more curing agents and the epoxy equivalents of the one or more epoxy resins plays a certain role for the performance of the coating composition.
  • hydrogen equivalents is intended to cover only reactive hydrogen atoms linked to nitrogen.
  • the number of "hydrogen equivalents" in relation to the one or more curing agents is the sum of the contribution from each of the one or more curing agents.
  • the contribution from each of the one or more curing agents to the hydrogen equivalents is defined as grams of the curing agent divided by the hydrogen equivalent weight of the curing agent, where the hydrogen equivalent weight of the curing agent is determined as: grams of the curing agent equivalent to 1 mol of active hydrogen.
  • grams of the curing agent divided by the hydrogen equivalent weight of the curing agent is determined as: grams of the curing agent equivalent to 1 mol of active hydrogen.
  • the number of "epoxy equivalents" in relation to the one or more epoxy resins is the sum of the contribution from each of the one or more epoxy resins.
  • the contribution from each of the one or more epoxy resins to the epoxy equivalents is defined as grams of the epoxy resin divided by the epoxy equivalent weight of the epoxy resin, where the epoxy equivalent weight of the epoxy resin is determined as: grams of the epoxy resin equivalent to 1 mol of epoxy groups.
  • grams of the epoxy resin divided by the epoxy equivalent weight of the epoxy resin is determined as: grams of the epoxy resin equivalent to 1 mol of epoxy groups.
  • the ratio between the hydrogen equivalents of the one or more curing agents and the epoxy equivalents of the one or more epoxy resins is in the range of 50: 100 to 140: 100.
  • Especially preferred epoxy-based binder systems for use in Industrial corrosion protective coatings have a ratio between the hydrogen equivalents of the one or more curing agents and the epoxy equivalents of the one or more epoxy resins in the range of 60: 100 to 130: 100 such as 80: 100 to 120: 100, e.g. 90: 100 to 110: 100.
  • the epoxy primer composition may also comprise a particulate material (e.g. a powder) which increases the anticorrosive properties of the coat.
  • a particulate material e.g. a powder
  • Zinc powder or zinc dust which is well known to incorporate in epoxy primer to produce a zinc epoxy primer, is in this respect of special interest.
  • Zinc powder or zinc dust can all or partly be replaced by a zinc alloy, e.g. as disclosed in WO 2008/125610.
  • Auxiliary corrosion inhibitor for example a molybdate, phosphate, tungstate or vanadate, ultrafine titanium dioxide, and/or zinc oxide and/or a filler such as silica, calcined clay, alumina silicate, talc, barytes or mica may also be incorporated.
  • the D 50 of the particulate material being in the range of 2.5-30 ⁇ m, in particular 2.5-20 ⁇ m. With respect to the particle size, it is preferred that the D 50 of the particulate material is in the range of 2.5-15 ⁇ m, and preferably in the range of 2.5-12 ⁇ m. Additionally, the D 99 of the particulate material should preferably be less than 100 ⁇ m.
  • the particle size distribution of the particulate material e.g. zinc or a zinc alloy
  • a D 50 of less than 15 ⁇ m is often more preferred, and less than 12 ⁇ m is even more preferred.
  • the lower limit of the D 50 is dictated by economic considerations. At a D 50 of less than 2.5 ⁇ m, a too large fraction of the powder has to be sieved out and recycled for the complete process to run economically.
  • other relevant materials include phosphates, aluminum, graphite, carbon black, micaceous iron oxide (MIO), etc.
  • the amount of the anticorrosive constituent is typically 1-65 % by solids volume of the paint.
  • the primer composition comprises 20-35 % by solids volume of zinc, such as 25-30 % by solids volume of zinc.
  • the anticorrosive filler material may be present as a combination of one or more of the before-mentioned materials.
  • the anticorrosive constituents in particular zinc, are preferably present in the form of a particulate material.
  • particulate material is intended to cover both fine spherical or somewhat irregularly shaped particles and other shapes such as flakes, disc, spheres, needles, platelets, fibres and rods.
  • a preferred particulate material is a powder.
  • the coating system generally has excellent anticorrosive properties, in particular in the embodiments where zinc is included as described above.
  • particularly interesting embodiments are those where the rust creep of the dry coating system as determined according to ISO 12944-6 is at the most 1 mm.
  • the primer composition may also comprise fibres. Special fibres with high tensile strength will when incorporated in the epoxy matrix increase the ability to withstand higher mechanical stress. This facilitates the possibility to formulate epoxy coatings with even faster curing and higher cracking resistance at the same time.
  • fibres is intended to cover any fibres within the groups of natural inorganic fibres, synthetic inorganic fibres, natural organic fibres, synthetic organic fibres, and metallic fibres, or mixtures thereof. Without being bound to any specific theory, it is however presently believed that natural inorganic fibres and synthetic inorganic fibres, in particular mineral fibres of these types, are especially preferred.
  • the fibres to be used within the present invention should fulfil certain criteria with respect to dimensions in order to provide the improved properties of a coat of the primer composition.
  • such fibres have an average length, of at the most 250 ⁇ m and an average thickness of 1-50 ⁇ m
  • Preferred fibres are fibres having an average thickness of 1-25 ⁇ m and an average length, of at the most 250 ⁇ m, especially an average length of 25-250 ⁇ m and an average thickness of 1-25 ⁇ m, in particularly an average length of 50-250 ⁇ m (such as 50-170 ⁇ m) and an average thickness of 2-10 ⁇ m.
  • the preferred organic fibres furthermore have a ratio between the average length and the average thickness of at least 2, such as at least 3 e.g. at least 5.
  • the concentration of the fibres is normally in the range of 2-50 % by solids volume of the dry primer composition ⁇ i.e. the composition devoid of the solvents), such as 3-40 % by solids volume of the dry paint.
  • concentrations of fibres depending upon the type and size of the fibres, may be 4-35 %, such as 5-30 %, such as 6-25 %, such as 7-20 % by solids volume of the dry paint.
  • mineral fibres such as mineral-glass fibres, wollastonite fibres, tobermorite fibres, attapulgite fibres, volcanic rock fibres, bauxite fibres, rockwool fibres, and processed mineral fibres from mineral wool.
  • mineral-glass fibres such as Wollastonite, tobermorite fibres, attapulgite fibres, volcanic rock fibres, bauxite fibres, rockwool fibres, and processed mineral fibres from mineral wool.
  • the primer composition comprises:
  • the second layer of a top-coat composition comprises a polyurea-based binder system.
  • polyurea-binder system is intended to mean a binder system having as the primary components one or more di- or poly-isocyanate components and one or more di- or polyamine components. It should be understood that the amine component may be either primary or secondary in nature, i.e. they may include either one or two hydrogens (R-NH 2 or R-NH-R 1 ).
  • Reaction (curing) of the isocyanate component(s) and the amine component(s) results in the formation of a urea-functionality.
  • reaction of an isocyanate (R-NCO) with a secondary amine R'-NH-R"
  • the one or more di- or polyamine components include a secondary amine.
  • X represents an organic group which has a valence of n and which is inert towards isocyanate groups at temperatures of up to 100 0 C;
  • R 1 and R 2 each independently is selected from organic groups which are inert towards isocyanate groups at temperatures of up to 100 0 C;
  • R 3 and R 4 each independently is selected from hydrogen and organic groups which are inert towards isocyanate groups at temperatures of up to 100 0 C;
  • n is an integer of at least 2.
  • cross-linking which takes place is based on an addition reaction between poly-isocyanate component a) and isocyanate-reactive component b), in particular the polyamines containing secondary amino groups, which are also known as "polyaspartic acid derivatives.”
  • Suitable poly-isocyanates for use as poly-isocyanate component a) in the top-coat composition include the known poly-isocyanates of polyurethane chemistry.
  • suitable low molecular weight poly-isocyanates having a molecular weight of 168 to 300 include hexamethylene diisocyanate, 2,2,4-and/or 2,4,4-trimethyl-l,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 1-isocyanato- 3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 2,4'-and/or 4,4'-diisocyanato- dicyclohexyl methane, 2,4-and/or 4,4'-diisocyanato-diphenyl methane and mixtures of these isomers with their higher homologues which are obtained in known manner by the phosgenation of aniline
  • derivatives of these monomeric poly-isocyanates include poly-isocyanates containing biuret groups.
  • modified poly-isocyanates are particularly preferred : N,N',N"-tris-(6-isocyanatohexyl)- biuret and mixtures thereof with its higher homologues and N,N',N"-tris-(6-isocyanatohexyl)- isocyanurate and mixtures thereof with its higher homologues containing more than one isocyanurate ring.
  • Isocyanate group-containing prepolymers and semi-prepolymers based on the monomeric simple or modified poly-isocyanates exemplified above and organic polyhydroxyl compounds are also preferred for use as poly-isocyanate component a).
  • These pre-polymers and semi pre-polymers generally have an isocyanate content of 0.5-30 % by weight, preferably 1-20 % by weight, and are prepared in known manner by the reaction of the above mentioned starting materials at an NCO/OH equivalent ratio of 1.05: 1 to 10: 1 preferably 1.1 : 1 to 3: 1, this reaction being optionally followed by distillative removal of any un-reacted volatile starting poly-isocyanates still present.
  • the pre-polymers and semi pre-polymers may suitable be prepared from low molecular weight polyhydroxyl compounds having a molecular weight of 62 to 299, such as ethylene glycol, propylene glycol, trimethylol propane, 1,6-dihydroxy hexane; low molecular weight, hydroxyl-containing esters of these polyols with dicarboxylic acids of the type exemplified hereinafter; low molecular weight ethoxylation and/or propoxylation products of these polyols; and mixtures of the preceding polyvalent modified or unmodified alcohols.
  • low molecular weight polyhydroxyl compounds having a molecular weight of 62 to 299, such as ethylene glycol, propylene glycol, trimethylol propane, 1,6-dihydroxy hexane; low molecular weight, hydroxyl-containing esters of these polyols with dicarboxylic acids of the type exemplified hereinafter; low molecular weight ethoxy
  • the pre-polymers and semi pre-polymers are, however, preferably prepared from the known relatively high molecular weight polyhydroxyl compounds of polyurea chemistry which have a molecular weight of 300-8000, preferably 1000-5000, as determined from the functionality and the OH number. These polyhydroxyl compounds have at least two hydroxyl groups per molecule and generally have a hydroxyl group content of 0.5-17 % by weight, preferably 1-5 % by weight.
  • polyester polyols based on the previously described low molecular weight, monomeric alcohols and polybasic carboxylic acids such as adipic acid, sebacic acid, phthalic acid, isophthalic acid, tetrahydrophthalic acid, hexadydrophthalic acid, maleic acid, the anhydrides of these acids and mixtures of these acids and/or acid anhydrides.
  • Hydroxyl group-containing polylactones especially poly- ⁇ -caprolactones, are also suitable for the preparation of the pre-polymers and semi pre-polymers.
  • Polyether polyols which are obtained in known manner by the alkoxylation of suitable starting molecules, are also suitable for the preparation of the isocyanate group-containing pre-polymers and semi pre-polymers.
  • suitable starting molecules for the polyether polyols include the previously described monomeric polyols, water, organic polyamines having at least two NH bonds and any mixtures of these starting molecules.
  • Ethylene oxide and/or polylene oxide are particularly suitable alkylene oxides for the alkoxylation reaction. These alkylene oxides may be introduced into the alkoxylation reaction in any sequence or as a mixture.
  • hydroxyl group-containing polycarbonates which may be prepared by the reaction of the previously described monomeric diols with phosgene and diaryl carbonates such as diphenyl carbonate. It is found that the selection of constituents of polyurea top-coat primer renders it possible to completely eliminate the need for tin-based catalyst. Hence, in particular embodiments of the invention, the polyurea top-coat primer is free of any tin-based catalyst.
  • Desmodur N3900 (formerly VP2410), ex Bayer (Germany), aliphatic polyisocyanate Desmodur N3600, ex Bayer (Germany), aliphatic polyisocyanate Desmodur N3800, ex Bayer (Germany), aliphatic polyisocyanate Tolonate HDT-LV2, ex Rhodia (France), aliphatic polyisocyanate Desmodur N3390, ex Bayer (Germany), aliphatic polyisocyanate Tolonate HDT90, ex Rhodia (France), aliphatic polyisocyanate
  • Basonat HI 190 B/S ex BASF (Germany), aliphatic polyisocyanate Desmodur N75, ex Bayer (Germany), aliphatic polyisocyanate Bayhydur VP LS 2319, ex Bayer (Germany), aliphatic polyisocyanate Tolonate IDT 7OB, ex Rhodia (France), aliphatic polyisocyanate
  • Component b) is based in whole or in part on compounds corresponding to formula 1 wherein R 1 to R 4 and n have the meanings previously set forth. It is particularly preferred to use "poly aspartic acid derivatives" corresponding to the above formula wherein X represents a divalent hydrocarbon group obtained by the removal of the amino groups from 1,4-diaminobutane, 1,6-diaminohexane, 2,2,4- and 2,4,4-trimethyl-l,6-diaminohexane, l-amino-3,3,5-trimethyl- 5-aminomethyl-cyclohexane, 4,4'-diamino-dicyclohexyl methane or 3,3-dimentyl-4,4'- diamino-dicyclohexyl methane, and n is 2.
  • the preferred starting components b) also include those compounds corresponding to formula (I) wherein R 1 and R 2 represent for methyl or ethyl groups and R 3 and R 4 represent hydrogen.
  • Suitable polyamines include ethylene diamine, 1,2-diaminopropane, 1,4-diaminobutane, 1,6- diaminohexane, 2,5-diamino-2,5-dimethylhexane, 2,2,4-and/or 2,4,4-trimethyl-l,6- diaminohexane, 1,11-diaminoundecane, 1,12-diaminododecane, l-amino-3,3,5-trimethyl-5- aminomethyl-cyclohexane, 2,4-and/or 2,6-hexahydrotoluylene diamine, 2,4'-and/or 4,4'- diamino-dicyclohexyl methane and 3,3'-dimethyl-4,4'-diamino-dicyclohexyl methane.
  • Aromatic polyamines such as 2,4-and/or 2,6-diaminotoluene and 2,4'-and/or 4,4'- diaminodiphenyl methane are also suitable but less preferred.
  • Relatively high molecular weight polyether polyamines containing aliphatically bound primary amino groups for example, the products marketed under the Jeffamine trademark, are also suitable.
  • optionally substituted maleic or fumaric acid esters suitable for use in the preparation of the compounds corresponding for formula (I) include dimethyl, diethyl and din-butyl esters of maleic acid and fumaric acid and the corresponding maleic or fumaric acid esters substituted by methyl in the 2- and/or 3-position.
  • the preparation of the "poly aspartic acid derivatives" corresponding to Formula (I) from the above mentioned starting materials may be carried out, for example, at a temperature of 0 0 C to 100 0 C, using the starting materials in such proportions that at least 1, preferably 1, olefinic double bond is present for each primary amino group. Excess starting materials may be removed by distillation after the reaction. The reaction may be carried out solvent-free or in the presence of suitable solvents such as methanol, ethanol, propanol, dioxane and mixtures of such solvents.
  • the binders present in the coating compositions according to the invention are preferably based on mixtures of poly-isocyanate component a) with the secondary polyamines corresponding to Formula (I) or mixtures of poly-isocyanate component a) with the secondary polyamines corresponding to Formula (I) and other isocyanate-reactive compounds.
  • isocyanate-reactive compounds are preferably organic polyhydroxyl compounds known from polyurethane chemistry and include both the low molecular weight polyhydroxyl compounds and the relatively high molecular weight polyhydroxyl compounds previously set forth for the preparation of the pre-polymers and semi pre-polymers suitable for use as poly-isocyanate component a).
  • Particularly preferred isocyanate-reactive compounds which may be used as a portion of component b) are the hydroxy functional poly acrylates known for use in polyurethane coatings. These compounds are hydroxyl-containing copolymers of olefinically unsaturated compounds having a number average molecular weight (Mn) determined by vapour pressure or membrane osmometry of 800-50,000, preferably 1000-20,000 and more preferably 5000- 10,000, and having a hydroxyl group content of 0.1-12 % by weight, preferably 1-10 % by weight and most preferably 2-6 % by weight.
  • Mn number average molecular weight
  • the copolymers are based on olefinic monomers containing hydroxyl groups and olefinic monomers which are free from hydroxyl groups.
  • Suitable monomers include vinyl and vinylidene monomers such as styrene, ⁇ -methyl styrene, o- and p-chloro styrene, o-, m- and p-methyl styrene, p-tert.- butyl styrene; acrylic acid; (methy)acrylonitrile; acrylic and methacrylic acid esters of alcohols containing 1 to 8 carbon atoms such as ethyl acrylate, methyl acrylate, n- and isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, iso- octyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and iso-octyl methacrylate; diesters of fumaric acid, itaconic acid or male
  • components a) and b) are used in amounts sufficient to provide an equivalent ratio of isocyanate groups to isocyanate-reactive groups of 0.8: 1 to 20: 1, preferably 0.8: 1 to 2: 1, more preferably 0.8: 1 to 1.5: 1, even more preferably 0.8: 1 to 1.2: 1 and most preferably about 1 : 1.
  • the optional poly hydroxyl compound is present in component b) in an amount such that up to 20 hydroxyl groups are present for each secondary amino group from the compounds corresponding to formula (I), preferably the equivalent ratio of hydroxyl groups to secondary amino groups is 10: 1 to 1 : 10.
  • Desmophen NH 1220 ex Bayer (Germany), Poly aspartic based polyurea binder Desmophen NH 1420, ex Bayer (Germany), Poly aspartic based polyurea binder Desmophen NH 1520, ex Bayer (Germany), Poly aspartic based polyurea binder
  • Each of the primer composition and the top-coat compositions may further comprise other paint constituents as will be apparent for the person skilled in the art.
  • paint constituents are solvents, pigments, fillers, additives ⁇ e.g. thickening agents, wetting agents, suspending agents, anti-sag agents, anti-sediment agents, stabilizers, coalescing agents, and thixothropic agents).
  • compositions typically comprise a solvent or solvents.
  • solvents are alcohols such as water, methanol, ethanol, propanol, isopropanol, butanol, isobutanol and benzyl alcohol; alcohol/water mixtures such as ethanol/water mixtures; aliphatic, cycloaliphatic and aromatic hydrocarbons such as white spirit, cyclohexane, toluene, xylene and naphtha solvent; ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone, methyl isoamyl ketone, diacetone alcohol and cyclohexanone; ether alcohols such as l-methoxy-2- propanol, 2-butoxyethanol and butyl diglycol; esters such as methoxypropyl acetate, n-butyl acetate and 2-ethoxyethyl acetate; and mixtures thereof.
  • solvents useful for the epoxy primer composition are alcohols such as water, methanol, ethanol, propanol, isopropanol, butanol, isobutanol and benzyl alcohol; alcohol/water mixtures such as ethanol/water mixtures; aliphatic, cycloaliphatic and aromatic hydrocarbons such as white spirit, cyclohexane, toluene, xylene and naphtha solvent; ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone, methyl isoamyl ketone, diacetone alcohol and cyclohexanone; ether alcohols such as l-methoxy-2-propanol, 2-butoxyethanol and butyl diglycol; esters such as methoxypropyl acetate, n-butyl acetate and 2-ethoxyethyl acetate; and mixtures thereof.
  • alcohols such as water, methanol, ethanol, prop
  • solvents useful for the top-coat composition are aliphatic, cycloaliphatic and aromatic hydrocarbons such as white spirit, cyclohexane, toluene, xylene and naphtha solvent; ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone, methyl isoamyl ketone, diacetone alcohol and cyclohexanone; esters such as methoxypropyl acetate, n-butyl acetate and 2-ethoxyethyl acetate; and mixtures thereof.
  • aliphatic, cycloaliphatic and aromatic hydrocarbons such as white spirit, cyclohexane, toluene, xylene and naphtha solvent
  • ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone, methyl isoamyl ketone, diacetone alcohol and cyclohexanone
  • the primer composition and the top-coat composition may be prepared by any suitable technique that is commonly used within the field of paint production.
  • the various constituents may be mixed together using a high speed disperser, a ball mill, a pearl mill, a three-roll mill etc.
  • the paints according to the invention may be filtered using bag filters, patron filters, wire gap filters, wedge wire filters, metal edge filters, EGLM turnoclean filters (ex Cuno), DELTA strain filters (ex Cuno), and Jenag Strainer filters (ex Jenag), or by vibration filtration.
  • primer and top-coat compositions to be used herein are conveniently prepared by mixing two or more components e.g. two pre-mixtures. It should be understood that when reference is made to the paint composition, it is the mixed paint composition ready to be applied.
  • the epoxy primer base component and the curing agent component for the epoxy primer composition are mixed (e.g. in a ratio of approx. 3: 1 by volume) by adding the curing agent to the base and stir well until the mixture is homogeneous.
  • the mixture is immediately ready for application, e.g. by spray application.
  • the polyurea top-coat base component and the curing agent for the polyurea top-coat composition are mixed ⁇ e.g. in a ratio of approx. 3: 1 by volume) by adding the curing agent to the base and stir well until the mixture is homogeneous.
  • the mixture is then immediately ready for application, e.g. by spray application.
  • the primer composition and the top-coat composition can be applied to a substrate (in particular a steel structure) by well known standard application methods like conventional air-spraying or by airless- or airmix-spraying equipment (or alternatively by means of a brush or a roller, in particular when used as a stripe coat). Due to the relatively short pot life of the coating systems of the present invention, two-component spray systems with automatic measure of the mixing ratio are preferred.
  • the coating system is typically applied in a total dry film thickness of 120-400 ⁇ m, such as 150-350 ⁇ m.
  • the dry film thickness of the first layer is higher that the dry film thickness of the second layer (the top-coat).
  • the dry film thickness of the first layer is at least 100 ⁇ m.
  • the coating system is selected such that:
  • the dry film thickness of the first layer is 80-160 ⁇ m, such as 100-140 ⁇ m;
  • the dry film thickness of the second layer is 40-120 ⁇ m, such as 60-100 ⁇ m.
  • the coating system is selected such that:
  • the dry film thickness of the first layer is 100-180 ⁇ m, such as 120-160 ⁇ m; and (ii) the dry film thickness of the second layer is 60-140 ⁇ m, such as 80-120 ⁇ m.
  • the coating system is selected such that:
  • the dry film thickness of the first layer is 160-240 ⁇ m, such as 180-220 ⁇ m;
  • the dry film thickness of the second layer is 80-160 ⁇ m, such as 100-140 ⁇ m.
  • a first layer of a primer composition comprising an epoxy-based binder system, said primer composition having a volume solids % of at least 86 %;
  • top-coat composition comprising a polyurea-based binder system, said top-coat composition having a volume solids % of at least 78 %;
  • weighted average volume solids % of the coating system is at least 82 %, such as at least 83 % or at least 84 %.
  • the coating system follows the directions, embodiments, and variants described for the coating system described further above (mutatis mutandis), including the details in the sections "The Coating System”, “High Volume Solids Percentage”, “First Layer - The Primer Composition”, “Second Layer - The Polyurea-Based Binder System”, “Other Constituents of the Primer and Top-Coat Compositions”, “Preparation of the Primer and Top- Coat Compositions", “Application of the Primer and Top-Coat Compositions", and “Film Thickness”.
  • the primer composition has a volume solids % of at least 86 %, such as at least 87 %, e.g. at least 88 %.
  • the top-coat composition has a volume solids % of at least 78 %, such as at least 79 %, e.g. at least 80 %.
  • the weighed average volume solids % of the coating system is at least 82 %, such as at least 83 %, e.g. at least 84 %.
  • the invention in particular provides a coating system suitable for aggressive corrosive environments, consisting of:
  • a first layer of a zinc primer composition comprising an epoxy-based binder system and 25-30 % by solids volume of the primer composition of zinc, said primer composition having a volume solids % of at least 82 %;
  • top-coat composition comprising a polyurea-based binder system, said top-coat composition having a volume solids % of at least 82 %, and said binder system comprising an isocyanate-reactive component of the formula (I) :
  • X represents an organic group which has a valence of n and which is inert towards isocyanate groups at temperatures of up to 100 0 C;
  • R 1 and R 2 each independently is selected from organic groups which are inert towards isocyanate groups at temperatures of up to 100 0 C;
  • R 3 and R 4 each independently is selected from hydrogen and organic groups which are inert towards isocyanate groups at temperatures of up to 100 0 C;
  • n is an integer of at least 2;
  • the weighed average volume solids % of the coating system is at least 84 %;
  • the dry film thickness of the first layer is higher than the dry film thickness of the second layer, said first layer having a dry film thickness of at least 100 ⁇ m.
  • the invention further provides a coating system suitable for aggressive corrosive environments, consisting of: (i) a first layer of a zinc primer composition comprising an epoxy-based binder system and 25-30 % by solids volume of the primer composition of zinc, said primer composition having a volume solids % of at least 86 %; and
  • top-coat composition comprising a polyurea-based binder system, said top-coat composition having a volume solids % of at least 78 %, and said binder system comprising an isocyanate-reactive component of the formula (I) :
  • X represents an organic group which has a valence of n and which is inert towards isocyanate groups at temperatures of up to 100 0 C;
  • R 1 and R 2 each independently is selected from organic groups which are inert towards isocyanate groups at temperatures of up to 100 0 C;
  • R 3 and R 4 each independently is selected from hydrogen and organic groups which are inert towards isocyanate groups at temperatures of up to 100 0 C;
  • n is an integer of at least 2;
  • the weighed average volume solids % of the coating system is at least 82 %, such as at least 83 %, or at least 84 %;
  • the dry film thickness of the first layer is higher than the dry film thickness of the second layer, said first layer having a dry film thickness of at least 100 ⁇ m.
  • the "dry-to-handle" time of the whole coating system is less than 11 hours, such as less than 9 hours, in particular less than 7 hours, at 20 0 C.
  • the rust creep of the dry coating system as determined according to ISO 12944-6 is at the most 1 mm.
  • the present invention further relates to a coated structure carrying on at least a part of the surface thereof a coating system as described above in dry form.
  • Such a structure is typically a steel or iron structure, in particular steel.
  • interesting examples hereof are structures such as off-shore platforms, windmill towers, steel chimneys, power stations, steel bridges, cranes, rail cars, containers, wind turbines, etc. in costal, off-shore, or industrial environments, but also tidal zone areas where fast salt water resistance is required. Of particular interest are windmill towers.
  • the present invention also relates to a method for the establishment of a coated structure using a coating system consisting of a primer composition and a top-coat composition, said primer composition comprising an epoxy-based binder system and said a top-coat composition comprising a polyurea-based binder system, said method comprising :
  • said primer composition has a volume solids % of at least 82 %, said top-coat composition having a volume solids % of at least 82 %; and the weighted average volume solids % of the coating system being at least 84 %, or
  • the primer composition has a volume solids % of at least 86 %, said top-coat composition having a volume solids % of at least 78 %; and the weighted average volume solids % of the coating system being at least 82 %.
  • the primer composition comprises 20-35 % by solids volume of zinc, such as 25-30 % by solids volume of zinc.
  • the method of the invention can be further specified in accordance with the details disclosed above in relation to the coating system, the preferred embodiment, the coated structure, etc.
  • the present invention also provides a zinc epoxy primer composition
  • a zinc epoxy primer composition comprising an epoxy-based binder system and 20-40 % by solids volume of the primer composition of zinc; said primer composition having a volume solids % of at least 82 %, such as at least 84 %, or at least 86%.
  • the epoxy-based binder system comprises a curing agent selected from Mannich bases, aliphatic polyamines and modified aliphatic polyamines.
  • the epoxy-based binder system comprises a curing agent selected from Mannich bases.
  • the "dry-to-handle" time of the zinc epoxy primer composition is less than 5 hours, such as less than 4 hours, in particular less than 3 hours, at 20 0 C.
  • the "dry-to-walk-on" time of the zinc epoxy primer composition is less than 5 hours, such as less than 4 hours, in particular less than 3 hours, at 20 0 C.
  • said curing agent is at least partly further reacted with a glycidyl ether functional reactive diluent.
  • the present invention also provides an epoxy primer composition
  • an epoxy primer composition comprising an epoxy-based binder system; said primer composition having a volume solids % of at least 82 %, such as at least 84 %, or at least 86%; and a "dry-to-handle" time which is less than 5 hours, such as less than 4 hours, in particular less than 3 hours, at 20 0 C.
  • the present invention also provides an epoxy primer composition
  • an epoxy primer composition comprising an epoxy-based binder system; said primer composition having a volume solids % of at least 82 %, such as at least 84 %, or at least 86%; and a "dry-to-walk-on" time which is less than 5 hours, such as less than 4 hours, in particular less than 3 hours, at 20 0 C.
  • HEMPADUR ZINC 17320 (ex Hempel A/S) is a two-component zinc rich epoxy paint. It cures to a strong and corrosion resistant coating. Recommended use: As a primer on steel in medium to severely corrosive environment or for on-line application on containers. Volume solids %: 61.
  • HEMPADUR 47140 (ex Hempel A/S) is a two-component polyamide adduct cured, high build epoxy paint which combines a relatively high volume solids content with a short drying time.
  • HEMPATHANE TOPCOAT 55210 (ex Hempel A/S) is a two-component, semi-gloss acrylic polyurethane coating, cured with aliphatic isocyanate, with good gloss and color retention. Recommended use: As a finishing coat for protection of structural steel in severely corrosive atmospheric environment, where light-fastness and gloss retention are required. Volume solids %: 51.
  • PERMATEX NCG BASE COAT (ex Sika GmbH) is a two-component fast drying low solvent epoxy primer. Recommended use: As a long lasting corrosion protection for wind turbines. Volume solids %: 81.
  • PERMACOR 2230 VHS (ex Sika GmbH) is a two-component low solvent fast drying acryl- polyurethane top-coat. Recommended use: As a long lasting weather resistant coat for corrosive environment. Volume solids %: 70. INTERZINC 52 (ex International) is a two-component, metallic zinc rich epoxy primer. Recommended use: As a high performance primer for aggressive environments. Volume solids %: 59.
  • INTERCURE 99 (ex International) is a two-component DTM primer finish polyurethane coating. Recommended use: As a Direct to Metal (DTM) finish coat for mild to medium corrosive environments or as top-coat on a zinc epoxy primer for severe corrosive environments. Volume solids %: 80.
  • DTM Direct to Metal
  • Table 1 Composition of Primer A (parts by weight)
  • Table 2 Composition of Top-coats 1-3 (parts by weight)
  • Top-coat 3 is a top-coat pertaining to the "Alternative Coating System" described herein.
  • Charge curing agent Mannich base, modified aliphatic polyamine. Mix and add under agitation the epoxy binder and leave it for 24 hours. Add epoxy accelerator. Mix approx. 50 % of the adduct with defoamer, rheological additive, pigment and extender. Grind to 50 ⁇ m, temperature minimum 50 0 C. Add the rest of the adduct. Add xylene and stir well. Add adhesion promoter and mix.
  • the epoxy primer base component and the curing agent component for the epoxy primer is mixed in ratio 3: 1 by volume by adding the curing agent to the base and stir well until the mixture is homogeneous. The mixture is immediately ready for application.
  • binder Mix Charge binder Mix and add under agitation water scavenger, rheological additive I, wetting agent, pigment, extender, and matting agent. Grind to 40 ⁇ m. Add light stabilizer, rheological additive II under high speed. Add butyl acetate and adhesion promoter. Adjust viscosity with xylene.
  • the curing agent consists only of the binder component.
  • the polyurea top coat base component and the curing agent for the polyurea top coat is mixed in ratio 3: 1 by volume by adding the curing agent to the base and stir well until the mixture is homogeneous. The mixture is immediately ready for application.
  • the coatings of the present invention can be applied by well known standard application methods like conventional air spraying or by air-less or air-mix spraying equipment. Due to the relatively short pot life of the coating systems of the present invention, two-component spray systems with automatic measure of the mixing ratio are preferred.
  • volume solids % (VS%) is determined according to ISO 3233 with the modification that drying is carried out at 23 0 C and 50 % relative humidity for 7 days.
  • Ten test items (i.e. ten-fold repetition) are prepared.
  • the Volume Solids (VS) figure expresses in percentage the ratio:
  • Volume solids are usually slightly higher than the theoretical value (referred to as "solids volume”), which is found by a calculation based on the paint composition taking specific gravity and solid content of each individual raw material into consideration. Volume solids take into account that small amounts of solvents are usually retained, and that air may be entrapped in the dry paint film either in the form of vacuoles or as interstices. Volume solids are in general in better agreement with practical measurements of dry film thickness than the theoretical value.
  • the test method is used for determining the "dry-to-handle" time.
  • the freshly painted panels (DFT typically 120-400 ⁇ m) are applied a pressure of 100 kg/cm 2 for 3 minutes after the application of the outermost paint coat. This pressure is applied in order to simulate the pressure applied by tools and equipment used when handling and transporting the coated object.
  • a Teflon-coated steel block (base area 3.14 cm 2 ) was pressed towards the painted surface by means of a pneumatic compression machine with a mobile arm. If the paint is not "dry-to-handle", the paint will ooze out from underneath the pressure block resulting in a visible indentation mark.
  • the appearance ofthe painted surface, resulting from the pressure applied, is rated on a scale from 1 to 5, where 1 is unsatisfactory and 5 is perfect with no visible mark after testing. Any rating of 3 or above is termed "acceptable”.
  • the pressure is applied at intervals of 1 hour after application of the outermost paint coat (starting a full number of hours after application when the panel was considered ready for testing) (a new panel for each test) and until a rating of 5 is obtained, or until no more panels are available.
  • dry-to-handle is the time after application of the outermost coat required in order to obtain a rating of 5. After this period of time, the paint surface is sufficiently hardened to be handled with care without coming off/being damaged.
  • the "dry-to-walk-on" time is determined essentially as the dry-to-handle time, however using a pressure of 5 kg/cm 2 . This pressure is applied in order to simulate the pressure applied by the shoes or boots of a person walking on the surface coated with the primer composition.
  • the freshly painted panels (DFT typically 50-150 ⁇ m) are applied a pressure of 5 kg/cm 2 for 3 minutes after the application of the primer layer.
  • a Teflon-coated steel block (base area 25 cm 2 ) was pressed towards the painted surface by means of a pneumatic compression machine with a mobile arm. If the paint is not "dry-to-walk-on", the paint will ooze out from underneath the pressure block resulting in visible indentation marks.
  • the appearance of the painted surface, resulting from the pressure applied, is rated on a scale from 0 to 5, where 1 is unsatisfactory and 5 is perfect with no visible mark after testing.
  • the pressure is applied at intervals of 1 hour after application of the primer (starting a full number of hours after application when the panel was considered ready for testing) (a new panel for each test) and until a rating of 5 is obtained, or until no more panels are available.
  • Salt spray test according to ASTM B 117 (ISO 9227 (formerly ISO 7253)). Test for evaluation of corrosion resistance in salt spray or reproducing corrosion that occurs in atmosphere containing salt spray or splash. Constant spray with 5 % NaCI solution at 35 0 C. When the test is stopped, blisters and rust are evaluated according to ASTM D 714 (ISO 4628-2) and ASTM D 610 (ISO 4628-3), respectively. Adhesion is evaluated according to X-cut method according to ASTM D 3359, method A (see below).
  • Adhesion test is used to evaluate the adhesion of a paint system to the substrate and between coats (layers).
  • X-cut according to ASTM D 3359, method A.
  • An "X” is cut into the film to the substrate, pressure tape (TESAPACK 4287) is applied over the "X” and then removed, and adhesion is evaluated by comparison with descriptions and pictures.
  • the method is used to establish whether the adhesion of the coating to the substrate may occur between the coats (adhesive break) or in the coating (cohesive break).
  • the type of rupture is reported, and the severity is judged on a scale from 5 (perfect) to 0 (poor).
  • the coating systems were evaluated according corrosion category C5-M, high, cf. ISO 12944-6. The overall evaluation was rated either "Pass” or “Fail” in accordance with the ISO 12944 standard.
  • Panel dimension is 70x150x5 mm, with a surface roughness (profile) similar to ISO 8503-1 medium (G).
  • ADH - Reference panels A set of three reference panels were prepared for each system in order to evaluate the adhesion on unexposed panels according to ISO 4624, pull-off test.
  • the Blister Box Test was conducted according to ISO 6270-1. This method was performed in order to evaluate the water resistance of a coating system using controlled condensation. Three panels were used for each test.
  • the panel surface with the coating system were exposed to 40 0 C, saturated water vapour, at an angle of 15° to the horizontal.
  • the reverse side of the panel was exposed to room temperature.
  • blistering and rust were evaluated according to ISO 4628-2 and ISO 4628-3, respectively.
  • Cracking was evaluated according to ISO 4628-4.
  • Adhesion was evaluated according to ISO 4624 (pull-off tests). The actual adhesion test was performed 48 hours after the end of the exposure.
  • the Salt Spray Test was conducted according to ISO 9227. This method was performed in order to evaluate the corrosion resistance of a coating system by reproducing the corrosion that occurs in an atmosphere containing salt spray or splash. Six panels were used for each test.
  • the operation conditions of the salt spray test were constant spray with 5% NaCI solution at 35°C. After ending of the exposure (1440 hours), blistering and rust were evaluated on both panel and around the score (in mm from centre), according to ISO 4628-2 and ISO 4628-3, respectively. Cracking was evaluated according to ISO 4628-4. Adhesion was evaluated according to ISO 4624 (pull-off tests). At score the paint film was removed, and the width of the rusting was measured at nine points, where from the M-max and M-avg. values were calculated. The actual adhesion test is performed 48 hours after the end of the exposure.
  • a coated panel was exposed to the Salt Spray Test and was exposed for 2171 hours. Subsequently, the panel was evaluated in accordance with the test details.
  • Both tested systems showed excellent performance blistering and perfect adhesion after a very aggressive anticorrosive test.
  • the coating system according to the invention further showed only minimal rust creep ( ⁇ 1 mm).
  • the primer composition according to the invention and the commercial primers Hempadur zinc 17320 and Interzinc 52 have equivalent "walk-on times", and all three seem to be faster than the commercial NCG Base Coat. Corrosion Test - Method II
  • the systems Hempadur zinc 17320/Hempadur 47140/Hempathane topcoat 55210 and Permatex NCG Base Coat/Permacor 2230 VHS do not pass the requirements to C5-M High due to excess rust creep, M-value (>1 mm).
  • the three coating systems according to the invention passed the test. All coating systems exhibited excellent properties with respect to adhesion and lack of blistering.

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Abstract

The present application discloses a non-thermosetting coating system consisting of : a first layer of a primer composition comprising an epoxy-based binder system having a volume solids % (VS%) of at least 82%; and a second layer of top-coat composition comprising a polyurea-based binder system having a VS% of at least 82%; wherein the weighted average VS% of the coating system is at least 84%. The application further discloses a coated structure carrying the coating system; a method for the establishment of a coated structure using the coating system; a zinc epoxy primer composition comprising an epoxy-based binder system and 20-40% by solids volume of the primer composition of zinc and having a VS% of at least 82%; and an epoxy primer composition comprising an epoxy-based binder system having a VS% of at least 82% and a "dry-to-handle" time which is less than 5 h at 20 °C.

Description

NOVEL FAST CURING ULTRA HIGH SOLIDS LOW VOC COATING SYSTEM FOR AGGRESSIVE CORROSIVE ENVIRONMENTS
FIELD OF THE INVENTION
The present invention relates to novel fast curing coating systems consisting of an epoxy primer and a polyurea top-coat. The coating systems have improved drying time and low VOC and still maintain excellent rust creep resistance. The present invention provides improved drying time and low VOC by using an ultra high solid polyurea top-coat on top of an epoxy primer. The coating systems of the present invention are non-thermosetting compositions.
BACKGROUND OF THE INVENTION
Epoxy coatings are used mainly as part of an anti -corrosive coating system on steel substrates due to outstanding corrosion and chemical resistance.
Epoxy coating compositions are typically one or two-component products. If the product is two-component, component one normally consists of an epoxy base and component two consists of a curing agent. If the epoxy is a zinc epoxy, the zinc will normally be present in the base composition.
Zinc epoxies are superior to standard epoxies concerning anticorrosive properties due to their function as a sacrificial anode applied directly on top of the clean steel surface. When the coating layer is damaged the zinc will protect the damage by a galvanic process. The function is similar to that of galvanized steel.
Epoxies can be used as a primer, i.e. first coating layer in a multiple coat system with subsequent layers of suitable generic types of coatings, or as an intermediate coat with subsequent suitable coats e.g. polyurethane or polyurea, or as a top-coat. However, epoxy paints can also be used as one-coat systems.
Polyurea is the general term used for coatings based on amines reacted with iso-cyanates or poly-isocyanates. The polymerization reaction between amine and isocyanates is in general extremely fast. Both aromatic and aliphatic isocyanates are used in polyurea coatings. However, it is only aliphatic iso-cyanates that give acceptable outdoor durability. Poly aspartic acid esters are a special type of polyurea binder where an amine is pre-reacted with di-ethyl maleate. The amine functionality is by this pre-reaction becoming partly sterically hindered. The reaction speed is dependent on the amine used.
Poly aspartic esters are available in different reaction speed from fast to slow reaction polymers.
Polyurea top-coats based on poly aspartic acid esters are well known to give excellent outdoor durability with excellent gloss and color stability. Poly aspartic esters can be designed to give fast cure at ambient condition and with the partly sterical hindrance of the amine the reaction speed gives a reasonable pot-life to be handled in either two-component application equipment or standard airless spray equipment.
Epoxy and polyurea paint systems are normally used where superior corrosion protection and fast process time is needed. Such paint systems are designed to be used in aggressive corrosive environments like off-shore platforms, windmill towers, steel chimneys, power stations, steel bridges, cranes etc. in costal, off-shore, or industrial environments, but also tidal zone areas where fast salt water resistance is required.
Corrosive environments are rated according to ISO 12944 on a scale from C2 to C5 with C2 being mildly corrosive and C5 being an aggressively corrosive environment.
In recent years faster curing products have appeared. Fast curing lower the overall processing time and has become a very important parameter for paint applicators and contractors. However it has so far only been possible to decrease the curing time to a certain level if the workability and corrosion properties should be preserved.
The curing process starts on the surface of the coating. When curing is too fast the soft uncured part of the coating will not have sufficient strength to "carry" the stress built up during curing and defects will develop on the surface leading to subsequent loss of adhesion, cohesion and corrosion problems.
Another important parameter is the content of Volatile Organic Compound (VOC) of a coating system. VOC emissions influence the environment in a negative way. In recent years there has been an increasing focus on environmental aspects and awareness and discussions of green house effect. It is therefore an important parameter to keep the VOC of a coating system to an absolute minimum. So far, the coating solution for the mentioned application areas has been medium solids coatings used in either two or three coat systems with relatively long drying /curing schedules resulting in long process time and with relatively high VOC emissions.
There is thus a need for a coating system for aggressive corrosive environments, enabling faster processing and lower VOC.
SUMMARY OF THE INVENTION
It has now surprisingly been discovered that it is possible to provide a non-thermosetting coating system consisting of an epoxy primer composition and a polyurea top-coat composition with significantly reduced processing time and low VOC, which still provides the superior protection needed for aggressive corrosion classes.
The present invention provides a high solids coating system consisting of an epoxy primer and a top-coat, enabling faster processing time and low VOC.
More particular, the present invention relates to coating system according to claim 1.
The present invention also provides a coated structure carrying such a coating system, cf. claim 9, and a method for the establishment of a coated structure, cf. claim 10.
Moreover, the present invention also provides a zinc epoxy primer composition, cf. claim 12, and an epoxy primer composition, cf. claim 14.
DETAILED DESCRIPTION OF THE INVENTION
The Coating System
As mentioned above, the present invention relates to a coating system consisting of:
(i) a first layer of a primer composition comprising an epoxy-based binder system, said primer composition having a volume solids % of at least 82 %; and
(ii) a second layer of top-coat composition comprising a polyurea-based binder system, said top-coat composition having a volume solids % of at least 82 %. When used herein, the expression "coating system" is intended to mean the combination of the first and second layers in wet form when applied to the surface of a substrate. It should be understood that the second layer is applied subsequent to the first layer so as to be in direct contact with said first layer. It should further be understood that one or more layers of other coating compositions may be applied to the surface of the substrate prior to the application of the first layer, although such other coating layer are generally not necessary or desirable. Moreover, it should be understood that one or more layers of other coating compositions may be applied subsequent to the application of the second layer, although such other coating layer are generally not necessary or desirable.
Hence, in a preferred embodiment, the coating system consists of the above-defined first and second layers, where the first layer is in direct contact with the surface of the substrate and where the second layer is the outermost layer.
The coating systems disclosed herein are designed to cure at ambient temperatures (i.e. typically the temperature at the location at which the coating system is applied, e.g. in paint shops or outdoor where the temperature will depend on the general climate at the geographical location), e.g. at temperatures of 0-50 0C (either in cold or in very hot regions of the world), such as 5-30 0C, in particular about 15-25 0C, such as around 200C. In other words, the coating system disclosed herein is of the non-thermosetting type. In contrast hereto, other coating systems are of the thermosetting type, which require heating of the substrate with the coating to temperature of several hundred degrees Celsius. Such conditions are of course in practise inapplicable with the types of substrates for which the present coating systems are designed.
High Volume Solids Percentage
A particular feature of the coating system of the invention is the very high volume solids % ("VS%") and thereby the low content of volatile organic compounds (VOC).
In fact, the primer composition has a volume solids % of at least 82 %, such as at least 84 %, e.g. at least 85 %. Similarly, the top-coat composition has a volume solids % of at least 82 %, such as at least 84 %, e.g. at least 85 %.
This being said, and most importantly, the weighed average volume solids % of the coating system is at least 84 %, such as at least 85 %, e.g. at least 86 %. The volume solids (expressed in %) is often referred to as "VS%". VS% is determined according to ISO 3233 with the modification that drying is carried out at 23 0C and 50 % relative humidity for 7 days instead of drying at higher temperatures.
The expression "weighed average volume solids %" refers to average of volume solid percentages taking into account that the primer composition and the top-coat composition may not be applied with the same wet film thicknesses. If the primer composition having a VS% of 90 % is applied in a thickness of 200 μm and a top-coat composition having a VS% of 84 % is applied in a thickness of 100 μm, the weighed average volume solids % will be 88 %.
The very low content of VOC renders it possible to establish a fast curing coating system which has a very short "dry-to-handle" time, i.e. preferably a "dry-to-handle" time which is less than 11 hours at 20 0C. In certain preferred embodiments, the "dry-to-handle" time is less than 9 hours at 20 0C, or even less than 7 hours at 20 0C. The "dry-to-handle" time is conveniently determined as described in the Examples section.
The Volatile Organic Compound (VOC) of the coating system is important because VOC emissions influence the environment in a negative way and should therefore be kept to a minimum.
The coatings system of the present invention has very low VOC emission compared to the coatings systems as presented in Table 5. VOC can be determined by various methods e.g. ISO 11890 or EPA method 24.
First Layer - The Primer Composition
The first layer of the primer composition comprises an epoxy-based binder system.
The primer composition may further include other constituents as it is described further below. In particular, the primer composition may include anticorrosive constituents and/or fibres.
Epoxy-based binder system
The term "epoxy-based binder system" should be construed as the combination of one or more epoxy resins, one or more curing agents and any reactive epoxy diluents. The epoxy-based binder system is one of the most important constituents of the primer composition, in particular with respect to the anticorrosive properties.
The epoxy-based binder system comprises one or more epoxy resins selected from aromatic or non-aromatic epoxy resins (e.g. hydrogenated epoxy resins), containing more than one epoxy group per molecule, which is placed internally, terminally, or on a cyclic structure, together with one or more suitable curing agents to act as cross-linking agents. Combinations with reactive diluents from the classes of functional glycidyl ethers or esters of aliphatic, cyclo aliphatic or aromatic compounds can be included in order to reduce viscosity and for improved application and physical properties. The binder system can also include reactive acrylic modifiers such as acrylate monomers and oligomers comprising at least two alpha, beta unsaturated carbonyl groups, reacting with the one or more curing agents via a Michael- type addition reaction.
Suitable epoxy-based binder systems are believed to include epoxy and modified epoxy resins selected from bisphenol A, bisphenol F, Novolac epoxies, non-aromatic hydrogenated epoxies, cyclo aliphatic epoxies, glycidyl esters and epoxy functional acrylics or any combinations hereof.
Examples of suitable commercially available epoxy resins are:
Epikote 828, ex Resolution Performance Products (The Netherlands), bisphenol A type Araldite GY 250, ex Huntsman Advanced Materials (Switzerland), bisphenol A type DER 664-20, ex Dow Chemicals (Germany), bisphenol A type
Epikote 1001 X 75, ex Resolution Performance Products (The Netherlands), bisphenol A type Araldite GZ 7071X75BD, ex Huntsman Advanced Materials (Germany), bisphenol A type DER 352, ex Dow Chemicals (Germany), mixture of bisphenol A and bisphenol F Epikote 232, ex Resolution Performance Products (The Netherlands), mixture of bisphenol A and bisphenol F
Epikote 862, ex Resolution Performance Products (The Netherlands), bisphenol F type DEN 438-X 80, ex Dow Chemical Company (USA), epoxy novolac Epikote 154, ex Resolution Performance Products (The Netherlands), epoxy novolac DYD-128, ex Dalian Qihua Chemicals, China, bisphenol A type Epikote 872-X-75, ex. Hexion (former Resolution performance products, Netherlands), bisphenol A/ epichlorohydrin resin reacted with dimer fatty acids.
The epoxy-based binder system can comprise one or more reactive epoxy diluents. Examples of suitable commercially available reactive epoxy diluents are:
Polypox R24, ex UIf Prummer, Germany, aliphatic monofunctional diglycidylether Araldite DY-L/BD, ex Huntsmann Advanced Materials, Germany, polyoxypropylene- triglycidylether Grilonit RV 1812, ex EMS-Primid, Switzerland, hexandiol-diglycidylether
Epodil 757, ex Air products PIc, USA, cyclohexane-dimethanoldiglycidylether Epilox P 13-20, ex Leuna, Germany, Hexanediol diglycedylether.
The epoxy primer composition can comprise one or more epoxy accelerators.
Examples of suitable commercially available epoxy accelerators are:
Ancamine K 54, ex Air Products PIc, United Kingdom, tris-(dimethylamino methyl) phenol TL 0712, ex Vantico Ltd., Germany, phenol free Mannich base Hiescat HI-K54, ex Keum Jung, Korea, Tris-(dimethylaminomethyl)phenol.
The epoxy-based binder system comprises one or more curing agents selected from compounds or polymers comprising at least two reactive hydrogen atoms linked to nitrogen.
Suitable curing agents are believed to include amines or amino functional polymers selected from aliphatic amines and polyamines {e.g. cyclo-aliphatic amines and polyamines), polyamido amines, polyoxy alkylene amines {e.g. polyoxy alkylene diamines), aminated polyalkoxy ethers {e.g. those sold commercially as "Jeffamines"), alkylene amines {e.g. alkylene diamines), aralkyl amines, aromatic amines, Mannich bases {e.g. those sold commercially as "phenalkamines"), amino functional silicones or silanes, and including epoxy adducts and derivatives thereof.
Examples of suitable commercially available curing agents are:
Cardolite NC-541, ex Cardanol Chemicals (USA), Mannich base Cardolite Lite 2001, ex Cardanol Chemicals (USA), Mannich base Sunmide CX-105X, ex Sanwa Chemical Ind. Co. Ltd. (Singapore), Mannich base
Epikure 3140 Curing Agent, ex Resolution Performance Products (USA), polyamidoamine SIQ Amin 2030, ex SIQ Kunstharze GmbH (Germany), polyamidoamine Epikure 3115X-70 Curing Agent, ex Resolution Performance Products (USA), polyamidoamine SIQ Amin 2015, ex SIQ Kunstharze GmbH (Germany), polyamidoamine Polypox VH 40309/12, ex UIf Prummer Polymer-Chemie GmbH (Germany), polyoxyalkylene amine
Polypox VH 40294, ex UIf Prϋmmer Polymer-Chemie GmbH (Germany), Mannich base
Ancamine 2609, ex Air Products (UK), Mannich base
Adeka Hardener, ex Adeka Corporation (Japan), Mannich base CeTePox 1490 H, ex CTP Chemicals and Technologies for Polymers (Germany), polyoxyalkylene amine
Epoxy hardener MXDA, ex Mitsubishi Gas Chemical Company Inc (USA), aralkyl amine
Diethylaminopropylamine, ex BASF (Germany), aliphatic amine
Gaskamine 240, ex Mitsubishi Gas Chemical Company Inc (USA), aralkyl amine Cardolite Lite 2002, ex Cardanol Chemicals (USA), Mannich base
Aradur 42 BD, ex Huntsman Advanced Materials (Germany), cycloaliphatic amine
Isophorondiamin, ex BASF (Germany), cycloaliphatic amine
Epikure 3090 Curing Agent, ex Resolution Performance Products (USA), polyamidoamine adduct with epoxy Crayamid E260 E90, ex Cray Valley (Italy), polyamidoamine adduct with epoxy
Aradur 943 CH, ex Huntsman Advanced Materials (Switzerland), alkylene amine adduct with epoxy
Preferred epoxy-based binder systems comprises a) one or more epoxy resins selected from bisphenol A, bisphenol F and Novolac; and b) one or more curing agents selected from Mannich Bases, polyamido amines, polyoxy alkylene amines, alkylene amines, aralkyl amines, polyamines, and adducts and derivatives thereof.
Preferably the epoxy resin has an epoxy equivalent weight of 100-2000, such as 100-1500 e.g. 150-1000 such as 150-700.
Especially preferred epoxy-based binder systems comprises one or more bisphenol A epoxy resins having an epoxy equivalent weight of 150-700 and one or more polyamine or adducts and derivatives thereof.
Preferred epoxy-based binder systems are ambient curing binder systems.
In the primer composition, the total amount of epoxy-based binder system is in the range of 15-80 %, such as 35-80 %, e.g. 40-75 % by solids volume of the primer composition. In one particularly interesting embodiment, the total amount is in the range of 45-55 % by solids volume. Without being bound to any particular theory, it is believed that the selection of the ratio between the hydrogen equivalents of the one or more curing agents and the epoxy equivalents of the one or more epoxy resins plays a certain role for the performance of the coating composition.
When used herein, the term "hydrogen equivalents" is intended to cover only reactive hydrogen atoms linked to nitrogen.
The number of "hydrogen equivalents" in relation to the one or more curing agents is the sum of the contribution from each of the one or more curing agents. The contribution from each of the one or more curing agents to the hydrogen equivalents is defined as grams of the curing agent divided by the hydrogen equivalent weight of the curing agent, where the hydrogen equivalent weight of the curing agent is determined as: grams of the curing agent equivalent to 1 mol of active hydrogen. For adducts with epoxy resins the contribution of the reactants before adductation is used for the determination of the number of "hydrogen equivalents" in the complete epoxy-based binder system.
The number of "epoxy equivalents" in relation to the one or more epoxy resins is the sum of the contribution from each of the one or more epoxy resins. The contribution from each of the one or more epoxy resins to the epoxy equivalents is defined as grams of the epoxy resin divided by the epoxy equivalent weight of the epoxy resin, where the epoxy equivalent weight of the epoxy resin is determined as: grams of the epoxy resin equivalent to 1 mol of epoxy groups. For adducts with epoxy resins the contribution of the reactants before adductation is used for the determination of the number of "epoxy equivalents" in the epoxy- based binder system.
Preferably the ratio between the hydrogen equivalents of the one or more curing agents and the epoxy equivalents of the one or more epoxy resins is in the range of 50: 100 to 140: 100.
Especially preferred epoxy-based binder systems for use in Industrial corrosion protective coatings have a ratio between the hydrogen equivalents of the one or more curing agents and the epoxy equivalents of the one or more epoxy resins in the range of 60: 100 to 130: 100 such as 80: 100 to 120: 100, e.g. 90: 100 to 110: 100.
Anticorrosive Constituents
The epoxy primer composition may also comprise a particulate material (e.g. a powder) which increases the anticorrosive properties of the coat. Zinc powder or zinc dust, which is well known to incorporate in epoxy primer to produce a zinc epoxy primer, is in this respect of special interest. Zinc powder or zinc dust can all or partly be replaced by a zinc alloy, e.g. as disclosed in WO 2008/125610. Auxiliary corrosion inhibitor, for example a molybdate, phosphate, tungstate or vanadate, ultrafine titanium dioxide, and/or zinc oxide and/or a filler such as silica, calcined clay, alumina silicate, talc, barytes or mica may also be incorporated.
The D50 of the particulate material being in the range of 2.5-30 μm, in particular 2.5-20 μm. With respect to the particle size, it is preferred that the D50 of the particulate material is in the range of 2.5-15 μm, and preferably in the range of 2.5-12 μm. Additionally, the D99 of the particulate material should preferably be less than 100 μm. The particle size distribution of the particulate material (e.g. zinc or a zinc alloy) is of major importance in painting applications. For example too coarse particulate materials would result in particles sticking through the dry paint film. Therefore, it is highly preferred to use particulate materials with a D50 (mean particle size) of less than 30 μm, in particular less than 20 μm. A D50 of less than 15 μm is often more preferred, and less than 12 μm is even more preferred. The lower limit of the D50 is dictated by economic considerations. At a D50 of less than 2.5 μm, a too large fraction of the powder has to be sieved out and recycled for the complete process to run economically. However, other relevant materials include phosphates, aluminum, graphite, carbon black, micaceous iron oxide (MIO), etc.
If present, the amount of the anticorrosive constituent is typically 1-65 % by solids volume of the paint.
In one preferred embodiment, the primer composition comprises 20-35 % by solids volume of zinc, such as 25-30 % by solids volume of zinc.
The anticorrosive filler material may be present as a combination of one or more of the before-mentioned materials.
The anticorrosive constituents, in particular zinc, are preferably present in the form of a particulate material.
The term "particulate material" is intended to cover both fine spherical or somewhat irregularly shaped particles and other shapes such as flakes, disc, spheres, needles, platelets, fibres and rods. A preferred particulate material is a powder.
It is believed that the coating system generally has excellent anticorrosive properties, in particular in the embodiments where zinc is included as described above. Hence, particularly interesting embodiments are those where the rust creep of the dry coating system as determined according to ISO 12944-6 is at the most 1 mm.
When used herein, all amounts stated as % by solids volume of the paint should be understood as % by solids volume of the mixed paint composition ready to be applied, and is based on the constitution of the paint composition. (In contrast hereto, the expression "volume solids %" is determined experimentally.)
Fibres
The primer composition may also comprise fibres. Special fibres with high tensile strength will when incorporated in the epoxy matrix increase the ability to withstand higher mechanical stress. This facilitates the possibility to formulate epoxy coatings with even faster curing and higher cracking resistance at the same time.
Generally, "fibres" is intended to cover any fibres within the groups of natural inorganic fibres, synthetic inorganic fibres, natural organic fibres, synthetic organic fibres, and metallic fibres, or mixtures thereof. Without being bound to any specific theory, it is however presently believed that natural inorganic fibres and synthetic inorganic fibres, in particular mineral fibres of these types, are especially preferred.
It is presently believed that the fibres to be used within the present invention should fulfil certain criteria with respect to dimensions in order to provide the improved properties of a coat of the primer composition. Thus, with respect to average length and average thickness of the fibres which are added to the primer composition during manufacture of the primer composition or mixed with the primer composition before application, such fibres have an average length, of at the most 250 μm and an average thickness of 1-50 μm
Preferred fibres are fibres having an average thickness of 1-25 μm and an average length, of at the most 250 μm, especially an average length of 25-250 μm and an average thickness of 1-25 μm, in particularly an average length of 50-250 μm (such as 50-170 μm) and an average thickness of 2-10 μm. The preferred organic fibres furthermore have a ratio between the average length and the average thickness of at least 2, such as at least 3 e.g. at least 5.
The concentration of the fibres is normally in the range of 2-50 % by solids volume of the dry primer composition {i.e. the composition devoid of the solvents), such as 3-40 % by solids volume of the dry paint. Especially relevant concentrations of fibres, depending upon the type and size of the fibres, may be 4-35 %, such as 5-30 %, such as 6-25 %, such as 7-20 % by solids volume of the dry paint.
It should be understood that the above ranges refer to the total amount of fibres, thus, in the case where two or more fibre types are utilised, the combined amounts should fall within the above ranges.
At present, especially preferred are mineral fibres such as mineral-glass fibres, wollastonite fibres, tobermorite fibres, attapulgite fibres, volcanic rock fibres, bauxite fibres, rockwool fibres, and processed mineral fibres from mineral wool. Examples of commercially available mineral fibres which are believed to improve the mechanical properties according to the invention are (average fibre length in μm; average fibre thickness in μm) :
1. Coatforce CFlO, ex Lapinus Fibres BV (The Netherlands), volcanic rock fibre (125;5.5)
2. MS 603 Roxul 1000, ex Lapinus Fibres BV (The Netherlands), volcanic rock fibre (125;5)
3. MS 610 Roxul 1000, ex Lapinus Fibres BV (The Netherlands), (225;5.5)
4. FG 400/060, ex Schwarzwalder Textil-Werke (Germany), E-glass (230;9-14)
5. Nyad G, ex Nyco Minerals (USA), wollastonite (length/diameter ratio 15: 1)
6. RCF-160, ex Sumitomo (Japan), C-glass (250;-)
7. Isofrax 1260C High Index, ex Unifrax (United Kingdom) (-;2-3μm)
In a further preferred embodiment, the primer composition comprises:
35-40 % by solids volume of epoxy binder, 13-18 % by solids volume of curing agent, 25-30 % by solids volume of zinc powder, 1-3 % by solids volume of reactive diluents, 5-10 % by solids volume of pigments and fillers, and 6-12 % by solids volume of additives Second Layer - The Polyurea-Based Binder System
The second layer of a top-coat composition comprises a polyurea-based binder system.
Polyurea-Based Binder System
The term "polyurea-binder system" is intended to mean a binder system having as the primary components one or more di- or poly-isocyanate components and one or more di- or polyamine components. It should be understood that the amine component may be either primary or secondary in nature, i.e. they may include either one or two hydrogens (R-NH2 or R-NH-R1).
Reaction (curing) of the isocyanate component(s) and the amine component(s) results in the formation of a urea-functionality. Reaction of an isocyanate (R-NCO) with a primary amine (R'-NH2) results in an urea-functionality of the formula R-NH-C(=O)-NH-'R, whereas reaction of an isocyanate (R-NCO) with a secondary amine (R'-NH-R") results in an urea-functionality of the formula R-NH-C(=O)-N(R')-R".
In one particularly interesting embodiment, the one or more di- or polyamine components include a secondary amine.
One currently preferred type is the polyurea-based binder system previously described in US 5,126,170 which hereby is incorporated as reference. This polyurea coating contains
a) a poly-isocyanate component and
b) an isocyanate-reactive component at least one compound corresponding to the formula (I) below:
Figure imgf000014_0001
wherein X represents an organic group which has a valence of n and which is inert towards isocyanate groups at temperatures of up to 100 0C; R1 and R2 each independently is selected from organic groups which are inert towards isocyanate groups at temperatures of up to 100 0C;
R3 and R4 each independently is selected from hydrogen and organic groups which are inert towards isocyanate groups at temperatures of up to 100 0C; and
n is an integer of at least 2.
The cross-linking which takes place is based on an addition reaction between poly-isocyanate component a) and isocyanate-reactive component b), in particular the polyamines containing secondary amino groups, which are also known as "polyaspartic acid derivatives."
Suitable poly-isocyanates for use as poly-isocyanate component a) in the top-coat composition include the known poly-isocyanates of polyurethane chemistry. Examples of suitable low molecular weight poly-isocyanates having a molecular weight of 168 to 300 include hexamethylene diisocyanate, 2,2,4-and/or 2,4,4-trimethyl-l,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 1-isocyanato- 3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 2,4'-and/or 4,4'-diisocyanato- dicyclohexyl methane, 2,4-and/or 4,4'-diisocyanato-diphenyl methane and mixtures of these isomers with their higher homologues which are obtained in known manner by the phosgenation of aniline/formaldehyde condensates, 2,4-and/or 2,6-diisocyanatotoluene and any mixtures of these compounds.
It is preferred, however, to use derivatives of these monomeric poly-isocyanates, as is conventional in coatings technology. These derivatives include poly-isocyanates containing biuret groups.
The modified poly-isocyanates are particularly preferred : N,N',N"-tris-(6-isocyanatohexyl)- biuret and mixtures thereof with its higher homologues and N,N',N"-tris-(6-isocyanatohexyl)- isocyanurate and mixtures thereof with its higher homologues containing more than one isocyanurate ring.
Isocyanate group-containing prepolymers and semi-prepolymers based on the monomeric simple or modified poly-isocyanates exemplified above and organic polyhydroxyl compounds are also preferred for use as poly-isocyanate component a). These pre-polymers and semi pre-polymers generally have an isocyanate content of 0.5-30 % by weight, preferably 1-20 % by weight, and are prepared in known manner by the reaction of the above mentioned starting materials at an NCO/OH equivalent ratio of 1.05: 1 to 10: 1 preferably 1.1 : 1 to 3: 1, this reaction being optionally followed by distillative removal of any un-reacted volatile starting poly-isocyanates still present.
The pre-polymers and semi pre-polymers may suitable be prepared from low molecular weight polyhydroxyl compounds having a molecular weight of 62 to 299, such as ethylene glycol, propylene glycol, trimethylol propane, 1,6-dihydroxy hexane; low molecular weight, hydroxyl-containing esters of these polyols with dicarboxylic acids of the type exemplified hereinafter; low molecular weight ethoxylation and/or propoxylation products of these polyols; and mixtures of the preceding polyvalent modified or unmodified alcohols.
The pre-polymers and semi pre-polymers are, however, preferably prepared from the known relatively high molecular weight polyhydroxyl compounds of polyurea chemistry which have a molecular weight of 300-8000, preferably 1000-5000, as determined from the functionality and the OH number. These polyhydroxyl compounds have at least two hydroxyl groups per molecule and generally have a hydroxyl group content of 0.5-17 % by weight, preferably 1-5 % by weight.
Examples of suitable relatively high molecular weight polyhydroxyl compounds which may be used for the preparation of the pre-polymers and semi pre-polymers include the polyester polyols based on the previously described low molecular weight, monomeric alcohols and polybasic carboxylic acids such as adipic acid, sebacic acid, phthalic acid, isophthalic acid, tetrahydrophthalic acid, hexadydrophthalic acid, maleic acid, the anhydrides of these acids and mixtures of these acids and/or acid anhydrides. Hydroxyl group-containing polylactones, especially poly-ε-caprolactones, are also suitable for the preparation of the pre-polymers and semi pre-polymers.
Polyether polyols, which are obtained in known manner by the alkoxylation of suitable starting molecules, are also suitable for the preparation of the isocyanate group-containing pre-polymers and semi pre-polymers. Examples of suitable starting molecules for the polyether polyols include the previously described monomeric polyols, water, organic polyamines having at least two NH bonds and any mixtures of these starting molecules. Ethylene oxide and/or polylene oxide are particularly suitable alkylene oxides for the alkoxylation reaction. These alkylene oxides may be introduced into the alkoxylation reaction in any sequence or as a mixture.
Also suitable for the preparation of the pre-polymers and semi pre-polymers are the hydroxyl group-containing polycarbonates which may be prepared by the reaction of the previously described monomeric diols with phosgene and diaryl carbonates such as diphenyl carbonate. It is found that the selection of constituents of polyurea top-coat primer renders it possible to completely eliminate the need for tin-based catalyst. Hence, in particular embodiments of the invention, the polyurea top-coat primer is free of any tin-based catalyst.
Examples of suitable commercially available poly-isocyanate resins are:
Desmodur N3900 (formerly VP2410), ex Bayer (Germany), aliphatic polyisocyanate Desmodur N3600, ex Bayer (Germany), aliphatic polyisocyanate Desmodur N3800, ex Bayer (Germany), aliphatic polyisocyanate Tolonate HDT-LV2, ex Rhodia (France), aliphatic polyisocyanate Desmodur N3390, ex Bayer (Germany), aliphatic polyisocyanate Tolonate HDT90, ex Rhodia (France), aliphatic polyisocyanate
Basonat HI 190 B/S, ex BASF (Germany), aliphatic polyisocyanate Desmodur N75, ex Bayer (Germany), aliphatic polyisocyanate Bayhydur VP LS 2319, ex Bayer (Germany), aliphatic polyisocyanate Tolonate IDT 7OB, ex Rhodia (France), aliphatic polyisocyanate
Component b) is based in whole or in part on compounds corresponding to formula 1 wherein R1 to R4 and n have the meanings previously set forth. It is particularly preferred to use "poly aspartic acid derivatives" corresponding to the above formula wherein X represents a divalent hydrocarbon group obtained by the removal of the amino groups from 1,4-diaminobutane, 1,6-diaminohexane, 2,2,4- and 2,4,4-trimethyl-l,6-diaminohexane, l-amino-3,3,5-trimethyl- 5-aminomethyl-cyclohexane, 4,4'-diamino-dicyclohexyl methane or 3,3-dimentyl-4,4'- diamino-dicyclohexyl methane, and n is 2.
The preferred starting components b) also include those compounds corresponding to formula (I) wherein R1 and R2 represent for methyl or ethyl groups and R3 and R4 represent hydrogen.
Suitable polyamines include ethylene diamine, 1,2-diaminopropane, 1,4-diaminobutane, 1,6- diaminohexane, 2,5-diamino-2,5-dimethylhexane, 2,2,4-and/or 2,4,4-trimethyl-l,6- diaminohexane, 1,11-diaminoundecane, 1,12-diaminododecane, l-amino-3,3,5-trimethyl-5- aminomethyl-cyclohexane, 2,4-and/or 2,6-hexahydrotoluylene diamine, 2,4'-and/or 4,4'- diamino-dicyclohexyl methane and 3,3'-dimethyl-4,4'-diamino-dicyclohexyl methane. Aromatic polyamines such as 2,4-and/or 2,6-diaminotoluene and 2,4'-and/or 4,4'- diaminodiphenyl methane are also suitable but less preferred. Relatively high molecular weight polyether polyamines containing aliphatically bound primary amino groups, for example, the products marketed under the Jeffamine trademark, are also suitable. Examples of optionally substituted maleic or fumaric acid esters suitable for use in the preparation of the compounds corresponding for formula (I) include dimethyl, diethyl and din-butyl esters of maleic acid and fumaric acid and the corresponding maleic or fumaric acid esters substituted by methyl in the 2- and/or 3-position.
The preparation of the "poly aspartic acid derivatives" corresponding to Formula (I) from the above mentioned starting materials may be carried out, for example, at a temperature of 0 0C to 100 0C, using the starting materials in such proportions that at least 1, preferably 1, olefinic double bond is present for each primary amino group. Excess starting materials may be removed by distillation after the reaction. The reaction may be carried out solvent-free or in the presence of suitable solvents such as methanol, ethanol, propanol, dioxane and mixtures of such solvents. The binders present in the coating compositions according to the invention are preferably based on mixtures of poly-isocyanate component a) with the secondary polyamines corresponding to Formula (I) or mixtures of poly-isocyanate component a) with the secondary polyamines corresponding to Formula (I) and other isocyanate-reactive compounds.
These other optionally used isocyanate-reactive compounds are preferably organic polyhydroxyl compounds known from polyurethane chemistry and include both the low molecular weight polyhydroxyl compounds and the relatively high molecular weight polyhydroxyl compounds previously set forth for the preparation of the pre-polymers and semi pre-polymers suitable for use as poly-isocyanate component a).
Particularly preferred isocyanate-reactive compounds which may be used as a portion of component b) are the hydroxy functional poly acrylates known for use in polyurethane coatings. These compounds are hydroxyl-containing copolymers of olefinically unsaturated compounds having a number average molecular weight (Mn) determined by vapour pressure or membrane osmometry of 800-50,000, preferably 1000-20,000 and more preferably 5000- 10,000, and having a hydroxyl group content of 0.1-12 % by weight, preferably 1-10 % by weight and most preferably 2-6 % by weight. The copolymers are based on olefinic monomers containing hydroxyl groups and olefinic monomers which are free from hydroxyl groups. Examples of suitable monomers include vinyl and vinylidene monomers such as styrene, α-methyl styrene, o- and p-chloro styrene, o-, m- and p-methyl styrene, p-tert.- butyl styrene; acrylic acid; (methy)acrylonitrile; acrylic and methacrylic acid esters of alcohols containing 1 to 8 carbon atoms such as ethyl acrylate, methyl acrylate, n- and isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, iso- octyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and iso-octyl methacrylate; diesters of fumaric acid, itaconic acid or maleic acid having 4 to 8 carbon atoms in the alcohol component; (methy)acrylic acid amide; vinyl esters of alkane monocarboxylic acids having 2 to 5 carbon atoms such as vinyl acetate or vinyl propionate; and hydroxyalkyl esters of acrylic acid or methacrylic acid having 2 to 4 carbon atoms in the hydroxyalkyl group such as 2-hydroxyethyl-, 2, hydroxy propyl-, 4-hydroxybutyl-acrylate and methacrylate and trimethylol propane-mono- or pentaerythritomono-acrylate or methyacrylate. Mixtures of the monomers exemplified above may also be used for the preparation of the hydroxy functional poly acrylates.
Mixtures of the polyhydroxyl compounds previously described may be used as a portion of component b).
In the binders used according to the invention, components a) and b) are used in amounts sufficient to provide an equivalent ratio of isocyanate groups to isocyanate-reactive groups of 0.8: 1 to 20: 1, preferably 0.8: 1 to 2: 1, more preferably 0.8: 1 to 1.5: 1, even more preferably 0.8: 1 to 1.2: 1 and most preferably about 1 : 1. The optional poly hydroxyl compound is present in component b) in an amount such that up to 20 hydroxyl groups are present for each secondary amino group from the compounds corresponding to formula (I), preferably the equivalent ratio of hydroxyl groups to secondary amino groups is 10: 1 to 1 : 10.
Examples of suitable commercially available isocyanate-reactive resins are:
Desmophen NH 1220, ex Bayer (Germany), Poly aspartic based polyurea binder Desmophen NH 1420, ex Bayer (Germany), Poly aspartic based polyurea binder Desmophen NH 1520, ex Bayer (Germany), Poly aspartic based polyurea binder
Other Constituents of the Primer and Top-Coat Compositions
Each of the primer composition and the top-coat compositions may further comprise other paint constituents as will be apparent for the person skilled in the art. Examples of such paint constituents are solvents, pigments, fillers, additives {e.g. thickening agents, wetting agents, suspending agents, anti-sag agents, anti-sediment agents, stabilizers, coalescing agents, and thixothropic agents).
The compositions typically comprise a solvent or solvents. Examples of solvents are alcohols such as water, methanol, ethanol, propanol, isopropanol, butanol, isobutanol and benzyl alcohol; alcohol/water mixtures such as ethanol/water mixtures; aliphatic, cycloaliphatic and aromatic hydrocarbons such as white spirit, cyclohexane, toluene, xylene and naphtha solvent; ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone, methyl isoamyl ketone, diacetone alcohol and cyclohexanone; ether alcohols such as l-methoxy-2- propanol, 2-butoxyethanol and butyl diglycol; esters such as methoxypropyl acetate, n-butyl acetate and 2-ethoxyethyl acetate; and mixtures thereof.
Typical examples of solvents useful for the epoxy primer composition are alcohols such as water, methanol, ethanol, propanol, isopropanol, butanol, isobutanol and benzyl alcohol; alcohol/water mixtures such as ethanol/water mixtures; aliphatic, cycloaliphatic and aromatic hydrocarbons such as white spirit, cyclohexane, toluene, xylene and naphtha solvent; ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone, methyl isoamyl ketone, diacetone alcohol and cyclohexanone; ether alcohols such as l-methoxy-2-propanol, 2-butoxyethanol and butyl diglycol; esters such as methoxypropyl acetate, n-butyl acetate and 2-ethoxyethyl acetate; and mixtures thereof.
Typical examples of solvents useful for the top-coat composition are aliphatic, cycloaliphatic and aromatic hydrocarbons such as white spirit, cyclohexane, toluene, xylene and naphtha solvent; ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone, methyl isoamyl ketone, diacetone alcohol and cyclohexanone; esters such as methoxypropyl acetate, n-butyl acetate and 2-ethoxyethyl acetate; and mixtures thereof.
Preparation of the Primer and Top-Coat Compositions
The primer composition and the top-coat composition may be prepared by any suitable technique that is commonly used within the field of paint production. Thus, the various constituents may be mixed together using a high speed disperser, a ball mill, a pearl mill, a three-roll mill etc. The paints according to the invention may be filtered using bag filters, patron filters, wire gap filters, wedge wire filters, metal edge filters, EGLM turnoclean filters (ex Cuno), DELTA strain filters (ex Cuno), and Jenag Strainer filters (ex Jenag), or by vibration filtration.
The primer and top-coat compositions to be used herein are conveniently prepared by mixing two or more components e.g. two pre-mixtures. It should be understood that when reference is made to the paint composition, it is the mixed paint composition ready to be applied.
As an example, the epoxy primer base component and the curing agent component for the epoxy primer composition are mixed (e.g. in a ratio of approx. 3: 1 by volume) by adding the curing agent to the base and stir well until the mixture is homogeneous. The mixture is immediately ready for application, e.g. by spray application. As an example, the polyurea top-coat base component and the curing agent for the polyurea top-coat composition are mixed {e.g. in a ratio of approx. 3: 1 by volume) by adding the curing agent to the base and stir well until the mixture is homogeneous. The mixture is then immediately ready for application, e.g. by spray application.
Application of the Primer and Top-Coat Compositions
The primer composition and the top-coat composition can be applied to a substrate (in particular a steel structure) by well known standard application methods like conventional air-spraying or by airless- or airmix-spraying equipment (or alternatively by means of a brush or a roller, in particular when used as a stripe coat). Due to the relatively short pot life of the coating systems of the present invention, two-component spray systems with automatic measure of the mixing ratio are preferred.
Film Thickness
The coating system is typically applied in a total dry film thickness of 120-400 μm, such as 150-350 μm.
In contrast to many of the available coating systems, it is typically preferred that the dry film thickness of the first layer (the primer) is higher that the dry film thickness of the second layer (the top-coat).
This being said, it is preferred that the dry film thickness of the first layer is at least 100 μm.
In one embodiment which is particularly applicable for, e.g., inner structures, the coating system is selected such that:
(i) the dry film thickness of the first layer is 80-160 μm, such as 100-140 μm; and
(ii) the dry film thickness of the second layer is 40-120 μm, such as 60-100 μm.
In another embodiment which is particularly applicable for, e.g., windmill towers, the coating system is selected such that:
(i) the dry film thickness of the first layer is 100-180 μm, such as 120-160 μm; and (ii) the dry film thickness of the second layer is 60-140 μm, such as 80-120 μm.
In still another embodiment which is particularly applicable for, e.g., offshore purposes, the coating system is selected such that:
(i) the dry film thickness of the first layer is 160-240 μm, such as 180-220 μm; and
(ii) the dry film thickness of the second layer is 80-160 μm, such as 100-140 μm.
Alternative Coating System
An alternative to the coating system described above is the one consisting of:
(i) a first layer of a primer composition comprising an epoxy-based binder system, said primer composition having a volume solids % of at least 86 %; and
(ii) a second layer of top-coat composition comprising a polyurea-based binder system, said top-coat composition having a volume solids % of at least 78 %;
wherein the weighted average volume solids % of the coating system is at least 82 %, such as at least 83 % or at least 84 %.
Except for the volume solids % of the primer composition and the volume solids % of the top-coat composition, the coating system follows the directions, embodiments, and variants described for the coating system described further above (mutatis mutandis), including the details in the sections "The Coating System", "High Volume Solids Percentage", "First Layer - The Primer Composition", "Second Layer - The Polyurea-Based Binder System", "Other Constituents of the Primer and Top-Coat Compositions", "Preparation of the Primer and Top- Coat Compositions", "Application of the Primer and Top-Coat Compositions", and "Film Thickness".
In fact, the primer composition has a volume solids % of at least 86 %, such as at least 87 %, e.g. at least 88 %. Similarly, the top-coat composition has a volume solids % of at least 78 %, such as at least 79 %, e.g. at least 80 %.
This being said, and most importantly, the weighed average volume solids % of the coating system is at least 82 %, such as at least 83 %, e.g. at least 84 %. Preferred Embodiment
In view of the preliminary results, the invention in particular provides a coating system suitable for aggressive corrosive environments, consisting of:
(i) a first layer of a zinc primer composition comprising an epoxy-based binder system and 25-30 % by solids volume of the primer composition of zinc, said primer composition having a volume solids % of at least 82 %; and
(ii) a second layer of top-coat composition comprising a polyurea-based binder system, said top-coat composition having a volume solids % of at least 82 %, and said binder system comprising an isocyanate-reactive component of the formula (I) :
Figure imgf000023_0001
wherein X represents an organic group which has a valence of n and which is inert towards isocyanate groups at temperatures of up to 100 0C;
R1 and R2 each independently is selected from organic groups which are inert towards isocyanate groups at temperatures of up to 100 0C;
R3 and R4 each independently is selected from hydrogen and organic groups which are inert towards isocyanate groups at temperatures of up to 100 0C; and
n is an integer of at least 2;
wherein the weighed average volume solids % of the coating system is at least 84 %; and
wherein the dry film thickness of the first layer is higher than the dry film thickness of the second layer, said first layer having a dry film thickness of at least 100 μm.
According to the alternative coating system described above, the invention further provides a coating system suitable for aggressive corrosive environments, consisting of: (i) a first layer of a zinc primer composition comprising an epoxy-based binder system and 25-30 % by solids volume of the primer composition of zinc, said primer composition having a volume solids % of at least 86 %; and
(ii) a second layer of top-coat composition comprising a polyurea-based binder system, said top-coat composition having a volume solids % of at least 78 %, and said binder system comprising an isocyanate-reactive component of the formula (I) :
Figure imgf000024_0001
wherein X represents an organic group which has a valence of n and which is inert towards isocyanate groups at temperatures of up to 100 0C;
R1 and R2 each independently is selected from organic groups which are inert towards isocyanate groups at temperatures of up to 100 0C;
R3 and R4 each independently is selected from hydrogen and organic groups which are inert towards isocyanate groups at temperatures of up to 100 0C; and
n is an integer of at least 2;
wherein the weighed average volume solids % of the coating system is at least 82 %, such as at least 83 %, or at least 84 %; and
wherein the dry film thickness of the first layer is higher than the dry film thickness of the second layer, said first layer having a dry film thickness of at least 100 μm.
In particularly interesting embodiments of the above coating systems, the "dry-to-handle" time of the whole coating system is less than 11 hours, such as less than 9 hours, in particular less than 7 hours, at 20 0C.
In further interesting embodiments hereof, the rust creep of the dry coating system as determined according to ISO 12944-6 is at the most 1 mm. Coated Structure
The present invention further relates to a coated structure carrying on at least a part of the surface thereof a coating system as described above in dry form.
Such a structure is typically a steel or iron structure, in particular steel. Interesting examples hereof are structures such as off-shore platforms, windmill towers, steel chimneys, power stations, steel bridges, cranes, rail cars, containers, wind turbines, etc. in costal, off-shore, or industrial environments, but also tidal zone areas where fast salt water resistance is required. Of particular interest are windmill towers.
A Method for the Establishment of a Coated Structure
The present invention also relates to a method for the establishment of a coated structure using a coating system consisting of a primer composition and a top-coat composition, said primer composition comprising an epoxy-based binder system and said a top-coat composition comprising a polyurea-based binder system, said method comprising :
(i) applying the primer composition onto a predetermined part of the surface of the structure thereby forming a curable primer film on said surface,
(ii) allowing said curable primer film to at least partially cure thereby forming an epoxy primer coat,
(iii) applying the top-coat composition onto the epoxy primer coat thereby forming a curable top-coat film on said epoxy primer coat, and
(iv) allowing said curable top-coat film to cure, and if necessary allowing said epoxy primer coat to fully cure, thereby forming a cured coating system consisting of the epoxy primer coat and a polyurea top-coat;
wherein said primer composition has a volume solids % of at least 82 %, said top-coat composition having a volume solids % of at least 82 %; and the weighted average volume solids % of the coating system being at least 84 %, or
wherein said primer composition has a volume solids % of at least 86 %, said top-coat composition having a volume solids % of at least 78 %; and the weighted average volume solids % of the coating system being at least 82 %. In a particularly interesting embodiment, the primer composition comprises 20-35 % by solids volume of zinc, such as 25-30 % by solids volume of zinc.
Otherwise, the method of the invention can be further specified in accordance with the details disclosed above in relation to the coating system, the preferred embodiment, the coated structure, etc.
Novel Primer Compositions
In view of the details disclosed above and the preliminary results obtained, it is believed that certain of the primer compositions (see above) which are useful in the coating system and in the method disclosed herein are novel per se.
Hence, the present invention also provides a zinc epoxy primer composition comprising an epoxy-based binder system and 20-40 % by solids volume of the primer composition of zinc; said primer composition having a volume solids % of at least 82 %, such as at least 84 %, or at least 86%. In preferred embodiments hereof, the epoxy-based binder system comprises a curing agent selected from Mannich bases, aliphatic polyamines and modified aliphatic polyamines. In specially preferred embodiments hereof, the epoxy-based binder system comprises a curing agent selected from Mannich bases.
Preferably, the "dry-to-handle" time of the zinc epoxy primer composition is less than 5 hours, such as less than 4 hours, in particular less than 3 hours, at 20 0C.
Also preferably, the "dry-to-walk-on" time of the zinc epoxy primer composition is less than 5 hours, such as less than 4 hours, in particular less than 3 hours, at 20 0C.
In a further preferred embodiment, said curing agent is at least partly further reacted with a glycidyl ether functional reactive diluent.
Moreover, the present invention also provides an epoxy primer composition comprising an epoxy-based binder system; said primer composition having a volume solids % of at least 82 %, such as at least 84 %, or at least 86%; and a "dry-to-handle" time which is less than 5 hours, such as less than 4 hours, in particular less than 3 hours, at 20 0C.
Further, the present invention also provides an epoxy primer composition comprising an epoxy-based binder system; said primer composition having a volume solids % of at least 82 %, such as at least 84 %, or at least 86%; and a "dry-to-walk-on" time which is less than 5 hours, such as less than 4 hours, in particular less than 3 hours, at 20 0C.
For a further specification of the zinc epoxy primer composition and the epoxy primer composition, see further above.
EXAMPLES
Materials
Commercial paint systems used in examples
HEMPADUR ZINC 17320 (ex Hempel A/S) is a two-component zinc rich epoxy paint. It cures to a strong and corrosion resistant coating. Recommended use: As a primer on steel in medium to severely corrosive environment or for on-line application on containers. Volume solids %: 61.
HEMPADUR 47140 (ex Hempel A/S) is a two-component polyamide adduct cured, high build epoxy paint which combines a relatively high volume solids content with a short drying time. Recommended use: As a primer in mild to medium atmospheric environments or as an intermediate or finishing coat in epoxy systems in medium to severely corrosive atmospheric environment or as a finishing coat where the usual outdoor cosmetic appearance of epoxy paints is acceptable. Volume solids %: 70.
HEMPATHANE TOPCOAT 55210 (ex Hempel A/S) is a two-component, semi-gloss acrylic polyurethane coating, cured with aliphatic isocyanate, with good gloss and color retention. Recommended use: As a finishing coat for protection of structural steel in severely corrosive atmospheric environment, where light-fastness and gloss retention are required. Volume solids %: 51.
PERMATEX NCG BASE COAT (ex Sika GmbH) is a two-component fast drying low solvent epoxy primer. Recommended use: As a long lasting corrosion protection for wind turbines. Volume solids %: 81.
PERMACOR 2230 VHS (ex Sika GmbH) is a two-component low solvent fast drying acryl- polyurethane top-coat. Recommended use: As a long lasting weather resistant coat for corrosive environment. Volume solids %: 70. INTERZINC 52 (ex International) is a two-component, metallic zinc rich epoxy primer. Recommended use: As a high performance primer for aggressive environments. Volume solids %: 59.
INTERCURE 99 (ex International) is a two-component DTM primer finish polyurethane coating. Recommended use: As a Direct to Metal (DTM) finish coat for mild to medium corrosive environments or as top-coat on a zinc epoxy primer for severe corrosive environments. Volume solids %: 80.
Composition of the Primers and Top-coats
Table 1 : Composition of Primer A (parts by weight)
Figure imgf000029_0001
Table 2: Composition of Top-coats 1-3 (parts by weight)
Figure imgf000030_0001
Top-coat 3 is a top-coat pertaining to the "Alternative Coating System" described herein.
Preparation of the Paint Compositions
Manufacturing of Epoxy Primer Base
Add binder, defoamer, wetting agent, and rheological additive under agitation. Grind for 10 min. Add xylene, zinc dust, and aluminum pigment while stirring. Grind to max. 50 μm. Cool the mill base with butanol, plasticizer, and benzyl alcohol. Add adhesion promoter when the temperature is below 50 0C. Adjust viscosity with xylene.
Manufacturing of Epoxy Primer Curing Agent
Charge curing agent: Mannich base, modified aliphatic polyamine. Mix and add under agitation the epoxy binder and leave it for 24 hours. Add epoxy accelerator. Mix approx. 50 % of the adduct with defoamer, rheological additive, pigment and extender. Grind to 50 μm, temperature minimum 50 0C. Add the rest of the adduct. Add xylene and stir well. Add adhesion promoter and mix.
Preparation of the Primer Composition
The epoxy primer base component and the curing agent component for the epoxy primer is mixed in ratio 3: 1 by volume by adding the curing agent to the base and stir well until the mixture is homogeneous. The mixture is immediately ready for application.
Manufacturing of Polyurea Top-Coat Base
Charge binder Mix and add under agitation water scavenger, rheological additive I, wetting agent, pigment, extender, and matting agent. Grind to 40 μm. Add light stabilizer, rheological additive II under high speed. Add butyl acetate and adhesion promoter. Adjust viscosity with xylene.
Manufacturing of Polyurea Top-Coat Curing Agent
The curing agent consists only of the binder component.
Preparation of the Polyurea Top-Coat Composition
The polyurea top coat base component and the curing agent for the polyurea top coat is mixed in ratio 3: 1 by volume by adding the curing agent to the base and stir well until the mixture is homogeneous. The mixture is immediately ready for application. Application Procedure
The coatings of the present invention can be applied by well known standard application methods like conventional air spraying or by air-less or air-mix spraying equipment. Due to the relatively short pot life of the coating systems of the present invention, two-component spray systems with automatic measure of the mixing ratio are preferred.
Test Methods
Determination of Volume solids %
Volume solids % (VS%) is determined according to ISO 3233 with the modification that drying is carried out at 23 0C and 50 % relative humidity for 7 days.
Ten test items (i.e. ten-fold repetition) are prepared.
The Volume Solids (VS) figure expresses in percentage the ratio:
(Dry film thickness measured after 7 days) / (Wet film thickness measured immediately after application) x 100%.
Volume solids are usually slightly higher than the theoretical value (referred to as "solids volume"), which is found by a calculation based on the paint composition taking specific gravity and solid content of each individual raw material into consideration. Volume solids take into account that small amounts of solvents are usually retained, and that air may be entrapped in the dry paint film either in the form of vacuoles or as interstices. Volume solids are in general in better agreement with practical measurements of dry film thickness than the theoretical value.
Determination of "dry-to-handle" time
The test method is used for determining the "dry-to-handle" time. The freshly painted panels (DFT typically 120-400 μm) are applied a pressure of 100 kg/cm2 for 3 minutes after the application of the outermost paint coat. This pressure is applied in order to simulate the pressure applied by tools and equipment used when handling and transporting the coated object. A Teflon-coated steel block (base area 3.14 cm2) was pressed towards the painted surface by means of a pneumatic compression machine with a mobile arm. If the paint is not "dry-to-handle", the paint will ooze out from underneath the pressure block resulting in a visible indentation mark.
The appearance ofthe painted surface, resulting from the pressure applied, is rated on a scale from 1 to 5, where 1 is unsatisfactory and 5 is perfect with no visible mark after testing. Any rating of 3 or above is termed "acceptable". The pressure is applied at intervals of 1 hour after application of the outermost paint coat (starting a full number of hours after application when the panel was considered ready for testing) (a new panel for each test) and until a rating of 5 is obtained, or until no more panels are available.
The definition of "dry-to-handle" according to this test is the time after application of the outermost coat required in order to obtain a rating of 5. After this period of time, the paint surface is sufficiently hardened to be handled with care without coming off/being damaged.
Determination of the "dry-to-walk-on" time
The "dry-to-walk-on" time is determined essentially as the dry-to-handle time, however using a pressure of 5 kg/cm2. This pressure is applied in order to simulate the pressure applied by the shoes or boots of a person walking on the surface coated with the primer composition.
Hence, the freshly painted panels (DFT typically 50-150 μm) are applied a pressure of 5 kg/cm2 for 3 minutes after the application of the primer layer. A Teflon-coated steel block (base area 25 cm2) was pressed towards the painted surface by means of a pneumatic compression machine with a mobile arm. If the paint is not "dry-to-walk-on", the paint will ooze out from underneath the pressure block resulting in visible indentation marks.
The appearance of the painted surface, resulting from the pressure applied, is rated on a scale from 0 to 5, where 1 is unsatisfactory and 5 is perfect with no visible mark after testing. The pressure is applied at intervals of 1 hour after application of the primer (starting a full number of hours after application when the panel was considered ready for testing) (a new panel for each test) and until a rating of 5 is obtained, or until no more panels are available.
The definition of "dry-to-walk-on" according to this test is the time after application of the outermost coat required in order to obtain a rating of 5. After this period of time, the paint surface is sufficiently hardened to be walked on without coming off/being damaged. Corrosion Test - Method I
a) Salt Sprav Test (SST) - Method I
Salt spray test according to ASTM B 117 (ISO 9227 (formerly ISO 7253)). Test for evaluation of corrosion resistance in salt spray or reproducing corrosion that occurs in atmosphere containing salt spray or splash. Constant spray with 5 % NaCI solution at 35 0C. When the test is stopped, blisters and rust are evaluated according to ASTM D 714 (ISO 4628-2) and ASTM D 610 (ISO 4628-3), respectively. Adhesion is evaluated according to X-cut method according to ASTM D 3359, method A (see below).
b) Adhesion Test (ADH) - Method I
Adhesion test is used to evaluate the adhesion of a paint system to the substrate and between coats (layers).
X-cut according to ASTM D 3359, method A. An "X" is cut into the film to the substrate, pressure tape (TESAPACK 4287) is applied over the "X" and then removed, and adhesion is evaluated by comparison with descriptions and pictures. The method is used to establish whether the adhesion of the coating to the substrate may occur between the coats (adhesive break) or in the coating (cohesive break). The type of rupture is reported, and the severity is judged on a scale from 5 (perfect) to 0 (poor).
Corrosion Test - Method II
The coating systems were evaluated according corrosion category C5-M, high, cf. ISO 12944-6. The overall evaluation was rated either "Pass" or "Fail" in accordance with the ISO 12944 standard.
Panel dimension is 70x150x5 mm, with a surface roughness (profile) similar to ISO 8503-1 medium (G).
The evaluation consisted of the following tests a)-c) :
a) ADH - Reference panels A set of three reference panels were prepared for each system in order to evaluate the adhesion on unexposed panels according to ISO 4624, pull-off test.
b) BBT - Blister Box Test
The Blister Box Test was conducted according to ISO 6270-1. This method was performed in order to evaluate the water resistance of a coating system using controlled condensation. Three panels were used for each test.
The panel surface with the coating system were exposed to 400C, saturated water vapour, at an angle of 15° to the horizontal. The reverse side of the panel was exposed to room temperature. After ending of the exposure (720 hours), blistering and rust were evaluated according to ISO 4628-2 and ISO 4628-3, respectively. Cracking was evaluated according to ISO 4628-4. Adhesion was evaluated according to ISO 4624 (pull-off tests). The actual adhesion test was performed 48 hours after the end of the exposure.
c) SST - Salt Spray Test - Method II
The Salt Spray Test was conducted according to ISO 9227. This method was performed in order to evaluate the corrosion resistance of a coating system by reproducing the corrosion that occurs in an atmosphere containing salt spray or splash. Six panels were used for each test.
The operation conditions of the salt spray test were constant spray with 5% NaCI solution at 35°C. After ending of the exposure (1440 hours), blistering and rust were evaluated on both panel and around the score (in mm from centre), according to ISO 4628-2 and ISO 4628-3, respectively. Cracking was evaluated according to ISO 4628-4. Adhesion was evaluated according to ISO 4624 (pull-off tests). At score the paint film was removed, and the width of the rusting was measured at nine points, where from the M-max and M-avg. values were calculated. The actual adhesion test is performed 48 hours after the end of the exposure.
Results
Corrosion Test - Method I
A coated panel was exposed to the Salt Spray Test and was exposed for 2171 hours. Subsequently, the panel was evaluated in accordance with the test details.
Figure imgf000036_0001
Both tested systems showed excellent performance blistering and perfect adhesion after a very aggressive anticorrosive test. The coating system according to the invention further showed only minimal rust creep (< 1 mm).
Dry-to-handle time
Figure imgf000036_0002
The results from the "dry-to-handle" time test show that the coating system of Primer A and Top-coat 1 has superior dry-to-handle time, as a pressure of 100 kg/cm2 leaves no visible mark after indentation (rated 5).
Process time/VOC
Figure imgf000037_0001
" Based on data supplied from product data sheets
@ Weighed average volume solids %
* based on dry-to-handle time results above.
#Total VOC for whole system (g/m2) (calculated value) :
For each coat:
(VOC (g/L)) / (theoretical coverage (m2/L) at the mentioned DFT) = (VOC for coat (g/m2))
The total VOC for the whole system equals the total amount of the contribution for each coat: (Total VOC for system) = (VOC for 1. coat) + (VOC for 2. coat) + (VOC for 3. coat (if any))
Figure imgf000038_0001
Weighed average volume solids %
* based on dry-to-handle time results below. "Process time in paint shop" has been calculated as dry-to-walk-on time or the recommended over-coating time plus dry-to-handle time. Regarding Hempadur 47140 a recommended over-coating time has been observed (approx. 3 h at a DFT of 200 μm) #Total VOC for whole system (g/m2) (calculated value) : determined as for Table 5.
The coating system of Primer A and Top-coat 1 supplies superior performance with respect to both process times in paint shop and VOC. "Dry-to-handle" results at room temperature (23 0C, 50% relative humidity)
Figure imgf000039_0001
The systems according to the invention, reached a "dry-to-handle" state considerably faster than the commercial reference systems.
Dry-to-walk-on time at room temperature
Figure imgf000039_0002
When compared at the dry film thicknesses specified for practical use, the primer composition according to the invention and the commercial primers Hempadur zinc 17320 and Interzinc 52 have equivalent "walk-on times", and all three seem to be faster than the commercial NCG Base Coat. Corrosion Test - Method II
Figure imgf000040_0001
The systems Hempadur zinc 17320/Hempadur 47140/Hempathane topcoat 55210 and Permatex NCG Base Coat/Permacor 2230 VHS do not pass the requirements to C5-M High due to excess rust creep, M-value (>1 mm). The three coating systems according to the invention passed the test. All coating systems exhibited excellent properties with respect to adhesion and lack of blistering.

Claims

1. A coating system consisting of:
(i) a first layer of a primer composition comprising an epoxy-based binder system, said primer composition having a volume solids % of at least 82 %; and
(ii) a second layer of top-coat composition comprising a polyurea-based binder system, said top-coat composition having a volume solids % of at least 82 %;
wherein the weighted average volume solids % of the coating system is at least 84 %.
2. The coating composition according to claim 1, wherein the primer composition comprises 20-35 % by solids volume of zinc.
3. The coating system according to any one of the preceding claims wherein the dry film thickness of the first layer is higher that the dry film thickness of the second layer.
4. The coating composition according to any one of the preceding claims, wherein the polyurea-based binder system comprises an isocyanate-reactive component of the formula (I) :
Figure imgf000041_0001
wherein X represents an organic group which has a valance of n and which is inert towards isocyanate groups at temperatures of up to 100 0C;
R1 and R2 each independently is selected from organic groups which are inert towards isocyanate groups at temperatures of up to 100 0C;
R3 and R4 each independently is selected from hydrogen and organic groups which are inert towards isocyanate groups at temperatures of up to 100 0C; and n is an integer of at least 2.
5. The coating system according to any one of the preceding claims, wherein the "dry-to- handle" time is less than 11 hours at 20 0C.
6. The coating system according to any one of the preceding claims, wherein the rust creep of the dry coating system as determined according to ISO 12944-6 is at the most 1 mm.
7. A coating system according to claim 1, which is suitable for aggressive corrosive environments, consisting of:
(i) a first layer of a zinc primer composition comprising an epoxy-based binder system and 20-40 % by solids volume of the primer composition of zinc, said primer composition having a volume solids % of at least 82 %; and
(ii) a second layer of top-coat composition comprising a polyurea-based binder system, said top-coat composition having a volume solids % of at least 82 %, and said binder system comprising an isocyanate-reactive component of the formula (I) :
Figure imgf000042_0001
wherein X represents an organic group which has a valence of n and which is inert towards isocyanate groups at temperatures of up to 100 0C;
R1 and R2 each independently is selected from organic groups which are inert towards isocyanate groups at temperatures of up to 100 0C;
R3 and R4 each independently is selected from hydrogen and organic groups which are inert towards isocyanate groups at temperatures of up to 100 0C; and
n is an integer of at least 2;
wherein the weighted average volume solids % of the coating system is at least 84 %; and wherein the dry film thickness of the first layer is higher that the dry film thickness of the second layer, said first layer having a dry film thickness of at least 100 μm.
8. A coating system consisting of:
(i) a first layer of a primer composition comprising an epoxy-based binder system, said primer composition having a volume solids % of at least 86 %; and
(ii) a second layer of top-coat composition comprising a polyurea-based binder system, said top-coat composition having a volume solids % of at least 78 %;
wherein the weighted average volume solids % of the coating system is at least 82 %.
9. A coated structure carrying on at least a part of the surface thereof a coating system according to any one of the preceding claims in dry form.
10. A method for the establishment of a coated structure using a coating system consisting of a primer composition and a top-coat composition, said primer composition comprising an epoxy-based binder system and said a top-coat composition comprising a polyurea-based binder system, said method comprising :
(i) applying the primer composition onto a predetermined part of the surface of the structure thereby forming a curable primer film on said surface,
(ii) allowing said curable primer film to at least partially cure thereby forming an epoxy primer coat,
(iii) applying the top-coat composition onto the epoxy primer coat thereby forming a curable top-coat film on said epoxy primer coat, and
(iv) allowing said curable top-coat film to cure, and if necessary allowing said epoxy primer coat to fully cure, thereby forming a cured coating system consisting of the epoxy primer coat and a polyurea top-coat;
wherein primer composition has a volume solids % of at least 82 %, said top-coat composition having a volume solids % of at least 82 %; and the weighted average volume solids % of the coating system being at least 84 %, or wherein said primer composition has a volume solids % of at least 86 %, said top-coat composition having a volume solids % of at least 78 %; and the weighted average volume solids % of the coating system being at least 82 %.
11. The method according to claim 10, wherein the primer composition comprises 20-35 % by solids volume of zinc.
12. A zinc epoxy primer composition comprising an epoxy-based binder system and 20-40 % by solids volume of the primer composition of zinc; said primer composition having a volume solids % of at least 82 %.
13. The zinc epoxy primer composition according to claim 12, wherein the epoxy-based binder system comprises a curing agent selected from the group consisting of Mannich bases, aliphatic polyamines and modified aliphatic polyamines and said curing agent is at least partly further reacted with a glycidyl ether functional reactive diluent.
14. An epoxy primer composition comprising an epoxy-based binder system; said primer composition having a volume solids % of at least 82 %; and a "dry-to-walk-on" time which is less than 5 hours at 20 0C.
PCT/EP2009/056248 2008-05-23 2009-05-22 Novel fast curing ultra high solids low voc coating system for aggressive corrosive environments WO2009141438A2 (en)

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BRPI0913054-3A BRPI0913054B1 (en) 2008-05-23 2009-05-22 LOW VOC COATING SYSTEM, ULTRA-HIGH SOLID CONTENT, FAST CURING, FOR AGGRESSIVE CORROSIVE ENVIRONMENTS
EP09749928A EP2283056B1 (en) 2008-05-23 2009-05-22 Novel fast curing ultra high solids low voc coating system for aggressive corrosive environments
ES09749928T ES2394149T3 (en) 2008-05-23 2009-05-22 New coating system with low VOC content and ultra-high solids fast curing for aggressive corrosive environments
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