coating composition; parts kit containing a coating composition; coated structure; and method for co

专利摘要:
coating composition summary; kit of parts containing a coating composition; coated structure; and method for coating a metal structure the present invention relates to anti-corrosion coating compositions, in particular, coating compositions to protect iron and steel structures. in particular, the present invention relates to coating compositions comprising particulate zinc, conductive pigments and hollow glass microspheres, for example, epoxy based coatings. the invention additionally relates to a kit of parts containing the composition, a method for its application, as well as metal structures coated with the composition.
公开号:BR112015004103A2
申请号:R112015004103
申请日:2013-07-12
公开日:2020-02-18
发明作者:Lundtang Paulsen Andreas；Colominas Tutusaus Salvador；Arias Codolar Santiago；Alhambra Redondo Tomás；Schandel Torben
申请人:Hempel As；
IPC主号:

专利说明:

COATING COMPOSITION; KIT OF PARTS CONTAINING A COATING COMPOSITION; COATED STRUCTURE; AND METHOD FOR COVERING A METAL STRUCTURE
FIELD OF THE INVENTION [001] The present invention relates to the field of anticorrosive coating compositions, in particular, coating compositions to protect iron and steel structures. In particular, the present invention relates to coating compositions comprising particulate zinc, conductive pigments and glass microspheres, for example, epoxy based coatings.
BACKGROUND OF THE INVENTION [002] Zinc initiator coatings, both organic and inorganic, are used extensively in the marine and offshore industry and can also be specified for, for example, bridges, containers, refineries, petrochemical industry, power plants, tanks storage, cranes, mills and steel structures that are part of civil structures, for example, airports, stadiums, tall buildings. Such coatings can be based on several bonding systems, such as bonding systems based on silicates, epoxy, polyurethanes, cyclized rubbers, phenoxy resin, epoxy ester, alkyd urethane etc.
[003] In zinc initiators, zinc is used as a conductive pigment to produce an anodically active coating. Zinc acts as an anodic sacrificial material and protects the steel substrate, which becomes the cathode. Corrosion resistance is dependent on the transfer of galvanic current through the
2/70 zinc, however, as long as the conductivity in the system is preserved and as long as there is enough zinc to act as an anode, the steel will be galvanically protected. Therefore, the zinc pigment particles in the zinc initiators are tightly packed together and the zinc initiators are typically formulated with very high loads of zinc powder.
[004] Several approaches have been used to reduce zinc loads in the technique. U.S. 4,621,024 discloses coating microspheres with a metal substrate, such as zinc, resulting in a general reduction in the metallic component of the coating. U.S. 5,252,632 discloses the use of uncoated hollow glass microspheres to improve corrosion protection of zinc-based coating compositions, as well as to decrease the density of the composition. Both U.S. 5,580,907 and U.S. 6,287,372 disclose additional efforts to reduce the amount of zinc dust in the compositions by incorporating microspheres. WO 2008/125610 discloses the inclusion of certain zinc alloys to improve protection against corrosion of coating compositions. It is further revealed that conductive pigments, such as carbon black, can improve corrosion inhibition.
[005] WO 96/29372 discloses dry coating compositions to dissolve in a solvent in situ, said dry coating compositions containing graphite to prevent rigid sedimentation of the coating compositions.
[006]
WO 99/58274 discloses a
3/70 coating composition containing carbon-modified zinc dust, zinc dust and hollow glass beads on an epoxy ester resin base. Carbon-modified zinc dust is not a simple mixture of carbon and zinc.
[007] However, there is still a need for improved corrosion resistance of steel-based metal structures that is economical and limits the amount of zinc applied to protective coatings.
[008] In order to provide sufficient protection against corrosion and to ensure optimal coating performance, it is necessary to specify the requirements for the protective paint system together with the relevant laboratory performance tests to assess its likely durability. The use of new technologies and ink formulations also means that coatings are developed with little or no registration. This resulted in more emphasis on accelerated laboratory testing to assess coating performance. Several of these accelerated exposure tests will not, during their exposure time, show negative effects visually on intact coated surfaces. Therefore, the behavior of coatings for damage done artificially, for example, cooling, is widely considered and several prequalification tests are based, among others, on rust creep and bubble formation, as well as cooling detachment, ISO 12944 , NORSOK M-501, ISO 20340, NACE TM 0104, 0204, 0304, 0404, etc. (Weinell, C. E. and S. N. Rasmussen, Advancement in zinc rich epoxy primers for corrosion protection, NACE International, trial n- 07007
4/70 (2007)). Such methods of accelerated weathering seek to intensify the effects of the environment, so that the decomposition of film occurs more quickly (Mitchell, M. J., Progress in offshore coatings, NACE International, trial n-04001 (2004)). The less the rust spreads, the better the overall anti-corrosion performance.
SUMMARY OF THE INVENTION [009] The enhanced corrosion resistance of steel-based metal structures is achieved with a coating composition comprising:
a) a binder system selected from epoxy-based binder systems, polysiloxane-based binder systems, polyurethane-based binder systems, cyclized rubber-based binder systems and phenoxy resin-based binder systems,
b) zinc particles,
c) hollow glass microspheres, and
d) a conductive pigment selected from the group consisting of graphite, carbon black, aluminum pigments, black iron oxide, antimony-doped tin oxide, mica coated with antimony-doped tin oxide, indium tin oxide, carbon nanotubes, carbon fibers and any mixture thereof.
[010] In one embodiment, in order to provide particularly good corrosion resistance, the coating composition according to the present invention contains a conductive pigment selected from carbon black, graphite and any mixture thereof.
DETAILED DESCRIPTION OF THE INVENTION [011] It should be understood that the present invention,
5/70 in principle, it is applicable for any type of binder system in which the zinc powder can be incorporated, for example, anti-corrosion coating compositions of the conventional type. Some examples of this document are coating compositions that comprise a binder system selected from epoxy-based binder systems, polysiloxane-based binder systems, polyurethane-based binder systems, cyclized rubber-based binder systems and binder-based binder systems phenoxy resin, In one embodiment, the coating composition of the present invention comprises a binder system selected from epoxy-based binder systems, polyurethane-based binder systems and polysiloxane-based binder systems. In another embodiment, the coating composition of the present invention comprises a binder system selected from epoxy-based binder systems and polysiloxane-based binder systems. In yet another embodiment, said binder system is an epoxy-based binder system.
EPOXY-BASED BINDING SYSTEM [012] The term epoxy-based binder system should be interpreted as the combination of one or more epoxy resins, any curing agents, any reactive epoxy thinners, any epoxy modifiers, any extender resins, any epoxy accelerators and any epoxy flexibilizers.
[013] Examples of suitable reactive epoxy diluents include, for example, monofunctional glycidyl ethers or esters of aliphatic, cycloaliphatic or aromatic compounds, for example, Araldite
6/70
DY-E / BD, e.g. Huntsman Advanced Materials - Germany, Cardolite NC 513, ex. Cardanol Chemicals (USA) and Cardura E10P ex. Momentive - Netherlands.
[014] Examples of suitable epoxy modifiers include, for example, oils, oil derivatives, modified oils, such as linseed oil and derivatives thereof, castor oil and derivatives thereof, soybean oil and derivatives thereof. same.
[015] Examples of suitable extender resins include, for example, saturated polyester resins, polyvinyl acetate, polyvinyl butyrate, vinyl acetate and vinyl isobutyl ether copolymers, vinyl chloride copolymers and isobutyl vinyl ether, polyvinyl methyl ether, polyvinyl isobutyl ether, polyvinyl ethyl ether, modified aromatic hydrocarbon resins; styrene copolymers, such as styrene / butadiene copolymers; acrylic resins; hydroxyl acrylate copolymers; fatty acids; and cyclized rubbers.
[016] The epoxy-based binder system may comprise one or more epoxy resins selected from aromatic or non-aromatic epoxy resins (eg hydrogenated epoxy resins), which contain more than one epoxy group per molecule, which are placed internally, terminally or in a cyclic structure, together with any suitable curing agent to act as a crosslinking agent. Combinations with reactive diluents, such as from the classes: monofunctional glycidyl ethers or esters of aliphatic, cycloaliphatic or aromatic compounds can be included to reduce viscosity and for improved physical and application properties.
7/70 [017] Suitable epoxy-based binder systems are believed to include modified epoxy and epoxy resins selected from bisphenol A, bisphenol F, Novolac epoxies, non-aromatic epoxies, cycloaliphatic epoxies, epoxy polysulfides and any functional epoxy acrylics combinations thereof. A specific epoxy-based binder system includes bisphenol A. Epoxy-based binder systems can be of the conventional type, such as solvent-borne and water-borne epoxy resin-based systems. Examples of suitable commercially available solvent-borne epoxy resins are:
[018] Epikote 828, ex. Momentive (USA), type bisphenol A [019] Araldite GY 250, ex. Huntsman Advanced Materials (Switzerland), type bisphenol A.
[020] Epikote 1004, ex. Bisphenol A Momentive (USA)
[021] DER 664-20, ex. Dow Chemicals (Germany), type bisphenol A.
[022] Epikote 1001 X 75, ex. Momentive (USA), type bisphenol A.
[023] Araldite GZ 7071X75BD, ex. Huntsman
Advanced Materials (Germany), type bisphenol A in xylene.
[024] Araldite GZ 7071X75CH, ex. Huntsman
Advanced Materials (Switzerland), type bisphenol A.
[025] DER 352, ex. Dow Chemicals (Germany), mixture of bisphenol A and bisphenol F. Epikote 235, ex. Momentive (USA), mixture of bisphenol A and bisphenol F.
[026] Epikote 862, ex. Momentive (USA), type
8/70 bisphenol F.
[027] DEN 438-X 80, ex. Dow Chemical Company (USA), epoxy novolac.
[028] Epikote 1009, ex. Momentive (USA), type bisphenol A.
[029] DER 684-EK40, ex. Dow Chemicals (Germany), type bisphenol A. Epikote 154, ex. Momentive (USA) novolac epoxy.
[030] Examples of suitable commercially available water-borne epoxy resins are:
[031] Beckopox EP 385 W, ex Cytex Surface Specialties (Germany).
[032] Epicote 3540 WY-55A, ex. Momentive (USA).
[033] EPI-REZ DPW 6520, ex. Momentive (USA).
[034] Beckopox VEP 2381 W, ex. Cytex Surface Specialties (Germany).
[035] The epoxy-based binder system may comprise one or more curing agents selected from the compounds or polymers comprising at least two reactive hydrogen atoms bound to nitrogen.
[036] Suitable curing agents for solvent-borne epoxy resins include amines or aminofunctional polymers selected from aliphatic amines and polyamines (eg, cycloliphatic amines and polyamines), polyamidoamines, polyoxyalkylene amines (eg. polyoxyalkylene), amine polyalkoxy ethers (for example, those commercially available as Jeffamines), alkylene amines (for example, alkylene diamines), aralkylamines, aromatic amines, Mannich bases (for example
9/70 example, those commercially available as phenalcamines), aminofunctional silicones or silanes, isocyanates and even amine adducts and derivatives thereof. In one embodiment, the curing agents are polyamidoamines.
[037] Examples of suitable commercially available curing agents are:
[038] Jeffamina EDR-148 ex. Huntsman Corporation (USA), triethylene glycodiamine.
[039] Jeffamina D-230 ex. Huntsman Corporation (USA), diamine of polyoxypropylene [040] Jeffamina D-400 ex. Huntsman Corporation (USA), diamine of polyoxypropylene [041] Jeffamina T-403 ex. Huntsman Corporation (USA), triamine of polyoxypropylene [042] Ancamine 1693 ex. Air Products (USA), adduct polyamine cycloaliphatic. [043] Ancamine X2280 ex. Air Products (USA),
cycloaliphatic amine.
[044] Ancamine 2074 ex. Air Products (USA), polyamine adduct cycloaliphatic [045] Ancamide 350 A ex. Air Products (USA),
polyaminoamide.
[046] Sunmide CX-105X, ex. Air Products Inc., Mannich base. [047] Agent Epikure 3140 cure system, ex.
Momentive (USA), polyamidoamine.
[048] SIQ Amin 2030, ex. SIQ Kunstharze GmbH (Germany), polyamidoamine.
[049] Epikure Curing Agent 3115X-70, ex. Momentive (USA), polyamidoamine.
10/70 [050] SIQ Amin 2015, ex. SIQ Kunstharze GmbH (Germany), polyamidoamine.
[051] Polipox VH 40309/12, ex. Dow Chemicals (USA), amine of polyoxyalkylene. [052] CeTePox 1490 H, e.g. CTP Chemicals and Technologies for Polymers (Germany), amine of polyoxyalkylene • [053] Stiffener MXDA epoxy, ex. Mitsubishi
Gas Chemical Company Inc (USA), aralkyl amine.
[054] Diethylaminopropylamine, e.g. BASF (Germany) , the mine aliphatic. [055] Gaskamine 240, ex. Mitsubi shi Gas Chemical Company Inc (USA), amine of aralkyl. [056] Cardolite Lite 2 0 02, ex. Cardanol Chemicals (USA), Mannich base. [057] Aradur 42 BD, ex. Huntsman Advanced
Materials (Germany), cycloaliphatic amine.
[058] Isophoronadiamine, ex. BASF (Germany), cycloaliphatic amine.
[059] Epikure 3090 Curing Agent, ex.
Momentive (USA), polyamidoamine adduct with epoxy.
[060] Crayamid E260 E90, ex. Arkema (France), polyamidoamine adduct with epoxy.
[061] Crayamid 140, ex. Arkema (France), amine polyamide resin.
[062] Aradur 943 CH, ex. Huntsman Advanced
Materials (Switzerland), alkylene amine adduct with epoxy.
[063] Aradur 863 XW 80 CH, ex. Huntsman
Advanced Materials (Switzerland), aromatic amine adduct with epoxy.
11/70 [064] Cardolite NC-541, ex. Cardanol Chemicals (USA), Mannich base.
[065] Cardolite Lite 2001, ex. Cardanol
Chemicals (USA), Mannich base.
[066] Suitable curing agents for water-borne epoxy resins may include amine adducts selected from:
[067] Beckopox Specialharter EH 623W, ex. Cytex Surface Specialties (Germany).
[068] Beckopox EH 613W, ex. Cytex Surface Specialties (Germany).
[069] EPICURE DPC 6870, ex. Momentive (USA).
[070] Epilink 660, ex. Air Products (Italy).
[071] Epilink 701, ex. Air Products (United Kingdom).
[072] In one embodiment, epoxy-based bonding systems comprise 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, polyamidoamines, polyoxyalkylene amines, alkylene amines, aralkylamines, polyamines and adducts and derivatives thereof. In an additional embodiment, epoxy-based binder systems can comprise both bisphenol A and polyamidoamines.
[073] In another embodiment, the epoxy resin can have an epoxy equivalent weight of 100 to 9,000, 100 to 2,000, such as 100 to 1,500 for example, 150 to 1,000, such as 150 to 700.
[074] In yet another embodiment, epoxy-based bonding systems may comprise one or more
12/70 bisphenol A epoxy resins having an epoxy equivalent weight of 150 to 700 and one or more polyamidoamines or adducts and derivatives thereof.
[075] In one embodiment, epoxy-based bonding systems are ambient-curing bonding systems.
[076] For some epoxy based binder systems, the composition will form a suitable film without the addition of a curing agent. For this reason, in another embodiment, no curing agent is added to the paint composition.
[077] In the coating composition, the total amount of epoxy-based binder system can, in one embodiment, be in the range of 15 to 80%, such as 20 to 65%, for example, 30 to 50%, by volume of solids, of the coating composition.
[078] When used in this document, the term hydrogen equivalents is intended to cover only reactive hydrogen atoms bonded to nitrogen.
[079] The amount of hydrogen equivalents in relation to one or more curing agents is the sum of the contribution of each of the one or more curing agents. The contribution of each of the one or more curing agents to the hydrogen equivalents is defined as the quantity in grams of the curing agent divided by the weight of the hydrogen equivalent of the curing agent, where the weight of the hydrogen equivalent of the curing agent curing time is determined as follows: grams of curing agent equivalent to 1 mole of active hydrogen. For adducts with epoxy resins, the contribution of reagents before adduction is used to determine the
13/70 amount of hydrogen equivalents in the epoxy-based binder system.
[080] The amount of epoxy equivalents in relation to one or more epoxy resins is the sum of the contribution of each of the one or more epoxy resins. The contribution of each of the one or more epoxy resins to the epoxy equivalents is defined as the quantity in 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 follows : grams of epoxy resin equivalent to 1 mol of epoxy groups. For adducts with epoxy resins, the contribution of reagents prior to adducting is used to determine the amount of epoxy equivalents in the epoxy-based binder system.
[081] The ratio between the hydrogen equivalents of the one or more curing agents and the equivalents of
epoxy gives one or more epoxy resins Can be in the range 20: 100 The 120: 100 , as in the range 60: 100 to 110: 100 or 70: 100 The 100: 110, or such as 80: 100 to 110: 100. [082] Alternatively, the system binder
The coating composition is selected from the polysiloxane-based bonding systems, polyurethane-based bonding systems, cyclized rubber-based bonding systems and phenoxy resin-based bonding systems. Examples of such commercial coating compositions are of the type in which the zinc powder was conveniently used. The binder system may or may not need, depending on the specific binder system, a curing agent. For this reason, in one embodiment, the binding system comprises one or more curing agents. In another
14/70 modality, the binder system does not comprise any curing agent.
[083] Other suitable binder systems include one-component coatings, such as binder systems based on vinyl-based polymers; copolymers of vinyl chloride and vinyl isobutyl ether; phenoxy; polyurethanes; cyclized rubbers, including aromatic hydrocarbon resins, such as oil fraction condensates. Typically, no curing agent is added to such types of one component binder systems.
[084] Examples of such commercially available resins suitable for one-component coatings containing zinc are:
[085] Alplex CK 450, Cytec (based on cyclized rubber) [086] Phenoxy PKHH, InChem (based on phenoxy)
POLYSILOXAN-BASED BINDING SYSTEMS [087] The term polysiloxane-based binder system should be interpreted as a binder system comprising at least one curable polysiloxane-modified constituent, where a major part of the binder system consists of chemical portions of polysiloxane, that is, at least 20% by volume of solids, such as at least 25% by volume of solids, preferably at least 35% by volume of solids, for example, more than 50% by volume , of solids in the binder system are represented by the chemical portions of polysiloxane.
[088] The chemical portion of polysiloxane should be interpreted including any organic substituents
15/70 pendants, such as alkyl, phenyl, and / or saturated cyclic structures and may also comprise curable substituents, examples in this document are alkoxy groups, unsaturated acrylic groups, etc.
[089] In one embodiment, the polysiloxane-based binder system is a combination of one or more compound (s) modified by aminofunctional silicone, one or more epoxy resins, any polysiloxane-binding compound or polysiloxane-modified binder, any aminosilanes, any reactive epoxy thinners, any epoxy modifiers, any extender resins, any epoxy accelerators and any epoxy flexibilizers.
[090] The term compound modified by aminofunctional silicone should be understood in the conventional sense, that is, a silicone compound, for example, a silane or polysiloxane compound, which has pendant and / or terminal amino groups. Illustrative examples of aminofunctional silicone compounds are polysiloxanes and aminofunctional aminosilanes.
[091] In a further embodiment of the invention, the aminofunctional silicone compound (s) is / are aminofunctional polysiloxane (s). The term aminofunctional polysiloxane means a linear or branched polymeric constituent that has one or more polysiloxane blocks and that has pending and / or terminal aminofunctionalities.
[092] Aminofunctionalities can, for example, be introduced into the reactive polysiloxane in the middle of an aminosilane (i.e., an aminosilane such as those defined below), cf. U.S. 4,857,608. It must be understood,
16/70 further, that the aminofunctional polysiloxane can be prepared in situ. In some examples, a functional hydroxyl or functional alkoxy polysiloxane is reacted with an aminosilane, through which aminofunctionalities are introduced. For example, an aminosilane can be reacted with an α, ωdihydroxypolidimethylsiloxane at a temperature in the range of 20 to 80 ° C, preferably with the use of 0.4 to 5.0 alkoxy groups of the aminosilane per sianol group of the polysiloxane. If an excess of aminosilane is used or if the reaction cannot be completed, a small amount of aminosilane may remain in the product. In one embodiment, at least one aminofunctional polysiloxane is the reaction product of a polysiloxane and an aminosilane.
[093] Examples of aminofunctional polysiloxanes are α, ω-dipolysiloxanes aminofunctional (for example, polysiloxane fluids). Illustrative examples of commercially available aminofunctional polysiloxanes are SILRES HP 2000 (aminofunctionalized methylphenyl silicone) ex Wacker Chemie - Germany; SF1708 (aminofunctionalized polysiloxane fluid) ex General Electric Co. etc.
[094] In another embodiment, the aminofunctional silicone compound (s) is / are aminosilane (s). In this embodiment, a constituent of polysiloxane binder or polysiloxane modified binder that acts as a reactive coagglutinant / flexibilizer is preferably present. Aminosilanes are often defined as silanes of the formula:
where each R, independently, is selected
17/70 among C1-4 alkyl (e.g. methyl, ethyl, hexyl, octyl, etc.), C1-4-alkyl-O-C2-4-alkyl; aryl (for example, phenyl) and aryl-C1-4-alkyl (for example, benzyl); Ri is selected from - (CH2) 2-4 ^_ , methyl and - (CH ₂ ) 2-3-O- (CH ₂ ) 2-3; hydrogen and - (CH2) 2-4 ^_ NH2; x is such as 0, 1, 2 or 3.
[095] Examples are (CH ₃ O) ₃ Si (CH ₂ ) ₃ NH (CH ₂ ) 2NH2;
trimethylene replaced by
R is selected from an integer from 0 to 3, illustrative of aminosilanes (ch3ch ₂ och ₂ ch ₂ o) ₃ si (ch ₂ ) ₂ nh ₂ ;
(C2H ₅ O) ₃ Sí (CH2) ₃ NH ₂ ;
(CH ₃ OCH ₂ CH ₂ O) ₃ Si (CH ₂ ) ₃ nh ₂ ;
(C2H5O) ₃ Si (CH ₂ ) ₃ o (CH ₂ ) ₃ nh ₂ ;
(C2H5O) 2C ₆ H ₅ Si (CH ₂ ) ₃ NH ₂ ;
(C2H5O) ₃ SiCH ₂ O (CH ₂ ) 2NH2;
(C ₂ H5O) ₃ Sí (CH2) ₃ O (CH2) 2NH ₂ ; and (C2H5O) 2CH ₃ Si (CH ₂ ) ₃ NH ₂ . Illustrative examples of commercially available aminosilanes are Dynasilan ΆΜΕΟ (3-aminopropyltriethoxysilane) ex Degussa Hills; KBM603 (Ν-βaminoethyl-y-aminopropyltrimethoxysilane) ex Shin Etsu; etc.
[096] Examples of polysiloxane binder or polysiloxane modified binder include polysiloxanes having the formula:
R /
The —— 4 ,, - 4p—j—.O.:·— laugh that n is an integer from 3 to 50, each Ri is independently selected from Farinaceous I (for example, methyl, ethyl, etc.) ; hydroxy C 1-6 alkyl (for example, hydroxymethyl, hydroxyethyl, etc.); C1-6 alkoxy (for example, methoxy, ethoxy, propoxy, etc.) and each R and, independently, selected from silanol, C1-6 alkyl (for example, methyl, ethyl, etc.); hydroxy C 1-6 alkyl (for example, hydroxymethyl, hydroxyethyl etc.); C1-6 alkoxy (for
18/70 (example, methoxy, ethoxy, propoxy etc.). In one embodiment, the polysiloxane binder or polysiloxane modified binder is a polysiloxane binder that includes methoxy groups.
[097] Still in an additional modality, the aminofunctional silicone compound (s) is / are the combination of aminofunctional polysiloxane (s) and aminosilane (s), that is, the binder phase comprises one or more aminofunctional polysiloxanes, as well as one or more aminosilanes. Such a combination can be achieved by adding an aminofunctional polysiloxane (as described above) and an aminosilane (as defined above), or by using a reaction product between an aminosilane and a polysiloxane in which a portion of the aminosilane remains unreacted.
[098] The one or more epoxy resins are similar to the epoxy resins described in the section on the epoxy-based binder system above.
[099] Examples of suitable commercially available epoxy resins include, for example, Adeka EP-4080E resin, ADEKA Corporation - Japan (aliphatic epoxy resin) and Epikote 828, ex. Momentive (USA), type bisphenol A.
[0100] Other suitable polysiloxane based binder systems are, for example, described in WO 96/16109, WO 01/51575 and WO 2009/823691.
POLYURETHANE-BASED BINDING SYSTEM [0101] The term polyurethane-based binder system is intended to mean a binder system that has, with the main components, one or more
19/70 diisocyanates or polyisocyanates components and a hydroxy functional component that contains two or more hydroxyl groups (two-component systems) or that has, as the main components, one or more isocyanate polymers (typically, one-component systems).
[0102] The reaction (cure) of the isocyanate component (s) and the hydroxy functional component (s) results in the formation of a urethane functionality.
[0103] A type of polyurethane-based binder system contains:
a) a polyisocyanate component and
b) a hydroxy functional component comprising at least two hydroxyl groups [0104] The cross-linking that occurs is based on a reaction between the polyisocyanate component a) and the hydroxy functional component b).
[0105] Polyisocyanates for use as a polyisocyanate component a) in the composition include the known polyurethane chemistry polyisocyanates. Examples of suitable low molecular weight polyisocyanates having a molecular weight of 168 to 300 include hexamethylene diisocyanate (HDI), 2,2,4- and / or 2,4,4 trimethyl-1,6-hexamethylene diisocyanate, diisocyanate dodecamethylene, 2,4-diisocyanate-1-methyl benzene (toluene diisocyanate, TDI), 2,4-diisocyanate-1-methylbenzene, 1,4diisocyanatocyclohexane, l-isocyanate-3,3,5-trimethyl-5isocyanatomethylcyclohexane ( IPDI), 2,4'-e / or 4,4'diisocyanate-dicyclohexyl methane, 2,4-e / or 4,4'diisocyanate-diphenyl methane and mixtures of these isomers with their superior counterparts that are obtained from a known way
20/70 by the phosgenation of aniline / formaldehyde condensates, 2,4-and / or 2,6-toluene diisocyanate and any mixtures of these compounds.
[010 6] In one embodiment, the one or more polyisocyanates are selected from aliphatic polyisocyanates, for example, hexamethylene diisocyanate (HDI), 2, 2,4-and / or 2,4,4-trimethyl-l diisocyanate, 6-hexamethylene, dodecamethylene diisocyanate, 1,4cyclohexane diisocyanate, l-isocyanate-3,3,5-trimethyl-5methylcyclohexane (IPDI), 2,4'-e / or 4,4'-diisocyanate-dicyclohexyl isocyanate and 2,4-e / or 4,4-diisocyanato-diphenyl methane.
[0107] In some variants of this document, the coating composition also comprises one or more catalysts, for example, one or more selected from tetramethylbutanidiamine (TMBDA), N-alkyl morpholines, triethylamine (TEA), 1,8-diazabicyclo [5.4 .0] unedecene-7 (DBU), pentamethyldiethylene triamine (PMDETA), zinc octate, dioctyltin dilaurate, dibutiltin dilaurate and dibutiltin oxide, in particular, dioctyltine dilaurate, dibutiltine dilaurate and dibutiltine dilaurate. In other variants, the coating composition is devoid of any such catalysts.
[0108] In one embodiment, the one or more polyisocyanates are selected from aromatic polyisocyanates, for example, 2,4-diisocyanate-1-methyl benzene (toluene diisocyanate, TDI), 2,4-diisocyanatol-methyl benzene and mixtures of these isomers with their superior counterparts which are obtained in a known manner through the phosgenation of aniline / formaldehyde condensates,
21/70 2,4-and / or 2,6-toluene diisocyanate and any mixtures of these compounds.
[0109]
However, it is preferable to use the derivatives of these monomeric polyisocyanates, as is conventional in coating technology. Such derivatives include polyisocyanates that contain biuret groups.
[0110]
The modified polyisocyanates are particularly preferred: N, Ν ', N-tris- (6isocyanatohexila) biuret and mixtures of them with superior homologues and N, Ν', N-tris- (6isocyanatohexila) isocyanurate and mixtures thereof with their superior counterparts that contain more than one isocyanurate ring.
[0111]
Examples of suitable commercially available polyisocyanate resins are:
[0112] Desmodur N3900 (formerly VP2410), ex. Bayer (Germany), aliphatic polyisocyanate.
[0113] Desmodur N3600, ex. Bayer (Germany), aliphatic polyisocyanate.
[0114] Desmodur N3800, ex. Bayer (Germany), aliphatic polyisocyanate.
[0115] Tolonate HDT-LV2, ex. Rhodia (France), aliphatic polyisocyanate.
[0116] Desmodur N3390, ex. Bayer (Germany), aliphatic polyisocyanate.
[0117] Tolonate HDT90, ex. Rhodia (France), aliphatic polyisocyanate.
[0118] Basonat HI 190 B / S, ex. BASF (Germany), aliphatic polyisocyanate.
[0119] Desmodur N75, ex. Bayer (Germany), aliphatic polyisocyanate.
22/70 [0120] Bayhydur VP LS 2319, ex. Bayer (Germany), aliphatic polyisocyanate.
[0121] Tolonate IDT 70B, ex. Rhodia (France), aliphatic polyisocyanate.
[0122] Desmodur H, ex Bayer (Germany).
[0123] Basonat HB 175 MP / X BASF - Germany aliphatic polyisocyanate.
[0124] Examples of commercially available aromatic polyisocyanate resins are:
[0125] Desmodur L67 BA (Bayer Material Science) [0126] Desmodur E21 (Bayer Material Science) [0127] Desmodur VL (Bayer Material Science) [0128] Voratron EC 112 (Dow Chemicals) [0129] Desmodur E23 (Bayer Material Science) ) [0130] Desmodur E 1660 (Bayer Material Science) [0131] Suprasec 2495 (Huntsman Advanced Materials).
[0132] Semi-prepolymer prepolymers containing isocyanate group based on the simple or modified monomeric polyisocyanates exemplified above and organic polyhydroxyl compounds are also preferred for use as a polyisocyanate component a). Such prepolymers and semi-polymers, in general, have an isocyanate content of 0.5 to 30% by weight, preferably 1 to 20% by weight and are prepared in a manner known for the reaction of the mentioned starting materials above in an equivalent NCO / OH ratio of 1.05: 1 to 10: 1, preferably 1, 1: 1 to 3: 1, such reaction being optionally followed by the distillation removal of any volatile initial polyisocyanates unreacted still present.
23/70 [0133] Prepolymers and semi-prepolymers can be suitably prepared from low molecular weight polyhydroxyl compounds that have a molecular weight of 62 to 299, such as ethylene glycol, propylene glycol, trimethylol propane , 1,6-dihydroxy hexane; low molecular weight hydroxyl ethers of such polyols with dicarboxylic acids of the type exemplified below; low molecular weight ethoxylation and / or propoxylation products of such polyols; and mixtures of the previous modified or unmodified polyvalent alcohols.
[0134] Prepolymers and semi-polymers are, however, preferably prepared from relatively high molecular weight polyhydroxyl compounds.
[0135] Such polyhydroxyl compounds have at least two hydroxyl groups per molecule (and, in general, have a hydroxyl group content of 0.5 to 17% by weight, preferably 1 to 5% by weight.
[0136] Examples of suitable relatively high molecular weight polyhydroxyl compounds that can be used for the preparation of prepolymers and semi-prepolymers include polyester polyols based on the low molecular weight described above.
[0137] Examples of commercially available polyester polyols include:
[0138] Desmophen 651 MPA, ex. Bayer (Germany) [0139] Desmophen VP LS 2089, ex. Bayer Material Science (Germany) [0140] Polyester polyols, which are obtained in a known way through the alkoxylation of molecules
24/70 suitable initials are also suitable for the preparation of prepolymer and semi-prepolymer containing isocyanate group. Examples of suitable starting molecules for the polyether polyols include the monomeric polyols described above, water and any mixtures of such starting molecules. Ethylene oxide and / or polyylene oxide are particularly suitable alkylene oxides for the alkoxylation reaction. Such alkylene oxides can be introduced into the alkoxylation reaction in any sequence or as a mixture.
[0141] Examples of commercially available polyether polyols include:
[0142] Desmophen 1380 BT 03/2008 (formerly Desmophen 550 U), ex. Bayer Material Science (Germany) [0143] Polyol Voranol CP 450, ex. Dow Chemicals (Germany) [0144] They are also suitable for the preparation of pre-polymers and semi-polymers of polycarbonates containing hydroxyl group which can be prepared by reacting the monomeric diols described above with phosgene and diaryl carbonates, such as diphenyl carbonate.
[0145] Component b) is based, in whole or in part, on organic polyhydroxyl compounds known for polyurethane chemistry and includes both low molecular weight polyhydroxyl compounds and relatively high molecular weight polyhydroxyl compounds previously established for the preparation of prepolymers and semi-polymers suitable for use as a polyisocyanate component a).
25/70 [0146] The specifically preferred functional hydroxyl reactive isocyanate compounds that can be used as component b) are the functional hydroxyl polyacrylates known for use in polyurethane coatings. Such compounds are hydroxyl-containing copolymers of olefinically unsaturated compounds that have an average numerical molecular weight (Mn) determined by vapor pressure or membrane osmometry of 800 to 50,000, preferably 1,000 to 20,000, and more preferably 5,000 to 10,000 and which has a hydroxyl group content of 0.1 to 12% by weight, preferably 1 to 10% by weight and, more preferably, 2 to 6% by weight. Copolymers are based on olefinic monomers that contain hydroxyl groups and olefinic monomers that are free from hydroxyl groups. Examples of suitable monomers include vinyl and vinylidene monomers, such as styrene, α-methyl styrene, o- and p-chlorine styrene, o-, m- and p-methyl styrene, p-tertbutyl styrene; acrylic acid; (meth) 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, isooctyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and isooctyl methacrylate; diesters of fumaric acid, itaconic acid or maleic acid which have 4 to 8 carbon atoms in the alcohol component; (methyl) 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 acid
26/70 acrylic or methacrylic acid that has 2 to 4 carbon atoms in the hydroxyalkyl group, such as acrylate and metracrylate 2-hydroxyethyl, 2, hydroxypropyl, 4hydroxybutyl and acrylate or methacrylate of propane-mono or trimethylol pentaerythritone. Mixtures of the monomers exemplified above can also be used for the preparation of functional hydroxyl polyacrylates. Mixtures of the polyhydroxyl compounds described above can be used as component b).
[0147] In such a type of polyurethane-based binder system, components a) and b) are used in sufficient quantities to provide an equivalent ratio of isocyanate groups to isocyanate-reactive (hydroxyl) 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 functional hydroxyl compound b) is present in an amount so that up to 20 hydroxyl groups are present; preferably, the equivalent ratio of hydroxyl groups to secondary amino groups is 10: 1 to 1:10.
[0148] Examples of commercially available functional hydroxyl (isocyanate reactive) resins include:
[0149] Synocure 878 N 60, ex Arkem (Spain), acrylic resin hydroxyl functional hydrocarbon aromatic. [0150] Synthalat THE 0 77, ex Synthopol Chemie (Germany) [0151] Synthalat THE 045, ex. Synthopol Chemie
(Germany)
27/70 [0152] Synthalat A 088 MS, ex. Synthopol Chemie (Germany) [0153] Synthalat A 141 HS 05, ex. Synthopol
Chemie (Germany) [0154] Synthalat A 060, ex. Synthopol Chemie (Germany) [0155] Desmophen A XP 2412, ex. Bayer Material Science (Germany) [0156] Synthalat A-TS 1603, ex. Synthopol Chemie (Germany) [0157] Acrylamac 332-2629, ex. Momentive (Germany) [0158] A polyurethane coating system of the type described above is typically supplied as a two-component system, in which a package comprising the component (s) containing hydroxyl (s), any pigments, solvents and additives and another package comprises the compound containing polyisocyanate and solvents free from moisture. Zinc particles, conductive pigment (s) and hollow glass microspheres are typically added to the hydroxyl containing package. An example of such a coating is provided in Table 9.
[0159] Other types of polyurethane coating systems are a one component system, where all components are filled in the same container and the paint is cured with moisture (typically at room temperature and ambient conditions or at slightly increased temperatures, for example example, 60 to 100 °, optionally with the presence of an accelerator, for example, an accelerator that comprises tin. An example of such a coating is
28/70 provided in Table 8.
[0160] In one embodiment, the moisture-cured polyurethane-based binder system contains one or more isocyanate polymers, for example, polyisocyanate prepolymer based on toluene diisocyanate (TDI).
[0161] Examples of isocyanate polymers include:
[0162] Desmodur E21 (Bayer Material Science) [0163] Desmodur E1361 (Bayer Material Science) [0164] Desmodur E14 (Bayer Material Science) [0165] Desmodur E23 (Bayer Material Science) [0166] Desmodur E 1660 (Bayer Material Science) ) [0167] Voratron EC 112 (Dow Chemicals) [0168] A polyurethane coating system of the type described above is typically supplied as a one component system, wherein the package comprises the one or more isocyanate polymers, pigment ( s) conductive (s), zinc particles, hollow glass microspheres and any non-conductive pigments, fillers, solvents, additives etc.
THE ZINC PARTICLES [0169] The material called zinc particles is a particulate material with a high zinc content, such as at least 90% by weight of zinc.
[0170] The term particulate material is intended to cover both fine spherical particles and relatively irregular shaped particles and other shapes such as flakes, discs, spheres, needles, platelets, fibers and rods. The particulate material can be a powder or a dust.
29/70 [0171] The particle size distribution of the particulate material is of some importance in dye applications. For example, very coarse particulate materials can result in spare particles in the dry paint film. Therefore, in one embodiment, particulate materials with a D50 (average particle size) less than 50 pm are used. In an additional modality, a D50 less than 20 pm is used, still in an additional modality, a D50 less than 15 pm is used and still in an additional modality, a D50 less than 12 pm is used.
[0172] In addition to the statements above, particles thicker than 100 pm should be avoided as much as possible, due to the fact that they can be spare in the paint film. This leads to defects in the paint film and deterioration of the barrier effect and anti-corrosion properties. Therefore, it is useful to discard, for example, through sieving, any particles larger than 100 pm. In practice, a D99 less than 100 pm is considered adequate.
[0173] The particle size distribution of the materials can, for example, be measured using a Helos® Sympatec GmbH laser diffraction apparatus. Parameters D50 and D99 are equivalent particle diameters for which the cumulative distribution of volume, Q3, assumes values of 50 and 99%, respectively.
[0174] Particulate materials can be manufactured through classical gas atomization of a corresponding thick zinc material. Due to the fact that particulate materials directly obtained from such a process still include coarse particles, which are
30/70 incompatible with the intended application, a screening operation or a classification operation must be carried out.
[0175] The zinc particles comprised in the present invention can also be obtained directly commercially. Suppliers include Purity Zinc Metals, Horsehead Corporation, Umicore, US zinc, Jiashan Baiwei and Garrison Minerals, among many others, for example, ZMP 4P16, Umicore (Belgium).
[0176] The zinc particles are present, in one embodiment, in the coating composition of the present invention in an amount of about 10 to 55%, by volume of solids, as well as in an amount of about 15 to 50%, in volume of solids, for example, in the amount of about 18 to 40%, in volume of solids, more particularly, in the amount of about 20 to about 36%, in volume of solids, even more particularly, in the amount of about from 20 to about 30%, by volume of solids, of the mixed coating composition. In another embodiment, the zinc particles are present in the coating composition of the present invention in an amount of about 30 to 50%, by volume of solids, as well as in the amount of 35 to 45%, by volume of solids, of the composition mixed coating.
Hollow glass microspheres [0177] Uncoated hollow glass microspheres can be purchased commercially. Suppliers include 3M Corporation, Minerals i Derivats S.A. and Potter Industries.
[0178] Potter Industries markets its hollow glass microspheres under the trade name
31/70
SPHERICEL®. SPHERICEL® are available in different sizes, entitled 110P8, 60P18, 45P25, 34P30 and 25P45. The 110P8 microspheres are slightly heavier than water (in terms of specific gravity) and have an actual density of 1.1 g / ml, while the densities of 60P18, 45P25, 34P30 and 25P45 are 0, 60, 0.45, 0.34 and 0.25 g / ml, respectively. They have a maximum working pressure of 68.95, 55.16, 27, 58, 20, 68 and 5.17 MPa (10,000, 8,000, 4,000, 3,000 and 750 psi), respectively.
[0179] The microspheres supplied by Minerais i Derivats SA (produced by Larand Chem Corp, US) under the designation ESFERIGLASS-U6 are spherical, white, ultra-low density glass spheres with a true density of 0.224 g / cc, a volume density of 0.16 g / cc and an oil absorption of 38 g / 100cc. The particle size of such microspheres is such that 10% is less than 15 pm, 50% is less than 25 pm and 90% is less than 40 pm.
[0180] The revealed hollow glass microspheres can be prepared from the uncoated hollow glass microspheres according to the method disclosed in U.S. 4,621,024. However, in a currently preferred embodiment of the invention, the hollow glass microspheres comprised in the coating composition of the invention are not coated.
[0181] The density of hollow glass microspheres can influence the performance of the coating composition. Thus, in a currently preferred embodiment, the actual density of hollow glass microspheres is about 0.05 to 0.75, for example, 0.1 to 0.5, such as about 0.2 to 0.4 g / cc.
32/70 [0182] In a further embodiment of the coating composition of the present invention the hollow glass microspheres are uncoated and have an actual density of about 0.05 to 0.75, for example, 0.1 to 0, 5, such as about 0.2 to 0.4 g / cc.
[0183] Still in one embodiment of the coating composition of the present invention, the hollow glass microspheres have a particle size such as 90%, have a diameter less than 120 pm, such as less than 100 pm, for example, less than 60 pm, more particularly, less than 50 pm.
[0184] Still in a embodiment of the coating composition of the present invention, the hollow glass microspheres have an average particle size such as 50%, have a diameter of less than 80 pm, such as less than 70 pm, for example , less than 60 pm or less than 50 pm, more particularly, less than 45.
[0185] Hollow glass microspheres are present in the coating composition of the present invention in an amount suitable to achieve improved corrosion resistance. Thus, in one embodiment, the hollow glass microspheres are present in an amount between about 10 and 30%, by volume of solids, of the mixed paint composition, such as between 15 and 25%, by volume of solids, for example. example, between 18 and 24% by volume of solids. In another embodiment, the hollow glass microspheres are uncoated and are present in an amount between about 10 and 30%, in volume of solids, such as between 15 and 25%, in volume of solids, for example, between 18 and 24% by volume of solids. In another embodiment, the hollow glass microspheres
33/70 are uncoated and are present in an amount between about 10 and 30% by volume of solids, such as between 15 and 25% by volume of solids, for example, between 18 and 24%, by volume of solids and 90% have a diameter of less than 120 pm, such as less than 100 pm, for example, less than 60 pm, more particularly, less than 50 pm. More specifically, in such an additional embodiment, the hollow glass microspheres are uncoated, are present in an amount between about 10 and 30% by volume of solids, and 90% have a diameter less than 120 pm; hollow glass microspheres are uncoated, are present in an amount between about 10 and 30% by volume of solids, and 90% have a diameter less than 100 pm; hollow glass microspheres are uncoated, are present in an amount between about 10 and 30% by volume of solids, and 90% have a diameter less than 60 pm; at
microspheres in glass hollow are no coated, are present in an amount in between fence 10 and 30%, in volume of solids, and 90% have a diameter less than 50 pm; at microspheres in glass hollow are no coated, are present in an amount in between fence 15 and 25%, in volume of solids, and 90% have a diameter less than 120 pm; at microspheres in glass hollow are no coated, are present in an amount in between fence 15 and 25%, in volume of solids, and 90% have a diameter less than 100 pm; at microspheres in glass hollow are no coated, are present in an amount in between fence 15 and 25%, in volume of solids, and 90% have a diameter less than 60 pm; at microspheres in glass hollow are no coated, are present in an amount in between fence 15 and 25%, in
volume of solids, and 90% have a diameter less than 50 pm; at
34/70 hollow glass microspheres are uncoated, are present in an amount between about 18 and 24%, in volume of solids, and 90% have a diameter less than 120 pm; hollow glass microspheres are uncoated, are present in an amount between about 18 and 24%, by volume of solids, and 90% have a diameter less than 100 pm; hollow glass microspheres are uncoated, are present in an amount between about 18 and 24%, by volume of solids, and 90% have a diameter less than 60 pm; hollow glass microspheres are uncoated, are present in an amount between about 18 and 24% by volume of solids, and 90% have a diameter of less than 50 pm.
[0186] In an additional embodiment, the hollow glass microspheres are present in an amount of less than 5.9% by weight of the composition such as less than 5.5% by weight, for example, in the range 0.1 to 5.0% by weight, 0.2
4.5% by weight, 0.5 to 4.0% by weight Weight or 1.0 to 3.0% by weight composition. [0187] In a modality currently preferential, microspheres in glass hollow are not
added to the remaining components until after the final grinding.
CONDUCTIVE PIGMENTS [0188] The conductive pigment comprised in the coating composition of the present invention can be selected from the group consisting of graphite, carbon black, aluminum pigments, black iron oxide, antimony doped tin oxide, tin oxide indium, mica coated with tin oxide doped with antimony, carbon nanotubes, carbon black fibers, graphene and
35/70 any mixture thereof. In one embodiment, the conductive pigment is selected from graphite, carbon black, aluminum pigments, tin oxide doped with antimony, carbon nanotubes, carbon black and any mixture thereof. In an additional embodiment, the conductive pigment is
selected from among graphite, black smoking, nanotubes in carbon and any mixture of same . In another modality, O pigment conductive it's graphite. Still in another modality, O pigment conductive is black from smoke. [0189] In the context of the present invention, by if
referring to graphite, the term is used in the sense that it can still be recognized by the person versed as graphite itself and not as, in some way, being incorporated into other materials, in particular zinc, through chemical bonding or otherwise .
[0190] In the coating composition of the present invention, the conductive pigment, such as graphite or carbon black, with graphite currently being more preferred, is in a modality present in an amount between about 0.5 to 5.0%, by volume of solids, such as about 0.5 to 4.0%, by volume of solids, for example, about 1.0 to 3.0%, by volume of solids, more particularly about 1.5 to 2.5%, by volume of solids, of the coating composition.
[0191] In an additional embodiment, the coating composition of the invention comprises graphite in an amount of less than 4%, by weight, of the total composition, such as about 0.1 to 3.8%, by weight, of the total compositions. , for example, 0.5 to 3.5%, by weight, of the total composition.
[0192] Conductive pigments included in
36/70 the present invention can be obtained directly commercially.
[0193] Examples of suitable conductive pigments are:
[0194] Graphite AF96 / 97 Graphitwerk Kropfmuhl AG - Germany (graphite) [0195] Cond 8/96, Graphite Tyn, spol, s.r.o. Czech Republic (micronized graphite).
[0196] DonaCarbo S-241, Osaka Gas Chemicals Co, Ltd - Japan (carbon fiber) [0197] Minatec 40 cm, Merck KGaA - Germany (mica coated with antimony-doped tin oxide) [0198] Raven 1000, ex . Columbian Carbon - USA (carbon black) [0199] Powercarbon 4300F of carbon black, ex. Yongfeng Chemicals - China [0200] Lamp Black 103, ex. Degussa AG - Germany (carbon black) [0201] Special Black 1000, ex. Orion Engineered Carbons GmbH - Germany (carbon black)
OTHER CONSTITUENTS [0202] The paint composition may comprise plasticizers. Examples of plasticizers are hydrocarbon resins, phthalates and benzyl alcohol. In one embodiment, the ink composition comprises a hydrocarbon resin as a plasticizer.
[0203] The ink composition may comprise other constituents of ink as will be evident to the person skilled in the art. Examples of such ink constituents are non-conductive pigments, for example, TiO2,
37/70 yellow or red iron oxides, cobalt blue, bismuth vanadates and organic pigments; fillers, for example, Al / K / Na silicates (for example, Silicate MN / SA 15 12/2009. Minerals I Derivats S.A., Spain), talc, mica and BaS04; additives (for example, wetting agents, dispersing agents, sequestrants, rheological agents, thickening agents, antifoaming agents and thixotropic agents (such as bentonites)).
[0204] In the paint composition, the total amount of fillers and non-conductive pigments can be in the range of 0 to 50%, such as 0 to 40%, 0 to 30% or 0 to 25%, by volume of solids, of the mixed paint composition. Alternatively, the total amount of fillers and non-conductive pigments can be in the range 5 to 40%, in volume of solids, as in the range 10 to 35%, in volume of solids.
[0205] In the ink composition, the total amount of additives can be in the range of 0 to 10%, such as 0.1 to 8%, by volume of solids, of the mixed ink composition.
[0206] In one embodiment, the coating composition of the invention contains less than 10%, by weight, of the charge-modified CaSiOs, also known as Wollastonite.
[0207] In another embodiment, the paint composition comprises one or more additives selected from the group of wetting agents and dispersing agents. Wetting agents and dispersing agents help to achieve a homogeneous dispersion of the re-zinc material. Examples of suitable wetting agents and dispersing agents are:
[0208] Cargill Lecikote 20 ex.
Cargill Foods
38/70 (Belgium) [0209] Lipotin 100 ex. Degussa Texturant Systems (Germany) [0210] Nuosperse 657 ex. Elementis Specialties (Netherlands) [0211] Anti Terra U ex. BYK Chemie (Germany) [0212] Disperbyk 164 ex. BYK Chemie (Germany) [0213] Anti Terra 204 ex. BYK Chemie (Germany) [0214] The paint composition can comprise epoxy accelerators. Examples are substituted phenols, such as 2,4,6-tris phenol (methyl dimethylamine), p-tert. Butylphenol, nonyl phenol, etc. or salicylic acid. Examples include Ancamine K54 from Air Products Pic. (UK). Epoxy accelerators can be included in an amount of 0 to 7%, by volume of solids, such as about 0.5 to 6%, by volume of solids, for example, about 1 to 5%, by volume of solids, more specifically, about 2 to 4%, by volume of solids.
[0215] Examples of suitable epoxy modifiers include, for example, oils, oil derivatives, modified oils, such as linseed oil and derivatives thereof, castor oil and derivatives thereof, soybean oil and derivatives of same.
[0216] The paint composition may also comprise reactive epoxy diluents, such as diluents from the glycidyl monofunctional ether classes of aliphatic, cycloaliphatic or aromatic compounds. Examples include Cardolite NC 513 from Cardanol Chemicals (USA), Araldite DY-E / BD, ex. Huntsman Advanced Materials Germany and Cardura E10P ex. Momentive - Netherlands. The thinners
39/70 epoxy can be included in an amount from 0 to 9%, in
volume of solids, such as fence in 2.5 to 8%, in volume of solids, for example, fence from 3 to 7% , in volume of solids, more specifically, fence from 4 to 6%, in volume of solids. [0217] A composition in ink can, also,
understand epoxy flexibilizers.
[0218] The ink composition typically comprises a solvent or solvents. Examples of solvents are water; alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol or 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 ethyl methyl ketone, acetone, methyl isobutyl ketone, methyl isoamyl ketone, diacetone alcohol and cyclohexanone; ether alcohols, such as 2-butoxyethanol, monomethyl propylene glycol ether and butyl diglycol; esters, such as methoxypropyl acetate, n-butyl acetate and 2-ethoxyethyl acetate; and mixtures thereof.
[0219] Depending on the set of application procedures, it is desirable that the ink comprises solvent (s) so that the ratio of volume of solids (SVR - ratio of the volume of the solid constituents to the total volume) also called% of SV - be in the range of 30 to 100%, such as 50 to 100%, in particular, 55 to 100%, for example, 60 to 100%.
[0220] SVR is determined according to ISO 3233 or ASTM D 2 697 with the modification that drying is carried out at 20 ° C and 60% relative unit for 7 days
40/70 instead of drying at higher temperatures.
PARTS KIT [0221] As mentioned above, the binder system comprised in the coating composition of the invention, based on epoxy or otherwise, may contain one or more curing agents. The person skilled in the art will observe that the curing agent can advantageously be mixed with the remaining components of the binder system, for example, an epoxy resin, in situ, just before being applied. Said remaining components of the binder system are often referred to as the base component and in the context of the present invention, the term base component is intended to refer to components of the binder system in addition to one or more curing agents.
[0222] For this reason, another aspect of the invention relates to a kit of parts containing a coating composition as defined in this document, which comprises two or more containers, in which one container contains one or more curing agents and another container contains the base component.
[0223] The components of the coating composition of the invention as defined in this document, in addition to the binder system and the curing agent, can be contained in either of the two containers in the parts kit or possibly in one or more additional containers. Typically, said components will be present in the container that contains said base component. Thus, in one embodiment, the components of the coating composition of the invention, in addition to the curing agent, are
41/70 contained in the container containing the base component.
[0224] In a specific embodiment of the kit of parts according to the present invention, a polysiloxane-modified binder system comprises an epoxy resin part and a (modified) polysiloxane and aminofunctional polysiloxane binder part, which are kept in two separate containers and mixed immediately before use. Thus, in one embodiment, the conductive pigment and hollow glass microspheres are added to the epoxy resin part while the zinc particles are added to the part containing polysiloxane resin.
SPECIFIC MODALITIES [0225] For each of the components a), b), c) and d) as disclosed in this document for the ink composition of the invention, several specific modalities have been revealed. It is, in fact, envisaged to combine each of the specific modalities for component a) with each of said specific modalities for component b), each of said specific modalities for component c) and each of said specific modalities for component d).
[0226] More specifically, one embodiment of the invention relates to a coating composition comprising:
The) a bonding system to the basis of epoxy,B) zinc particles with a D ₅ q less than 2 0 pm gifts in an amount of about from 10 to 55% by volume of solids, ç) glass microspheres hollow uncoated gifts in an amount between about 10 and 30%, in
42/70 volume of solids and 90% that have a diameter less than 50 pm, and
d) a conductive pigment selected from the group consisting of graphite, carbon black, carbon nanotubes and any mixture thereof.
[0227] Another embodiment of the invention relates to a coating composition comprising: a) an epoxy-based binder system,
b) zinc particles with a D50 less than 20 pm present in an amount of about 10 to 55%, by volume of solids,
c) uncoated hollow glass microspheres present in an amount between about 10 and 30%, in volume of solids and 90% that have a diameter less than 50 pm, and
d) graphite.
[0228] Yet another embodiment of the invention relates to a coating composition comprising:
a) an epoxy-based binder system,
B) zinc particles with a smaller D50 that 20 pm gifts in an amount of about from 10 to 55%, in volume of solids,ç) glass microspheres hollow no coated gifts in an amount between about 10 and 30%, in
volume of solids and 90% that have a diameter less than 120 pm, and
d) a conductive pigment selected from the group consisting of graphite, carbon black, carbon nanotubes and any mixture thereof.
[0229] Yet another embodiment of the invention is
43/70 refers to a coating composition comprising:
a) an epoxy-based binder system,
b) zinc particles with a D ₅ q less than 20 pm present in an amount of about 10 to 55%, by volume of solids,
c) uncoated hollow glass microspheres present in an amount between about 10 and 30%, in volume of solids and 90% that have a diameter less than 120 pm, and
d) graphite.
[0230] A further embodiment of the invention relates to a coating composition which comprises:
a) an epoxy-based binder system,
b) zinc particles with a D50 less than 20 pm present in an amount of about 18 to 40%, by volume of solids,
c) uncoated hollow glass microspheres present in an amount between about 10 and 30%, in volume of solids and 90% that have a diameter less than 50 pm, and
d) a conductive pigment selected from the group consisting of graphite, carbon black, carbon nanotubes and any mixture thereof.
[0231] A further embodiment of the invention relates to a coating composition which comprises:
a) an epoxy-based binder system,
b) zinc particles with a D50 of less than 20 pm present in an amount of about 18 to 40%, by volume of solids,
c) uncoated hollow glass microspheres
44/70 present in an amount between about 10 and 30%, in volume of solids and 90% that have a diameter less than 50 pm and d) graphite.
[0232] A further embodiment of the invention relates to a coating composition comprising:
a) an epoxy-based binder system,
B) zinc particles with a smaller D50 that 20 pm gifts in an amount of about from 18 to 40%, in volume of solids,ç) glass microspheres hollow no coated gifts in an amount between about 10 and 30%, in
volume of solids and 90% that have a diameter less than 120 pm, and
d) a conductive pigment selected from the group consisting of graphite, carbon black, carbon nanotubes and any mixture thereof.
[0233] Still an additional modality of
invention if refers to an composition coating what comprises: The) a system binder to epoxy based, B) particles in zinc with one D50 less than 20 pm gifts in an amount of fence in 18 to 40% by volume
of solids,
c) uncoated hollow glass microspheres present in an amount between about 10 and 30%, in volume of solids and 90% that have a diameter less than 120 pm, and
d) graphite.
[0234] The specific modalities can also
45/70 comprise polysiloxane based binder systems. For this reason, one embodiment of the invention relates to a coating composition that comprises:
a) a polysiloxane-based binder system,
b) zinc particles with a D50 less than 20 pm present in an amount of about 10 to 55%, by volume of solids,
c) uncoated hollow glass microspheres present in an amount between about 10 and 30%, in volume of solids and 90% that have a diameter less than 50 pm, and
d) a conductive pigment selected from the group consisting of graphite, carbon black, carbon nanotubes and any mixture thereof.
[0235] Another embodiment of the invention relates to a coating composition comprising:
The) a bonding system to the polysiloxane based,B) zinc particles with a smaller D ₅₀ that 20 pm gifts in an amount of about from 10 to 55%, in volume of solids, ç) glass microspheres hollow not coated gifts in an amount between about 10 and 30%, in
volume of solids and 90% that have a diameter less than 50 pm, and
d) graphite.
[0236] Yet another embodiment of the invention relates to a coating composition comprising:
a) a polysiloxane-based binder system,
b) zinc particles with a D50 less than 20 pm present in an amount of about 10 to 55%, by volume
46/70 solids,
c) uncoated hollow glass microspheres present in an amount between about 10 and 30%, in volume of solids and 90% that have a diameter less than 120 pm, and
d) a conductive pigment selected from the group consisting of graphite, carbon black, carbon nanotubes and any mixture thereof.
[0237]
Yet another embodiment of the invention relates to a coating composition which comprises:
a) a polysiloxane-based binder system
b) zinc particles with a D50 less than 20 pm present in an amount of about 10 to 55%, by volume of solids, uncoated hollow glass microspheres present in an amount between about 10 and 30%, in volume of solids and 90% that have a diameter less than 120 pm, and
d) graphite.
[0238]
A further embodiment of the invention relates to a coating composition which comprises:
a) a polysiloxane-based binder system
b) zinc particles with a D50 of less than 20 pm present in an amount of about 18 to 40%, by volume of solids, uncoated hollow glass microspheres present in an amount between about 10 and 30%, in volume of solids and 90% that have a diameter less than 50 pm, and
d) a conductive pigment selected from the group
47/70 consisting of graphite, carbon black, carbon nanotubes and any mixture thereof.
[0239] A further embodiment of the invention relates to a coating composition which comprises:
a) a polysiloxane-based binder system,
b) zinc particles with a D ₅ q less than 20 pm present in an amount of about 18 to 40%, by volume of solids,
c) uncoated hollow glass microspheres present in an amount between about 10 and 30%, in volume of solids and 90% that have a diameter less than 50 pm, and
d) graphite.
[0240] A further embodiment of the invention relates to a coating composition comprising:
The) a bonding system to the polysiloxane based,B) zinc particles with a smaller D50 that 20 pm gifts in an amount of about from 18 to 40%, in volume of solids, ç) glass microspheres hollow not coated gifts in an amount between about 10 and 30%, in
volume of solids and 90% that have a diameter less than 120 pm, and
d) a conductive pigment selected from the group consisting of graphite, carbon black, carbon nanotubes and any mixture thereof.
[0241] A further embodiment of the invention relates to a coating composition comprising:
48/70
The) a bonding system to the polysiloxane based,B) zinc particles with a smaller D50 that 20 pm gifts in an amount of about from 18 to 40%, in volume of solids, ç) glass microspheres hollow not coated gifts in an amount between about 10 and 30%, in
volume of solids and 90% that have a diameter less than 120 pm, and
d) graphite.
[0242] The specific modalities may also comprise polyurethane-based bonding systems. For this reason, one embodiment of the invention relates to a coating composition that comprises:
a) a polyurethane-based binder system,
b) zinc particles with a D50 less than 20 pm present in an amount of about 10 to 55%, by volume of solids,
c) uncoated hollow glass microspheres present in an amount between about 10 and 30%, in volume of solids and 90% that have a diameter less than 50 pm, and
d) a conductive pigment selected from the group consisting of graphite, carbon black, carbon nanotubes and any mixture thereof.
[0243] Another embodiment of the invention relates to a coating composition comprising:
a) a polyurethane-based binder system,
b) zinc particles with a D50 less than 20 pm present in an amount of about 10 to 55%, by volume of solids,
49/70
c) uncoated hollow glass microspheres present in an amount between about 0.2 and 4.5%, by weight, and 90%, which have a diameter of less than 50 pm, and
d) graphite.
[0244] Yet another embodiment of the invention relates to a coating composition comprising:
a) a polyurethane-based binder system,
B) zinc particles with one D50 smaller that 20 pm gifts in an amount of fence in 10 at 55%, in volume of solids, ç) microspheres of glass hollow no coated gifts in an amount between fence in 0.2 and ! 4.5%, in
weight, and 90% that have a diameter less than 120 pm, and
d) a conductive pigment selected from the group consisting of graphite, carbon black, carbon nanotubes and any mixture thereof.
[0245] Yet another embodiment of the invention relates to a coating composition comprising:
a) a polyurethane-based binder system,
B) zinc particles with one D50 smaller that 20 pm gifts in an amount of fence in 10 at 55%, in volume of solids, ç) microspheres of glass hollow no coated gifts in an amount between fence in 0.2 and ! 4.5%, in
weight, and 90% that have a diameter less than 120 pm, and
d) graphite.
[0246] An additional embodiment of the invention relates to a coating composition comprising:
a) a polyurethane-based binder system,
b) zinc particles with a D50 less than 20 pm
50/70 present in an amount of about 18 to 40%, by volume of solids,
c) uncoated hollow glass microspheres present in an amount between about 0.2 and 4.5%, by weight, and 90%, which have a diameter of less than 50 pm, and
d) a conductive pigment selected from the group consisting of graphite, carbon black, carbon nanotubes and any mixture thereof.
[0247] An additional embodiment of the invention relates to a coating composition comprising:
a) a polyurethane-based binder system,
b) zinc particles with a D50 less than 20 pm present in an amount of about 18 to 40%, by volume of solids,
c) uncoated hollow glass microspheres present in an amount between about 0.2 and 4.5%, by weight, and 90%, which have a diameter of less than 50 pm, and
d) graphite.
[0248] A further embodiment of the invention relates to a coating composition comprising:
a) a polyurethane-based binder system,
B) zinc particles with one D50 smaller that 20 pm gifts in an amount of fence in 18 at 40%, in volume of solids, ç) microspheres of glass hollow no coated gifts in an amount between fence in 0.2 and ! 4.5%, in
weight, and 90% that have a diameter less than 120 pm, and
d) a conductive pigment selected from the group consisting of graphite, carbon black, carbon nanotubes
51/70 and any mixture thereof.
[0249] Still an additional modality of
invention if refers to an composition coating what comprises: The) a system binder to polyurethane based, B) particles in zinc with one D50 less than 20 pm gifts in an amount of fence in 18 to 40% by volume
of solids,
c) uncoated hollow glass microspheres
present in an amount between about in 0.2 and 4.5%, in weight, and 90% that have a diameter less than 120 pm, and d) graphite. COATING SYSTEMS [0250] 0 term apply is used without I normal meaning in the paint industry. Of that form, The
application is carried out by any conventional means, for example, by brush, by roller, by airless spray, by air spray, by immersion, etc. The most commercially interesting way to apply the coating composition is by spraying. Spraying is carried out by means of conventional spraying equipment known to the person skilled in the art. The coating is typically applied on a dry film thickness of 5 to 300 pm, such as 5,125 pm or 25 to 300 pm.
[0251] In a specific embodiment of the invention, an outer coating composition is subsequently applied to said zinc-containing coating. The outer coating is typically of a coating composition selected from
52/70 epoxy based, polyurethane based coating compositions, acrylic based coating compositions, polyurea based coating compositions, polysiloxane based coating compositions and fluorine polymer based coating compositions. In addition, ο external coating is typically applied on a dry film thickness of 30 to 300 pm, such as 30 to 200 pm or 35 to 300 Mm.
[0252] In a specific variant of this document, an intermediate coating composition is first subsequently applied to said zinc containing coating, whereupon the outer coating is applied to the outer coating. The intermediate coating is typically of a coating composition selected from epoxy-based coating compositions, acrylic-based coating compositions and polyurethane-based coating compositions. In addition, the intermediate coating is typically applied on a dry film thickness of 50 to 200 pm. In one embodiment, a first epoxy-based coating according to the present invention is applied, followed by an external coating that contains polyurethane-based resin.
[0253] For this reason, the present invention also provides a coated structure that comprises a metal structure that has a first coating of the zinc-containing coating composition defined herein applied to at least part of the metal structure at a thickness of dry film from 5 to 100 pm or 5 to 300 pm, such as 25 to 300 pm; and an external coating applied to said coating containing zinc in a thickness of
53/70 film dries from 30 to 300 pm, such as 30 to 200 pm. Preferably, the outer coating is of a coating composition selected from epoxy-based coating compositions, polyurethane-based coating compositions, acrylic-based coating compositions, polyurea-based coating compositions, based-coating compositions polysiloxane and fluorine polymer based coating compositions.
[0254] In an interesting variant of this document, an intermediate coating was applied to said coating containing zinc in a dry film thickness of 50 to 200 pm before application of the external coating composition. Preferably, the intermediate coating is of a coating composition selected from epoxy-based coating compositions, acrylic-based coating compositions and polyurethane-based coating compositions.
[0255] The structure is typically selected from fixed or floating offshore equipment, for example, for the oil and gas industry, such as oil rigs, bridges, containers, refineries, petrochemical industry, power plants, storage tanks , cranes, mills, steel structures that are a part of civil structures, for example, airports, stadiums and tall buildings.
[0256] The structure is made of metal, in particular steel.
PREPARING THE INK COMPOSITION [0257] The ink can be prepared using any set of suitable products that are commonly used in the field of ink production. In this way, the various
54/70 constituents can be mixed together using a high speed dispersant, a ball mill, a pearl mill, a three-cylinder mill, etc. The paints according to the invention can be filtered using bag filters, patron filters, wire span filters, wedge wire filters, metal edge filters, EGLM turnclean filters (eg Cuno), DELTA traction filters (eg Cuno) and Jenag Strainer filters (eg Jenag) or through vibration filtration.
[0258] Typically, the solid components of the ink composition are mixed and ground. However, hollow glass microspheres are advantageously not included until after crushing occurs. Thus, in one embodiment, the hollow glass microspheres are included in the ink composition of the invention after any crushing of the remaining ink components. In a further embodiment, the invention comprises an ink composition that can be obtained including hollow glass microspheres after any grinding of the remaining ink components.
[0259] The ink composition can be prepared as a one-component ink or by mixing two or more components, for example, two premixes, a premix comprising one or more resins and a premix comprising the one or more healing agents. Or, as a three component system in which a premix comprises one or more resins and a premix comprises the one or more curing agents and a third container comprises the zinc particles.
[0260] The hollow glass microspheres and the conductive pigment can be added, together or
55/70
separately to any of the components in a ink composition prepared from two or more
components.
[0261] It should be understood that when Is made reference to ink composition, is the composition of ink
mixed. In addition, all quantities mentioned as%, by volume of solids, of the paint should be understood as%, by volume of solids, of the mixed paint composition, except when stated otherwise.
EXAMPLES
EXAMPLE 1
PREPARATION OF TEST PANELS [0262] The steel panels are coated with 1 x 70 pm of the paint to be tested. The steel panels (10 x 15 cm x 1.6 mm) are cold-rolled sweet steel, sandblasted with abrasives to Sa 3 (ISO 8501-1), with a surface profile equivalent to BN 9 (Rugotest N-3) . After the samples are coated, the panels are conditioned at a temperature of 23 ± 2 ° C and 50 ± 5% relative unit over a period of 7 days.
SALT SPRAY TEST ACCORDING TO ISO 9227, NEUTRAL SALT SPRAY.
[0263] This method is carried out to evaluate the corrosion resistance of a coating system by reproducing the corrosion that occurs in the atmosphere that contains sprinkling or splashing salt.
[0264] The operating conditions of the test of
salt spray is a constant spray with 5% NaCI solution at 35 ° C.
[0265] After finishing the exposure, bubble formation and rust creep are assessed both on the panel
56/70 and around the groove (in mm from the center), according to ISO 4628-2 and ISO 4628-3, respectively. Cracking is evaluated according to ISO 4628-4. Adherence is assessed according to ISO 4624 (tensile tests).
[0266] After removing the coating in a groove using an appropriate method (mechanical or chemical cleaning), the width of the corrosion is measured in nine points. The rust creep M is calculated from the equation M = (C - W) / 2, where C is the average of the nine width measurements and W is the original scratch width (0.5 mm).
PREPARATION OF COATING COMPOSITIONS [0267] Component 1 was prepared as follows:
[0268] Epoxy resin (s), filler, wetting agent, dispersing agent, scavenger, rheological and thickening agent and 60% of solvents (xylene: nbutanol 3: 1, by weight) were pre-mixed in a high speed mixer equipped with a disc propellant (90 mm in diameter) in a 2.5 liter can for 15 minutes at 1,000 rpm. The zinc particles were then added and mixed for about 15 minutes at 2,000 rpm. The microspheres were added by slowly stirring together with 30% of the solvents. The remaining 10% of the solvent was then added.
[0269] Component 2 was prepared as follows:
[0270] The polyaminoamide and the reactive epoxy diluent were mixed with 50% solvent. After a minimum of 16 hours, the epoxy accelerator, the charge, the graphite, the
57/70 antifoam, the thixotropic agent was pre-mixed in a high speed mixer equipped with a disc propeller (90 mm in diameter) in a 2.5 liter can for 15 minutes at 1,000 rpm. Then, the benzyl alcohol and the remaining 50% solvent were mixed.
[0271] Immediately before application, component 2 was added to component 1 and the paint composition was mixed with a homogeneous mixture.
TABLE 1 - BASIC FORMULATION OF PAINTS BASED ON
EPOXY
Table 1 Model A ink Model B ink Model C paint Model D ink E mode ink F mode ink G mode ink Component 1: % inSV % inSV % inSV % inSV % inSV % inSV % SV Functional epoxy compound Epoxy resin (Bisphenol A glycidyl ether epoxy binder, Araldite GZ 7071X75CH, eg Huntsman Advanced Materials Switzerland) 17 17 17 17 16 24 24 Epoxy resin (131sphenol A-epichlorohydrin, Araldite DT-E / 130, eg Huntsman Advanced Materials Germany 8 8 8 8 B 4 4 zinc particles, ZMP 4P16, Unlit: ore- Belgium 22 22 22 22 34 34 43 nephelinic syenite, AVK / Na silicate, Cargo Silicate MN / SA 15 12/2009, Minerals i Derlvats S.A. - Spain 11 32 13 34 Additives ¹ ' 3 3 3 3 3 4Solvents: Xylene
58/70
Butanol 23 Uncoated aluminosilicate glass spheres (EsferiglassU6, Minerals I Derivats S.A. - Spain 2121 Total component 1: 82 82 84 84 84 78 Component 2: Polyaminoamide (Crayamid 140, Arkema - Italy 8 8 8 8 8 13 13 Reactive epoxy thinner (Cardolite NC 513, Cardanol Chemicals - USA) 5 5 5 5 4 5 5 Epoxy accelerator (ancamine K54, Air Products Pic - United Kingdom 3 3 3 3 2 3 3 Macrocrystalline graphite, Graphite AF 96/97, Graphitwerk Kropfmahl AG - Germany 2 2 2 Additives ² ' <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 Semi-alcohol Total component 2: 18 18 16 16 16 21 21 Component 1 and 2 total: 100 100 100 100 100 100 100 PVC, 40 57, 6 57, 6 57, 6 57, 6 58, 9 51.3 51.3 SVR,% 72, 1 72, 1 72, 1 72, 1 77.3 61.4 61.4 SVR,% of Component 1 72.8 72.8 72.8 72, 8 79, 5 61.7 61.7 SVR,% of Component 2 69, 1 69, 1 69, 1 69, 1 68.5 60.2 60.2 Mixing ratio by volume, Component 1/2 3: 1 4: 1 4: 1 4: 1 4: 1 4: 1 4: 1
Wetting agent (s) 7dispersant 7 sequestrant / rheological / thickener ²⁾ Defoamers / thixotropic agents
3)
PVC: Pigment volume concentration. The ratio of the volume of pigment to the volume of total non-volatile material.
RESULTS
59/70
TABLE 2: RESULTS OF FLUENCE OF RUST, M
Ink Composition SST * of 924 hours of Maximum Relative Rust Fluency SST * of 924 hours of Relative Average rust creep Model A ink 100 100 Model B ink 213 643 Model C ink 213 657 Model D ink 287 943
* Rust flow related to the composition according to the invention. The lower the relative rust creep, the better the performance.
TABLE 3: RESULTS OF FLUENCE OF RUST, M
Ink Composition SST * of 6,000 hours of Relative Average rust creep Ink model E 100 Model F ink 188 Ink model G 200
* Rust flow related to the composition according to the invention. The lower the relative rust creep, the better the performance.
[0272] From tables 2 and 3 it will be evident that the Model A and E inks comprising the present invention show a significant improvement in rust creep compared to the comparative Model B, C, D, F and G inks .
EXAMPLE 2
PREPARATION OF TEST PANELS [0273] The steel panels are coated with 1 x 80 pm of the paint to be tested. The steel panels (75 x 150 x 10 mm) are cold-rolled sweet steel, sandblasted with Sa2 Vi abrasives (ISO 8501- 1), with an equivalent surface profile
60/70 to BN 9 (Rugotest N-3). After the samples are coated, the panels are conditioned at a temperature of 23 ± 2 ° C and 50 ± 5% relative unit over a period of 7 days.
SALT SPRAY TEST ACCORDING TO ISO 46283: 2003, NEUTRAL SALT SPRAY.
[0274] This method is carried out to evaluate the corrosion resistance of a coating system by reproducing the corrosion that occurs in the atmosphere that contains sprinkling or splashing salt.
[0275] The operating conditions of the salt spray test are constant spraying with 5% NaCI solution at 35 ° C.
[0276] The SST evaluated through ISO 4628-3: 2003, which measures the oxidation stage in a coated panel.
PREPARATION OF COATING COMPOSITIONS [0277] Component 1 was prepared as follows:
[0278] The aliphatic epoxy resin (s), filler / extending pigment, wetting and dispersing agent, rheological and thickening agent and antifoaming agent and graphite were pre-mixed in a high speed mixer equipped with a disc propellant (90 mm in diameter) in a 2 liter can for 15 minutes at 1,500 rpm. The microspheres were added by slowly stirring at 600 rpm together with 10% of the solvents. The remaining 90% of the solvent was then added.
[0279] Component 2 was prepared as follows:
[0280] The aminofunctional siloxane and polysiloxane resin, the antifoam agent, the thixotropic agent,
61/70 the wetting agent and dispersant were premixed in a high speed mixer equipped with a disc propellant (90 mm in diameter) in a 2 liter can for 15 minutes at 1,200 rpm. The zinc particles with 10% solvent were added and mixed for about 15 minutes at 2,000 rpm. The remaining 90% of the solvent was then added.
[0281] When preparing the comparative model paints, the steps of adding graphite and / or glass beads were omitted.
[0282] Immediately before application, component 2 was added to component 1 and the paint composition was mixed with a homogeneous mixture.
TABLE 4 - BASIC FORMULATION OF POLYSYLOXAN BASED PAINTS
Table 4 Model A ink Model B ink Template inkÇ Model D ink Component 1: % inSV % inSV % inSV % inSV Aliphatic epoxy resin (Acleka EP-4050E resin, ADEKA Corporation - Japan) 21.8 20.3 20, 4 21, 9 calcium carbonate, coated with stearic acid, extending pigment 2.8 17, 9 19, 3 4.2 macrocrystalline graphite,P.Bk. 10 1, 9 1.8- Additives ¹ ' 1.3 1.3 2.2 1.3 Solvents: Xylene Butanol
62/70
Butyl acetate Aluminum acetate glass spheres, 19, 8 - - 19.9 Total component 1: 47 41 41 47 Component 2: aminofunctional siloxane resin solution (SILRES HP 2000, Wacker Chem and GmbH Germany) 19, 8 18.4 18, 5 19, 9 Polysiloxane with methoxy groups 11.1 10.3 10, 4 11, 1 Zinc dust, metallic pigment 20.3 28.8 28, 9 20, 4 Additives ² ' 1.3 1.1 1.2 1.3 Solvents: Xylene Total component 2: 53 59 59 53 Component 1 and 2 total: 100 100 100 100 PVC,% 46 49.7 49, 4 45, 8 SVR,% 88 88.7 88, 7 88
¹⁾ Wetting agent (s) is dispersing / rheological and thickening / defoaming ²⁾ Anti-foaming / thixotropic / wetting and dispersing agent (s)
RESULTS
TABLE 5: OSH RESULTS
Results ofSST after 275 hours Results ofSST after 500 hours OSH results after 1,000 hours Composition page panel panel panel panel panel of ink 1 1 2 1 2 1 2
63/70
Template inkTHE Ril Ril Ril Ril Laugh 2 Laugh 2 Template inkB Laugh 3 Laugh 2 Laugh 4 Laugh 3 Laugh 4 Laugh 4 Model C ink Laugh 2 Laugh 3 Laugh 2 Laugh 3 Laugh 3 Laugh 3 Template inkD Laugh 3 Laugh 3 Laugh 3 Laugh 3 Laugh 4 Laugh 4
* SST results are evaluated on an aspect scale, starting from R ± 0 = Very good to R ± 5 = Very poor.
EXAMPLE 3
TEST ACCORDING TO ISO 20340 [0283] The panels are exposed according to ISO 20340 Procedure A: The standard procedure with low temperature exposure (thermal shock). The exposure cycle used in such a procedure lasts for an entire week (168 hours) and includes 72 hours of QUV, 72 hours of Salt Spray Test (SST) and 24 hours of thermal shock (- 20 ° C) • Exposure QUV is according to ISO 11507, accelerated weathering, through exposure to fluorescent ultraviolet (UV) light and condensation to simulate the deterioration caused by sunlight and water such as rain or dew. QUV cycle: 4 hour UV light at 60 ± 3 ° C with UVA-340 lamps and 4 hour condensation at 50 ± 3 ° C.
• SST exposure is in accordance with ISO 7253, exposure to constant spraying with 5% NaCI solution at 35
Exposure to thermal shock consists of placing
64/70 the panels in a freezer, at - 20 ± 2 ° C.
[0284] Exposure period total: 25 cycles equivalent to 4,200 hours. [0285] Before the panels were initiates at the climate cycle, they receive a stretch mark of 2 mm in realized width horizontally at 20 mm of bottom and From
sides.
[0286] When the test is interrupted, the paint film is removed from the groove and the width of the rust is evaluated. After removing the coating using a suitable method, the corrosion width is measured at nine points (the midpoint of the scratch line and four other points, 5 mm apart, on each side of the midpoint). The rust creep M is calculated from the equation M = (C - W) / 2, where C is the average of the nine width measurements and W is the original width of the streak.
PREPARATION OF TEST PANELS FOR TESTING ACCORDING TO ISO 20340 [0287] The steel panels used for the test (7 x 15 cm x 5 mm) are cold-rolled sweet steel, sandblasted with Sa 3 abrasives ( ISO 8501-1), with a surface profile equivalent to BN 9 (Rugotest N-3).
[0288] The complete coating system that was applied to the steel panels is shown below:
• First Coating: Model paint on a film thickness of 60 pm • Second Coating: Hempadur 45880 intermediate epoxy coating on a film thickness of 140 pm • Third Coating: Polyurethane
65/70 Hempathane 55610 topcoat at 80 pm film thickness
An overnight drying period was used between the coating layers.
After the samples are coated, the panels are conditioned at a temperature of 23 ± 2 ° C and 50 ± 5% relative unit over a period of 7 days.
PREPARATION OF COATING COMPOSITIONS [0289] The model paint of the first coat was prepared in the same way as the model paints in the
Example 1.
Table 6 Model paint 1 Model paint 2 Model paint 3 Model 4 ink Component 1: % inSV % inSV % inSV % inSV Functional epoxy compound Epoxy resin (Bisphenol Aepichlorhydrin, Araldite DY-E / BD, eg Huntsman Advanced Materials - Germany 28.0 29.1 28.5 30.4 reactive, aliphatic epoxy diluent (Cu-CIO monoglycidyl ether) 4.0 4.0 3, 8 4.0 zinc dust, metallic pigment, 95 to 97% Zn fine particle size 39, 6 39, 8 49.5 52.2 Scotchlite Glass Bubbles 538, 3M - France, soda lime boron silicate glass, microspheres with insulating properties. 11.1 11.1 Additives ¹ ' 4, 9 5, 1 3, 8 4.0 Solvents: Xylene, butanol, isopropanol, medium boiling aromatic hydrocarbon solvent, propylene glycol monoethyl ether.
66/70
P.Bk.10, macrocrystalline graphite, antistatic and heat-resistant pigment 4, 6 - - - P.Bk.6 / 7, Carbon Black - 3.0 5, 6 - Total component 1: 92.1 92.1 91.1 90.5 Component 2: Epoxy hardener, Hempadur 98382, Hempel 7, 9 7, 9 8, 9 9, 5 Total component 2: 7, 9 7, 9 8, 9 9, 5 Component 1 and 2 total: 100 100 100 100 PVC,% ²⁾ 58.2 56, 8 57, 9 55, 1 SVR 60 60 60 57
wetting and dispersing agent / thickening agent / rheological modifier
2)
PVC: Pigment volume concentration. The ratio of the volume of pigment to the volume of total non-volatile material.
RESULTS
TABLE 7: RUST FLUENCE RESULTS, M
Ink Composition Rust creep * Ink model 1 100 Ink model 2 97 Ink model 3 134 Ink model 4 159
* Rust flow related to the model 1 paint according to the invention. The lower the relative rust creep, the better the performance.
[0290] From table 7, it will be evident that the Model 1 and 2 inks comprising the present invention show a significant improvement in rust creep compared to the comparative Model 3 and 4 inks.
[0291]
This example shows that although
When the amount of zinc is lower in the compositions according to the present invention than in comparative compositions, the corrosion inhibition has been improved.
EXAMPLE 4
TABLE 8 - BASIC FORMULATION OF CURE INK
HUMIDITY OF A POLYURETHANE BASED COMPONENT. THE
COMPONENTS ARE MIXED VACUUM.
Table 8 Template ink% inSV Diphenylmethane diisocyanate (MDI) isocyanate prepolymer, Desmodur MT Ex Bayer Materialscience - Germany 8 Toluene diisocyanate (TDI) polyisocyanate prepolymer, Desmodur E 14 Ex Bayer Material Science - Germany 8 Aromatic polyisocyanate prepolymer based on diphenylmethane diisocyanate (MDI) Desmodur E 21 exBayer Material Science - Germany 22 aromatic hydrocarbon resin modified with K064, Novares LA 700 ex Rutgers Novares, Germany 4 Additives ¹⁾ 5 macrocrystalline graphite, Graphite AF 96/97, Graphitwerk Kropfmahl AG - Germany 2 Zinc particles, ZMP 4P16, Umicore - Belgium 45 Solvents:Aromatic hydrocarbonMethoxypropyl acetateHollow glass microspheres, Scotchlite Glass Bubbles 538 ex 3M - France 6 Total component: 100 % PVC 56
68/70
SVR% 67
Plasticizer / humectant / sequestering / rheological / thickener
EXAMPLE 5
PREPARATION OF COATING COMPOSITIONS
[0292] 0 component 1 was prepared from Following form:[0293] The solution acrylic resin functional hydroxyl, the wetting agents and dispersing, the agent
defoamer, thickeners, filler, graphite and 75% of solvents were premixed in a high speed mixer equipped with a disc propeller (90 mm in diameter) in a 2 liter can for 15 minutes at 1,200 rpm . The zinc particles were then added and mixed for about 15 minutes at 2500 rpm. A catalyst dissolved in solvent was added by stirring as an immersion component. The microspheres were added by slowly stirring at 600 rpm together with 5% of the solvents. The remaining 20% of the solvent was then added.
[0294] Component 2 was prepared as follows:
[0295] The polyfunctional aliphatic isocyanate resin was mixed with 70% solvent in a high speed mixer equipped with a disc propeller (90 mm in diameter) in a 5 liter can for 15 minutes at 1,000 rpm. The remaining 30% of solvent was mixed.
[0296] Immediately before application, component 2 was added to component 1 and the composition of
69/70 ink was mixed with a homogeneous mixture.
TABLE 9 - BASIC FORMULATION OF TWO INK
POLYURETHANE BASED COMPONENTS.
Table 9 Model paint 1 Model paint 2 Model paint 3 Model 4 ink Component 1: % inSV % inSV % inSV % inSV Functional hydroxyl acrylic resin solution in aromatic hydrocarbon, Synocure 878 N 60, Arkema - Spain 32, 7 32.7 32.7 32, 7 calcium carbonate, coated with stearic acid, extending pigment 26.0 11.5 23.7 9, 6 zinc dust, metallic pigment, 95 to 97% Zn fine particle size 31, 2 22.0 31.2 21, 7 Aluminum acetate glass spheres23.7 - 23, 6 Additives ¹¹ 1.3 1, 3 1, 3 1, 3 Solvents: Butyl ester acetate, xylene, aromatic hydrocarbon solvent. P, Bk.lO, macrocrystalline graphite, antistatic and thermoresistant pigment- 2.3 2.3 Total component 1: 91, 1 91.2 Component 2: Polyfunctional aliphatic isocyanate resin (Basonal HB 175 MP'X BASF- Germany) 8, 9 8, 9 8, 9 8, 9 Total component 2: 8, 9 8, 9 8, 9 8, 9 Component 1 and 2 total: 100 100 100 100 PVC,% ²⁾ 57, 6 57.6 57.6 57, 6 SVR 63.5 63.5 63.5 72, 1
EXAMPLE 6 [0297]
Various types of glass microspheres
Hollow 70/70 were tested according to Example 1. The hollow glass microspheres that have real densities of 0.2,
0.2, 0.3, 0.38 and 0.40 g / cc, respectively, all offered qualitatively similar results.

权利要求:
Claims (18)
[1]
1. COATING COMPOSITION, characterized by comprising:
a) a binder system selected from epoxy-based binder systems, polysiloxane-based binder systems, polyurethane-based binder systems, cyclized rubber-based binder systems and phenoxy resin-based binder systems,
b) zinc particles,
c) hollow glass microspheres, and
d) a conductive pigment selected from the group consisting of graphite, carbon black, aluminum pigments, black iron oxide, antimony-doped tin oxide, mica coated with antimony-doped tin oxide, indium tin oxide, carbon nanotubes, carbon black fibers and any mixture thereof.
[2]
2. COATING COMPOSITION, according to claim 1, characterized by the conductive pigment being selected from carbon black, carbon nanotubes, graphite and any mixture thereof.
[3]
3. COATING COMPOSITION, according to claim 2, characterized in that the conductive pigment is graphite.
[4]
4. COATING COMPOSITION, according to claim 2, characterized in that the conductive pigment is carbon black.
[5]
5. COATING COMPOSITION, according to any one of the preceding claims, characterized in that said binder system is an epoxy-based binder system, a polyurethane-based binder system
2/4 or a polysiloxane-based binder system.
[6]
6. COATING COMPOSITION, according to any one of the preceding claims, characterized in that said binder system is an epoxy-based binder system or a polysiloxane-based binder system.
[7]
7. COATING COMPOSITION, according to any one of the preceding claims, characterized in that said binder system is an epoxy based binder system.
[8]
COATING COMPOSITION according to any one of the preceding claims, characterized in that the conductive pigment is present in an amount between about 0.5 to 5.0%, by volume of solids, such as about 0.5 to 4 0. 0% by volume of solids, preferably about 1.0 to 3.0% by volume of solids, more preferably about 1.5 to 2.5%, by volume of solids, of the coating composition.
[9]
9. COATING COMPOSITION, according to any one of the preceding claims, characterized in that the conductive pigment is the graphite present in an amount less than 4%, by weight, of the total composition, such as about 0.1 to 3.8% by weight of the total compositions, for example 0.5 to 3.5% by weight of the total composition.
[10]
10. COATING COMPOSITION, according to any one of the preceding claims, characterized in that the hollow glass microspheres are not coated.
[11]
11. COATING COMPOSITION according to any one of the preceding claims, characterized in that the composition additionally comprises a solvent.
3/4
[12]
12. COATING COMPOSITION, according to any one of the preceding claims, characterized by the hollow glass microspheres being present in a
amount less than 5.9% , in weight, such as less than 5, 5%, in weight, for example, in banner from 0.1 to 5.0%, in weight, 0.2 to 4.5 % by weight 0.5 to 4.0% 5, in weight, or 1.0 to 3.0%, in Weight, gives composition.13. COMPOSITION IN COATING, chord i with
any one of claims 1 to 11, characterized in that the hollow glass microspheres are present in an amount between about 10 and 30%, by volume of solids, such as between 15 and 25%, by volume of solids, preferably between 18 and 24% by volume of solids.
[13]
14. COATING COMPOSITION according to any one of the preceding claims, characterized in that the hollow glass microsphere has an actual density of about 0.05 to 0.75 g / cm ³ .
[14]
15. COATING COMPOSITION, according to any one of the preceding claims, characterized in that it comprises one or more curing agents.
[15]
16. KIT OF PARTS CONTAINING A COATING COMPOSITION, as defined in claim 15, characterized by comprising two or more containers, in which one container contains one or more curing agents and another container contains the remaining components of part a), as defined in any one of claims 1 to 13.
[16]
17. PARTS KIT, according to claim
16, characterized in that components b) and c), as defined in claim 1, are contained in the same container as the components of part a) in addition to the one or more
4/4 curing agents and component d) is contained in the same container as the curing agent (s).
[17]
18. COATED STRUCTURE, characterized in that it comprises a metal structure that has a coating of the coating composition, as defined in any one of claims 1 to 15, applied to at least a part of the metal structure.
[18]
19. METHOD FOR COATING A METAL STRUCTURE, characterized in that it comprises the steps of applying, at least part of its structure, a layer of a coating composition, as defined in any one of claims 1 to 15.

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法律状态:
2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

---

2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |

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2018-03-27| B15K| Others concerning applications: alteration of classification|Ipc: C09D 5/10 (2006.01), C09D 5/24 (2006.01), C09D 7/0 |

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2020-03-31| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-09-15| B11B| Dismissal acc. art. 36, par 1 of ipl - no reply within 90 days to fullfil the necessary requirements|

---

2021-10-13| B350| Update of information on the portal [chapter 15.35 patent gazette]|

优先权:

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申请号 | 申请日 | 专利标题

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EP12182173|2012-08-29|

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PCT/EP2013/064867|WO2014032844A1|2012-08-29|2013-07-12|Anti-corrosive zinc primer coating compositions comprising hollow glass spheres and a conductive pigment|

---