WO2011092278A1 - Compositions d'apprêt à base d'époxyde - Google Patents

Compositions d'apprêt à base d'époxyde Download PDF

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Publication number
WO2011092278A1
WO2011092278A1 PCT/EP2011/051194 EP2011051194W WO2011092278A1 WO 2011092278 A1 WO2011092278 A1 WO 2011092278A1 EP 2011051194 W EP2011051194 W EP 2011051194W WO 2011092278 A1 WO2011092278 A1 WO 2011092278A1
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WO
WIPO (PCT)
Prior art keywords
free
phenol
epoxy
alkyl
coat
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Application number
PCT/EP2011/051194
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English (en)
Inventor
Søren KIIL
Per Aggerholm SØRENSEN
Kim Dam-Johansen
Claus Erik Weinell
Erik KALLESØE
Original Assignee
Hempel A/S
The Technical University Of Denmark
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hempel A/S, The Technical University Of Denmark filed Critical Hempel A/S
Priority to EP11700967A priority Critical patent/EP2528979A1/fr
Publication of WO2011092278A1 publication Critical patent/WO2011092278A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • C09D5/086—Organic or non-macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/48—Stabilisers against degradation by oxygen, light or heat
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates

Definitions

  • the present invention relates to epoxy-based primer compositions having improved properties with respect to corrosive delamination from an underlying metallic substrate, and to a method for applying the primer composition to a metal substrate by spraying.
  • the problem underlying the invention is that of delamination/disbondment/damage of a paint coat at the interface between the metal surface (e.g. steel surface) and the primer coat (typically an epoxy primer).
  • the delamination/disbondment is believed to be caused by an electrochemical process at the metal surface which reduces oxygen at the metal surface, thereby forming peroxides and/or superoxide or hydroxy radicals, which cause degradation of the polymer.
  • JP 05140503 (MAT) relates to metal coating compositions which have cathodic disbondment- proofing properties and waterproofing adhesive properties. It is disclosed that: "It is arbitrary to add auxiliary agents, such as a catalyst for promoting a hardening reaction, an
  • compositions comprise a polyepoxide, an epoxy curing agent, a catalyst and a bonding additive (e.g. barium sulphate, strontium chromate, o-nitrophenol, phosphoric acid, and aminosilanes).
  • a bonding additive e.g. barium sulphate, strontium chromate, o-nitrophenol, phosphoric acid, and aminosilanes.
  • US 4,612,049 discloses corrosion-inhibiting coating compositions comprising aliphatic or cycloaliphatic carboxylic acids containing a heterocyclic radical.
  • US 4,818,777 and US 4,894,091 disclose phenolic corrosion inhibitors for coating materials comprising phenolic derivatives of benzothiazole or mercaptobenzothiazole.
  • EP 385941 A2 discloses corrosion-resistant compositions comprising N-substituted pyrrole derivatives.
  • N-(2-Hydroxyphenyl)-2,5-dimethylpyrrole is one of several examples.
  • US 5,624,979 discloses phosphorous-modified epoxy resins.
  • delamination/disbondment in particular for application to a metal substrate by spraying.
  • the present invention provides a method of applying a liquid epoxy-based anti- corrosive primer composition comprising one or more free-radical scavengers in an amount of 0.5-20 % by weight, wherein the free-radical scavengers are selected from specifically defined phenols and phenol multimers, to at least at part of the surface of a metal substrate by spraying.
  • cathodic delamination of organic coatings from metallic surfaces is, at least in part, due to a chemical attack of the coating by free radicals, namely superoxide and hydroxy radicals, which are formed as an intermediate during the electrochemical reduction of oxygen on the cathodically polarized steel surface.
  • free radicals namely superoxide and hydroxy radicals
  • the aforementioned degradation of the coating by free radicals can be minimized by incorporation of free-radical scavengers into the primer of the coating system.
  • the free-radical scavengers are selected from (a) phenols which are substituted with one or more electron-donating groups selected from Ci-6-alkyl optionally substituted with a substituent selected from phenyl, C 1 -24- alkyloxycarbonyl, Ci-24-alkylcarbonyloxy, Ci-24-alkylaminocarbonyl, Ci-24-alkylcarbonylamino, di(Ci- 6 -alkyl)phosphono-oxy, Ci- 24 -alkoxy, and Ci- 24 -alkylthio; phenyl optionally substituted with one or more Ci-6-alkyl ; hydroxy; Ci-6-al koxy; Ci-6-al kylthio; amino; Ci-6-alkylamino; and di(Ci-6-alkyl)amino.
  • the phenol is substituted with at least one group selected from optionally substituted Ci- 6 -al kyl, e.g . Ci- 6 -alkyl optionally substituted with phenyl . If the phenol is exclusive substituted with optionally substituted Ci- 6 -alkyl, preferably at least one C 2 -6-alkyl is present in the ortho position relative to the phenol functionality.
  • the phenol is substituted with one or more groups selected from hydroxy and Ci- 6 -alkyl . In one variant hereof, the phenol is substituted with at least one or more groups selected from Ci-6-al kyl . In one specific variant hereof, the phenol is substituted with at least one tert-butyl group.
  • At least one substituent is preferably ortho or para, in particular ortho, relative to the phenol functionality.
  • Illustrative examples of interesting free-radical scavengers are the phenols selected from 2,5- di(tert-butyl)-hydroquinone, 4-tert-butyl-catechol, tert-butyl-hydroquinone, 2,6-di(tert- butyl)-4-methyl-phenol, 2,6-di(tert-butyl)-phenol, 2-tert-butyl-4,6-dimethyl-phenol, 2-tert- butyl-4-methoxy-phenol, l-(2-hydroxyphenyl)-l-phenyl -ethane, 2,6-di(tert-butyl)-4- (phosphono-oxymethyl)-phenol, 2,6-di(tert-butyl)-4-(iso-octyloxycarbonylethyl)-phenol, 4- amino-phenol, 2, 6-diphenyl-4-methyl -phenol, 2,4-bis(C 5 -i 2 -alkylthio
  • Particularly interesting examples are 2,5-di(tert-butyl)-hydroquinone, tert-butyl- hydroquinone, 4-tert-butyl-catechol, 2,6-di(tert-butyl)-phenol, 2,6-di(tert-butyl)-4-methyl- phenol, 2-tert-butyl-4-methoxy-phenol .
  • the free-radical scavenger should be represented by a fairly uncomplicated structure.
  • the phenols to be used in the context of the present invention preferably have a phenol equivalent weight of less than 400 g/mol, preferably less than 350 g/mol .
  • the "phenol equivalent weight” is defined as the molar mass of the free-radical scavenger for free-radical scavengers that contain a single phenol functionality. Additional hydroxyl groups attached to the same benzene ring cannot act as radical scavengers and are therefore not considered .
  • the phenol equivalent weight for free-radical scavengers with multiple phenol groups is defined as the molar mass of the free-radical scavenger divided by the number of phenol groups.
  • the free-radical scavengers are selected from (b) phenol multimers of the formula Z(Y) n , wherein n is 2, 3, 4 or 5; and wherein Z is a central scaffold having a valence of n and having covalently bonded thereto n phenol moieties, Y, each phenol moiety, Y, independently being optionally substituted with one or more electron-donating groups selected from Ci-6-alkyl optionally substituted with a substituent selected from phenyl, Ci-24-alkyloxycarbonyl, Ci-24-alkylcarbonyloxy, C 1 -24- alkylaminocarbonyl, Ci-24-alkylcarbonylamino, di(Ci- 6 -alkyl)phosphono-oxy, Ci-24-alkoxy, and Ci-24-alkylthio; phenyl optionally substituted with one or more Ci- 6 -alkyl; hydroxy; Ci- 6 - alkoxy; Ci-
  • the scaffold preferably is not optionally substituted methylene.
  • the central scaffold of the phenol multimer may be represented by a single atom or of a moiety, each having a valence, n, corresponding to that of the number of phenols covalently attached thereto.
  • At least one substituent is preferably ortho or para, in particular ortho, relative to the phenol functionality.
  • the central scaffold, Z is selected from Ci- 6 -alkylene, -0-, -S-, and -N ⁇ .
  • the central scaffold, Z is selected from Ci-6-alkyl-l,l-ene, such as methylene, ethyl-l,l-ene, propyl-l,l-ene, propyl-2,2-ene, butyl-l,l-ene, and 2-methyl- propyl-l,l-ene.
  • Illustrative examples of interesting free-radical scavengers of this type are the phenol multimer selected from bis(3,5-di(tert-butyl)-4-hydroxyphenyl)methane, bis(3-tert-butyl-5- methyl-2-hydroxyphenyl)methane, bis(3-tert-butyl-5-ethyl-4-hydroxyphenyl)methane, 1,1- bis(3-tert-butyl-6-methyl-4-hydroxyphenyl)-butane, 2-methyl-l,l-bis(3,5-dimethyl-2- hydroxyphenyl)-propane, and l,l,3-tris(3-tert-butyl-6-methyl-4-hydroxyphenyl)-butane.
  • the central scaffold, Z is selected from -0-, -S-, and -N ⁇ .
  • interesting free-radical scavengers of this type are the phenol multimer selected from di(3-tert-butyl-2-hydroxyphenyl)sulfide, and tri(4- hydroxyphenyl)amine, tri(3-hydroxyphenyl)amine.
  • free-radical scavengers of the phenol multimer type are tetra(4-hydroxy-3,5-di(tert-butyl)phenylmethylcarbonyloxymethyl)methane, tetra(4- hydroxy-3,5-di(tert-butyl)phenylethylcarbonyloxymethyl)methane, l,3,5-tris(4-hydroxy-3,5- di (tert-butyl)phenylmethyl)-2, 4, 6-trimethyl -benzene, l,2-bis(3,5-di-tert-butyl-4-hydroxy- hydrocinnamoyl) hydrazide, triethylene glycol bis(3-tert-butyl-4-hydroxy-5-methylphenyl)- propionate, 3,5-bis(l, l-dimethylethyl)-4-hydroxybenzenepropanoic acid thiodi-2,1- ethanediyl ester
  • the phenyl multimer should preferably be represented by a fairly uncomplicated structure.
  • the phenol multimers to be used in the context of the present invention should preferably have a phenol equivalent weight of less than 400 g/mol, preferably as less than 350 g/mol .
  • the one or more free-radical scavengers are present in a total amount of 0.5-20 % by weight, in particular in a total amount of 1.0-15 % by weight. In some embodiments, the one or more free-radical scavengers are present in a total amount of 2.0-20 % by weight, e.g .
  • each of the one or more free-radical scavengers should be rather sparsely soluble in water.
  • each of the one or more free-radical scavengers have a solubility in water of less than 0.2 g/mL at 25 °C, in particular less than 0.1 g/mL at 25 °C.
  • the free-radical scavengers to be used within the present invention are preferably solid at a temperature of 25 °C.
  • Ci-i 2 -alkyl and “Ci- 6 -alkyl” are intended to mean a linear, cyclic or branched hydrocarbon group having 1 to 12 carbon atoms and 1 to 6 carbon atoms, respectively, such as methyl, ethyl, propyl, /so-propyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, dodecanyl, etc.
  • alkoxy means "alkyl-oxy” (“alkyl-O”), e.g. Ci-24-alkoxy means Ci-24-alkyl-oxy.
  • alkylthio means "alkyl-S-".
  • the liquid epoxy-based anti-corrosive primer composition is the liquid epoxy-based anti-corrosive primer composition
  • the liquid epoxy-based anti -corrosive primer composition may - beside the above-specified free-radical scavengers - be of any conventional type.
  • epoxy-based primer system should be construed as the combination of the one or more epoxy resins, one or more curing agents, any reactive epoxy diluents and any reactive acrylic modifiers.
  • the epoxy-based primer system is one of the most important constituents of the paint composition, in particular with respect to the anticorrosive properties.
  • the epoxy-based primer system comprises one or more epoxy resins selected from aromatic or non-aromatic epoxy resins (e.g. hydrogenated epoxy resins), containing more than one glycidyl group per molecule, which is placed internally, terminally, or on a cyclic structure, together with one or more suitable curing agents to act as cross-linking agents.
  • suitable curing agents to act as cross-linking agents.
  • Combinations with reactive diluents from the classes mono functional glycidyl ethers or esters of aliphatic, cycloaliphatic or aromatic compounds can be included in order to reduce viscosity and for improved application and physical properties.
  • the primer system can also include reactive acrylic modifiers, such as acrylate monomers and oligomers comprising at least two alpha, beta unsaturated carbonyl groups, reacting with the one or more curing agents via a Michael- type addition reaction.
  • Suitable epoxy-based primer systems are believed to include epoxy and modified epoxy resins selected from bisphenol A, bisphenol F, Novolac epoxies, non-aromatic epoxies, cycloaliphatic epoxies, glycidyl esters and epoxy functional acrylics or any combinations hereof.
  • suitable commercially available epoxy resins are : Epikote 828, ex.
  • the epoxy-based primer system comprises one or more curing agents selected from compounds or polymers comprising at least two reactive hydrogen atoms linked to nitrogen.
  • Suitable curing agents are believed to include amines or amino functional polymers selected from aliphatic amines and polyamines (e.g. cycloaliphatic amines and polyamines), amidoamines, polyamidoamines, polyoxyalkylene amines (e.g. polyoxyalkylene diamines), aminated polyalkoxyethers (e.g. those sold commercially as "Jeffamines”), alkylene amines (e.g. alkylene diamines), aralkylamines, aromatic amines, Mannich bases (e.g. those sold commercially as "phenalkamines”), amino functional silicones or silanes, and including epoxy adducts and derivatives thereof.
  • amines or amino functional polymers selected from aliphatic amines and polyamines (e.g. cycloaliphatic amines and polyamines), amidoamines, polyamidoamines, polyoxyalkylene amines (e.g. polyoxyal
  • Epoxy hardener MXDA ex. Mitsubishi Gas Chemical Company Inc (USA), aralkyl amine
  • Preferred epoxy-based primer systems comprises a) one or more epoxy resins selected from bisphenol A, bisphenol F and Novolac; and b) one or more curing agents selected from Mannich Bases, polyamidoamines, polyoxyalkylene amines, alkylene amines, aralkylamines, polyamines, and adducts and derivatives thereof.
  • Especially preferred epoxy-based primer systems comprise one or more bisphenol A epoxy resins and one or more curing agents selected from Mannich Bases, polyamidoamines and adducts and derivatives thereof.
  • the epoxy resin has an epoxy equivalent weight of 100-2000, such as 100-1500, e.g. 150-1000, such as 150-700.
  • Especially preferred epoxy-based primer systems comprise one or more bisphenol A epoxy resins having an epoxy equivalent weight of 150-700 and one or more polyamidoamine or adducts and derivatives thereof.
  • the epoxy-based primer systems are ambient curing primer systems, i.e. the primer composition is curable at a temperature in the range from 0 °C to 50 °C, such as from 2 °C to 40 °C, e.g. from 5 °C to 30 °C.
  • the total amount of epoxy-based primer system is in the range of 15-80%, such as 35-80%, e.g. 40-75% by solids volume of the paint.
  • the term "hydrogen equivalents" is intended to cover only reactive hydrogen atoms linked to nitrogen.
  • the number of "hydrogen equivalents" in relation to the one or more curing agents is the sum of the contribution from each of the one or more curing agents.
  • the contribution from each of the one or more curing agents to the hydrogen equivalents is defined as grams of the curing agent divided by the hydrogen equivalent weight of the curing agent, where the hydrogen equivalent weight of the curing agent is determined as: grams of the curing agent equivalent to 1 mole of active hydrogen.
  • the contribution of the reactants before adductation is used for the determination of the number of "hydrogen equivalents" in the epoxy-based primer system.
  • the number of "epoxy equivalents" in relation to the one or more epoxy resins is the sum of the contribution from each of the one or more epoxy resins.
  • the contribution from each of the one or more epoxy resins to the epoxy equivalents is defined as grams of the epoxy resin divided by the epoxy equivalent weight of the epoxy resin, where the epoxy equivalent weight of the epoxy resin is determined as: grams of the epoxy resin equivalent to 1 mole of epoxy groups.
  • the contribution of the reactants before adductation is used for the determination of the number of "epoxy equivalents" in the epoxy- based primer system. It should be understood that if the epoxy-based primer system contains reactive acrylic modifiers then the number of "epoxy equivalents" is to be increased accordingly. E.g. if the epoxy-based primer system contains an acrylate oligomer comprising alpha, beta
  • unsaturated carbonyl groups then the number of "alpha, beta unsaturated carbonyl group equivalents" are to be added to the epoxy equivalents of the one or more epoxy resins for the purpose of establishing the ratio between the hydrogen equivalents of the one or more curing agents and the epoxy equivalents of the one or more epoxy resins.
  • the ratio between the hydrogen equivalents of the one or more curing agents and the epoxy equivalents of the one or more epoxy resins is in the range of 20 : 100 to 120 : 100.
  • Especially preferred epoxy-based primer systems have a ratio between the hydrogen equivalents of the one or more curing agents and the epoxy equivalents of the one or more epoxy resins in the range of 60 : 100 to 120 : 100, such as 70 : 100 to 110 : 100.
  • the primer composition typically has a viscosity in the range of 25-25,000 mPa-s, such as in the range of 150-15,000 mPa-s, in particular in the range of 200-1000 mPa-s.
  • coating compositions adapted for powder coating are solids and have no measurable viscosity. In the present application with claims, viscosity is measured at 25 °C in accordance with ISO 2555 : 1989.
  • the primer composition advantageously may further comprise one or more adhesion promoters, especially of the silane type.
  • Adhesion promoters of the silane type are organosilicon compounds that have two different functional groups, including one that reacts with organic materials and one that reacts with inorganic materials. This unique characteristic enables them to bond organic materials (coatings) to inorganic materials (substrate) .
  • Silanes could have a wide variety of organic functional groups and chemical reactivities.
  • the organic functional groups can include, epoxy, amino, ketimino, vinyl, methacryloxy, acryloxy, mercapto, polysulfido, isoyanato, styryl, as well as other organic groups.
  • Silanes can boost mechanical strength of compound materials, improve moisture resistance and adhesion.
  • Adhesion promoters may be selected from organofuntional silanes of the general formula : Y-R 1 -Si(R 2 )n(R 3 )3 n / wherein n is 0, 1 or 2, in particular 0 or 1; R 1 is selected from Ci-s- alkylene (e.g. methyl, ethyl, hexyl, octyl, etc.), Ci- 4 -alkylene-0-C 2 -4-alkyl; arylene (e.g.
  • R 2 is selected from Ci- 8 -alkyl (e.g.
  • Ci- 4 -alkyl-0-C 2 -4-alkyl aryl (e.g. phenyl) and aryl-Ci- 4 -alkyl (e.g. benzyl), etc.
  • R 3 is a hydrolysable group, e.g. methoxy, ethoxy, 2-methoxy-ethoxy, etc.
  • Y is a reactive substituent, e.g. epoxy, amino, ketimino, vinyl, methacryloxy, acryloxy, mercapt, polysulfido, isoyanato, styryl, etc.
  • adhesion promoters are: a) Epoxysilanes, e.g. of the formula A-Si(R 2 ) n (R 3 )(3- n ) / wherein A is an epoxide-substituted monovalent hydrocarbon radical having 2 to 12 carbon atoms; and each of n, R 2 and R 3 are as above.
  • the group A in the epoxysilane is preferably a glycidoxy-substituted alkyl group, for example 3-glycidoxypropyl.
  • the epoxysilane can for example be 3-glycidoxypropyltri- methoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldiethoxymethoxysilane, 2- glycidoxypropyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 2-(3,4- epoxy-4-methylcyclohexyl)-ethyltrimethoxysilane, 5,6-epoxy-hexyltriethoxysilane.
  • epoxysilanes are 5,6-epoxy-hexyl triethoxysilane (ABCR GmbH & Co. KG, Germany); 3-glycidoxypropyl methyldiethoxysilane (ABCR GmbH & Co. KG, Germany), ⁇ -glycidoxypropyyltrimethoxysilane (Dynasylan, Glymo, Sivento Chemie GmbH, Germany).
  • Methacrylatesilanes 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyl - trimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyl - triethoxysilane.
  • aminosilanes are (CH 3 0)3Si (CH2)3N H (CH2)2N H 2 ; (CHaCHzOCHzCHzOJsS CHzk- NH 2 ; (C 2 H50)3Si (CH2)3N H 2 ; (CHaOCHzCHzOJsS CHzJsN Hz ; (CzHsOJsS CHzJsC CHzJsN Hz ;
  • silanes are bis[3-(triethoxy- silyl)propyl]disulfide, bis[3-(triethoxysilyl)propyl]tetrasulfide, bis(3-trimethoxysilylpropyl)- amine; N,N'-bis[3-(trimethoxysilyl)propyl]ethylene-diamine; and bis(triethoxysilyl)ethylene.
  • silanes are bis[3-(triethoxy- silyl)propyl]disulfide, bis[3-(triethoxysilyl)propyl]tetrasulfide, bis(3-trimethoxysilylpropyl)- amine; N,N'-bis[3-(trimethoxysilyl)propyl]ethylene-diamine; and bis(triethoxysilyl)ethylene.
  • the adhesion promoter is typically present in an amount of 0-10 % by weight, in particular in an amount of 0.1-8% by weight.
  • the paint composition may comprise plasticizers.
  • plasticizers are hydrocarbon resins, phthalates and benzyl alcohol.
  • the paint composition comprises a hydrocarbon resin as plasticizer.
  • the total amount of plasticizers e.g. hydrocarbon resins
  • the total amount of plasticizers may be in the range of 0-30%, such as 0-25% by solids volume of the paint, preferably 1-25%, such as 1-20% by solids volume of the paint.
  • the paint composition may comprise other paint constituents as will be apparent for the person skilled in the art.
  • paint constituents are pigments, fillers, additives (e.g. epoxy accelerators, surfactants, hydroxy-functional modifying resins, wetting agents and dispersants, de-foaming agents, catalysts, stabilizers, corrosion inhibitors, coalescing agents, thixothropic agents (such as polyamide waxes), anti-settling agents and dyes).
  • the total amount of pigments and fillers may be in the range of 0- 50%, such as 5-50% by solids volume of the paint, preferably 10-45%, such as 10-40% by solids volume of the paint.
  • the paint composition comprises 0-10% by solids volume of the paint of aluminium pigments, preferably 1-7%, such as 2-6% by solids volume of the paint. In an alternative embodiment, the composition comprises at the most 10% by dry weight of the paint of aluminium pigments. In the paint composition, the total amount of additives may be in the range of 0-10%, such as 0.1-8% by solids volume of the paint.
  • the paint composition may further comprise epoxy accelerators.
  • the paint composition typically comprises a solvent or solvents.
  • solvents are alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol and benzyl alcohol; aliphatic, cycloaliphatic and aromatic hydrocarbons, such as white spirit,
  • ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone, methyl isoamyl ketone, diacetone alcohol and cyclo- hexanone
  • ether alcohols such as 2-butoxyethanol, propylene glycol monomethyl ether and butyl diglycol
  • esters such as methoxypropyl acetate, n-butyl acetate and 2-ethoxyethyl acetate; and mixtures thereof.
  • the paint comprises solvent(s) so that the solids volume ratio (SVR - ratio between the volume of solid constituents to the total volume) is in the range of 30-100%, preferably 50-100%, in particular 55-100% e.g. 60- 100%.
  • SVR is determined according to ISO 3233 or ASTM D 2697 with the modification that drying is carried out at 20°C and 60% relative humidity for 7 days instead of drying at higher temperatures.
  • the coating composition comprises 0% by solids volume of the paint of coal-tar.
  • the primer composition may be prepared by any suitable technique that is commonly used within the field of paint production.
  • the various constituents may be mixed together using a high speed disperser, a ball mill, a pearl mill, a three-roll mill etc.
  • the paints according to the invention may be filtrated using bag filters, patron filters, wire gap filters, wedge wire filters, metal edge filters, EGLM turnoclean filters (ex. Cuno), DELTA strain filters (ex. Cuno), and Jenag Strainer filters (ex. Jenag), or by vibration filtration.
  • the primer composition to be used in the method of the invention is prepared by mixing two or more components, e.g. two pre-mixtures, one component, e.g.
  • a pre-mixture comprising the one or more epoxy resins and one component, e.g. a pre-mixture, comprising the one or more curing agents.
  • a pre-mixture comprising the one or more epoxy resins and one component, e.g. a pre-mixture, comprising the one or more curing agents.
  • the primer composition of the invention is typically applied to at least a part of the surface of a substrate.
  • applying is used in its normal meaning within the paint industry.
  • “applying” is conducted by means of any conventional means, e.g. by brush, by roller, by spraying, by dipping, etc.
  • the commercially most interesting way of “applying” the coating composition is by spraying, however, often in combination with brush application on touch-up areas and/or on edges, corners etc. in the paint business named “stripe coating”.
  • the primer composition is adapted for application by spraying, i.e. the viscosity thereof allows for application using conventional spraying equipment.
  • the primer composition is typically applied in a dry film thickness of 100- 600 ⁇ per coat, such as 150-450 ⁇ , e.g. 200-400 ⁇ , but could also be as low as 30 ⁇ and as thick as 3000 ⁇ per coat. In shop application the so called “shop primers" are typically applied in a thickness of 15-20 ⁇ .
  • the term "at least a part of the surface of a substrate” refers to the fact that the primer composition may be applied to any fraction of the surface.
  • the primer composition is at least applied to the part of the substrate (e.g. a vessel) where the surface (e.g. the ship's hull), possibly after application of further coating layers, may come in contact with water, e.g. sea-water or another corrosive environment.
  • the term "substrate” is intended to mean a solid material onto which the coating composition is applied.
  • the substrate comprises a metal such as steel (i.e. carbon steel and stainless steel alloys), electro galvanized steel, hot dip galvanized steel, thermally spray metallized steel, copper and copper alloys, aluminium and aluminium alloys.
  • the substrate is a metal substrate, in particular a steel substrate.
  • the substrate is at least a part of the outermost surface of a structure exposed to a corrosive environment.
  • surface is used in its normal sense, and refers to the exterior boundary of an object.
  • marine structures such as marine vessels (including but not limited to boats, yachts, motorboats, motor launches, ocean liners, vessels for floating production storages and offload (FPSOs), workboats, tugboats, tankers, container ships and other cargo ships, submarines, naval vessels of all types and barges), tanks, such as ballast water tanks, on-shore or off-shore storage tanks for water or water/oil mixtures), pipelines, such as oil and/or gas transporting pipelines immersed in water or soil), off-shore installations and structures, such as oil and gas producing installations, platforms, under-water oil well structures, off-shore wind-turbines, water power installations and structures, other constructions and objects of all types, such as piers, pilings, bridge substructures and other aquatic culture installations, and buoys, etc.
  • marine vessels including but not limited to boats, yachts, motorboats, motor launches, ocean liners, vessels for floating production storages and offload (FPSOs), workboats, tugboats, tankers, container ships and other cargo ships, submarines
  • the present invention provides a single paint coat on a metal surface, comprising coat of an epoxy-based primer composition. But it also provides a coating system on a metal surface, comprising coat of an epoxy-based primer composition (i.e. a primer coat) on at least a part of the metal surface, and one of multiple coats of another coating composition (e.g.
  • the coating system is typically established by application of the primer composition as described above.
  • the coat of the second coating composition represents a non-transparent coat.
  • the present invention also relates to an article coated with a primer composition as defined hereinabove.
  • a primer composition as defined hereinabove.
  • Such article may without limitations encompass marine vessels, bridges, containers, tanks, pipes, offshore installations, etc.
  • the primer composition is typically applied in accordance with the method described above.
  • the present invention also provides a marine structure comprising on at least a part of the outer surface thereof a primer coating prepared from a coating composition as defined hereinabove.
  • the primer composition is typically applied in two coats in a dry film thickness of 100-200 ⁇ per coat, such as 125-175 ⁇ , e.g. 150 ⁇ .
  • the coating system of the internal tank system may consist of 2-3 coats of an anticorrosive layer of 100-200 ⁇ per coat.
  • the primer composition of the external system may consist of 1-3 coats of an anticorrosive layer of 200-600 ⁇ per coat or even 1 coat in a dry film thickness of 1000-3000 ⁇ .
  • the primer composition of the internal system may consist of 2-3 coats of an anticorrosive layer of 100-200 ⁇ per coat.
  • the primer composition of the external system may consist of 1-3 coats of an anticorrosive layer of 200-600 ⁇ per coat or even 1 coat in a dry film thickness of 1000-3000 ⁇ .
  • the coating system may consist of 2-3 coats of an anticorrosive layer of 100-500 ⁇ per coat, or the primer composition may consist of 1-3 coats of an anticorrosive layer of 200-600 ⁇ per coat or even 1 coat in a dry film thickness of 1000-3000 ⁇ .
  • the coating system may consist of 2-3 coats of an anticorrosive layer of 100- 200 ⁇ per coat.
  • a typically specification may consist of 2-3 coats of an anticorrosive layer of 100-200 ⁇ per coat.
  • any combination of two or more of the embodiments described herein is to be construed as falling within the scope of the present invention.
  • the coating compositions defined herein may comprise one, two or more types of the individual constituents.
  • the total amount of the respective constituent should correspond to the amount defined above for the individual constituent.
  • the "(s)" in the expressions: scavenger(s), polysiloxane(s), etc. indicates that one, two or more types of the individual constituents may be present.
  • the expression "one" is used, only one (1) of the respective constituent is present.
  • the Cathodic Protection Test is carried out in accordance with ISO 15711: Determination of resistance to cathodic disbonding of coatings exposed to sea water (method A, Impressed current). This test method simulates the conditions experienced in real life by cathodically- protected structures immersed in sea water, e.g., ship hulls, ballast tanks or offshore structures. Before testing, the coating is artificially damaged in the form of a bare spot (holiday) of 6 mm in examples series B, and 11 mm in examples series A, in diameter located approximately in the middle of the panel. The panels are exposed in a test tank containing circulating artificial sea water at 17°C. The electrical stress is produced by connecting the panels to a cathodic protection circuit.
  • the panels are cathodically polarized at -1050 mV SCE (saturated calomel electrode). Inspections are carried out regularly over the testing time until completion of the exposure. At each inspection, blisters are reported according to ISO 4628-2 by using a template which divides the area of the panel into four zones, corresponding to four rings of different radial length distributed from the perimeter of the holiday outwards ( Figure 1 - illustrating "Zones for blistering evaluation").
  • the panels are exposed for 9 weeks in example series B and 8 weeks in examples series A.
  • the evaluation of the panels is done immediately at completion of the exposure by making two radial cuts through the coating at 45° to each other approximately, intersecting at the centre of the holiday.
  • the disbonding is determined by picking off the paint with a sharp knife or scalpel from the edge of the holiday outwards. The maximum radial length of disbonding is measured and reported in mm from the edge of the holiday.
  • the Blister Box Test is carried out according to ISO 6270-1 : Determination of resistance to humidity (Part 1, continuous condensation). This method is performed in order to evaluate the water resistance of a coating system by exposing it to controlled condensation conditions. The panel surface with the coating system is exposed to saturated water vapour at 40°C and at an angle of 15° to 60° with the horizontal. The reverse side of the panel is exposed to room temperature (23°C approximately). The panels are exposed for 9 weeks. At completion of the exposure, blistering and rust are evaluated according to ISO 4628-2 and ISO 4628-3, respectively.
  • the Salt Spray Test is conducted according to ISO 9227: Corrosion tests in artificial atmospheres - Salt spray tests. This method is performed in order to evaluate the corrosion resistance of a coating system by reproducing the corrosion that occurs in atmospheres containing salt spray or splash. Before testing, the coating is artificially damaged by making a 2-mm-wide scribe line of 50 mm in length. The scribe line is 20 mm above the bottom of the panels, with a spacing of 10 mm on either side. The panels are exposed for 9 weeks in examples series B, and 26 weeks in examples series A, to constant salt spray at 35°C in a spray cabinet. The salt fog is generated by using a NaCI solution of 50 g/l.
  • blistering and rust are evaluated on both panel and around the scribe (in mm from centre), according to ISO 4628-2 and ISO 4628-3, respectively.
  • the paint is picked off and the degree of under-film corrosion and delamination is determined according to ISO 4628-8.
  • the sea water immersion test is carried out according to ISO 2812-2: Determination of resistance to liquids (Part 2, Water immersion method).
  • the panels are immersed in a test tank with circulating, aerated artificial sea water in accordance with ISO 15711, at 40 ⁇ 1°C.
  • the coating is artificially damaged by making a 2-mm-wide scribe line of 50 mm in length.
  • the scribe line is 20 mm above the bottom of the panels, with a spacing of 10 mm on either side.
  • the panels are exposed for 9 weeks in total.
  • blistering and rust are evaluated on both panel and around the scribe (in mm from centre), according to ISO 4628-2 and ISO 4628-3, respectively.
  • the paint is picked off and the degree of under-film corrosion and delamination is determined according to ISO 4628-8.
  • This test method is a slight variation of the sea water immersion test as the electrolyte is a 0.5 M solution of KCI instead of the artificial sea water described in the standard.
  • the coating is artificially damaged in the form of a bare spot (holiday) of 11 mm in diameter located approximately in the middle of the panel.
  • the panels are exposed in a test tank containing circulating artificial sea water at 17°C for 8 weeks.
  • the paint is picked off and the degree of under-film corrosion and delamination is determined according to ISO 4628-8.
  • epoxy resins used in examples series A were diglycidyl ethers of bisphenol A, either a low molecular weight epoxy resin (Epikote 828) or a medium molecular weight epoxy resin
  • the curing agent was a polyamide adduct prepared by combining Epikote 828 with Epicure 3140.
  • the free-radical scavengers tested were Irganox 1010 and Irganox 1135, both supplied by Ciba and DTBHQ (2,5-di-tert-butylhydroquinone) supplied by Eastman Chemicals.
  • Irganox 1010, Irganox 1135 and DTBHQ are all sterically hindered phenols.
  • Irgafos 168 supplied by Ciba is a triarylphosphite, i.e. a peroxide decomposer.
  • Coatings with compositions as shown in Table 1 were produced in batches of about 1200 mL
  • the binder and pigment phase were mixed in a metal container and dispersed for 10-15 minutes on a high speed dissolver before addition of additional solvents and additives.
  • All the free-radical scavengers and Irgafos 168 are practically insoluble in water ( ⁇ 0.01 g per 100 mL) and very soluble in organic solvents such as toluene and/or n-butanol.
  • the free-radical scavengers and Irgafos 168 were dissolved in n-butanol prior to incorporation to ensure that they were properly mixed with the epoxy resin.
  • the maximum particle size was measured using a grindometer and found to be 15-25 ⁇ for all coatings. Dispersion continued until the liquid coating reached a temperature of 70 °C. Thereafter, the kinematic viscosity of the coatings was adjusted to approximately 9-10 "3 mV 1 with a mixture of solvents. The reduced pigment volume concentration (ratio between the pigment volume concentration and the critical pigment volume concentration) was 0.6, which is a typical value for barrier coatings.
  • Titanium dioxide 2.6 2.6 2.6 2.6 2.6
  • Table 1 Composition (percentage by solids volume) of the tested coatings.
  • the free-radical scavengers were all tested at various levels in the range 0.5 % to 25 % per solids volume.
  • the reduced pigment volume concentration was maintained at 0.6 for coatings with the amount of free-radical scavengers given as vol% by reducing the amount of plasticizer.
  • the amount of free-radical scavenger is given as percentage by weight, the free-radical scavengers were added to the reference coating. This means that the amount of filler versus the amount of binder in the coatings with the amount of free-radical scavenger given as wt% is gradually reduced as the amount of free-radical scavenger is increased.
  • the coating was applied by airless spray at a pressure of 100 bars.
  • the desired coating thickness was obtained by application of two layers of coating with similar thickness. The first coat was allowed to cure for 1 day at ambient temperature before the second coat was applied.
  • a conventional circular sticker with a diameter of 11 mm was attached to the steel surface prior to application of the coating for substrates intended for immersion in sea water.
  • the acid number was calculated as the amount of sodium hydroxide in milligrams required for neutralizing the phenol groups in one gram of free-radical scavenger.
  • Table 2 Effect of free-radical scavenger content on the extent of delamination of coating based on Epikote 1001 under cathodic polarization at -1050 mV (SCE). after 6 weeks of exposure to 0.5 M sodium chloride at 18 °C.
  • Table 3 Effect of free-radical scavenger content on the extent of cathodic delamination of coatings based on Epikote 1001 at free corrosion potential after 6 weeks of exposure to 0.5 M sodium chloride at 18 °C.
  • Table 4 Effect of free-radical scavenger content on the extent of cathodic delamination of coatings based on Epikote 828 under cathodic polarization at -1050 mV (SCE) after 6 weeks of exposure to 0.5 M sodium chloride at 18 °C.
  • Table 5 Effect of free-radical scavenger content on the extent of cathodic delamination of coatings based on Epikote 828 at free corrosion potential after 6 weeks of exposure to 0.5 M sodium chloride at 18 °C.
  • the free-radical scavengers are all capable of reducing the extent of cathodic delamination of coatings based on both low and medium molecular weight epoxy resins. This means that the high concentration of tertiary amine groups in cured coatings based on low molecular weight epoxy resins does not affect the ability of the free-radical scavengers to reduce the extent of cathodic delamination.
  • cathodic delamination is reduced equally at free corrosion potential and under cathodic polarization, which indicates that free radicals are also important for cathodic delamination at free corrosion potential.
  • the extent of cathodic delamination is reduced when the concentration of radical scavengers is increased from 0.5 vol% to 5.0 vol%, which shows that the concentration of the radical scavengers has a significant impact on cathodic delamination.
  • the extent of cathodic delamination is increased significantly, probably because the high amount of free-radical scavengers increases the permeability of the coating towards corrosive species.
  • the superior performance of DBTHQ compared with Irganox 1010 and Irganox 1135 can be partly explained in terms of molecular weight per active group. Sterically hindered phenols interact with free radicals through the phenol group. Although other factors such as steric hindrance can be important, the efficiency of sterically hindered phenols is therefore related to the equivalent weight per phenol group. Table 6 shows that the phenol equivalent weights for Irganox 1010 and Irganox 1135 are respectively 33 % and 75% greater than the molecular weights per active phenol group for DBTHQ. Thus, the ranking of the efficiency of the radical scavengers corresponds to the variations in the phenol equivalent weight.
  • the free-radical scavengers were unable to reduce the rate of cathodic delamination, when they were incorporated into the intermediate or topcoat. Thereby, the free-radical scavengers are solely effective when they are incorporated into the primer. This is because the radical scavengers must be present at the coating-steel interface where the free radicals are formed by the corrosion process. Furthermore, neither the free-radical scavengers nor the peroxide decomposer affected the strength of adhesion of intact coatings (18 ⁇ 2 MPa) or the free corrosion potential of the steel substrate (-745 mV SCE). This confirms that the mechanism by which free-radical scavengers reduce the rate of cathodic delamination is different from the mechanism of corrosion inhibitors and that the effect cannot be ascribed to
  • a hindered amine light stabilizer (Tinuvin 292 from Ciba), another specific type of antioxidant, was unable to reduce the rate of cathodic delamination when incorporated into the primer, intermediate or top-coat.
  • HALS hindered amine light stabilizers
  • HALS will also be inefficient during natural outdoor exposure because multilayer systems typically consists of a primer and one or more intermediate coats and/or a topcoat, which are non- permeable to ultraviolet radiation and thereby prevents the conversion of HALS to nitroxyl radicals.
  • Secondary aromatic amines are efficient free-radical scavengers in the absence of ultraviolet radiation but will react with the epoxide groups in the epoxy resin and thereby be consumed. This was confirmed by monitoring the viscosity of a mixture with 50 wt% Epikote 828 and a secondary aromatic amine continuously by the Gardner-Holdt method (the kinematic viscosity increased from around 6.3-10 "3 m 2 s _1 to 16- 10 "3 m 2 s _1 within 3 hours). Thereby, secondary aromatic amines will not protect an epoxy coating from degradation by free radicals to the same extent as hindered phenols, when there is an excess of epoxide groups in the coating.
  • hydrophilic compounds such as ascorbic acid should not be incorporated into solvent-borne primers although they may be efficient free-radical scavengers. Concentration of free-radical scavenger
  • the rate of cathodic delamination of epoxy coatings modified with free-radical scavengers is highly dependent on the amount of free-radical scavengers as demonstrated in Table 7.
  • the incorporation of 1-3 wt% free-radical scavengers results in significant improvements in the resistance towards cathodic delamination.
  • the amount of free-radical scavengers is increased further, up to 8 wt%, the resistance towards cathodic delamination is improved further.
  • the extent of cathodic delamination is increased. This may be the result of an increase in excess free volume caused by the incorporation of free-radical scavengers, which subsequently increases the permeability of the coating and the rate of cathodic delamination.
  • Table 7 Extent of cathodic delamination as function of the amount of free-radical scavenger (DTBHQ) of coatings based on a 50: 50 (w/w%) mixture of Epikote 828 and Epikote 1001 after 8 weeks of exposure to 0.5 M potassium chloride at free corrosion potential.
  • DTBHQ free-radical scavenger
  • reactive intermediates during electrochemical reduction of oxygen is not restricted to substrates prepared from cold rolled steel.
  • specific examples of other types of metals, which under cathodic polarization will reduce oxygen to reactive intermediates include aluminium, copper, and stainless steel .
  • Table 8 shows the extent of cathodic delamination of a reference coating without free-radical scavengers and an identical coating modified with 3 wt% of free-radical scavenger (DBTHQ) for various types of metallic substrates under cathodic polarization.
  • Table 8 Extent of cathodic delamination of a reference coating based on a 50: 50 (w/w%) mixture of Epikote 828 and Epikote 1001 without free-radical scavengers and an identical coating containing 3 wt% radical scavengers (DBTHQ) for various types of substrates under cathodic polarization at -1050 mV (SCE). All specimens were immersed in 0.5 M sodium chloride for 9 weeks. * Polarized to -1200 mV (SCE).
  • Table 9 Effect of combinations of adhesion promoters and free-radical scavengers in coatings based on a 50 : 50 (w/w%) mixture of Epikote 828 and Epikote 1001 on cathodic delamination under cathodic polarization at -1050 mV (SCE) for 9 weeks at 20°C as well as delamination and under-film corrosion curing salt spray testing for 26 weeks according to ISO 9227.
  • adhesion promoters do not inactivate free radicals.
  • Adhesion promoters are covalently bonded to the steel surface and the silicon-oxygen bond have a high bond energy (443 kJ/mol) compared to a typical bond strength of 360 kJ/mol for the carbon-carbon bond of organic binders.
  • the silanes are already oxidized, which prevents further oxidation by reactive intermediates.
  • a free-radical scavenger and an epoxy functional silane improves the resistance towards under-film corrosion compared to the coating containing the epoxy functional adhesion promoter. This suggests that free-radical scavengers may contribute to an improved resistance towards under-film corrosion.
  • the coating compositions were prepared by adding 3% by solids volume of the additives shown in Table 10 to Hempadur 17630-12170 ex Hempel. The additives were mixed into the curing agent.
  • a magnetic gauge instrument Elcometer Model 355 Top, was used to measure the dry film thickness of the coatings, which was 200 ⁇ ⁇ 25 ⁇ , representative of industrial coating thicknesses.
  • the final curing time of the coating specimens was at least 7 days at ambient temperature.
  • antioxidants are capable to reduce disbondment in epoxy resin coatings.
  • no adhesion promoters was used. These results could be explained in terms of free radicals reduction at the steel-primer interphase when antioxidants are present according. It was not possible to measure the delamination effect of ascorbic acid due to prompt blistering in all the tests. The poor performance of ascorbic acid is most likely due to its high water solubility (330 g/L).
  • Example series B demonstrate higher delamination tendency in CPT test of coating Example 7 (Vitamin E), and coating Example 8 (Beta Carotene) compared the others additives.
  • Results from Example series B are in accordance with the results obtained in Example series A. These results can be explained using the same principles and protection mechanism detailed in Example series A.
  • Example 4 15.0 14.5 13.7 1.1 18.5 0.0 0 chatecol
  • CPT Cathodic protection test, ISO 15711 (see above); CPT KCL: Cathodic protection test in KCL, ISO 15711 (see above); SST: Salt Spray Test, ISO 9227 (see above); SW IMS: Sea water immersion test, ISO 2812-2 (see above); BBT: Blister Box Test, ISO 6270-1 (see above); DLam : delamination; and Creep: Rust creep.

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Abstract

La présente invention porte sur une composition d'apprêt à base d'époxyde liquide comprenant un ou plusieurs fixateurs de radicaux libres à hauteur de 0,5-20 % en poids, lesdits fixateurs de radicaux libres étant choisis parmi les phénols et les multimères de phénols chacun substitué par des substituants donneurs d'électrons, et sur l'application de celle-ci par pulvérisation. L'invention porte également sur un système de revêtement sur une surface métallique, comprenant une couche de la composition d'apprêt à base d'époxyde (c'est-à-dire d'une couche d'apprêt) sur au moins une partie de la surface métallique et une couche d'une seconde composition de revêtement (par exemple une couche de finition) sur au moins une partie de la couche d'apprêt ; ainsi que sur un article revêtu de la composition d'apprêt.
PCT/EP2011/051194 2010-01-29 2011-01-28 Compositions d'apprêt à base d'époxyde WO2011092278A1 (fr)

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WO2015065816A1 (fr) * 2013-10-30 2015-05-07 Anocoil Corporation Précurseurs et revêtement de plaque d'impression lithographique
US9920216B2 (en) 2013-03-27 2018-03-20 Hempel A/S Curing agent for tie-coat composition comprising an amino-silane adduct
KR101927567B1 (ko) * 2011-11-03 2018-12-10 나믹스 코포레이션 수지 조성물
US10703927B2 (en) 2014-04-10 2020-07-07 3M Innovative Properties Company Adhesion promoting and/or dust suppression coating
WO2020159974A1 (fr) * 2019-01-28 2020-08-06 The Chemours Company Fc, Llc Composition pour fabriquer une couche de passivation et couche de passivation l'utilisant
WO2022130258A1 (fr) * 2020-12-18 2022-06-23 3M Innovative Properties Company Procédés de collage de cuivre et articles ainsi formés
WO2023111849A3 (fr) * 2021-12-17 2023-07-27 3M Innovative Properties Company Buse de distribution d'adhésif et procédés de distribution d'adhésif
WO2023111839A3 (fr) * 2021-12-17 2023-07-27 3M Innovative Properties Company Appareil de distribution d'adhésif et procédés de distribution d'adhésif

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KR101927567B1 (ko) * 2011-11-03 2018-12-10 나믹스 코포레이션 수지 조성물
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US11674047B2 (en) 2019-01-28 2023-06-13 The Chemours Company Fc, Llc Composition for manufacturing passivation layer and passivation layer using the same
WO2022130258A1 (fr) * 2020-12-18 2022-06-23 3M Innovative Properties Company Procédés de collage de cuivre et articles ainsi formés
WO2023111849A3 (fr) * 2021-12-17 2023-07-27 3M Innovative Properties Company Buse de distribution d'adhésif et procédés de distribution d'adhésif
WO2023111839A3 (fr) * 2021-12-17 2023-07-27 3M Innovative Properties Company Appareil de distribution d'adhésif et procédés de distribution d'adhésif

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