WO2009141444A1 - Durcissement favorisé en surface de compositions monocomposant cationiquement durcissables - Google Patents

Durcissement favorisé en surface de compositions monocomposant cationiquement durcissables Download PDF

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Publication number
WO2009141444A1
WO2009141444A1 PCT/EP2009/056257 EP2009056257W WO2009141444A1 WO 2009141444 A1 WO2009141444 A1 WO 2009141444A1 EP 2009056257 W EP2009056257 W EP 2009056257W WO 2009141444 A1 WO2009141444 A1 WO 2009141444A1
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WIPO (PCT)
Prior art keywords
metal
composition according
component
curable composition
metal salt
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PCT/EP2009/056257
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English (en)
Inventor
David Farrell
Ciaran Mcardle
Michael Doherty
Emilie Barriau
Rainer Schoenfeld
Original Assignee
Loctite (R&D) Limited
Henkel Ag & Co. Kgaa
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Application filed by Loctite (R&D) Limited, Henkel Ag & Co. Kgaa filed Critical Loctite (R&D) Limited
Priority to CN2009801260944A priority Critical patent/CN102083918A/zh
Priority to JP2011510001A priority patent/JP2011523670A/ja
Priority to EP09749934A priority patent/EP2288665A1/fr
Publication of WO2009141444A1 publication Critical patent/WO2009141444A1/fr

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    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/40—Redox systems
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00

Definitions

  • the present invention relates to stable one-part cationically curable compositions for curing on a surface, and uses there for.
  • RedOx cationic polymerizations involve oxidation and reduction processes [Holtzclaw, H. F.; Robinson, W.R.; Odom, J. D.; General Chemistry 1991 , 9 th Ed., Heath (Pub.), p. 44].
  • an atom either free or in a molecule or ion, loses an electron or electrons, it is oxidised and its oxidation number increases.
  • an atom, either free or in a molecule or ion gains an electron or electrons, it is reduced and its oxidation number decreases. Oxidation and reduction always occur simultaneously, as if one atom gains electrons then another atom must provide the electrons and be oxidised.
  • RedOx couple one species acts as a reducing agent, the other as an oxidizing agent.
  • the reducing agent gives up or donates electrons to another reactant, which it causes to be reduced. Therefore the reducing agent is itself oxidised because it has lost electrons.
  • the oxidising agent accepts or gains electrons and causes the reducing agent to be oxidised while it is itself reduced.
  • a comparison of the relative oxidising or reducing strengths of strength of the two reagents in a redox couple permits determination of which one is the reducing agent and which one is the oxidising agent.
  • the strength of reducing or oxidising agents can be determined from their standard reduction (E re ⁇ °) or oxidation (E 0x 0 ) potentials.
  • Onium salts have been widely used in cationically curable formulations. Extensive investigation into the use of onium salts as photoinitiators for cationic polymerisation led to the realisation that during the course of the photochemical reaction the onium cation undergoes photochemical reduction.
  • diaryliodonium salts have been used in cationically curable formulations. Extensive investigation into the use of diaryliodonium salts (1) as photoinitiators for cationic polymerisation led to the realisation that during the course of the photochemical reaction iodine undergoes a reduction in oxidation state from +3 to +1.
  • Diaryliodonium salts as initiators of cationic polymerisation via RedOx type chemistry have also been the subject of investigation.
  • the general premise here was that, in the presence of a chemical reducing agent, the iodine component of the diaryliodonium salt could be reduced resulting in the generation of the protonic acid species HX, as shown in Scheme 2 (below), which will in turn initiate cationic polymerisation.
  • Lewis acids in the form of metal salts have been used as initiators of cationic polymerization (Collomb, J. et al.; Eur. Poly. J. 1980, 16, 1135-1144; Collomb, J.; Gandini, A.; Cheradamme, H.; Macromol. Chem. Rapid Commun. 1980, 1 , 489-491 ). Many strong Lewis acid initiators have been shown to function by the direct initiation of the monomer (Scheme 3) (Collomb, J.; Gandini, A.; Cheradamme, H.; Macromol. Chem. Rapid Commun. 1980, 1 , 489-491 ). The stronger the Lewis acid the more pronounced is its initiating power.
  • Lewis acid metal salts react with cationically polymerizable monomers.
  • E-Coating is a method of painting which uses electrical current to deposit the paint.
  • the process works on the principal of "Opposites Attract”. This process is also known as electrodeposition.
  • the fundamental physical principle of electrocoat is that materials with opposite electrical charges attract each other.
  • An electrocoat system applies a DC charge to a metal part immersed in a bath of oppositely charged paint particles.
  • the paint particles are drawn to the metal part and paint is deposited on the part, forming an even, continuous film over every surface, in every crevice and corner, until the electrocoat reaches the desired thickness. At that thickness, the film insulates the part, so attraction stops and the electrocoat process is complete.
  • electrocoat is classified as either anodic or cathodic.
  • a major disadvantage of this technology is that it suffers from the Faraday Cage effect and so cannot coat inside metallic tubes, etc. It is necessary to bake the material in order to cross-link and cure the paint film.
  • the present inventors aim to utilise Redox chemistry as an alternative coating technology.
  • the present invention provides a stable one-part cationically curable composition for curing on a surface comprising: (i) a cationically curable component; and (ii) an initiator component comprising at least one metal salt;
  • Standard reduction potential of the initiator component is greater than the standard reduction potential of the surface, and wherein when the composition is placed in contact with the surface, the metal salt of the initiator component of the composition is reduced at the surface, thereby initiating cure of the cationically curable component of the composition.
  • References to standard reduction potentials in this specification indicate the tendency of a species to acquire electrons and thereby be reduced. Standard reduction potentials are measured under standard conditions: 25 0 C, 1 M concentration, a pressure of 1 atm and elements in their pure state.
  • the metal salt of the composition comprises a transition metal cation.
  • Suitable metals include silver, copper and combinations thereof.
  • the metal salt may be substituted with a ligand.
  • the metal salt counterions may be chosen from the group consisting Of CIO 4 " , BF 4 " , PF 6 “ , SbF 6 “ ,AsF 6 “ , (C 6 F 5 ) 4 B anion, (C 6 F 5 ) 4 Ga anion, Carborane anion, triflimide (trifluoromethanesulfonate) anion, bis-triflimide anion, anions based thereon and combinations thereof.
  • the metal salt counterions may be chosen from the group consisting Of CIO 4 “ , BF 4 “ , PF 6 “ , SbF 6 “ and combinations thereof.
  • the solubility of the metal salt may be modified by changing the counterion, the addition and/or substitution of ligands to the metal of the metal salt and combinations thereof. This will allow for efficient electron transfer between the surface and the metal salt to be observed as appropriate solubility is achieved.
  • the cationically curable component desirably has at least one functional group selected from the group consisting of epoxy, vinyl, oxetane, thioxetane, episulfide, tetrahydrofuran, oxazoline, oxazine, lactone, trioxane, dioxane, styrene with combinations thereof also being embraced by the present invention. Further desirably, the cationically curable component has at least one functional group selected from the group consisting of epoxy, episulfide, oxetane, thioxetane, and combinations thereof.
  • the cationically curable component has at least one functional group selected from the group consisting of epoxy, oxetane and combinations thereof.
  • the surfaces to which the compositions of the present invention are applied may comprise a metal, metal oxide or metal alloy.
  • the surface may comprise a metal or metal oxide.
  • the surface may comprise a metal.
  • Suitable surfaces can be selected from the group consisting of iron, steel, mild steel, gritblasted mild steel, aluminium, aluminium oxide, copper, zinc, zinc oxide, zinc bichromate, and stainless steel. References to aluminium and aluminium oxide include alclad aluminium (low copper content), and oxide removed alclad aluminium (low copper content) respectively.
  • the surface can be selected from the group consisting of steel and aluminium.
  • Metal salts suitable for use in compositions for curing on steel or aluminium surfaces may be chosen from the group consisting of silver salts, copper salts and combinations thereof, and wherein the counterions of the silver and copper salts may be chosen from the group consisting of CIO4 , BF 4 , PF 6 , SbF 6 and combinations thereof.
  • compositions disclosed herein can cure on oxidised metal surfaces without the need for additional etchant or oxide remover.
  • the compositions of the invention may optionally include an oxide remover.
  • an etchant or oxide remover such as those comprising chloride ions and/or a zinc (II) salt, in formulations of the invention may allow etching of any oxide layer. This will in turn expose the (zero-oxidation state) metal below, which is then sufficiently active to allow reduction of the transition metal salt.
  • the RedOx cationic systems discussed herein do not require any additional reducing agent. They are stable until applied to a substrate which is capable of participating in a RedOx reaction, thus fulfilling the role of a conventional reducing agent component.
  • the compositions of the present invention can thus be utilized in any application in which curing on a metal surface is required.
  • the compositions of the invention are storage stable even as a one-part composition and require no special packaging unlike prior art compositions, which tend to be multi-component compositions.
  • the compositions of the present invention do not require an additional catalyst for efficient curing.
  • the present invention utilizes appropriate selection of the initiator component relative to the surface on which the composition is to be applied and cured.
  • compositions according to the invention may optionally comprise a catalyst to effect electron transfer between the surface and the metal salt of the composition. This may be useful where even greater cure speeds are required. Suitable catalysts include transition metal salts.
  • inventive compositions described herein will generally be useful as adhesives, sealants or coatings, and can be used in a wide range of industrial applications including metal bonding, thread-locking, flange sealing, and structural bonding amongst others.
  • inventive compositions may be encapsulated if it is desired to do so.
  • Suitable encapsulation techniques comprise, but are not limited to, coacervation, softgel and co-extrusion.
  • the inventive compositions may be used in a pre-applied format.
  • pre-applied is to be construed as taking the material in an encapsulated form (typically but not necessarily micro-encapsulated) and dispersing said capsules in a liquid binder system that can be dried (e.g. thermal removal of water or an organic solvent, or by photo-curing the binder) on the desired substrate.
  • a film of material remains which contains the curable composition (for example adhesive liquid for example in the form of filled capsules).
  • the curable composition can be released for cure by physically rupturing the material (for example capsules) when the user wishes to activate the composition, e.g. in pre-applied threadlocking adhesives the coated screw threaded part is activated by screwing together with its reciprocally threaded part for example a threaded receiver or nut.
  • the invention further extends to a process for bonding two substrates together comprising the steps of:
  • composition comprising: i) a cationically curable component; and ii) an initiator component comprising at least one metal; to at least one substrate, and
  • both substrates comprise a metal.
  • the composition of the invention may comprise more than one type of metal salt.
  • the invention also provides for curable compositions wherein the inclusion of more than one type of metal salt can be used to bond different metal substrates together.
  • the metal of the metal salt of the inventive compositions of the present invention is lower in the reactivity series than the metal surface on which it is to be cured.
  • Metallic substrates can also be bonded to non-metallic substrates.
  • mild steel may be bonded to e-coated steel (e-coat is an organic paint which is electrodeposited, with an electrical current, to a metallic surface, such as steel).
  • e-coat is an organic paint which is electrodeposited, with an electrical current, to a metallic surface, such as steel.
  • inventive compositions of the present invention can be utilised to form (polymer) coatings on parts such as metallic parts.
  • the invention also relates to a pack comprising: a) a container; and b) a cationically curable composition according to the present invention, wherein the container may be air permeable. Alternatively, the container may not air permeable.
  • the present invention provides for a stable one-part cationically curable composition for curing on a surface comprising:
  • an initiator component comprising at least one metal salt
  • Standard reduction potential of the initiator component is greater than the standard reduction potential of the surface, and wherein when the composition is placed in contact with the surface, the metal salt of the initiator component of the composition is reduced at the surface, thereby initiating cure of the cationically curable component of the composition.
  • References to standard reduction potentials in this specification indicate the tendency of a species to acquire electrons and thereby be reduced. Standard reduction potentials are measured under standard conditions: 25 0 C, 1 M concentration, a pressure of 1 atm and elements in their pure state.
  • the accelerator species comprising at least one vinyl ether functional group greatly enhances the rate of cure.
  • the accelerator species may embrace the following structures:
  • n can be 0 - 5;
  • Ri, R 2 , and R 3 can be the same or different and can be selected from the group consisting of hydrogen, Ci-C 2 oalkyl chain (linear, branched or cyclic) and C 5 -C 2 O aryl moiety, and combinations thereof;
  • X can be a CrC 3 O saturated or unsaturated, cyclic or acyclic moiety; and Ri, R 2 , R 3 and X may or may not independently contain ether linkages, sulfur linkages, carboxyl groups, and carbonyl groups.
  • X, Ri, R 2 , and Ra in the above formulae may comprise substituted variants and derivatives thereof, e.g. halogen substituted, heteroatom substituted, etc. without substantially altering the function of the molecules.
  • the vinyl ether component is selected from the group consisting of 1 ,4- Butanediol divinyl ether, 1 ,4-Butanediol vinyl ether, bis-(4-vinyl oxy butyl) adipate, Ethyl- 1-propenyl ether, bis-(4-vinyl oxy butyl) isophthalate, Bis[4-(vinyloxy)butyl] succinate, Bis[4-(vinyloxy)butyl] terephthalate, Bis[[4-[(vinyloxy)methyl]cyclohexyl]methyl] isophthalate, Bis[[4-[(vinyloxy)methyl]cyclohexyl]methyl] glutarate, Tris(4- vinyloxybutyl)trimellitate, VEctomerTM 2020 (CAS no. 143477-70-7), and combinations thereof.
  • the accelerator component comprising the at least one vinyl ether functional group greatly accelerates the rate of cationic polymerization.
  • the accelerator component may be present in 5-98% w/w of the total composition, for example 5-50% w/w of the total composition, desirably from 5-30% w/w of the total composition.
  • the metal salt of the composition comprises a transition metal cation. Suitable metals include silver, copper and combinations thereof. The metal salt may be substituted with a ligand.
  • the metal salt counterions may be chosen from the group consisting Of CIO 4 “ , BF 4 “ , PF 6 “ , SbF 6 “ ,AsF 6 “ , (C 6 F 5 ) 4 B anion, (C 6 F 5 ) 4 Ga anion, Carborane anion, triflimide (trifluoromethanesulfonate) anion, bis-triflimide anion, anions based thereon and combinations thereof.
  • the metal salt counterions may be chosen from the group consisting Of CIO 4 “ , BF 4 " , PF 6 “ , SbF 6 “ and combinations thereof.
  • the solubility of the metal salt may be modified by changing the counterion, the addition and/or substitution of ligands to the metal of the metal salt and combinations thereof. This will allow for efficient electron transfer between the surface and the metal salt to be observed as appropriate solubility is achieved.
  • the cationically curable component desirably has at least one functional group selected from the group consisting of epoxy, vinyl, oxetane, thioxetane, episulfide, tetrahydrofuran, oxazoline, oxazine, lactone, trioxane, dioxane, styrene with combinations thereof also being embraced by the present invention. Further desirably, the cationically curable component has at least one functional group selected from the group consisting of epoxy, episulfide, oxetane, thioxetane, and combinations thereof.
  • the cationically curable component has at least one functional group selected from the group consisting of epoxy, oxetane and combinations thereof.
  • the surfaces to which the compositions of the present invention are applied may comprise a metal, metal oxide or metal alloy.
  • the surface may comprise a metal or metal oxide.
  • the surface may comprise a metal.
  • Suitable surfaces can be selected from the group consisting of iron, steel, mild steel, gritblasted mild steel, aluminium, aluminium oxide, copper, zinc, zinc oxide, zinc bichromate, and stainless steel. References to aluminium and aluminium oxide include alclad aluminium (low copper content), and oxide removed alclad aluminium (low copper content) respectively.
  • the surface can be selected from the group consisting of steel and aluminium.
  • Metal salts suitable for use in compositions for curing on steel or aluminium surfaces may be chosen from the group consisting of silver salts, copper salts and combinations thereof, and wherein the counterions of the silver and copper salts may be chosen from the group consisting of CIO 4 " , BF 4 " , PF 6 “ , SbF 6 " and combinations thereof.
  • the RedOx cationic systems discussed herein do not require any additional reducing agent. They are stable until applied to a substrate which is capable of participating in a RedOx reaction, thus fulfilling the role of a conventional reducing agent component.
  • the compositions of the present invention can thus be utilized in any application in which curing on a metal surface is required.
  • the compositions of the invention are storage stable even as a one-part composition and require no special packaging unlike prior art compositions, which tend to be multi-component compositions.
  • the compositions of the present invention do not require an additional catalyst for efficient curing.
  • the present invention utilizes appropriate selection of the initiator component relative to the surface on which the composition is to be applied and cured.
  • compositions according to the invention may optionally comprise a catalyst to effect electron transfer between the surface and the metal salt of the composition. This may be useful where even greater cure speeds are required. Suitable catalysts include transition metal salts.
  • inventive compositions described herein will generally be useful as adhesives, sealants or coatings, and can be used in a wide range of industrial applications including metal bonding, thread-locking, flange sealing, and structural bonding amongst others.
  • inventive compositions may be encapsulated if it is desired to do so. Suitable encapsulation techniques comprise, but are not limited to, coacervation, softgel and co-extrusion.
  • the inventive compositions may be used in a pre-applied format.
  • pre-applied is to be construed as taking the material in an encapsulated form (typically but not necessarily micro-encapsulated) and dispersing said capsules in a liquid binder system that can be dried (e.g. thermal removal of water or an organic solvent, or by photo-curing the binder) on the desired substrate.
  • a film of material remains which contains the curable composition (for example adhesive liquid for example in the form of filled capsules).
  • the curable composition can be released for cure by physically rupturing the material (for example capsules) when the user wishes to activate the composition, e.g. in pre-applied threadlocking adhesives the coated screw threaded part is activated by screwing together with its reciprocally threaded part for example a threaded receiver or nut.
  • the invention further extends to a process for bonding two substrates together comprising the steps of:
  • both substrates comprise a metal.
  • the composition of the invention may comprise more than one type of metal salt.
  • the invention also provides for curable compositions wherein the inclusion of more than one type of metal salt can be used to bond different metal substrates together.
  • the metal of the metal salt of the inventive compositions of the present invention is lower in the reactivity series than the metal surface on which it is to be cured.
  • Metallic substrates can also be bonded to non-metallic substrates. For instance mild steel may be bonded to e-coated steel (e-coat is an organic paint which is electrodeposited, with an electrical current, to a metallic surface, such as steel).
  • the inventive compositions of the present invention can be utilised to form (polymeric) coatings on parts, for example on metallic parts.
  • the invention also relates to a pack comprising: a) a container; and b) a cationically curable composition, comprising an accelerator species comprising at least one vinyl ether functional group; wherein the container may be air permeable. Alternatively, the container may not air permeable.
  • the present invention provides for a composition for and a method of coating surfaces. It is envisaged that cross-linking and cure can be achieved directly on the surface, thus eliminating the necessity for an additional baking step.
  • the coating method will allow coating of inside of surfaces, for example surfaces that can exhibit a Faraday Cage effect preventing coating inside tubes, etc.
  • the invention provides a stable one-part cationically curable coating composition for coating a surface comprising:
  • an initiator component comprising at least one metal salt; wherein the standard reduction potential of the initiator component is greater than the standard reduction potential of the surface, and wherein when the composition is placed in contact with the surface, the metal salt of the initiator component of the composition is reduced at the surface, thereby initiating cure of the cationically curable component of the composition.
  • References to standard reduction potentials in this specification indicate the tendency of a species to acquire electrons and thereby be reduced. Standard reduction potentials are measured under standard conditions: 25 0 C, 1 M concentration, a pressure of 1 atm and elements in their pure state.
  • the metal salt of the cationically curable coating composition comprises a transition metal cation.
  • Suitable metals include silver, copper and combinations thereof.
  • the metal salt may be substituted with a ligand.
  • the metal salt counterions may be chosen from the group consisting Of CIO 4 " , BF 4 " , PF 6 “ , SbF 6 “ ,AsF 6 “ , (C 6 F 5 ) 4 B anion, (CeFs) 4 Ga anion, Carborane anion, triflimide (trifluoromethanesulfonate) anion, bis-triflimide anion, anions based thereon and combinations thereof.
  • the metal salt counterions may be chosen from the group consisting of CIO 4 " , BF 4 " , PF 6 “ , SbF 6 “ and combinations thereof.
  • the cationically curable component of the coating composition desirably has at least one functional group selected from the group consisting of epoxy, vinyl, vinyl ether, oxetane, thioxetane, episulfide, tetrahydrofuran, oxazoline, oxazine, lactone, trioxane, dioxane, styrene with combinations thereof also being embraced by the present invention.
  • the cationically curable component has at least one functional group selected from the group consisting of vinyl ether, epoxy, oxetane, thioxetane, episulfide and combinations thereof.
  • the cationically curable component has at least one functional group selected from the group consisting of vinyl ether, epoxy, oxetane and combinations thereof.
  • the cationically curable component will comprise a vinyl ether and a least one other cationically curable component selected from the group consisting of epoxy, vinyl, oxetane, thioxetane, episulfide, tetrahydrofuran, oxazoline, oxazine, lactone, trioxane, dioxane, styrene and combinations thereof.
  • the vinyl ether functional group and the at least one other cationically curable functional group may be on the same molecule/monomer.
  • the cationically curable coating compositions of the present invention may optionally contain fillers, dyes, pigments, and lubricating elements.
  • the cationically curable monomer may be adapted to be provide curable hydrophobic monomers, bifunctional monomers and secondarily curable components, including vulcanising agents, curatives, etc.
  • Modification of the curable monomer can be utilised to modulate the properties of the deposited film, facilitating the control of: surface tension and polarity, lubriciousness, tacticity, colour hardness, scratch resistance, surface reactivity to subsequent coatings and or adhesives, and reactivity towards light, heat, moisture to promote further reaction within the surface deposited film itself or between the surface deposited film and a material in contact with same.
  • the solubility of the metal salt in the cationically curable coating compositions may be modified by changing the counterion, the addition and/or substitution of ligands to the metal of the metal salt and combinations thereof. This will allow for efficient electron transfer between the surface and the metal salt to be observed as appropriate solubility is achieved.
  • the surfaces to which the coating compositions of the present invention are applied may comprise a metal, metal oxide or metal alloy. Further desirably, the surface may comprise a metal or metal oxide. Preferably, the surface may comprise a metal. Suitable surfaces can be selected from the group consisting of iron, steel, mild steel, gritblasted mild steel, aluminium, aluminium oxide, copper, zinc, zinc oxide, zinc bichromate, and stainless steel. References to aluminium and aluminium oxide include alclad aluminium (low copper content), and oxide removed alclad aluminium (low copper content) respectively. Desirably, the surface can be selected from the group consisting of steel and aluminium.
  • Metal salts suitable for use in cationic coating compositions for coating on steel or aluminium surfaces may be chosen from the group consisting of silver salts, copper salts and combinations thereof, and wherein the counterions of the silver and copper salts may be chosen from the group consisting of CICU “ , BF 4 " , PF 6 “ , SbF 6 " and combinations thereof.
  • the metal of the metal salt of the inventive coating compositions of the present invention is lower in the reactivity series than the metal surface on which it is to be cured.
  • the inventive compositions of the present invention allow for coating on a number of different metal surfaces.
  • the curable component can be functionalized to confer desirable properties on the polymerised film.
  • the monomer can be modified to control the following characteristics of the coatings; surface tension and polarity, lubriciousness, tacticity, colour hardness, scratch resistance, and reactivity to subsequent coatings and/or adhesives.
  • the functionalized coating could be subjected to stimuli such as light, heat, moisture, etc. to encourage further reaction within the surface deposited coating itself or between the surface deposited coating and a material in contact with same.
  • a cationically curable monomer functionalized with a radically curable monomer to create a dual curable system a cationically curable monomer functionalized with secondary curable components, including vulcanising agents, curatives, etc., a coating functionalized for control of surface tension and polarity, lubriciousness, tacticity, colour hardness, scratch resistance, reactivity to subsequent coatings and/or adhesives, reactivity towards light, heat, moisture, etc. to promote further reaction within the surface deposited film itself or between the surface deposited film and a material in contact with same.
  • the RedOx cationically curable coating compositions discussed herein do not require any additional reducing agent. They are stable until contacted with a metallic substrate which is capable of participating in a RedOx reaction (or other surface capable of participating in a RedOx reaction), thus fulfilling the role of a conventional reducing agent component.
  • the RedOx cationically curable coating compositions of the invention are storage stable as a one-part composition and require no special packaging unlike prior art compositions, which tend to be multi-component compositions.
  • the coating compositions of the present invention do not require an additional catalyst for efficient curing. The present invention utilizes appropriate selection of the metal salt component relative to the surface on which the coating composition is to be applied and cured.
  • coating compositions according to the invention may optionally comprise a catalyst to effect electron transfer between the surface and the metal salt of the composition. This may be useful where even greater cure speeds are required. Suitable catalysts include transition metal salts. [0068] The kinetics of polymerisation/film formation is proportional to the difference in standard reduction potential between the surface and the metal salt in the composition. Cross-linking is achieved directly on the surface. However, it will be appreciated that a post polymerisation baking step can be applied.
  • the invention further extends to a method of coating a substrate comprising applying a coating composition comprising: i) a cationically curable component; and ii) an initiator component comprising at least one metal salt; to the substrate, wherein the standard reduction potential of the initiator component is greater than the standard reduction potential of the surface.
  • the method of coating a substrate may further comprise the steps of: i) cleaning the substrate prior to application of the coating composition; ii) dipping the substrate into said coating composition of the present invention or an emulsion of said coating composition; and iii) rinsing the coated substrate when polymerisation is complete.
  • the step of cleaning the substrate may comprise washing with acid, base, detergent, aqueous solutions, water, deionised water, organic solvents and combinations thereof.
  • the emulsion of the coating composition of the present invention, referred to in step (ii) may comprise an aqueous or an organic emulsion.
  • the step of rinsing the coated substrate may comprise rinsing with water and/or rinsing with a rinsing solution beneficial to the properties of the coating/film.
  • the invention also relates to a pack comprising: a) a container; and b) a cationically curable coating composition according to the present invention.
  • the container may be air permeable. Alternatively, the container may not air permeable.
  • the invention further extends to a coating applied to a substrate utilising the methods discussed above.
  • the substrate may be metallic.
  • the invention extends to a coated article comprising a coating applied to a substrate utilising the methods discussed above.
  • the substrate may be metallic.
  • the invention further provides for a coated article comprising a coating applied to a substrate.
  • the substrate may comprise a metallic component.
  • the coated article may have a curable composition applied thereto. Thus, facilitating mating with a second substrate.
  • the coated article may have a second substrate adhered thereto.
  • the metal salt in the compositions of the present invention will be chosen such that the anion of the metal salt will not result in quenching of the polymerization/cure process.
  • Figure 1 is a plot of the Exotherm of Polymerisation of a two-part system comprising the RedOx couple ascorbyl- ⁇ -palmitateidiphenyliodonium hexafluorophosphate in an epoxy resin as a function of time (in days) at a temperature of
  • Figure 2 is a FTIR-ATR spectra (3100 cm “1 to 600 cm “1 ) of surface promoted epoxy polymerisation on grit blasted mild steel at 25 ° C.
  • Figure 3 is a FTIR-ATR spectra (1 190 cm “1 to 760 cm “1 ) of surface promoted epoxy polymerisation on grit blasted mild steel at 25 ° C.
  • Figure 4 is a plot of percentage polymerisation versus time for the cationically curable coating composition depicted in Figures 2 and 3.
  • the Ascorbyl-6-hexadecanoate Diphenyliodonium Hexafluorophosphate was the least stable and not usable in a reliable two-component configuration. Polymerization did not occur without copper primer being applied to the substrate. All other possible redox couples based upon this and alternative onium-type salts were ineffective as surface curing adhesives even when the substrate was primed with copper.
  • Crivello's paper Crivello, J.V.; Lee, J. L.; J. Polym. Sci. Part A: PoIm. Chem.
  • Figure 1 is a graphical representation of the stability of a two-part system comprising the Ascorbyl-6-palmitate:Diphenyliodonium Hexafluorophosphate redox couple in the epoxy resin Cyracure 6110, monitored by the Exotherm of Polymerisation of 10 g samples.
  • the stability of the composition was evaluated by measuring the Exotherm of Polymerisation of 10 g samples of the above two-part system stored over varying periods of time.
  • the graph clearly shows an inverse relationship between heat liberated and the number of days the system was stored prior to use. After 112 days a significant reduction in the measured exotherm of polymerisation was observable indicating considerably reduced reactivity of the composition. Additionally, there was a significant increase in the formulation viscosity so the formulation was difficult to dispense and work with.
  • the electrochemical series is a measure of the oxidising and reducing power of a substance based on its standard potential.
  • the standard potential of a substance is measure relative to the hydrogen electrode.
  • a metal with a negative standard (reduction) potential has a thermodynamic tendency to reduce hydrogen ions in solution, whereas the ions of a metal with a positive standard potential have a tendency to be reduced by hydrogen gas.
  • the reactivity series shown in Scheme 4 (below), is an extension of the electrochemical series.
  • Tension testing machine equipped with a suitable load cell.
  • Lap-shear specimens as specified in the quality specification, product or test program.
  • Specimen surface was prepared where necessary, e.g. mild steel lap-shears are grit blasted with silicon carbide.
  • Test specimens were cleaned by wiping with acetone or isopropanol before assembly.
  • Bond area on each lap-shear was 322.6 mm 2 or 0.5 in 2 . This is marked before applying the adhesive sample.
  • test specimen was placed in the grips of the testing machine so that the outer 25.4 mm (1 in.) of each end were grasped by the jaws.
  • the long axis of the test specimen coincided with the direction of the applied tensile force through the centre line of the grip assembly.
  • the assembly was tested at a crosshead speed of 2.0 mm/min or 0.05 in./min, unless otherwise specified.
  • Identification of the adhesive including name or number, and lot number.
  • Test Conditions Standard Temperature and Pressure, i.e. Room temperature.
  • Aluminium Alclad - Low Copper: 2.0 N/mm 2
  • Diphenyliodonium PF 6 (0.2Og, 0.43mmol) was dissolved in the cycloaliphatic diepoxide monomer Cyracure 6110, 3,4-epoxycyclohexylmethy-3,4- epoxycyclohexane carboxylate, (8.Og) and the accelerator 1 ,4-Butanediol divinyl ether (2.Og). Adhesive performance following 24 hr at 25 0 C on:
  • Typical Cationic Formulation a. 3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate (77.6%); b. 1 ,4-Butanediol-Divinyl Ether (20%); and c. Silver(1 ,5-Cyclooctadiene) Hexafluoroantimonate (2.4%) [0092] It will be appreciated by a person skilled in the art that the above coating formulation is only a representative formulation given for the purpose of example. The coating formulation can be modified in terms of monomer, metal salt, concentration, etc. suitable to the end use of the coating formulation.
  • Metal substrates (10 x 2.5 cm) were cleaned by wiping with acetone and dipped into the formulations.
  • the metal substrates were submerged in the baths containing the formulations.
  • the duration of immersion was proportional to the difference in standard potential between the surface and the metal salt in the composition, and the thickness of the desired coating - if required to be less than the self-limiting thickness.
  • coating/polymerisation was complete, residual monomer was removed by washing.
  • the films formed were analysed by FTIR-ATR.
  • Figure 2 is a FTIR-ATR spectra of surface promoted epoxide coating on grit blasted mild steel at 25 ° C.
  • the epoxide monomer has a characteristic IR stretch at 700 cm "1 .
  • the desired polyether coating has a characteristic IR stretch at 1080 cm “1 . Iterative scanning of the sample over intervals of 10 mins illustrates increasing polyether concentration over time, substantiating the formation of a polymeric coating on the surface of the grit blasted mild steel.
  • the coating composition comprises Cyracure 6110 (3,4-Epoxycyclohexylmethyl-3,4-Epoxycyclohexane Carboxylate) (8.Og), 1 ,4- Butanediodivinyl Ether (2.Og) and [Ag(1 ,5-Cyclooctadiene) 2 ] SbF 6 (0.25 mmol) using Grit Blasted Mild Steel as the Substrate at 20 0 C.
  • the extent of polymerisation was determined utilising FTIR-ATR as per Figures 1 and 2 (vide supra).
  • the change in peak intensity in the spectrum over time at 1080 cm "1 is indicative of polyether formation, and thus polymerisation.
  • the plot illustrates that the initial rate of polymerisation is quick and linear up to approximately 30 mins, whereupon the onset of a plateau is gradually observed.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polymerization Catalysts (AREA)
  • Epoxy Resins (AREA)

Abstract

La présente invention concerne des compositions cationiquement durcissables pour le durcissement sur une surface comprenant un composant cationiquement durcissable, et un composant initiateur pouvant initier le durcissement du composant cationiquement durcissable. L'initiateur comprend au moins un sel métallique, qui est choisi de sorte qu'il est réduit au niveau de la surface, le potentiel de réduction standard du composant initiateur étant supérieur au potentiel de réduction standard de la surface, et en outre, lorsque la composition est placée en contact avec la surface, le sel métallique du composant initiateur de la composition est réduit au niveau de la surface, initiant ainsi le durcissement du composant cationiquement durcissable de la composition. Aucun composant catalytique n'est requis dans la composition pour un durcissement efficace.
PCT/EP2009/056257 2008-05-23 2009-05-22 Durcissement favorisé en surface de compositions monocomposant cationiquement durcissables WO2009141444A1 (fr)

Priority Applications (3)

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CN2009801260944A CN102083918A (zh) 2008-05-23 2009-05-22 单部分阳离子可固化组合物的表面促进固化
JP2011510001A JP2011523670A (ja) 2008-05-23 2009-05-22 一液型カチオン硬化性組成物の表面促進型硬化
EP09749934A EP2288665A1 (fr) 2008-05-23 2009-05-22 Durcissement favorisé en surface de compositions monocomposant cationiquement durcissables

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010077606A1 (fr) * 2008-12-08 2010-07-08 Rensselaer Polytechnic Institute Polymérisation cationique initiée par redox utilisant des agents réducteurs à l'état de vapeur
WO2010094634A1 (fr) * 2009-02-17 2010-08-26 Loctite (R & D) Limited Compositions pouvant durcir par voie cationique et amorce correspondante

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2366484A1 (fr) * 2010-03-18 2011-09-21 Siemens Aktiengesellschaft Procédé de brasage d'une surface de substrat métallique
JP6708382B2 (ja) * 2015-09-03 2020-06-10 サンアプロ株式会社 硬化性組成物及びそれを用いた硬化体
KR20230135563A (ko) * 2021-02-04 2023-09-25 세키스이가가쿠 고교가부시키가이샤 전자 디바이스용 광경화성 수지 조성물

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Publication number Priority date Publication date Assignee Title
US4717440A (en) * 1986-01-22 1988-01-05 Loctite Corporation Compositions curable by in situ generation of cations
US5004842A (en) * 1990-06-25 1991-04-02 Loctite Corporation Aromatic vinyl ether compounds and compositions, and method of making the same
JPH04120182A (ja) * 1990-09-10 1992-04-21 Nippon Kayaku Co Ltd 光ディスク用オーバーコート剤及びその硬化物
US6552140B1 (en) * 1998-09-17 2003-04-22 Loctite (R&D) Limited Auto-oxidation systems for air-activatable polymerisable compositions
EP1757633A1 (fr) * 1998-12-31 2007-02-28 3M Innovative Properties Company Accelerateurs utiles pour des compositions polymérisables par énergie

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4717440A (en) * 1986-01-22 1988-01-05 Loctite Corporation Compositions curable by in situ generation of cations
US5004842A (en) * 1990-06-25 1991-04-02 Loctite Corporation Aromatic vinyl ether compounds and compositions, and method of making the same
JPH04120182A (ja) * 1990-09-10 1992-04-21 Nippon Kayaku Co Ltd 光ディスク用オーバーコート剤及びその硬化物
US6552140B1 (en) * 1998-09-17 2003-04-22 Loctite (R&D) Limited Auto-oxidation systems for air-activatable polymerisable compositions
EP1757633A1 (fr) * 1998-12-31 2007-02-28 3M Innovative Properties Company Accelerateurs utiles pour des compositions polymérisables par énergie

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010077606A1 (fr) * 2008-12-08 2010-07-08 Rensselaer Polytechnic Institute Polymérisation cationique initiée par redox utilisant des agents réducteurs à l'état de vapeur
WO2010094634A1 (fr) * 2009-02-17 2010-08-26 Loctite (R & D) Limited Compositions pouvant durcir par voie cationique et amorce correspondante
US8614006B2 (en) 2009-02-17 2013-12-24 Henkel Ireland Limited Cationically curable compositions and a primer therefor

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CN102083918A (zh) 2011-06-01
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KR20110021917A (ko) 2011-03-04

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