KR20110021917A - Surface-promoted cure of one-part cationically curable compositions - Google Patents

Abstract

The present invention relates to a cation curable composition for curing on a surface comprising a cation curable component and an initiator component capable of initiating curing of the cation curable component. The initiator includes one or more metal salts selected to be reduced at the surface, where the standard reduction potential of the initiator component is higher than the standard reduction potential of the surface, and upon contacting the composition with the surface, the metal salt of the initiator component of the composition is reduced at the surface And curing of the cation curable composition of the present invention. No catalytic component is needed in the composition for efficient curing.

Description

SURFACE-PROMOTED CURE OF ONE-PART CATIONICALLY CURABLE COMPOSITIONS

The present invention relates to stable one-part cationically curable compositions for curing on surfaces, and uses thereof.

Oxidation-Reduction Cationic Polymerization

Redox cationic polymerizations include oxidation and reduction processes (Holtzclaw, HF; Robinson, WR; Odom, JD; General Chemistry 1991, 9 ^th Ed., Heath (Pub.), P. 44). When a free atom, or a valence in a molecule or ion, loses an electron or electrons, it is oxidized and its oxidation number increases. When a free atom, or a valence in a molecule or ion, gets electrons or electrons, it is reduced and its oxidation number decreases. Oxidation and reduction always happen simultaneously, as if one atom had electrons, another atom had to provide electrons and be oxidized. In a redox pair, one species acts as a reducing agent and the other species acts as an oxidant. When a redox reaction occurs, the reducing agent gives or donates electrons to another reactant to reduce this reactant. Thus, the reducing agent itself is oxidized because it loses electrons. The oxidant accepts or gains electrons and itself is reduced while allowing the reducing agent to oxidize. Comparing the relative oxidation or reduction strengths of the two reagents in the redox pair, one can determine which is the reducing agent and which is the oxidant. The strength of the oxidant or reducing agent can be determined from its standard reduction potential (E _red ⁰ ) or standard oxidation potential (E _ox ⁰ ).

Onium salts have been widely used in cationically curable formulations. Through extensive research on the use of onium salts as photoinitiators for cationic polymerization, it has been found that onium cations undergo photochemical reduction during photochemical reactions. In particular, diaryliodonium salts have been used in cationically curable formulations. Extensive studies on the use of the diaryliodonium salt of formula 1 as photoinitiator for cationic polymerization have shown that during photochemical reactions iodine is reduced from +3 oxidation water to +1 oxidation water.

[Formula 1]

Crivello et al. Reported that radical intermediates are liberated due to the action of light on diaryliodonium salts (JVCrivello and JHWLam, J. Polym. Sci. 1981, 19, 539-548). See 1. The resulting cascade reaction reduces the oxidation number of iodine in the diaryliodonium salt. Aryliode cationic radicals generated during the photolysis process are extremely reactive species and react with solvents, monomers or impurities (SH in the scheme) to produce protic acids. The protic acid also reacts with the cationically curable monomer resulting in polymerization.

<Scheme 1>

Diaryliodonium salts as initiators of cationic polymerization via redox type chemistry have been the subject of research. A general premise here is that, in the presence of a chemical reducing agent, as shown in Scheme 2 below, the iodine component of the diaryliodonium salt can be reduced resulting in the production of HX, a protic acid species, thereby also cationic Polymerization is initiated.

<Scheme 2>

Crivelo and colleagues described ascorbic acid (JVCrivello and JHWLam, J.Polym. Sci. 1981, 19, 539-548), and benzoin (JVCrivello and JLLee, J.Polym.Sci. 1983). , 21, 1097-1110), and diaryliodonium salt / reducing agent pairs with tin (JVCrivello and JLLee, Makromol. Chem. 1983, 184, 463-473). Direct reduction of the iodonium salt (onium salt) by the reducing agent is inefficient. Therefore, in order to achieve efficient polymerization, it is necessary to introduce a copper catalyst. Thus, these redox cationic initiation packages are in fact three-component (salt, reducing agent and catalyst) systems.

Thus, such Krivelo redox systems have the disadvantage that the direct reduction of the "onium" salt by the reducing agent is very inefficient. Copper salts were required for efficient electron transfer. However, even in the absence of a catalyst, very slow electron transfer between the reducing agent and the onium salt can be observed, so that a composition having a reducing agent and an onium salt together in one composition is unsuitable for long term storage. Thus, there is still an unmet need for suitable curable formulations that provide an alternative to the conventional onium formulations described above.

<Lewis acid metal salt as initiator for cationic polymerization>

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 act via direct initiation of monomers (Scheme 3) (Collomb, J .; Gandini, A .; Cheradamme, H .; Macromol. Chem. Rapid Commun. 1980, 1, 489 -491]). The stronger the Lewis acid is, the more pronounced its onset is.

<Scheme 3>

Not all Lewis acid metal salts react with cationic polymerizable monomers. Many Lewis acid metal salts can be formulated as starting components in storage stable one-component cationically polymerizable systems (Castell, P. et al., Polymer 2000, 41 (24), 8465-8474). In this case, the decomposition of the initiator and the activation of the polymerization are typically achieved by thermal or electromagnetic radiation curing processes (Castell, P. et al .; Polymer 2000, 41 (24), 8465-8474).

Thus, there is still an unmet need for suitable curable formulations that provide an alternative to the conventional Lewis acid metal salt formulations described above that are cured in the absence of thermal or electromagnetic radiation curing processes.

<Existing coating technology>

E-coating (electrocoating / deposition coating) is a painting method that uses a current to deposit paint. This process works on the principle of "Opposites Attract". This process is also known as electrodeposition. The fundamental physical principle of an electrocoat is that materials with opposite charges attract each other. The electrocoat system applies a DC charge to the metal parts impregnated in the bath of paint particles with opposite charges. Paint particles are attracted onto the metal part and paint is deposited on the part, forming a uniform and continuous film across all surfaces, at all gaps and edges, until the electrocoat reaches the desired thickness. At this thickness, the film insulates the part, so the attraction is stopped and the electrocoat process is complete. Depending on the polarity of the charge, the electron coat is classified as bipolar or negative. The main disadvantage of this technique is that it cannot coat inner metal tubes or the like because of the Faraday Cage effect. The material needs to be calcined in order to crosslink and cure the paint film.

The present invention aims to use redox chemistry as an alternative coating technique.

Summary of the Invention

In one aspect, the present invention

(i) a cation curable component; And

(ii) an initiator component comprising at least one metal salt,

The standard reduction potential of the initiator component is greater than the standard reduction potential of the surface,

When the composition is contacted with the surface, the metal salt of the initiator component of the composition is reduced at the surface, thereby initiating curing of the cationically curable component of the composition,

A stable one part cation curable composition for curing on the surface is provided.

In the present specification, the standard reduction potential refers to a tendency for a species to be reduced by obtaining electrons. The standard reduction potential is measured at standard conditions (25 ° C., 1 M concentration, 1 atm pressure and pure element).

Preferably, the metal salt of the composition comprises a transition metal cation. Suitable metals include silver, copper and combinations thereof. Metal salts may be substituted by ligands. Metal counter ion is ClO ₄ ^- _{yi, (C 6 F 5) 4} B _{anions, (C 6 F 5) 4} Ga anion, carboxylic borane anion, a triple ^{_{-, BF 4 -, PF 6}} -, SbF 6 -, AsF 6 Mid (trifluoromethanesulfonate) anions, bis-triflimide anions, anions based on them, and combinations thereof. More preferably, the metal salt as a counter ion is ClO ₄ ^-, and may be selected from the group consisting of ^{_{-, BF 4 -, PF 6}} -, SbF 6.

The solubility of the metal salts can be controlled by changing the counter ions, adding and / or substituting ligands to the metals of the metal salts, or a combination thereof. This will allow for efficient electron transfer between the surface and the metal salt because proper solubility is achieved.

The cationically curable component is preferably epoxy, vinyl, oxetane, thioxetane, episulfide, tetrahydrofuran, oxazoline, oxazine, lactone, trioxane, dioxane, styrene, and those also included in the present invention. Has at least one functional group selected from the group consisting of Further preferably, the cationically curable component has at least one functional group selected from the group consisting of epoxy, episulfide, oxetane, thioxetane and combinations thereof. Preferably, the cationically curable component has one or more functional groups selected from the group consisting of epoxy, oxetane and combinations thereof.

Preferably, the surface to which the composition of the present invention is applied may comprise a metal, a metal oxide or a metal alloy. Further preferably, the surface may comprise a metal or a metal oxide. Preferably, the surface may comprise a metal. Suitable surfaces can be selected from the group consisting of iron, steel, mild steel, grit blasted mild steel, aluminum, aluminum oxide, copper, zinc, zinc oxide, zinc dichromate and stainless steel. Aluminum and aluminum oxide include alclad aluminum (low copper content), and oxide removed alclad aluminum (low copper content), respectively. Preferably, the surface may be selected from the group consisting of steel and aluminum. Suitable metal salts for use in the composition that is cured on steel or aluminum surfaces may be selected from the group consisting of silver salts, copper salts, and combinations thereof, silver and copper salt counter ion is _{^{ClO 4 -, BF 4 -,}} PF 6 - , SbF ₆ ^- and combinations thereof.

In general, the compositions of the present invention disclosed herein can be cured on oxidized metal surfaces without the need for additional etchants or oxide removers. However, the composition of the present invention may optionally include an oxide remover. For example, if an etchant or oxide scavenger, such as including chloride ions and / or zinc (II) salts, is included in the formulations of the present invention, etching of any oxide layer may be allowed. This also exposes the metal below it (zero oxidation number), which is then active enough to allow reduction of the transition metal salt.

Redox cationic systems discussed herein do not require any additional reducing agent. It is stable until applied to a substrate that may be involved in the redox reaction, and thus serves as a conventional reducing agent component. Thus, the compositions of the present invention can be used in any application where curing on metal surfaces is desired. The compositions of the present invention, even as one-component compositions, are storage stable and do not require any special packaging unlike prior art compositions which tend to be multicomponent compositions.

The compositions of the present invention do not require additional catalysts for efficient curing. In the present invention, the initiator component is appropriately selected according to the surface to which the composition is applied and cured. Thus, surface-promoted redox chemistry can be used to initiate curing of the cationically curable composition. However, it will be appreciated that the compositions according to the invention may optionally comprise a catalyst which achieves electron transfer between the surface and the metal salt of the composition. This may be useful when faster curing rates are required. Suitable catalysts include transition metal salts.

The compositions of the present invention described herein will generally be useful as adhesives, sealants or coatings, and in particular will be used in a wide range of industrial applications, including metal bonding, thread-locking, flange sealing, and structural bonding. Can be.

The composition of the present invention may be encapsulated when it is desired to be encapsulated. Suitable encapsulation techniques include, but are not limited to, coacervation, softgels, and co-extrusion.

Alternatively, the compositions of the present invention can be used in pre-coated form. The term "pre-application" makes a material in an encapsulated form (typically in micro-encapsulated form, but not necessarily), and makes the capsule on a desired substrate (eg, water or organic solvents). By thermal removal, or by photocuring of the binder). A film of material is obtained that contains a curable composition (eg, in the form of a filled capsule, for example an adhesive liquid). If the user wants to activate the composition, the curable composition can be released for curing by physically blasting the material (eg a capsule), for example in a pre-coated screw-fastening adhesive, a coated thread The component having the thread is twisted together with the components having mutual threads, for example the receiver or nut having the thread, and activated.

The present invention

i) a cation curable component; And ii) applying a composition comprising at least one metal to an at least one substrate; And

(ii) mating the first substrate and the second substrate to form a bond with the composition

Including,

The standard reduction potential of the initiator component is greater than the standard reduction potential of one or more substrates,

It further extends to the process of joining the two substrates together.

In one particular embodiment, both substrates comprise a metal. If the second substrate comprises a metal substrate different from the first metal substrate, the composition of the present invention may comprise more than one type of metal salt. Thus, the present invention also provides curable compositions that may include more than one type of metal salt to bond different metal substrates together.

Preferably, the metal of the metal salt of the composition of the present invention has a lower reactivity in the reactive sequence than the metal surface on which the composition is cured.

The metallic substrate may be bonded to the non-metallic substrate. For example, mild steel can be bonded to e-coated steel (e-coat is an organic paint that is electrodeposited to a metallic surface such as steel using an electrical current).

Moreover, the compositions of the present invention can be used to form (polymeric) coatings on parts such as metallic parts.

The invention also

a) a container that can be air permeable; And

b) cationic curable compositions according to the invention

It is related to a pack containing. Alternatively, the container may not be air permeable.

In a further aspect, the present invention

(i) a cation curable component;

(ii) an accelerator species comprising at least one vinyl ether functional group; And

(iii) an initiator component comprising at least one metal salt

Including,

The standard reduction potential of the initiator component is greater than the standard reduction potential of the surface,

When the composition is contacted with the surface, the metal salt of the initiator component of the composition is reduced at the surface, thereby initiating curing of the cationically curable component of the composition,

A stable one-part cation curable composition for curing on the surface is provided.

In the present specification, the standard reduction potential refers to a tendency for a species to be reduced by obtaining electrons. The standard reduction potential is measured at standard conditions (25 ° C., 1 M concentration, 1 atm pressure and pure element).

Accelerator species comprising at least one vinyl ether functional group greatly improve the rate of cure. Accelerator species may have the following structure:

Wherein m may be 0 or 1;

n can be 0 to 5;

R ₁ , R ₂ and R ₃ may be the same or different and consist of hydrogen, a C ₁ -C ₂₀ alkyl chain (linear, branched or cyclic) and a C ₅ -C ₂₀ aryl moiety, and combinations thereof Can be selected from;

X can be a C ₁ -C ₃₀ saturated or unsaturated, cyclic or acyclic moiety;

R ₁ , R ₂ , R ₃ and X may independently contain or may not contain ether bonds, sulfur bonds, carboxyl groups and carbonyl groups.

Those skilled in the art, X, R ₁ , R ₂ and R ₃ in the above formulas are substituted variants and derivatives thereof, such as halogen substituted, and heteroatoms, in which the functionality of the molecule is not significantly altered. It will be appreciated that it may include substituted variations, derivatives, and the like.

Preferably, the vinyl ether component is 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, Vectomer (trade name) 2020 (CAS No. 143477-70 -7) and combinations thereof.

Accelerator components comprising at least one vinyl ether functional group significantly accelerate the cationic polymerization rate. The accelerator component may be present at 5 to 98% w / w of the total composition, for example 5 to 50% w / w of the total composition, preferably 5 to 30% w / w of the total composition.

Preferably, the metal salt of the composition comprises a transition metal cation. Suitable metals include silver, copper and combinations thereof. Metal salts may be substituted by ligands. Metal counter ion is ClO ₄ ^- _{yi, (C 6 F 5) 4} B _{anions, (C 6 F 5) 4} Ga anion, carboxylic borane anion, a triple ^{_{-, BF 4 -, PF 6}} -, SbF 6 -, AsF 6 Mid (trifluoromethanesulfonate) anions, bis-triflimide anions, anions based on them, and combinations thereof. More preferably, the metal salt as a counter ion is ClO ₄ ^-, and may be selected from the group consisting of ^{_{-, BF 4 -, PF 6}} -, SbF 6.

The solubility of the metal salts can be controlled by changing the counter ions, adding and / or substituting ligands to the metals of the metal salts, or a combination thereof. This will allow for efficient electron transfer between the surface and the metal salt because proper solubility is achieved.

The cationically curable component is preferably epoxy, vinyl, oxetane, thioxetane, episulfide, tetrahydrofuran, oxazoline, oxazine, lactone, trioxane, dioxane, styrene, and those also included in the present invention. Has at least one functional group selected from the group consisting of Further preferably, the cationically curable component has at least one functional group selected from the group consisting of epoxy, episulfide, oxetane, thioxetane and combinations thereof. Preferably, the cationically curable component has one or more functional groups selected from the group consisting of epoxy, oxetane and combinations thereof.

Preferably, the surface to which the composition of the present invention is applied may comprise a metal, a metal oxide or a metal alloy. Further preferably, the surface may comprise a metal or a metal oxide. Preferably, the surface may comprise a metal. Suitable surfaces can be selected from the group consisting of iron, steel, mild steel, grit blasted mild steel, aluminum, aluminum oxide, copper, zinc, zinc oxide, zinc dichromate and stainless steel. Aluminum and aluminum oxide include alclad aluminum (low copper content) and deoxidized alclad aluminum (low copper content), respectively. Preferably, the surface may be selected from the group consisting of steel and aluminum. Suitable metal salts for use in the composition that is cured on steel or aluminum surfaces may be selected from the group consisting of silver salts, copper salts, and combinations thereof, silver and copper salt counter ion is _{^{ClO 4 -, BF 4 -,}} PF 6 - , SbF ₆ ^- and combinations thereof.

Redox cationic systems discussed herein do not require any additional reducing agent. It is stable until applied to a substrate that may be involved in the redox reaction, and thus serves as a conventional reducing agent component. Thus, the compositions of the present invention can be used in any application where curing on metal surfaces is desired. The compositions of the present invention, even as one-component compositions, are storage stable and do not require any special packaging unlike prior art compositions which tend to be multicomponent compositions.

The compositions of the present invention do not require additional catalysts for efficient curing. In the present invention, the initiator component is appropriately selected according to the surface to which the composition is applied and cured. Thus, surface-promoted redox chemistry can be used to initiate curing of the cationically curable composition. However, it will be appreciated that the compositions according to the invention may optionally comprise a catalyst which achieves electron transfer between the surface and the metal salt of the composition. This may be useful when faster curing rates are required. Suitable catalysts include transition metal salts.

The compositions of the present invention described herein will generally be useful as adhesives, sealants or coatings and can be used in a wide variety of industrial applications, particularly including metal bonds, screw-fasteners, flange seals, and structural bonds.

The composition of the present invention may be encapsulated when it is desired to be encapsulated. Suitable encapsulation techniques include, but are not limited to, coacervation, softgels, and co-extrusion.

Alternatively, the compositions of the present invention can be used in pre-coated form. The term "pre-application" makes a material in an encapsulated form (typically in micro-encapsulated form, but not necessarily), and makes the capsule on a desired substrate (eg, water or organic solvents). By thermal removal, or by photocuring of the binder). A film of material is obtained that contains a curable composition (eg, in the form of a filled capsule, for example an adhesive liquid). If the user wants to activate the composition, the curable composition can be released for curing by physically blasting the material (eg a capsule), for example in a pre-coated screw-fastening adhesive, a coated thread The component having the thread is twisted together with the components having mutual threads, for example the receiver or nut having the thread, and activated.

The present invention

i) a cation curable component; ii) an accelerator species comprising at least one vinyl ether functional group; And iii) applying to the at least one substrate a composition comprising an initiator component comprising at least one metal salt; And

(ii) mating the first substrate and the second substrate to form a bond with the composition

Including,

The standard reduction potential of the initiator component is greater than the standard reduction potential of one or more substrates,

It further extends to the process of joining the two substrates together.

In one particular embodiment, both substrates comprise a metal. If the second substrate comprises a metal substrate different from the first metal substrate, the composition of the present invention may comprise more than one type of metal salt. Thus, the present invention also provides curable compositions that may include more than one type of metal salt to bond different metal substrates together.

Preferably, the metal of the metal salt of the composition of the present invention has a lower reactivity in the reactive sequence than the metal surface on which the composition is cured.

The metallic substrate may be bonded to the non-metallic substrate. For example, mild steel can be bonded to e-coated steel (e-coat is an organic paint that is electrodeposited to a metallic surface such as steel using an electrical current).

Moreover, the compositions of the present invention can be used to form (polymeric) coatings on parts such as metallic parts.

The invention also

a) a container that can be air permeable; And

b) a curable composition comprising an accelerator species comprising at least one vinyl ether functional group

It is related to a pack containing. Alternatively, the container may not be air permeable.

In a further aspect, the present invention provides compositions and methods for coating a surface. It is conceivable to achieve crosslinking and curing directly on the surface, eliminating the need for additional calcination steps. Moreover, it is contemplated that this coating method allows for the coating of the interior of the surface, which may exhibit a Faraday cage effect that prevents coating the surface, such as inner tubes and the like.

The present invention

(i) a cation curable component;

(ii) an initiator component comprising at least one metal salt

Including,

The standard reduction potential of the initiator component is greater than the standard reduction potential of the surface,

When the composition is contacted with the surface, the metal salt of the initiator component of the composition is reduced at the surface, thereby initiating curing of the cationically curable component of the composition,

A stable one-part cation curable composition is provided for coating a surface.

In the present specification, the standard reduction potential refers to a tendency for a species to be reduced by obtaining electrons. The standard reduction potential is measured at standard conditions (25 ° C., 1 M concentration, 1 atm pressure and pure element).

Preferably the metal salt of the cationically curable coating composition comprises a transition metal cation. Suitable metals include silver, copper and combinations thereof. Metal salts may be substituted by ligands. Metal counter ion is ClO ₄ ^- _{yi, (C 6 F 5) 4} B _{anions, (C 6 F 5) 4} Ga anion, carboxylic borane anion, a triple ^{_{-, BF 4 -, PF 6}} -, SbF 6 -, AsF 6 Mid (trifluoromethanesulfonate) anions, bis-triflimide anions, anions based on them, and combinations thereof. More preferably, the metal salt as a counter ion is ClO ₄ ^-, and may be selected from the group consisting of ^{_{-, BF 4 -, PF 6}} -, SbF 6.

The cationically curable component of the coating composition is preferably epoxy, vinyl, vinyl ether, oxetane, thioxetane, episulfide, tetrahydrofuran, oxazoline, oxazine, lactone, trioxane, dioxane, styrene, and again At least one functional group selected from the group consisting of combinations thereof included in the present invention. Further preferably, 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. Preferably, the cationically curable component has one or more functional groups selected from the group consisting of vinyl ethers, epoxies, oxetane and combinations thereof.

In a preferred embodiment, the cationically curable component is vinyl ether and epoxy, vinyl, oxetane, thioxetane, episulfide, tetrahydrofuran, oxazoline, oxazine, lactone, trioxane, dioxane, styrene and their One or more other cationically curable components selected from the group consisting of combinations. Vinyl ether functional groups and one or more other cationically curable functional groups may be present on the same molecule / monomer.

It will be appreciated that the cationically curable coating composition of the present invention may optionally contain fillers, dyes, pigments and lubricating elements. Moreover, the cationically curable monomer can be modified to provide an auxiliary curable component comprising a curable hydrophobic monomer, a bifunctional monomer, and a vulcanizing agent, a curing agent and the like. Modifying the curable monomers to control the properties of the deposited film, surface tension and polarity, lubricity, adhesion, color firmness, scratch resistance, surface reactivity to subsequent coatings and / or adhesives, and within the film itself deposited on the surface It may facilitate control of reactivity to light, heat, and moisture to promote further reaction between the film deposited on or at the surface and the material in contact with it.

The solubility of the metal salts in the cationically curable coating composition can be controlled by changing the counter ions, adding and / or substituting ligands to metals of the metal salts, or a combination thereof. This will allow for efficient electron transfer between the surface and the metal salt because proper solubility is achieved.

Preferably, the surface to which the coating composition of the present invention is applied may comprise a metal, a metal oxide or a metal alloy. Further preferably, the surface may comprise a metal or a metal oxide. Preferably, the surface may comprise a metal. Suitable surfaces can be selected from the group consisting of iron, steel, mild steel, grit blasted mild steel, aluminum, aluminum oxide, copper, zinc, zinc oxide, zinc dichromate and stainless steel. Aluminum and aluminum oxide include alclad aluminum (low copper content) and deoxidized alclad aluminum (low copper content), respectively. Preferably, the surface may be selected from the group consisting of steel and aluminum.

Suitable metal salts for use in the cationic coating composition to be coated on steel or aluminum surfaces may be selected from the group consisting of silver salts, copper salts, and combinations thereof, silver and copper salt counter ion is ClO ₄ ^-, BF ₄ ^-, PF ₆ ^-, SbF ₆ ^-, and may be selected from the group consisting of.

Further preferably, the metal of the metal salt of the coating composition of the present invention has a lower reactivity in the reactive sequence than the metal surface on which the composition is cured. Thus, the compositions of the present invention allow for coating on many different metal surfaces.

All references to the term "coating" herein should be interpreted to include polymeric films or coatings on the surface. In addition, all references relating to the functionalized polymeric film or coating below apply to both crosslinked and uncrosslinked coatings.

It will be appreciated that the curable component can be functionalized to impart desired properties to the polymerized film. The monomers can be modified to control the following properties of the coating: surface tension and polarity, lubricity, tack, color firmness, scratch resistance, and reactivity to subsequent coatings and / or adhesives. Moreover, functionalized coatings can be applied to stimuli such as light, heat, moisture, etc. to facilitate further reactions within the coating itself deposited on the surface or between the coating deposited on the surface and the material in contact with it. .

For example, cationically curable monomers functionalized with radically curable monomers to form a dual curable system; Cationically curable monomers functionalized as auxiliary curable components including vulcanizing agents, curing agents, etc., surface tension and polarity, lubricity, tackiness, color tightness, scratch resistance, responsiveness to subsequent coatings and / or adhesives, and deposited on surfaces It is a coating that is functionalized to control the reactivity to light, heat, moisture, etc. to promote further reaction between the film deposited in or on the film itself and the material in contact with it.

The redox cation curable coating systems discussed herein do not require any additional reducing agent. It is stable until contact with a metallic substrate (or other surface that may be involved in the redox reaction), which may be involved in the redox reaction, thus serving as a conventional reducing agent component. The redox cation curable coating compositions of the present invention are storage stable as one-part compositions and do not require any special packaging, unlike prior art compositions which tend to be multicomponent compositions.

The coating composition of the present invention does not require additional catalyst for efficient curing. In the present invention, the metal salt component is appropriately selected according to the surface to which the coating composition is applied and cured. However, it will be appreciated that the coating composition according to the present invention may optionally comprise a catalyst which achieves electron transfer between the surface and the metal salt of the composition. This may be useful when faster curing rates are required. Suitable catalysts include transition metal salts.

The kinetics of polymerization / film formation is proportional to the difference in standard reduction potential between the surface and the metal salts in the composition. Crosslinking is achieved directly on the surface. However, it will be appreciated that the calcination step can be applied after polymerization.

The present invention comprises: i) a cation curable component; And ii) applying a coating composition to the substrate, the coating composition comprising an initiator component comprising at least one metal salt,

The standard reduction potential of the initiator component is greater than the standard reduction potential of the surface,

It further extends to the coating method of the substrate.

Coating method of base material

i) cleaning the substrate before applying the coating composition;

ii) immersing the substrate in the coating composition or emulsion of the coating composition of the present invention; And

iii) rinsing the coated substrate upon completion of the polymerization

It will be appreciated that it may include more.

Cleaning the substrate may comprise washing with acid, base, detergent, aqueous solution, water, deionized water, organic solvent and combinations thereof. The emulsion of the coating composition of the present invention mentioned in step (ii) may comprise an aqueous or organic emulsion. Rinsing the coated substrate may include rinsing with water and / or rinsing solution, which is advantageous for the nature of the coating / film.

The invention also

a) a container; And

b) cationic curable compositions according to the invention

It is related to a pack containing. The container may be air permeable. Alternatively, the container may not be air permeable.

The present invention further extends to coatings applied to substrates using the methods discussed above. The substrate may be metallic.

In a further aspect, the present invention extends to a coated article comprising a coating applied to a substrate using the methods discussed above. The substrate may be metallic. The present invention further provides a coated article comprising a coating applied to a substrate. The substrate may comprise a metallic component.

Moreover, the coated article may have a curable composition applied thereto. Thus, the mating with the second substrate is facilitated. The coated article may have a second substrate attached thereto.

As will be appreciated by those skilled in the art, the metal salts in the compositions of the present invention will be selected so that the anions of the metal salts do not result in the termination of the polymerization / curing process.

If appropriate, it will be appreciated that all optional and / or additional aspects of one embodiment of the present invention may be combined with optional and / or additional aspect (s) of another / other embodiment of the present invention.

<Brief Description of Drawings>

Further aspects and advantages of the invention are described in the description and drawings of the invention and will be apparent from it.

1 is a polymerization of a two-part system comprising a redox pair ascorbyl-6-palmitate: diphenyliodonium hexafluorophosphate in an epoxy resin as a function of time (days) at a temperature of 25 ° C. Calorific value graph.

2 is an FTIR-ATR spectrum (3100 to 600 cm ⁻¹ ) of surface accelerated epoxy polymerization on grit blasted mild steel at 25 ° C. FIG.

3 is an FTIR-ATR spectrum (1190 to 760 cm ⁻¹ ) of surface promoted epoxy polymerization on grit blasted mild steel at 25 ° C. FIG.

FIG. 4 is a graph of percent polymerization versus time for the cationically curable coating composition shown in FIGS. 2 and 3.

<Detailed Description of the Invention>

Commercially available coatings on cycloaliphatic epoxy resin Cyracure 6110 containing crivelo-type redox pairs "ascorbyl-6-hexadecanoate: diphenyliodonium hexafluorophosphate" It has been found that by using copper priming aerosols, the polymerization can be carried out at room temperature to provide usable curing strength for a reasonable time (less than 24 hours).

Of the crivelo-type redox pairs, ascorbyl-6-hexadecanoate: diphenyliodonium hexafluorophosphate was the least stable and could not be used in a reliable bicomponent structure. Polymerization did not occur without the copper primer being applied to the substrate. All other possible redox pairs based on these or alternative onium-type salts were ineffective as surface hardening adhesives, even when the substrate was primed with copper. Crivelo's paper [Crivello, J.V .; Lee, J. L .; J. Polym. Sci. Part A: Polm. Chem. 1983, 21, 1097-1110, it has been proposed that a two-part structure of such redox cationic system components may be possible. The inventors of the present invention have found that this is unlikely because any combination of these three components in the two-part structure is storage unstable during actual time (see FIG. 1).

1 shows the stability of a two-part system comprising ascorbyl-6-palmitate: diphenyliodonium hexafluorophosphate redox pairs in epoxy resin Syracure 6110, monitored by polymerization calorific value of 10 g of sample. A graph representing. The stability of the composition was evaluated by measuring the polymerization calorific value of 10 g of the sample of the two-part system stored for various times. The graph clearly shows that an inverse relationship is established between the heat released and the days of storage of the system before use. After 112 days, a marked decrease in the measured polymerisation calorific value was observed, indicating a significant decrease in the reactivity of the composition. In addition, the viscosity of the formulation has increased markedly, thus making it difficult to dispense and process the formulation.

An electrochemical sequence is a measure of the oxidizing and reducing power of a material based on the standard potential of the material. The standard potential of a material is a measure compared to that of a hydrogen electrode. Metals with negative standard (reduction) potentials have a thermodynamic tendency to reduce hydrogen ions in solution, while metal ions with positive standard potentials tend to be reduced by hydrogen gas. The reactive sequence shown in Figure 4 is an extension of the electrochemical sequence.

<Figure 4>

Typically, only a metal or element located higher in the reactive sequence can reduce another metal or element located lower in the reactive sequence, for example iron can reduce tin but not potassium. none. It is understood that the order of the reactive sequences can be reversed (changed) as shown in Figure 4. However, the terms "higher" and "lower" will be understood to refer to the sequence shown in Figure 4 having the highest reactivity at the top and the lowest reactivity at the bottom. In any case it will be appreciated that the metal of the metal salt in the context of the present invention is selected such that the metal is reducible at the surface to which it is applied.

<Examples>

Since these salts were known to be photosensitive, all preparations discussed below were performed in the dark. All formulations were mixed well for 16 hours before use to ensure homogeneity.

General Procedure for Testing Blends

All adhesive formulations were tested according to standard test methods based on ASTM E177 and ASTM E6.

<Device>

Tensile Testing Machine with Suitable Load Cell

<Test sample>

Lap-shear samples as specified in the quality specification, product, or test program

Assembly procedure

1. Five test specimens were used for each test.

2. If necessary, the specimen surface was pretreated, for example by grit blasting mild steel overlap-shear specimens with silicon carbide.

3. Prior to assembly, the test specimens were cleaned by wiping with acetone or isopropanol.

4. The binding area on each overlap-shear specimen was 322.6 mm ² or 0.5 in ² . Marked here before applying the adhesive sample.

5. A sufficient amount of adhesive was applied on the pretreated surface of one overlap-shear specimen.

6. The second overlap-shear specimen was placed on the adhesive and the assembly was clamped on each side of the bonding area.

<Test Procedure>

After allowing the cure as specified in the test program, the shear strength was determined as follows:

1. The test specimen was placed in the grip of the tester so that it was tightened by a jaw by 25.4 mm (1 in.) Outward of each end. The long axis of the test specimen coincided with the direction of the tensile force applied through the centerline of the grip assembly.

2. Unless otherwise noted, the assembly was tested at a crosshead speed of 2.0 mm / min or 0.05 in / min.

3. Record the load at break.

<Recorded the following information>

1. Identification of the adhesive, including the name or number, and lot number

2. Identification of the test specimen used, including the description and dimensions

3. Surface pretreatment methods used to prepare test specimens

4. Curing conditions (typically ambient room temperature only, 20-25 ° C.)

5. Test conditions (standard temperature and pressure, ie room temperature)

6. If applicable, environmental conditioning (or all substrates to be joined are freshly manufactured before use)

7. The number if the sample tested was not five (typically, for each cited result, average 5 results)

8. Results for each sample

9. Average shear strength for all reanalyzed replicates

10. Failure mode for each specimen, if required by quality standards, product profiles or test programs

11. Any changes to these methods

<Redox cationic system without vinyl ether component ::>

General Procedure for Preparing Blends

An amount of initiator salt was added to the monomer (10 g). The salt was dissolved well in the monomer by continuing stirring at room temperature (for 16 hours). All samples were kept covered to exclude light during manufacturing and during storage.

&Lt; Example 1 >

(Diphenyliodonium) PF ₆ (0.20 g) was dissolved in cycloaliphatic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate (10 g). .

Adhesion performance after 24 hours at 25 ℃:

Grit Blasted Mild Steel Overlap Shear Specimen: Unhardened

Glass Overlay Shear Swatch: Uncured

<Example 2>

[Ag (cyclohexene) ₂ ] SbF ₆ (0.19 g, 0.47 mmol) was substituted with an alicyclic diepoxide monomer, Syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate (10 g )).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposition shear specimen: 3.5 N / mm2

<Example 3>

[Ag (cyclododeken) ₂ ] SbF ₆ (0.27 g, 0.47 mmol) was substituted with an alicyclic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate (10 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 4 N / ㎡

<Example 4>

[Ag (hexadiene) _n ] SbF ₆ (0.19 g, 0.47 mmol) was substituted with an alicyclic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate (10 g )).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 2.5 N / ㎡

Example 5

[Ag (1,9-decadiene) _n ] SbF ₆ (0.24 g, 0.47 mmol) was substituted with cycloaliphatic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxyl It was dissolved in the rate (10 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 2.5 N / ㎡

<Example 6>

[Ag (1,7-octadiene) _n ] SbF ₆ (0.21 g, 0.47 mmol) was substituted with cycloaliphatic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxyl It was dissolved in the rate (10 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposition shear specimen: 3.5 N / mm2

<Example 7>

[Ag (15-crown-5)] SbF ₆ (0.32 g, 0.47 mmol) was substituted with an alicyclic diepoxide monomer, Syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate ( 10 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 5.5 N / ㎡

<Example 8>

[Ag (1,5-cyclooctadiene) ₂ ] SbF ₆ (0.24 g, 0.47 mmol) was substituted with cycloaliphatic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarbox Dissolved in cyclate (10 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 5.5 N / ㎡

Aluminum: 3.5 N / mm2

Aluminum (Alclad-Low Copper Content): 2.0 N / mm2

Aluminum (oxides are removed by scratching): 5.0 N / mm 2

Stainless steel: 3.0 N / mm2

<Redox cationic system with vinyl ether component:>

General Procedure for Preparing Blends

An amount of initiator salt and an amount of accelerator were added to the amount of monomer. The salt was dissolved well in the monomer by continuing stirring at room temperature (for 16 hours). All samples were kept covered to exclude light during manufacturing and during storage.

Example 1 (Control A)

Diphenyliodonium PF ₆ (0.20 g, 0.43 mmol) was accelerated to cycloaliphatic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate (8.0 g) In 1,4-butanediol divinyl ether (2.0 g).

Adhesion performance after 24 hours at 25 ℃:

Grit Blasted Mild Steel Overlap Shear Specimen: Unhardened

Glass Overlay Shear Swatch: Uncured

Example 2 (Control B)

[Ag (1,5-cyclooctadiene) ₂ ] SbF ₆ (0.24 g, 0.43 mmol) was dissolved in alicyclic monomer Syraccure 6110 (10 g, 40 mmol).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 4 N / ㎡

<Example 3>

[Ag (1,5-cyclooctadiene) ₂ ] SbF ₆ (0.24 g, 0.43 mmol) was substituted with cycloaliphatic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarbox It was dissolved in carboxylate (8.0 g) and accelerator 1,4-butanediol divinyl ether (2.0 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 20 N / ㎡

Plain mild steel superposed shear specimen: 7 N / mm2

Alclad Aluminum (Low Copper Content) 2.5 N / mm2

Alclad aluminum (oxide removed) 5.0 N / mm2

Standard Aluminum 10 N / ㎡

Copper 5.2 N / ㎡

Stainless steel 6.2 N / mm2

Zinc Dichromate 5.0 N / ㎡

Grit blasted mild steel overlap shear specimens coupled to E-coated steel; 20 N / ㎡

Glass Overlay Shear Swatch: Uncured

Adhesion performance after 4 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 9 N / ㎡

<Example 3a>

[Ag (1,5-cyclooctadiene) ₂ ] SbF ₆ (0.12 g, 0.215 mmol) was substituted with cycloaliphatic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarbox It was dissolved in carboxylate (8.0 g) and accelerator 1,4-butanediol divinyl ether (2.0 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 20 N / ㎡

Adhesion performance after 4 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 9 N / ㎡

Accelerators & Accelerator Concentrates

<Example 4>

[Ag (1,5-cyclooctadiene) ₂ ] SbF ₆ (0.24 g, 0.43 mmol) was substituted with cycloaliphatic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarbox It was dissolved in carboxylate (8.0 g) and accelerator 1,4-butanediol vinyl ether (2.0 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 5 N / ㎡

Example 5

[Ag (1,5-cyclooctadiene) ₂ ] SbF ₆ (0.24 g, 0.43 mmol) was substituted with cycloaliphatic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarbox Dissolved in cyclate (9.5 g) and accelerator 1,4-butanediol vinyl ether (0.5 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 20 N / ㎡

<Example 6>

[Ag (1,5-cyclooctadiene) ₂ ] SbF ₆ (0.24 g, 0.43 mmol) was substituted with cycloaliphatic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarbox Cyclate (8.0 g) and accelerator Vectomer 4060: bis- (4-vinyl oxy butyl) adipate {CAS # 135876-36-7} (2.0 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 12 N / ㎡

<Example 7>

[Ag (1,5-cyclooctadiene) ₂ ] SbF ₆ (0.24 g, 0.43 mmol) was substituted with cycloaliphatic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarbox Cyclate (9.5 g) and accelerator Vectomer 4060: bis- (4-vinyl oxy butyl) adipate {CAS # 135876-36-7} (0.5 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 15 N / ㎡

<Example 8>

[Ag (1,5-cyclooctadiene) ₂ ] SbF ₆ (0.24 g, 0.43 mmol) was added to accelerator Vectomer 4060: bis- (4-vinyl oxy butyl) adipate {CAS # 135876-36-7} ( 10.0 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 7 N / ㎡

Example 9

[Ag (1,5-cyclooctadiene) ₂ ] SbF ₆ (0.24 g, 0.43 mmol) was substituted with cycloaliphatic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarbox It was dissolved in carboxylate (8.0 g) and accelerator 1,4-butanediol divinyl ether (2.0 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 20 N / ㎡

<Example 10>

[Ag (1,5-cyclooctadiene) ₂ ] SbF ₆ (0.24 g, 0.43 mmol) was substituted with cycloaliphatic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarbox Dissolved in cyclate (9.5 g) and accelerator 1,4-butanediol divinyl ether (0.5 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 20 N / ㎡

<Example 11>

[Ag (1,5-cyclooctadiene) ₂ ] SbF ₆ (0.24 g, 0.43 mmol) was substituted with cycloaliphatic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarbox Dissolved in carboxylate (8.0 g) and accelerator ethyl-1-propenyl ether, a mixture of cis and trans (2.0 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 18 N / ㎡

<Example 12>

[Ag (1,5-cyclooctadiene) ₂ ] SbF ₆ (0.24 g, 0.43 mmol) was substituted with cycloaliphatic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarbox Dissolved in carboxylate (9.5 g) and accelerator ethyl-1-propenyl ether, a mixture of cis and trans (0.5 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 18 N / ㎡

Example 13

[Ag (1,5-cyclooctadiene) ₂ ] SbF ₆ (0.24 g, 0.43 mmol) was substituted with cycloaliphatic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarbox Cyclate (8.0 g) and accelerator Vectomer 4010: bis- (4-vinyl oxy butyl) isophthalate {CAS # 130066-57-8} (2.0 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 9 N / ㎡

<Example 14>

[Ag (1,5-cyclooctadiene) ₂ ] SbF ₆ (0.24 g, 0.43 mmol) was substituted with cycloaliphatic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarbox Cyclate (9.5 g) and accelerator Vectomer 4010: dissolved in bis- (4-vinyl oxy butyl) isophthalate {CAS # 130066-57-8} (0.5 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 18 N / ㎡

<Example 15>

[Ag (1,5-cyclooctadiene) ₂ ] SbF ₆ (0.24 g, 0.43 mmol) was added to accelerator Vectomer 4010: bis- (4-vinyl oxy butyl) isophthalate {CAS # 130066-57-8} ( 10.0 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 15 N / ㎡

<Example 16>

[Ag (1,5-cyclooctadiene) ₂ ] SbF ₆ (0.24 g, 0.43 mmol) was substituted with cycloaliphatic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarbox It was dissolved in bixlate (8.0 g) and accelerator Vectoromer 4030: bis [4- (vinyl oxy) butyl] succinate {CAS # 135876-32-3} (2.0 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposition shear specimen: 23 N / mm2

<Example 17>

[Ag (1,5-cyclooctadiene) ₂ ] SbF ₆ (0.24 g, 0.43 mmol) was substituted with cycloaliphatic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarbox It was dissolved in carboxylate (9.5 g) and accelerator Vectoromer 4030: bis [4- (vinyloxy) butyl] succinate {CAS # 135876-32-3} (0.5 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 11 N / ㎡

&Lt; Example 18 >

[[Ag (1,5-cyclooctadiene) ₂ ] SbF ₆ (0.24 g, 0.43 mmol) was added to accelerator vectoromer 4030: bis [4- (vinyloxy) butyl] succinate. {CAS # 135876-32-3 } (10.0 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 10 N / ㎡

&Lt; Example 19 >

[Ag (1,5-cyclooctadiene) ₂ ] SbF ₆ (0.24 g, 0.43 mmol) was substituted with cycloaliphatic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarbox Cyclate (8.0 g) and accelerator Vectomer 4050: dissolved in bis [4- (vinyloxy) butyl] terephthalate {CAS # 117397-31-6} (2.0 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 11 N / ㎡

Example 20

[Ag (1,5-cyclooctadiene) ₂ ] SbF ₆ (0.24 g, 0.43 mmol) was substituted with cycloaliphatic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarbox Cyclate (9.5 g) and accelerator Vectomer 4050: dissolved in bis [4- (vinyloxy) butyl] terephthalate {CAS # 117397-31-6} (0.5 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 12 N / ㎡

&Lt; Example 21 >

[Ag (1,5-cyclooctadiene) ₂ ] SbF ₆ (0.24 g, 0.43 mmol) was substituted with cycloaliphatic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarbox Cyclate (8.0 g) and accelerator Vectomer 4040: dissolved in bis [[4-[(vinyloxy) methyl] cyclohexyl] methyl] isophthalate {CAS # 119581-93-0} (2.0 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 2 N / ㎡

<Example 22>

[Ag (1,5-cyclooctadiene) ₂ ] SbF ₆ (0.24 g, 0.43 mmol) was substituted with cycloaliphatic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarbox Carboxylate (9.5 g) and accelerator vectoromer 4040: bis [[4-[(vinyloxy) methyl] cyclohexyl] methyl] isophthalate {CAS # 119581-93-0} (0.5 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 4 N / ㎡

<Example 23>

[Ag (1,5-cyclooctadiene) ₂ ] SbF ₆ (0.24 g, 0.43 mmol) was substituted with cycloaliphatic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarbox Bixlate (8.0 g) and accelerator Vectomer 4020: bis [4- (vinyloxymethyl) cyclohexylmethyl] glutarate {CAS # 131132-77-9} (2.0 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 3 N / ㎡

<Example 24>

[Ag (1,5-cyclooctadiene) ₂ ] SbF ₆ (0.24 g, 0.43 mmol) was substituted with cycloaliphatic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarbox Carboxylate (9.5 g) and accelerator Vectomer 4020: bis [4- (vinyloxymethyl) cyclohexylmethyl] glutarate {CAS # 131132-77-9} (0.5 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 5 N / ㎡

<Example 25>

[Ag (1,5-cyclooctadiene) ₂ ] SbF ₆ (0.24 g, 0.43 mmol) was added to accelerator Vectomer 4020: bis [4- (vinyloxymethyl) cyclohexylmethyl] glutarate {CAS # 131132- 77-9} (10.0 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 13 N / mm2

<Example 26>

[Ag (1,5-cyclooctadiene) ₂ ] SbF ₆ (0.24 g, 0.43 mmol) was substituted with cycloaliphatic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarbox Cyclate (8.0 g) and Accelerator Vectoromer 5015: Tris (4-vinyloxybutyl) trimellitate {CAS # 196109-17-8} (2.0 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 16 N / ㎡

Example 27

[Ag (1,5-cyclooctadiene) ₂ ] SbF ₆ (0.24 g, 0.43 mmol) was substituted with cycloaliphatic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarbox Carboxylate (9.5 g) and accelerator Vectoromer 5015: tris (4-vinyloxybutyl) trimelitate {CAS # 196109-17-8} (0.5 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 12 N / ㎡

<Example 28>

[Ag (1,5-cyclooctadiene) ₂ ] SbF ₆ (0.24 g, 0.43 mmol) was added to accelerator Vectomer 5015: Tris (4-vinyloxybutyl) trimelitate {CAS # 196109-17-8} ( 10.0 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 12 N / ㎡

<Example 29>

[Ag (1,5-cyclooctadiene) ₂ ] SbF ₆ (0.24 g, 0.43 mmol) was substituted with cycloaliphatic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarbox Cyclate (9.5 g) and accelerator Vectomer 2020: dissolved in aliphatic urethane divinyl ether oligomer {CAS # 143477-70-7} (0.5 g).

Adhesion performance after 72 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 6 N / ㎡

<Monomer component>

<Example 30>

[Ag (1,5-cyclooctadiene) ₂ ] SbF ₆ (0.24 g, 0.43 mmol) was substituted with alicyclic resin bis (3,4-epoxy cyclohexyl methyl) adipate Syracure UVR 6128 (8.0 g) and accelerator It was dissolved in 1,4-butanediol divinyl ether (2.0 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 20 N / ㎡

<Example 31>

[Ag (1,5-cyclooctadiene) ₂ ] SbF ₆ (0.24 g, 0.43 mmol) was substituted with alicyclic epoxy resin Syracure UCB CAT-002, (8.0 g) and accelerator 1,4-butanediol divinyl ether ( 2.0 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 20 N / ㎡

<Example 32>

[Ag (1,5-cyclooctadiene) ₂ ] SbF ₆ (0.24 g, 0.43 mmol) was substituted with alicyclic resin PC 1000 (PolySet) (8.0 g) and accelerator 1,4-butanediol divinyl ether (2.0 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 9.0 N / ㎡

<Example 33>

[Ag (1,5-cyclooctadiene) ₂ ] SbF ₆ (0.24 g, 0.43 mmol) was added to epichlorohydrin-4,4'-isopropylidene diphenol resin, Araldite GY 266 (8.0). g) and accelerator 1,4-butanediol divinyl ether (2.0 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 26 N / ㎡

<Example 34>

[Ag (1,5-cyclooctadiene) ₂ ] SbF ₆ (0.24 g, 0.43 mmol) was substituted with cycloaliphatic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarbox It was dissolved in carboxylate (6.0 g), OXT-101, 3-ethyl-3-hydroxymethyl-oxetane (2.0 g) and accelerator 1,4-butanediol divinyl ether (2.0 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 20 N / ㎡

<Example 35>

[Ag (1,5-cyclooctadiene) ₂ ] SbF ₆ (0.24 g, 0.43 mmol) was substituted with cycloaliphatic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarbox Voxylate (6.0 g), OXT-121, 1,4-bis [3-ethyl-3-oxetanylmethoxy) methyl] benzene (2.0 g) and accelerator 1,4-butanediol divinyl ether (2.0 g) Dissolved in.

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 20 N / ㎡

<Example 36>

[Ag (1,5-cyclooctadiene) ₂ ] SbF ₆ (0.24 g, 0.43 mmol) was substituted with cycloaliphatic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarbox Voxylate (6.0 g), OXT-221, 3,3 '-[oxybis (methylene)] bis (3-ethyl-oxetane) (2.0 g) and accelerator 1,4-butanediol divinyl ether (2.0 g) )).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 20 N / ㎡

<Example 37>

[Ag (1,5-cyclooctadiene) ₂ ] SbF ₆ (0.24 g, 0.43 mmol) was substituted with cycloaliphatic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarbox To carboxylate (6.0 g), OXT-212, 3-ethyl-3-[(2-ethylhexyloxy) methyl] oxetane (2.0 g) and accelerator 1,4-butanediol divinyl ether (2.0 g) Dissolved.

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 20 N / ㎡

<Metal Salts, Concentrates & Combinations of Metal Salts>

<Example 38>

[Ag (1,5-hexadiene) ₂ ] SbF ₆ (0.22 g, 0.43 mmol) was substituted with cycloaliphatic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxyl Dissolved in rate (8.0 g) and accelerator 1,4-butanediol divinyl ether (2.0 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 20 N / ㎡

<Example 39>

[Ag (1,9-decadiene) ₂ ] SbF ₆ (0.26 g, 0.43 mmol) was substituted with cycloaliphatic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxyl Dissolved in rate (8.0 g) and accelerator 1,4-butanediol divinyl ether (2.0 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 20 N / ㎡

<Example 40>

[Ag (1,7-octadiene) ₂ ] SbF ₆ (0.24 g, 0.43 mmol) was substituted with cycloaliphatic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxyl Dissolved in rate (8.0 g) and accelerator 1,4-butanediol divinyl ether (2.0 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 20 N / ㎡

<Example 41>

[Ag (1,7-octadiene) ₂ ] PF ₆ (0.20 g, 0.43 mmol) was substituted with an alicyclic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxyl Dissolved in rate (8.0 g) and accelerator 1,4-butanediol divinyl ether (2.0 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 20 N / ㎡

<Example 42>

[Ag (1,7-octadiene) ₂ ] BF ₄ (0.18 g, 0.43 mmol) was added to the cycloaliphatic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxyl Dissolved in rate (8.0 g) and accelerator 1,4-butanediol divinyl ether (2.0 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 20 N / ㎡

<Example 43>

[Ag (1,7-octadiene) ₂ ] ClO ₄ (0.18 g, 0.43 mmol) was added to the cycloaliphatic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxyl Dissolved in rate (8.0 g) and accelerator 1,4-butanediol divinyl ether (2.0 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 20 N / ㎡

<Example 44>

[Ag (15-crown-5)] SbF ₆ (0.24 g, 0.43 mmol) was substituted with an alicyclic diepoxide monomer, Syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate ( 8.0 g) and accelerator 1,4-butanediol divinyl ether (2.0 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 20 N / ㎡

<Example 45>

[Ag (15-Crown-5)] SbF ₆ (0.20 g, 0.43 mmol) was substituted with an alicyclic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate ( 8.0 g) and accelerator 1,4-butanediol divinyl ether (2.0 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 20 N / ㎡

Example 46

[Ag (15-crown-5)] BF ₄ (0.18 g, 0.43 mmol) was substituted with an alicyclic diepoxide monomer, Syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate ( 8.0 g) and accelerator 1,4-butanediol divinyl ether (2.0 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 20 N / ㎡

<Example 47>

[Ag (1,5-cyclooctadiene) ₂ ] PF ₆ (0.22 g, 0.43 mmol) was added to the cycloaliphatic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarbox It was dissolved in carboxylate (8.0 g) and accelerator 1,4-butanediol divinyl ether (2.0 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 20 N / ㎡

<Example 48>

[Ag (1,5-cyclooctadiene) ₂ ] BF ₄ (0.18 g, 0.43 mmol) was added to the cycloaliphatic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarbox It was dissolved in carboxylate (8.0 g) and accelerator 1,4-butanediol divinyl ether (2.0 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 20 N / ㎡

<Example 49>

[Ag (1,5-cyclooctadiene) ₂ ] ClO ₄ (0.18 g, 0.43 mmol) was added to the cycloaliphatic diepoxide monomer syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarbox It was dissolved in carboxylate (8.0 g) and accelerator 1,4-butanediol divinyl ether (2.0 g).

Adhesion performance after 24 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 20 N / ㎡

<Example 50>

[Cu (1,5-cyclooctadiene) ₂ ] BF ₄ (0.026 g, 0.07 mmol) and [Ag (1,5-cyclooctadiene) ₂ ] SbF ₆ (0.20 g, 0.35 mmol) were alicyclic diepoxy The side monomers were dissolved in Syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate (8.0 g) and accelerator 1,4-butanediol divinyl ether (2.0 g).

Adhesion performance after 4 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 14 N / ㎡

<Example 51>

[Cu (1,5-cyclooctadiene) ₂ ] BF ₄ (0.052 g, 0.14 mmol) and [Ag (1,5-cyclooctadiene) ₂ ] SbF ₆ (0.16 g, 0.28 mmol) were alicyclic diepoxy The side monomers were dissolved in Syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate (8.0 g) and accelerator 1,4-butanediol divinyl ether (2.0 g).

Adhesion performance after 4 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 13 N / mm2

<Example 52>

[Cu (1,5-cyclooctadiene) ₂ ] BF ₄ (0.08 g, 0.21 mmol) and [Ag (1,5-cyclooctadiene) ₂ ] SbF ₆ (0.12 g, 0.21 mmol) were alicyclic diepoxy The side monomers were dissolved in Syracure 6110, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate (8.0 g) and accelerator 1,4-butanediol divinyl ether (2.0 g).

Adhesion performance after 4 hours at 25 ℃:

Grit blasted mild steel superposed shear specimen: 11.5 N / ㎡

Coating Example

100 ml of the cationically curable blend of the present invention was prepared. The formulation was bathed in the appropriate size.

Typical Cationic Formulations:

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%)

Those skilled in the art will appreciate that the coating formulations are only representative formulations given for purposes of illustration. The coating formulation can be varied in monomers, metal salts, concentrations, etc. to suit the end use of the coating formulation.

The metal substrate (10 x 2.5 cm) was washed by wiping with acetone and immersed in the blend. The metal substrate was immersed in a bath containing the blend. Immersion times were proportional to the difference in standard potential between the surface and the metal salt in the composition, and to the thickness of the desired coating (if less than the self-limiting thickness). After the coating / polymerization was completed, the remaining monomers were washed off. The formed film was analyzed by FTIR-ATR.

2 is an FTIR-ATR spectrum of a surface promoted epoxide coating on grit blasted mild steel at 25 ° C. Epoxide monomers have a characteristic IR stretching at 700 cm ⁻¹ . The desired polyether coating has a characteristic IR stretching at 1080 cm ^-1 .

The samples were repeatedly scanned at 10 minute intervals and found to increase in polyether concentration over time, demonstrating that a polymeric coating formed on the surface of the grit blasted mild steel.

An enlarged view of 1190 to 760 cm ⁻¹ , which is important in FIG. 2, is shown in FIG. 3. The IR spectrum clearly shows that the epoxide monomer concentration decreases with increasing polyether concentration over time.

A graph of percent polymerization versus time for the cationically curable coating composition is shown in FIG. 4. The coating composition was prepared by using grit blasted mild steel as a substrate at 20 ° C. and using Syracure 6110 (3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate) (8.0 g), 1,4-butane Diodivinyl ether (2.0 g) and [Ag (1,5-cyclooctadiene) ₂ ] SbF ₆ (0.25 mmol). The degree of polymerization was determined using FTIR-ATR in FIGS. 1 and 2 (see above). The change in peak intensity in the spectrum over time at 1080 cm ⁻¹ is indicative of polyether formation, thus polymerization. Looking at the graph, the initial polymerization rate is fast and linear up to about 30 minutes, after which the appearance of stagnation phase is gradually observed.

The words “comprises / comprising” and “having / comprising”, when used in connection with the present invention herein, are used to specify the presence of the recited aspects, integers, steps or components, but one or more other It does not exclude the presence or addition of embodiments, integers, steps, components or groups.

For clarity, it will be appreciated that certain aspects of the invention described in the individual embodiments may be provided in the form of combinations in a single embodiment. Conversely, in other words, various aspects of the invention described in a single embodiment may be provided separately or in the form of any suitable subcombination.

Claims (62)

(i) a cation curable component; And
(ii) 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,
When the composition is in contact with the surface, the metal salt of the initiator component of the composition is reduced at the surface to initiate curing of the cationically curable component of the composition,
Cationically curable composition for curing on the surface. The curable composition of claim 1, wherein the metal salt comprises a transition metal cation. The curable composition of claim 2 wherein the transition metal cation is selected from silver, copper and combinations thereof. The method of claim 1 wherein the metal salt is _{^{ClO 4 -, BF 4 -,}} PF 6 -, SbF 6 -, AsF 6 -, (C 6 F 5) 4 B, (C 6 F 5) 4 Ga, carboxylic borane, Triple A curable composition comprising a counterion selected from the group consisting of imides, bis-triplimides, and combinations thereof. The group of claim 1 wherein the cationically curable component consists of epoxy, vinyl, oxetane, thioxetane, episulfide, tetrahydrofuran, oxazoline, oxazine, lactone, trioxane, dioxane, styrene, and combinations thereof. Curable composition having one or more functional groups selected from. The curable composition of claim 1, wherein the surface comprises a metal, a metal oxide, or a metal alloy. The curable composition of claim 1 wherein the surface is selected from the group consisting of iron, steel, mild steel, grit blasted mild steel, aluminum, aluminum oxide, copper, zinc, zinc oxide, zinc dichromate, and stainless steel. The curable composition of claim 1 further comprising a metal oxide remover. The curable composition of claim 8, wherein the metal oxide remover is selected from the group consisting of chloride ions, zinc (II) salts, and combinations thereof. The curable composition of claim 1, further comprising a catalyst that achieves electron transfer between the surface and the metal salt. The curable composition of claim 1 for attaching the first metal substrate to another substrate. The curable composition of claim 1 for sealing. Use of the composition according to claim 1 in screw-fastening, flange sealing, structural bonding and / or metal bonding. Use of one or more metal salts having a standard reduction potential greater than the standard reduction potential of the surface in initiating curing of the cationically curable composition on a surface. i) a cation curable component; And ii) applying a composition comprising at least one metal salt to at least one substrate; And
(ii) mating the first substrate and the second substrate to form a bond with the composition
Including,
Wherein the standard reduction potential of the initiator component is greater than the standard reduction potential of one or more substrates,
Method of joining two substrates together. The method of claim 15, wherein the one or more substrates comprise a metal, metal oxide or metal alloy. The method of claim 16, wherein the one or more substrates comprise a metal. i) a container; And
ii) the cationically curable composition according to claim 1
Pack containing. The pack of claim 18 wherein the container is air permeable. The pack of claim 19 wherein the container is not air permeable. i) cationic curable components;
ii) an accelerator species comprising at least one vinyl ether functional group; And
iii) an initiator component comprising at least one metal salt
Including,
Wherein the standard reduction potential of the initiator component is greater than the standard reduction potential of the surface,
When the composition is in contact with the surface, the metal salt of the initiator component of the composition is reduced at the surface to initiate curing of the cationically curable component of the composition,
Cationically curable composition for curing on the surface. The curable composition of claim 21 wherein the metal salt comprises a transition metal cation. The curable composition of claim 22 wherein the transition metal cation is selected from the group consisting of silver, copper and combinations thereof. The method of claim 21 wherein the metal salt is _{^{ClO 4 -, BF 4 -,}} PF 6 -, SbF 6 -, AsF 6 -, (C 6 F 5) 4 B, (C 6 F 5) 4 Ga, carboxylic borane, Triple A curable composition comprising a counterion selected from the group consisting of imides, bis-triplimides, and combinations thereof. The curable composition of claim 21, wherein the accelerator species comprising at least one vinyl ether functional group has the formula:

Wherein m may be 0 or 1;
R ₁ , R ₂ and R ₃ may be the same or different and consist of hydrogen, a C ₁ -C ₂₀ alkyl chain (linear, branched or cyclic) and a C ₅ -C ₂₀ aryl moiety, and combinations thereof Can be selected from;
X can be a C ₁ -C ₃₀ saturated or unsaturated, cyclic or acyclic moiety;
R ₁ , R ₂ , R ₃ and X may independently contain or may not contain ether bonds, sulfur bonds, carboxyl groups and carbonyl groups. The curable composition of claim 21, wherein the accelerator species comprising at least one vinyl ether functional group has the formula:

Wherein m may be 0 or 1;
n can be 0 to 5;
R ₃ can be selected from the group consisting of hydrogen, a C ₁ -C ₂₀ alkyl chain (linear, branched or cyclic) and a C ₅ -C ₂₀ aryl moiety, and combinations thereof;
X can be a C ₁ -C ₃₀ saturated or unsaturated, cyclic or acyclic moiety;
R ₃ and X may independently contain or may not contain ether bonds, amine bonds, sulfur bonds, carboxyl groups and carbonyl groups. 22. The accelerator species of claim 21, wherein the accelerator species comprising at least one vinyl ether functional group is 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, vectoromer ) 2020 and combinations thereof. The curable composition of claim 21, wherein the accelerator species comprising at least one vinyl ether functional group is present at 2 to 98% w / w of the total composition. The curable composition of claim 21, wherein the accelerator species comprising at least one vinyl ether functional group is present at 5-50% w / w of the total composition. The curable composition of claim 21, wherein the accelerator species comprising at least one vinyl ether functional group is present at 5-30% w / w of the total composition. The group of claim 21, wherein the cationically curable component consists of epoxy, vinyl, oxetane, thioxetane, episulfide, tetrahydrofuran, oxazoline, oxazine, lactone, trioxane, dioxane, styrene, and combinations thereof. Curable composition having one or more functional groups selected from. The curable composition of claim 21, wherein the surface comprises a metal, a metal oxide, or a metal alloy. The curable composition of claim 21 wherein the surface is selected from the group consisting of iron, steel, mild steel, grit blasted mild steel, aluminum, aluminum oxide, copper, zinc, zinc oxide, zinc dichromate, and stainless steel. The curable composition of claim 21 applied to a metal, metal oxide or metal alloy. The curable composition of claim 21, further comprising a catalyst that achieves electron transfer between the metal surface and the metal salt. The curable composition of claim 21 for attaching the first metallic substrate to another substrate. The curable composition of claim 21 for sealing. Use of the composition according to claim 21 in screw-fastening, flange sealing, structural bonding and / or metal bonding. i) metal salts; And
ii) an accelerator species comprising at least one vinyl ether functional group
Initiator package for initiating curing of the cationically curable component, comprising. i) a) cation curable component; b) an accelerator species comprising at least one vinyl ether functional group; And c) applying to the at least one substrate a composition comprising an initiator component comprising at least one metal salt; And
ii) mating the first substrate and the second substrate to form a bond with the composition
Including,
Wherein the standard reduction potential of the initiator component is greater than the standard reduction potential of one or more substrates,
Method of joining two substrates together. 41. The method of claim 40, wherein the one or more substrates comprise a metal, metal oxide or metal alloy. The method of claim 40, wherein the one or more substrates comprise a metal. i) a container; And
ii) the cationic curable composition according to claim 21
Pack containing. The pack of claim 43 wherein the container is air permeable. The pack of claim 43, wherein the container is not air permeable. i) cationic curable components;
ii) an initiator component comprising at least one metal salt
Including,
Wherein the standard reduction potential of the initiator component is greater than the standard reduction potential of the surface,
When the composition is in contact with the surface, the metal salt of the initiator component of the composition is reduced at the surface to initiate curing of the cationically curable component of the composition,
Curable coating compositions for coating of surfaces. The coating composition of claim 46, wherein the metal salt comprises a transition metal cation. 48. The coating composition of claim 47 wherein the transition metal cation is selected from silver, copper and combinations thereof. The method of claim 46 wherein the metal salt is ^{_{ClO 4 -, BF 4 -,}} PF 6 -, SbF 6 -, AsF 6 -, (C 6 F 5) 4 B, (C 6 F 5) 4 Ga, carboxylic borane, Triple A coating composition comprising a counterion selected from the group consisting of imides, bis-triplimides, and combinations thereof. 47. The coating composition of claim 46, wherein the surface comprises a metal, a metal oxide or a metal alloy. 47. The coating composition of claim 46, wherein the surface is selected from the group consisting of iron, steel, mild steel, grit blasted mild steel, aluminum, aluminum oxide, copper, zinc, zinc oxide, zinc dichromate, and stainless steel. 47. The process of claim 46 wherein the cationically curable component is epoxy, vinyl, vinyl ether, oxetane, thioxetane, episulfide, tetrahydrofuran, oxazoline, oxazine, lactone, trioxane, dioxane, styrene and combinations thereof. Coating composition having at least one functional group selected from the group consisting of. 47. The cationically curable component of claim 46 wherein the cationically curable component consists of a vinyl ether component and an epoxy, vinyl, oxetane, thioxetane, episulfide, tetrahydrofuran, oxazoline, oxazine, lactone, trioxane, dioxane and styrene. A coating composition comprising at least one other cationically curable component selected from the group. i) cationic curable components; And
ii) an initiator component comprising at least one metal salt
Including coating the coating composition comprising a substrate,
Wherein the standard reduction potential of the initiator component is greater than the standard reduction potential of the surface,
Coating method of base material. A coating applied to a substrate using the method of claim 54. i) a coating according to claim 55; And
ii) description
Coated article comprising a. The coated article of claim 56 wherein the curable composition is applied. The coated article of claim 56 mated with the second substrate. The coated article of claim 56, wherein the second substrate is attached. i) a container; And
ii) the cationic curable coating composition according to claim 46
Pack containing. 61. The pack of claim 60, wherein the container is air permeable. 61. The pack of claim 60, wherein the container is not air permeable.

Images