JP2011521064A - Surface accelerated curing of one-part radical curable compositions - Google Patents

Abstract

  The present invention relates to a radical curable composition for curing on a surface, the composition comprising a radical curable component and an initiator component capable of initiating curing of the radical curable component. The initiator includes at least one metal salt and a free radical generating component. The metal salt of the composition is selected to be reduced at the surface. The standard reduction potential of the metal salt is higher than the standard reduction potential of the surface. When the composition is placed in contact with the surface, the metal salt is reduced on the surface and interacts with the free radical generating component, thereby causing a composition. Initiates curing of the radical curable component of the product. No catalyst component is required in the composition for efficient curing.

Description

  The present invention relates to a stable one-part radical curable composition for curing on a surface, and uses therefor.

Reduction-Oxidation (Redox) Radical Polymerization Redox polymerization involves an oxidation process and a reduction process (Holtzclaw, HF; Robinson, WR; Odom, JD; General Chemistry 1991, 9th edition, Heath ( Issue), page 44). When a free atom, an intramolecular atom or an ionic atom loses one or more electrons, this atom is oxidized and its oxidation number increases. When a free atom, an intramolecular atom or an ionic atom gains an electron or electrons, this atom is reduced and its oxidation number decreases. After one atom has acquired an electron, oxidation and reduction always occur simultaneously, as if another atom had to donate an electron and be oxidized. In a redox pair, one chemical species acts as a reducing agent and the other acts as an oxidizing agent. When a redox reaction occurs, the reducing agent passes or donates electrons to another reactant. Thereby, the reducing agent reduces this reactant. Therefore, the reducing agent itself is oxidized by losing electrons. The oxidizing agent accepts or acquires electrons and oxidizes the reducing agent. On the other hand, itself is reduced. By comparing the relative oxidizing power or reducing power of the two reagent forces of the redox couple, it can be determined which is the reducing agent and which is the oxidizing agent. The power of the reducing or oxidizing agent can be determined from these standard reduction (E _red ⁰ ) or oxidation (E _ox ⁰ ) potentials.

  Redox radical polymerization is an established bonding technique, for example in the field of anaerobic acrylic adhesive formulations (US Pat. Nos. 2,628,178, 2,895,950, 3,218, 305, and 3,435,012). Anaerobic adhesive formulations are used in a wide range of industrial applications, including screw locking, flange sealing, structural bonding, and engine block sealing, among others (Haviland, GS; Machinery Adhesives for Locking Retaining). & Sealing, Marcel Dekker (published), New York 1986).

  Anaerobic adhesive systems typically consist of radical sensitive monomers, oxidants and reducing agents (Rich, R .; Handbook of Adhesive Technology, Pizzi, A. & Mital, KL, edited by Marcel Dekker (published). 1994, Chapter 29, pages 467-479). A typical oxidizing agent is hydroperoxide, of which cumene hydroperoxide (CHP) is most commonly used, although other hydroperoxides including t-butyl hydroperoxide (BHP) are also used. In general, the reducing agent is dimethyl-p-toluidine (DMPT), saccharin (Moane, S. et al .; Int. J. Adh. & Adh. 1999, 19, 49-57), or acetylphenylhydrazine (APH) ( Rich, R .; Handbook of Adhesive Technology, Pizzi, A. & Mital, KL, edited by Marcel Dekker (published) 1994, chapter 29, pages 467-479).

Known incompatibilities between transition metal salts and hydroperoxides:
Hydroperoxides can act as oxidizing agents, as reducing agents, or both (Kharash, MS et al .; J. Org. Chem. 1952, chapter 17, pages 207-220). Several mechanisms of hydroperoxide oxidation include the extraction of one electron, the extraction of an electron pair from an electron donor, or the donation of an oxygen atom to an acceptor (Kharash, MS et al .; J. Org. Chem. 1952, Chapter 17, pages 207-220).

  Hydroperoxides are known to be unstable regardless of whether the metal salt is present in a low oxidation state or a high oxidation state. It is understood that this instability is what causes hydroperoxide reactivity when used as an initiating component in anaerobic acrylic adhesives. Scheme 1 shows the oxidative and reductive degradation of hydroperoxides by transition metal species in the high and low oxidation states of hydroperoxides.

  Accordingly, there remains an unmet need for a suitable hydroperoxide compatible radical curable formulation that provides an alternative to the amine / organic reducing agent blend described above. Furthermore, there is a need for a one-part radical curable composition that exhibits long-term stability and cures only when applied to the target surface.

Existing Coating Technology E-coating (electrocoating / electrodeposition coating) is a coating method that uses electrical current to deposit paint. This process works on the principle that "opposites attract each other". This process is also known as electrolytic deposition. The basic physical principle of electrocoating is that materials with opposite charges attract each other. In an electrocoating system, a DC charge is applied to a metal part immersed in a bath of oppositely charged paint particles. The paint particles are attracted to the metal part and the paint is deposited on the part, forming a uniform continuous film on all surfaces and on all cracks and corners until the electrocoating reaches the desired thickness. Because the film insulates the part at this thickness, the attractive force stops and the electrocoating process is complete. Depending on the polarity of the charge, the electrocoating is classified as anodic or cathodic. The main drawback of this technique is that it cannot be coated inside a metal tube or the like because this technique is affected by the Faraday cage effect. In order to crosslink and cure the coating, it is necessary to fire the material.

  The inventors aim to utilize redox chemistry as an alternative coating technique.

In one aspect, the present invention is a stable one-part radical curable composition for curing on a surface comprising:
i) a radical curable component;
ii) a free radical generating component;
iii) at least one metal salt,
A standard reduction potential of the at least one metal salt is higher than a standard reduction potential of the surface;
When the composition is placed in contact with the surface, the metal salt is reduced on the surface and interacts with the free radical generating component, thereby curing the radical curable component of the composition. Initiating radical curable compositions are provided.

  The standard reduction potential in the present specification indicates a tendency that a chemical species is reduced by acquiring electrons. The standard reduction potential is measured under the following standard conditions: 25 ° C., concentration 1M, pressure 1 atm, and pure state elements.

Desirably, the metal salt of the composition includes a transition metal cation. Suitable metals include copper, iron, zinc and combinations thereof. The metal salt can be replaced with a ligand. Desirably, the metal salt counterion is naphthenate, ethylhexanoate, benzoate, nitrate, chloride, acetylacetonate, ClO ₄ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , (C ₆ F ₅ ) ₄ B, (C ₆ F ₅ ) ₄ Ga, carborane, triflimide, bis-triflimide, anions based thereon and combinations thereof can be selected. More preferably, the metal salt counterion is from the group consisting of naphthenate, ethylhexanoate, benzoate, nitrate, chloride, acetylacetonate, ClO ₄ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ and combinations thereof. You can choose. Preferably, the metal salt counterion can be selected from the group consisting of ClO ₄ ⁻ , BF ₄ ⁻ and combinations thereof.

  The solubility of the metal salt can be adjusted by changing the counter ion, addition and / or substitution of ligands to the metal of the metal salt, and combinations thereof. Thereby, since appropriate solubility is obtained, efficient electron transfer between the surface and the metal salt is observed.

  The radical generating component can be selected from the group consisting of peroxides, hydroperoxides, hydroperoxide precursors, persulfates and combinations thereof. Suitable materials include cumene hydroperoxide, tert-butyl hydroperoxide, hydrogen peroxide, 2-butanone peroxide, di-tert-butyl peroxide, dicumyl peroxide, lauroyl peroxide, 2,4-pentanedione peroxide, pentamethyl- Trioxepane (such as that sold under the trade name Trigonox® 311), benzoyl peroxide and combinations thereof.

  The radically curable component desirably has at least one functional group selected from the group consisting of acrylate, methacrylate, thiolene, siloxane, vinyl, and combinations thereof are also encompassed in the present invention. Preferably, the radical curable component has at least one functional group selected from the group consisting of acrylates, methacrylates, thiolenes and combinations thereof.

Desirably, the surface to which the composition of the present invention is applied can comprise a metal, metal oxide or metal alloy. More desirably, the surface can include a metal or metal oxide. Preferably, this surface can 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. Desirably, the surface can be selected from the group consisting of steel and aluminum. Metal salts suitable for use in compositions for curing on steel or aluminum surfaces can be selected from the group consisting of iron salts, copper salts, zinc salts and combinations thereof, provided that the iron salt, copper The counterion of the salt and zinc salt can be selected from the group consisting of naphthenate, ethylhexanoate, benzoate, nitrate, chloride, acetylacetonate, ClO ₄ ⁻ , BF ₄ ⁻ and combinations thereof.

  In general, the inventive compositions disclosed herein can be cured on oxidized metal surfaces without the need for additional etchants or oxide removal agents. However, the compositions of the present invention can optionally include an oxide remover. For example, inclusion of etchants or oxide removers, such as those containing chloride ions and / or zinc (II) salts, in the formulations of the present invention allows the etching of any oxide layer. As a result, the lower (zero oxidation state) metal is exposed. This metal then has sufficient activity to be able to reduce the (transition) metal salt of the radically curable composition of the invention.

  The redox radical curable coating compositions described herein do not require an additional reducing agent. This composition is stable until contact with a metal substrate that can participate in the redox reaction (or other surface that can participate in the redox reaction), and thus serves as a conventional reducing agent component. . The radically curable composition of the present invention has storage stability as a one-part composition when stored in a breathable container. The stability of large amounts of the radically curable coating composition of the present invention can be improved by continuous stirring and / or bubbling air through the composition.

  The composition of the present invention does not require an additional catalyst for efficient curing. The present invention utilizes an appropriate selection of initiator components for the surface on which the composition is to be applied and cured. Thus, curing of the radically curable composition can be initiated using a surface-promoted redox chemical reaction. However, it will be understood that the composition according to the present invention may optionally include a catalyst to effect electron transfer between the surface and the metal salt of the composition. This can be useful when higher cure rates are required. Suitable catalysts include transition metal salts.

  The inventive compositions described herein are generally useful as adhesives, sealants or coatings and are used in a wide range of industrial applications, including metal bonding, screw locking, flange sealing, and structural bonding, among others. can do.

  The compositions of the invention can be encapsulated if desired. Suitable encapsulation techniques include, but are not limited to, coacervation, soft gel and coextrusion.

  Alternatively, the composition of the present invention can be used in a pre-coating system. The term pre-application utilizes a material in an encapsulated form (usually but not necessarily microencapsulated) and heats the capsule (eg, water or organic solvent) on the desired substrate. It will be understood that it is to be understood as being dispersed in a liquid binder system that can be dried (by removal or by photocuring the binder). A film of material containing a curable composition (eg, an adhesive liquid in the form of a filled capsule, for example) remains. The curable composition can be released and cured by physically rupturing the material (eg, capsule) if the user wishes to activate the composition. For example, with a pre-applied screw lock, the coated thread is activated by twisting together with its counter thread (eg, screw receiver or nut).

In another embodiment, the invention is an initiator package for initiating curing of a radical curable component comprising:
i) a free radical generating component;
ii) extends to an initiator package comprising at least one metal salt.

Metal salt counter ions are naphthenate, ethylhexanoate, benzoate, nitrate, chloride, acetylacetonate, ClO ₄ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , (C ₆ F ₅ ) _4. can be selected triflimide, from anions and combinations thereof based on these _{- B, (C 6 F 5} ) 4 Ga, carborane, triflimide, bis. More preferably, the metal salt counterion is from the group consisting of naphthenate, ethylhexanoate, benzoate, nitrate, chloride, acetylacetonate, ClO ₄ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ and combinations thereof. You can choose. Preferably, the metal salt counterion can be selected from the group consisting of ClO ₄ ⁻ , BF ₄ ⁻ and combinations thereof.

The present invention further provides a method of joining two substrates,
(I) i) a radical curable component;
ii) a free radical generating component;
iii) applying a composition comprising at least one metal salt to at least one of the substrates;
(Ii) combining the first substrate and the second substrate to form a bond with the composition;
This extends to methods in which the standard reduction potential of the at least one metal salt is higher than at least one standard reduction potential of the substrate.

  In one particular embodiment, both substrates include a metal. When the second substrate includes a metal substrate different from the first metal substrate, the composition of the present invention can include two or more metal salts. Thus, the present invention also provides a curable composition capable of joining different metal substrates by containing two or more metal salts.

  The metal of the metal salt of the inventive composition of the present invention preferably has a lower reactive series than the metal surface on which it will be cured.

  Metal substrates can also be bonded to non-metallic substrates. For example, mild steel can be joined to e-coated steel (e-coat is an organic paint that is electrodeposited using a current on a metal surface such as steel).

  Furthermore, the inventive compositions of the present invention can be utilized to form (polymer) coatings on parts such as metal parts.

The present invention further includes
a) a container;
b) It relates to a pack comprising the radical curable composition of the present invention. However, this container is breathable.

  In yet another aspect, the present invention provides compositions and surface coating methods for coating a surface. It is envisaged that crosslinking and curing can take place directly on the surface and thus no additional firing treatment is necessary. Further, it is envisioned that this coating method allows for the internal coating of surfaces (eg, surfaces that may exhibit Faraday cage effects that interfere with internal coatings such as tubes).

In another aspect, the present invention is a stable one-part radical curable coating composition for coating a surface comprising:
i) a radical curable component;
ii) a free radical generating component;
iii) at least one metal salt,
A standard reduction potential of the at least one metal salt is higher than a standard reduction potential of the surface;
When the composition is placed in contact with the surface, the metal salt is reduced on the surface and interacts with the free radical generating component, thereby curing the radical curable component of the composition. Initiated radical curable coating compositions are provided.

Desirably, the metal salt of the radically curable coating composition includes a transition metal cation. Suitable metals include copper, iron, zinc and combinations thereof. The metal salt can be replaced with a ligand. Desirably, the metal salt counterion is naphthenate, ethylhexanoate, benzoate, nitrate, chloride, acetylacetonate, ClO ₄ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , (C ₆ F ₅ ) ₄ B, (C ₆ F ₅ ) ₄ Ga, carborane, triflimide, bis-triflimide, anions based thereon and combinations thereof can be selected. More preferably, the metal salt counterion is from the group consisting of naphthenate, ethylhexanoate, benzoate, nitrate, chloride, acetylacetonate, ClO ₄ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ and combinations thereof. You can choose. Preferably, the metal salt counterion can be selected from the group consisting of ClO ₄ ⁻ , BF ₄ ⁻ and combinations thereof.

  The radical generating component of the coating composition can be selected from the group consisting of peroxides, hydroperoxides, hydroperoxide precursors, persulfates, and combinations thereof. Suitable materials include cumene hydroperoxide, tert-butyl hydroperoxide, hydrogen peroxide, 2-butanone peroxide, di-tert-butyl peroxide, dicumyl peroxide, lauroyl peroxide, 2,4-pentanedione peroxide, Trigonox ( Registered trademark 311 (3,3,5,7,7-pentamethyl-1,2,4-trioxepane, benzoyl peroxide and combinations thereof.

The radically curable component desirably has at least one functional group selected from the group consisting of acrylate, methacrylate, thiolene, siloxane, vinyl, and combinations thereof are also encompassed in the present invention.
Preferably, the radical curable component has at least one functional group selected from the group consisting of acrylates, methacrylates, thiolenes and combinations thereof.

  It will be appreciated that the radically curable coating composition of the present invention may optionally include fillers, dyes, pigments and lubricating elements. Further, the radical curable monomer can be configured to include a curable hydrophobic monomer, a bifunctional monomer, and secondary curable components including vulcanizing agents, curing agents, and the like. Modification of the curable monomer can be utilized to adjust the properties of the deposited film. This facilitates the following controls: surface tension and polarity, smoothness, stereoregularity, color, hardness, scratch resistance, subsequent surface reactivity to coatings and / or adhesives, and surface Reactivity to light, heat, and moisture that promotes further reactions within the deposited film itself or between the film deposited on the surface and the material in contact therewith.

  The solubility of the metal salt in the radical curable coating composition can be adjusted by changing the counter ion, addition and / or substitution of ligands to the metal of the metal salt, and combinations thereof. This will provide adequate solubility so that efficient electron transfer between the surface and the metal salt will be seen.

  Desirably, the surface to which the composition of the present invention is applied can comprise a metal, metal oxide or metal alloy. More desirably, the surface can include a metal or metal oxide. Preferably, this surface can 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. Desirably, the surface can be selected from the group consisting of steel and aluminum.

Metal salts suitable for use in radical coating compositions for steel or aluminum surfaces can be selected from the group consisting of iron salts, copper salts, zinc salts and combinations thereof, provided that the iron salt, copper salt And the counter ion of the zinc salt can be selected from the group consisting of naphthenate, ethylhexanoate, benzoate, nitrate, chloride, acetylacetonate, ClO ₄ ⁻ , BF ₄ ⁻ and combinations thereof.

  It is further desirable that the metal of the metal salt of the inventive coating composition of the present invention has a lower reactive series than the metal surface on which it is to be cured. Thus, the composition of the present invention can be coated on many different metal surfaces.

  All references to the term “coating” herein are taken to include coatings on polymer films or surfaces. Furthermore, all references to functionalized polymer films or coatings below apply to both crosslinked and non-crosslinked coatings.

  It will be appreciated that the radical curable component can be functionalized to impart desirable properties to the polymerized film. Monomers can be modified to control the following properties of the coating; surface tension and polarity, smoothness, stereoregularity, color, hardness, scratch resistance, and subsequent coating and / or adhesive Reactive. In addition, the functionalized coating can be stimulated by light, heat, moisture, etc. to further react within the coating itself deposited on the surface or between the coating deposited on the surface and the material in contact therewith. Can also be promoted.

  For example, a radical curable monomer functionalized with a cationic curable monomer to form a dual curable system; a radical curable monomer functionalized with a second curable component including a vulcanizing agent, a curing agent, etc .; and Surface tension and polarity, smoothness, stereoregularity, color, hardness, scratch resistance, subsequent reactivity to coatings and / or adhesives, further reaction in the film itself deposited on the surface or deposition on the surface Coatings functionalized to control reactivity to light, heat, and moisture, which facilitates further reaction between the deposited film and the material in contact therewith.

  The redox radical curable coating compositions described herein do not require an additional reducing agent. This composition is stable until contact with a metal substrate that can participate in the redox reaction (or other surface that can participate in the redox reaction), and thus serves as a conventional reducing agent component. . The radically curable composition of the present invention has storage stability as a one-part composition when stored in a breathable container. The stability of large amounts of the radically curable coating composition of the present invention can be improved by continuous stirring and / or bubbling air through the composition.

  The radical coating composition of the present invention does not require an additional catalyst for efficient curing. The present invention utilizes an appropriate selection of metal salt components for the surface to which the coating composition is to be applied and cured. However, it will be appreciated that the coating composition according to the present invention may optionally include a catalyst to provide electron transfer between the surface and the metal salt of the composition. This may be useful when higher cure rates are required. Suitable catalysts include transition metal salts.

  The rate of polymerization / film formation is proportional to the difference in standard reduction potential between the surface and the metal salt in the composition. Crosslinking takes place directly on the surface. However, it will be understood that a post-polymerization firing process can be performed.

The present invention is a method of coating a substrate comprising:
i) a radical curable component;
ii) a free radical generating component;
iii) applying to the substrate a coating composition comprising at least one metal salt;
Further provided is a method wherein the standard reduction potential of the at least one metal salt is higher than the standard reduction potential of the surface.

A method of coating a substrate using the radical composition of the present invention includes:
i) washing the substrate before applying the coating composition;
ii) immersing the substrate in the coating composition of the present invention or an emulsion of the coating composition;
It will be appreciated that the method may further comprise the step of: iii) flushing the coated substrate after polymerization is complete.

  Washing the substrate can include washing with an 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) can comprise an aqueous or organic emulsion. The step of rinsing the coated substrate may include rinsing with water and / or rinsing with a rinsing solution that is advantageous for the properties of the coating / film.

In another aspect, the invention provides:
a) a container;
b) relates to a pack comprising the radically curable coating composition of the invention, provided that the container is breathable.

  The present invention also extends to a coating applied to a substrate using the method described above. The substrate can be a metal.

  In another aspect, the present invention extends to a coated article comprising a coating applied to a substrate utilizing the method described above. The substrate can be a metal. The present invention further provides a painted article comprising a coating applied to a substrate comprising a metal component.

  Furthermore, the coated article can have a curable composition applied thereto. Therefore, it becomes easy to match with the second substrate. The painted article can have a second substrate attached thereto.

  As will be appreciated by those skilled in the art, the metal salt of the composition of the present invention will be selected such that the anion of the metal salt does not result in deactivation of the polymerization / curing process.

  Where appropriate, all of the optional features and / or additional features of one embodiment of the present invention are optional features of another / other embodiment (s) of the present invention and / or It will be understood that it can be combined with additional features.

  Additional features and advantages of the present invention are described in the detailed description of the invention, and will be apparent from the detailed description of the invention and the drawings.

It is a figure which shows the FTIR-ATR spectrum of the surface acceleration | stimulation type | mold triethylene glycol dimethyl acrylate superposition | polymerization on the grit blast finish mild steel in 25 degreeC.

  The electrochemical column is a measure of the oxidation and reduction power of a substance based on its standard potential. The standard potential of the material is the magnitude relative to the hydrogen electrode. Metals with a negative standard (reduction) potential have a thermodynamic tendency to reduce hydrogen ions in solution. On the other hand, metal ions having a positive standard potential tend to be reduced by hydrogen gas. The reactivity column shown in Scheme 2 (above) is an extension of the electrochemical column. Normally, only a metal or element placed higher in the reactive sequence can reduce another metal or element that is subordinate in the reactive sequence. For example, iron can reduce tin, but not potassium.

  It should be understood that the order of the reactive columns can be reversed (changed) from that shown in Scheme 2. However, the terms “higher” and “lower” are understood to refer to reactive columns having the most reactive at the top and the least reactive at the bottom. I want to be. In any case in the context of the present invention, it should be understood that the metal of the metal salt is selected such that it can be reduced on the surface to which it is applied.

Basic procedure for the preparation of radical composition adhesive formulations:
A predetermined amount of metal salt and peroxide initiator were added to the monomer (10 g). The salt and peroxide were completely dissolved in the monomer by continuous stirring at room temperature. All samples were covered to block light during preparation and storage. All metal salts were used in the hydrated state as received unless otherwise indicated. All “mmol” values given for metal salts are calculated on an anhydride basis. When the peroxide used is mixed with the diluent, all calculations are based on the effective concentration of peroxide necessary to achieve the molar equivalent.

Basic procedure for testing a formulation:
Standard testing methods based on ASTM E177 and ASTM E6 were used for testing all adhesive formulations.
Equipment Tensile tester equipped with a suitable load cell.
Specimen Lap shear piece as specified by quality standards, product or test program.
Assembly Procedure 1.5 specimens were used for each test.
2. Sample surfaces were prepared when necessary. For example, mild steel lap shear was grit blasted with silicon carbide.
3. The specimens were cleaned by wiping with acetone or isopropanol before assembly.
4). The adhesive surface on each lap shear piece was 322.6 mm ² or 0.5 in ² . Mark the adhesive sample before applying it.
5. A sufficient amount of adhesive was applied to the prepared surface of one lap shear.
6). A second lap shear was placed over the adhesive and the assembly clamped each side of the adhesive surface.
Test Method After curing as specified in the test program, the shear strength was determined as follows.
1. The test specimens were placed on the grips of the tester so that the jaws grip 25.4 mm (1 inch) outside each end. The major axis of the specimen was matched to the direction of the tensile force applied through the centerline of the grip assembly.
2. The assemblies were tested at a crosshead speed of 2.0 mm / min or 0.05 inches / min unless otherwise specified.
3. The breaking load was recorded.
The following information was recorded:
1. Identification of the adhesive, including name or number, and lot number.
2. Identification of the specimen used, including the substrate and dimensions.
3. Surface treatment used for preparation of test piece.
4). Cure conditions (usually ambient room temperature only, 20-25 ° C.).
5. Test conditions (standard temperature and pressure, ie room temperature).
6). Conditioning if necessary (none, all substrates to be bonded were freshly prepared before use).
If not 7.5, the number of specimens (usually the average of 5 results for each cited result).
8). Results for each specimen.
9. Average shear strength for all duplicate measurements.
10. Failure form of each specimen as required by quality standards, product introduction or testing program.
11. Everything that deviates from this method.

Peroxide component <Example 1>
Cu (BF ₄ ) ₂ (0.1 g, 0.42 mmol) and dodecanoyl peroxide (0.33 g, 0.82 mmol) were dissolved in triethylene glycol dimethacrylate (10 g).
Adhesion performance after 24 hours at 20 ° C .:
Grit blast mild steel lap shear piece: 6.2 N / mm ²

<Example 2>
Cu (BF ₄ ) ₂ (0.1 g, 0.42 mmol) and benzoyl peroxide (0.2 g, 0.82 mmol) were dissolved in triethylene glycol dimethacrylate (10 g).
Adhesion performance after 24 hours at 20 ° C .:
Grit blast mild steel lap shear piece: 6.5 N / mm ²

<Example 3>
_{Cu (BF 4) 2 (0.1g} , 0.42mmol) and 3,3,5,7,7-pentamethyl-1,2,4-trioxepane {Trigonox (R) 311} (0.14g, 0. 82 mmol) was dissolved in triethylene glycol dimethacrylate (10 g).
Adhesion performance after 24 hours at 20 ° C .:
Grit blast mild steel lap shear piece: 4.8 N / mm ²

<Example 4>
Cu (BF ₄ ) ₂ (0.1 g, 0.42 mmol) and cumene hydroperoxide (0.13 g, 0.82 mmol) were dissolved in triethylene glycol dimethacrylate (10 g).
Adhesion performance after 24 hours at 20 ° C .:
Grit blast mild steel lap shear piece: 6.0 N / mm ²

<Example 5>
Cu (BF ₄ ) ₂ (0.1 g, 0.42 mmol) and 2,4-pentanedione peroxide (0.1 g, 0.41 mmol) were dissolved in triethylene glycol dimethacrylate (10 g).
Adhesion performance after 24 hours at 20 ° C .:
Grit blast mild steel lap shear piece: 4.1 N / mm ²

Monomer Component <Example 6>
Cu (BF ₄ ) ₂ (0.1 g, 0.42 mmol) and benzoyl peroxide (0.2 g, 0.82 mmol) were dissolved in butanediol dimethacrylate (10 g).
Adhesion performance after 24 hours at 20 ° C .:
Grit blast mild steel lap shear piece: 4.75 N / mm ²

<Example 7>
Cu (BF ₄ ) ₂ (0.1 g, 0.42 mmol) and benzoyl peroxide (0.2 g, 0.82 mmol) were dissolved in hydroxyethyl methacrylate (10 g).
Adhesion performance after 24 hours at 20 ° C .:
Grit blast mild steel lap shear piece: 5.0 N / mm ²

<Example 8>
Cu (BF ₄ ) ₂ (0.1 g, 0.42 mmol) and benzoyl peroxide (0.2 g, 0.82 mmol) were dissolved in hydroxypropyl methacrylate (10 g).
Adhesion performance after 24 hours at 20 ° C .:
Grit blast mild steel lap shear piece: 5.0 N / mm ²

Metal salt concentration <Example 9>
Cu (BF ₄ ) ₂ (0.1 g, 0.42 mmol) and benzoyl peroxide (0.1 g, 0.41 mmol) were dissolved in triethylene glycol dimethacrylate (10 g).
Adhesion performance after 0.5 minutes at 20 ° C .:
Mild steel pin and collar: 8.5 N / mm ²
Adhesion performance after 5 minutes at 20 ° C .:
Mild steel pin and collar: 10.0 N / mm ²

<Example 10>
Cu (BF ₄ ) ₂ (0.02 g, 0.084 mmol) and benzoyl peroxide (0.1 g, 0.41 mmol) were dissolved in triethylene glycol dimethacrylate (10 g).
Adhesion performance after 0.5 minutes at 20 ° C .:
Mild steel pin and collar: 5.8 N / mm ²
Adhesion performance after 5 minutes at 20 ° C .:
Mild steel pin and collar: 10.0 N / mm ²

<Example 11>
Cu (BF ₄ ) ₂ (0.01 g, 0.042 mmol) and benzoyl peroxide (0.1 g, 0.41 mmol) were dissolved in triethylene glycol dimethacrylate (10 g).
Adhesion performance after 0.5 minutes at 20 ° C .:
Mild steel pin and collar: 9.0 N / mm ²
Adhesion performance after 5 minutes at 20 ° C .:
Mild steel pin and collar: ^2.5 N / mm ²

Metal salt component <Example 12>
Cu (ClO ₄ ) ₂ (0.08 g) and benzoyl peroxide (0.1 g, 0.41 mmol) were dissolved in triethylene glycol dimethacrylate (10 g).
Adhesion performance after 24 hours at 20 ° C .:
Grit blast mild steel lap shear piece: 8 N / mm ²

<Example 13>
Cu (naphthenate) ₂ {8% in white spirit} (0.08 g) and benzoyl peroxide (0.1 g, 0.41 mmol) were dissolved in triethylene glycol dimethacrylate (10 g).
Adhesion performance after 24 hours at 20 ° C .:
Grit blast mild steel lap shear piece: 3.7 N / mm ²

<Example 14>
Cu (ethyl hexanoate) ₂ (0.08 g) and benzoyl peroxide (0.1 g, 0.41 mmol) were dissolved in triethylene glycol dimethacrylate (10 g).
Adhesion performance after 24 hours at 20 ° C .:
Grit blast mild steel lap shear piece: 3.2 N / mm ²

<Example 15>
Cu (benzoate) ₂ (0.08 g) and benzoyl peroxide (0.1 g, 0.41 mmol) were dissolved in triethylene glycol dimethacrylate (10 g).
Adhesion performance after 24 hours at 20 ° C .:
Grit blast mild steel lap shear piece: 5.7 N / mm ²

<Example 16>
Cu (NO ₃ ) ₂ (0.08 g) and benzoyl peroxide (0.1 g, 0.41 mmol) were dissolved in triethylene glycol dimethacrylate (10 g).
Adhesion performance after 72 hours at 20 ° C .:
Grit blast mild steel lap shear piece: 2.0 N / mm ²

<Example 17>
CuCl ₂ (0.08 g) and benzoyl peroxide (0.1 g, 0.41 mmol) were dissolved in triethylene glycol dimethacrylate (10 g).
Adhesion performance after 72 hours at 20 ° C .:
Grit blast mild steel lap shear piece: 4.5 N / mm ²

<Example 18>
Cu (acetylacetonate) ₂ (0.08 g) and benzoyl peroxide (0.1 g, 0.41 mmol) were dissolved in triethylene glycol dimethacrylate (10 g).
Adhesion performance after 24 hours at 20 ° C .:
Grit blast mild steel lap shear piece: 2.6 N / mm ²

<Example 19>
Fe (ClO ₄ ) ₃ (0.08 g) and benzoyl peroxide (0.1 g, 0.41 mmol) were dissolved in triethylene glycol dimethacrylate (10 g).
Adhesion performance after 24 hours at 20 ° C .:
Grit blast mild steel lap shear piece: 7.0 N / mm ²

<Example 20>
Zn (ClO ₄ ) ₂ (0.08 g) and benzoyl peroxide (0.1 g, 0.41 mmol) were dissolved in triethylene glycol dimethacrylate (10 g).
Adhesion performance after 24 hours at 20 ° C .:
Grit blast mild steel lap shear piece: 7.0 N / mm ²

<Example 21>
Zn (BF ₄ ) ₂ (0.2 g) and benzoyl peroxide (0.1 g, 0.41 mmol) were dissolved in triethylene glycol dimethacrylate (10 g).
Adhesion performance after 24 hours at 20 ° C .:
Grit blast mild steel lap shear piece: 7.8 N / mm ²

<Example 22>
Cu (BF ₄ ) ₂ (0.2 g), Zn (BF ₄ ) ₂ (0.2 g) and benzoyl peroxide (0.1 g, 0.41 mmol) were dissolved in triethylene glycol dimethacrylate (10 g).
Adhesion performance after 24 hours at 20 ° C .:
Grit blast mild steel lap shear piece: 7.8 N / mm ²

<Example 23>
Cu (BF ₄ ) ₂ (0.2 g), Zn (ClO ₄ ) ₃ (0.2 g) and benzoyl peroxide (0.1 g, 0.41 mmol) were dissolved in triethylene glycol dimethacrylate (10 g).
Adhesion performance after 24 hours at 20 ° C .:
Grit blast mild steel lap shear piece: 5.5 N / mm ²

<Example 24>
Fe (ClO ₄ ) ₃ (0.2 g), Zn (BF ₄ ) ₂ (0.2 g) and benzoyl peroxide (0.1 g, 0.41 mmol) were dissolved in triethylene glycol dimethacrylate (10 g).
Adhesion performance after 24 hours at 20 ° C .:
Grit blast mild steel lap shear piece: 6.4 N / mm ²

<Example 25>
Fe (ClO ₄ ) ₃ (0.2 g), Zn (ClO ₄ ) ₂ (0.2 g) and benzoyl peroxide (0.1 g, 0.41 mmol) were dissolved in triethylene glycol dimethacrylate (10 g).
Adhesion performance after 24 hours at 20 ° C .:
Grit blast mild steel lap shear piece: 6.5 N / mm ²

Radical coating composition:
100 mL of the radical curable formulation of the present invention was prepared. This formulation was placed in an appropriately sized bath.

Typical radical formulation:
a. Triethylene glycol dimethacrylate (91%)
b. Benzoyl peroxide (30% water based) (3%)
c. Copper tetrafluoroborate hydrate (3%)
d. Zinc tetrafluoroborate hydrate (3%)

  It will be appreciated by those skilled in the art that the above coating formulations are only representative formulations listed for illustration. This coating formulation can be changed to monomers, metal salts, concentrations, etc. suitable for the end use of the coating formulation.

  Metal substrates (10 × 2.5 cm) were cleaned by wiping with acetone and immersed in these formulations. Metal substrates were submerged in baths containing these formulations. Immersion time was dependent on the difference in standard potential between the surface and the metal salt in the composition, as well as the desired coating thickness (if required to be less than the self-limit thickness). After coating / polymerization was complete, residual monomer was removed by washing. The resulting membrane was analyzed by FTIR-ATR.

A coating on a grit blasted mild steel substrate using a radical curable monomer is shown in FIG. Triethylene glycol dimethacrylate monomer has a characteristic C = C IR stretch at 1635 cm ⁻¹ . It can be seen that the IR stretching strength of triethylene glycol dimethacrylate C = C at 1635 cm ⁻¹ is decreased by repeatedly scanning the sample at intervals of 30 seconds. This demonstrates the formation of a polymeric coating on the surface of the grit blasted mild steel.

  As used herein with respect to the present invention, the terms “comprises / comprising” and “having / including” are express features Used to specify the presence of an integer, step or component, but does not exclude the presence or addition of one or more other features, integers, steps, components or groups thereof.

  It should be understood that certain features of the invention described in the context of separate embodiments for clarity may also be provided in combination as one embodiment. Conversely, various features of the invention described in the context of one embodiment for the sake of brevity can also be provided separately or in any suitable subcombination.

Claims (39)

A radical curable composition for curing on a surface,
i) a radical curable component;
ii) a free radical generating component;
iii) at least one metal salt,
A standard reduction potential of the at least one metal salt is higher than a standard reduction potential of the surface;
When the composition is placed in contact with the surface, the metal salt is reduced on the surface and interacts with the free radical generating component, thereby curing the radical curable component of the composition. Radical curable composition to be initiated.   The curable composition of claim 1, wherein the at least one metal salt comprises a transition metal cation.   The curable composition of claim 2, wherein the transition metal cation is selected from copper, iron, zinc, and combinations thereof. The metal salt is naphthenate, ethylhexanoate, benzoate, nitrate, chloride, acetylacetonate, ClO ₄ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , (C ₆ F ₅ ) ₄ B The curable composition of claim 1, comprising a counterion selected from the group consisting of: (C ₆ F ₅ ) ₄ Ga, carborane, triflimide, bis-triflimide, and combinations thereof.   The curable composition of claim 1, wherein the radical initiating component is selected from the group consisting of peroxides, hydroperoxides, hydroperoxide precursors, persulfates, and combinations thereof.   The radical initiating component is cumene hydroperoxide, tert-butyl hydroperoxide, hydrogen peroxide, 2-butanone peroxide, di-tert-butyl peroxide, dicumyl peroxide, lauroyl peroxide, 2,4-pentanedione peroxide, pentamethyl- The curable composition of claim 1 selected from the group consisting of trioxepane, benzoyl peroxide and combinations thereof.   The curable composition according to claim 1, wherein the radically curable component has at least one functional group selected from the group consisting of acrylate, methacrylate, thiolene, siloxane, vinyl, and combinations thereof.   The curable composition of claim 1, wherein the surface comprises a metal, metal oxide or metal alloy.   The hardening 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. Sex composition.   The curable composition of claim 1 further comprising a metal oxide remover.   The curable composition of claim 11, 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 for effecting electron transfer between the surface and the metal salt.   The curable composition of claim 1 for attaching a first metal substrate to another substrate.   The curable composition of claim 1 for sealing.   Use of the composition according to claim 1 in screw locking, flange sealing, metal bonding and / or structural bonding. An initiator package for initiating curing of a radical curable component,
i) a free radical generating component;
ii) an initiator package comprising at least one metal salt. The counter ion of the metal salt is naphthenate, ethylhexanoate, benzoate, nitrate, chloride, acetylacetonate, ClO ₄ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , (C ₆ F _{5 ) 4 B, (C 6 F} 5) 4 Ga, carborane, triflimide, bis - triflimide, and is selected from the group consisting of an initiator package according to claim 16. A method of joining two substrates,
(I) i) a radical curable component;
ii) a free radical generating component;
iii) applying a composition comprising at least one metal salt to at least one of the substrates;
(Ii) combining the first substrate and the second substrate to form a bond with the composition;
A method wherein a standard reduction potential of the at least one metal salt is higher than at least one standard reduction potential of the substrate.   The method of claim 18, wherein the at least one substrate comprises a metal, metal oxide or metal alloy.   The method of claim 18, wherein the at least one substrate comprises a metal. a) a container;
b) A pack comprising the radical curable composition according to claim 1.   The pack of claim 21, wherein the container is breathable. A curable coating composition for coating a surface,
i) a radical curable component;
ii) a free radical generating component;
iii) at least one metal salt,
A standard reduction potential of the at least one metal salt is higher than a standard reduction potential of the surface;
When the composition is placed in contact with the surface, the metal salt is reduced on the surface and interacts with the free radical generating component, thereby curing the radical curable component of the composition. A curable coating composition to be initiated.   24. The coating composition of claim 23, wherein the metal salt comprises a transition metal cation.   25. The coating composition of claim 24, wherein the transition metal cation is selected from copper, iron, zinc, and combinations thereof. The metal salt is naphthenate, ethylhexanoate, benzoate, nitrate, chloride, acetylacetonate, ClO ₄ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , (C ₆ F ₅ ) ₄ B _{, (C 6 F 5) 4} Ga, carborane, triflimide, bis - triflimide, and a counter ion selected from the group consisting of coating composition according to claim 23.   24. The coating composition of claim 23, wherein the radical generating component is selected from the group consisting of peroxides, hydroperoxides, hydroperoxide precursors, persulfates, and combinations thereof.   The radical generating component is cumene hydroperoxide, tert-butyl hydroperoxide, hydrogen peroxide, 2-butanone peroxide, di-tert-butyl peroxide, dicumyl peroxide, lauroyl peroxide, 2,4-pentanedione peroxide, 3, 24. The coating composition of claim 23, selected from the group consisting of 3,5,7,7-pentamethyl-1,2,4-trioxepane, benzoyl peroxide and combinations thereof.   24. The coating composition of claim 23, wherein the radical curable component of the coating composition has at least one functional group selected from the group consisting of acrylate, methacrylate, thiolene, siloxane, vinyl, and combinations thereof.   24. The coating composition of claim 23, wherein the surface comprises a metal, metal oxide or metal alloy.   24. The coating of claim 23, 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. Composition. A method of coating a substrate, comprising:
i) a radical curable component;
ii) a free radical generating component;
iii) applying to the substrate a coating composition comprising at least one metal salt, wherein the standard reduction potential of the at least one metal salt is higher than at least one standard reduction potential of the substrate.   33. A coating applied to a substrate using the method of claim 32.   34. A coated article comprising the coating of claim 33 and a substrate.   35. The coated article of claim 34, to which a curable composition is applied.   35. The coated article of claim 34, combined with a second substrate.   The coated article of claim 34, to which the second substrate is attached. a) a container;
b) A pack comprising the radically curable coating composition according to claim 23.   40. The pack of claim 38, wherein the container is breathable.

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