Underwater bonding method

Abstract

A method for bonding substrates in water, comprising applying a cyanoacrylate composition to at least one substrate in water, and curing the composition in water.

Description

[Technical Field]

[0001] This invention provides a method for underwater adhesion using a curable cyanoacrylate composition. [Background technology]

[0002] Curing compositions such as cyanoacrylate adhesives are well-established for their excellent ability to quickly bond a wide range of substrates, generally in minutes, and often in seconds, depending on the specific substrate.

[0003] Cyanoacrylate adhesive compositions are well known and widely used as fast-drying instant adhesives, with a wide range of applications. See HVCoover, DWDreifus, and JTO'Connor, “Cyanoacrylate Adhesives,” “Handbook of Adhesives,” 27, 463-77, edited by I. Skeist, Van Nostrand Reinhold, New York, 3rd edition (1990). See also GHMillet, “Cyanoacrylate Adhesives,” “Structural Adhesives: Chemistry and Technology,” edited by S.R. Hartshorn, Plenum Press, New York, pp. 249-307 (1986).

[0004] Cyanoacrylate adhesive compositions are extremely well-suited for curing in air. Benefitingly, these compositions achieve handling strength in seconds when cured in air, and >60% strength within one minute.

[0005] The polymerization of cyanoacrylate is initiated by nucleophiles found on most surfaces under normal atmospheric conditions. Surface chemistry initiation means that sufficient initiating species are available when two surfaces are in close contact with a small layer of cyanoacrylate between them. Under these conditions, strong adhesion is achieved in a short time. Therefore, essentially, cyanoacrylate often functions as a super glue.

[0006] Because cyanoacrylate adhesive compositions are difficult to dispense underwater, they have not conventionally been used in underwater applications. It will be understood that "underwater" means that the substrate to be bonded is completely immersed in water. The water is in contact with the substrate. As used herein, "underwater" does not refer to a situation where the substrate is in water but is not in contact with the water. For example, if the substrate is placed in a waterproof container and the container is in contact with water, but the waterproof container keeps the substrate dry, the substrate itself is not in contact with water; this is not considered "underwater." In particular, the present invention relates to a method of using a cyanoacrylate adhesive that is dispensed from a container while underwater. In such cases, the cyanoacrylate adhesive is dispensed through the water onto the surface of the substrate, and the surface of the substrate is also in contact with the water.

[0007] Dispensing cyanoacrylate adhesive compositions underwater can cause them to react with the water, potentially leading to faster curing than intended before application to the substrate they are intended to bond. In fact, cyanoacrylate compositions are well known to be susceptible to water, and in some cases, even small amounts of water can cause faster curing than intended, for example, during storage for later use.

[0008] The performance, particularly the durability, of cyanoacrylate adhesives is often questionable when exposed to water. Adhesion formed using cured cyanoacrylate compositions can be susceptible to water damage. For example, the formed adhesive may eventually peel off when exposed to water due to the degradation of the cured cyanoacrylate composition over time. In general, exposure to water causes a loss of adhesive strength over time.

[0009] When a cyanoacrylate adhesive composition is discharged in water, it may also partially cure when applied to a first substrate, but before bonding to a second substrate. In this case, it may be possible to form an adhesion between the substrates, but the bond will be weak because the composition partially cures before the substrates are joined together.

[0010] To overcome these problems, typically, the cyanoacrylate adhesive composition can be applied to the substrate in air, and then the bonded substrate is placed in water.

[0011] Underwater bonding using cyanoacrylate adhesive compositions would be advantageous for applications where the properties of cyanoacrylate adhesive compositions are beneficial. In situations where it is difficult to remove the substrate from the water, it would be beneficial to dispense and cure the cyanoacrylate adhesive composition underwater. For example, when repairing a boat, it would be beneficial to use a cyanoacrylate adhesive composition to bond boat parts underwater. [Prior art documents] [Non-patent literature]

[0012] [Non-Patent Document 1] HVCoover, DWDreifus, and JTO'Connor, “Cyanoacrylate Adhesives,” “Handbook of Adhesives,” 27, 463–77, edited by I. Skeist, Van Nostrand Reinhold, New York, 3rd edition (1990). [Non-Patent Document 2] GH Millet, “Cyanoacrylate Adhesives,” in “Structural Adhesives: Chemistry and Technology,” edited by S.R. Hartshorn, Plenum Press, New York, pp. 249–307 (1986). [Overview of the project] [Problems that the invention aims to solve]

[0013] It would be beneficial to provide an alternative adhesive that (1) is dispensed while immersed, (2) remains in an uncured state for a sufficient time to allow application to the substrate to be bonded, (3) then cures preferably with a short open time, (4) produces high-strength adhesion, and (5) can maintain adhesive strength. All of the above must be achieved in water. [Means for solving the problem]

[0014] In one embodiment, the present invention is a method for bonding substrates in water, (a) Applying a cyanoacrylate composition to at least one substrate in water, Here, the cyanoacrylate composition is i. A first part comprising a cyanoacrylate component and a peroxide catalyst; and ii. Second part containing free radical curable components and transition metals Includes, When mixed together, the peroxide catalyst initiates the curing of the free radical curable component, and the transition metal initiates the curing of the cyanoacrylate component, and (b) curing the composition in water This provides a method that includes [something].

[0015] "Underwater" means that the substrate is immersed in water so that the water comes into contact with the substrate at the same time the composition is applied. The substrate is not, for example, contained in a waterproof container so that the substrate is not directly exposed to water. Beneficially, this method enables underwater bonding in applications that were previously excluded because it was not possible to remove and dry the assembly before bonding.

[0016] Beneficially, the composition applied in this method can be dispensed while immersed, remains in an uncured state for a sufficient time to allow application to the substrate to be bonded, and then cures in a short curing time. Beneficially, the cured composition cured in water produces a high-strength bond that maintains its adhesive strength over a long period. Preferably, the composition has a sufficiently long open time to allow the composition to be dispensed, applied, and bonded to (one or more) substrates before it cures, but has a faster curing time than compositions used in previous methods to minimize the time the user must spend in water.

[0017] The recognized drawbacks of cyanoacrylate compositions for bonding substrates in water can be overcome by the cyanoacrylate hybrid compositions disclosed herein. The cyanoacrylate compositions used in the methods of the present invention are curable. All desirable properties of the present invention refer to the properties of the compositions in an underwater environment. The compositions of the present invention remain in place when discharged. The compositions of the method can be discharged in water and do not undergo premature curing upon first contact with water, which would, for example, prevent the discharge of the composition onto a substrate. A film may form at the site of first contact with water, but curing throughout the composition does not occur, which could prevent discharge. The compositions of the method may have an appropriate viscosity that allows for the discharge of the compositions of the method. The compositions may have appropriate buoyancy. For example, it is preferable that the compositions of the method are not carried away from their place by forces generated by normal water flow.

[0018] This composition can be used in a method of dispensing in water and bonding substrates submerged in water. While we do not wish to be bound by theory, it is believed that the combination of the curing rate adjustment by the hybrid acrylate portion and the material's inherently high viscosity results in this unexpected open time in an aqueous environment. The first portion of this composition may have a cone-plate viscosity of 4000 to 11000 mPa.s. The second portion may have a cone-plate viscosity of 45000 to 75000 mPa.s.

[0019] The cyanoacrylate composition may be applied in a volume ratio of approximately 1:1 between the first and second parts.

[0020] A method for bonding substrates in water may involve exposing the composition to water for up to 45 seconds before bonding the surface of the second substrate to the coated surface of the first substrate. This may be referred to as the composition's open time. The composition may have a good open time of up to 90 seconds, for example, up to 60 seconds, for example, up to 45 seconds. Beneficially, a good open time allows time for the substrates to bond properly before the composition hardens. The good open time allows time for assembly so that the substrates can be assembled into an assembly in the correct position. The composition has a good open time, allowing the nozzle (for dispensing the composition) to be replaced in water without the composition hardening. The composition has a good open time, although it may form a film on the top layer of the film, without hardening internally.

[0021] In a method for bonding substrates in water, the composition does not mix with water, for example, in a water column, nor does it disperse in water otherwise. The physical properties of the composition, such as its viscosity, are such that it does not mix with water and remains where it is applied. The outermost layer of the composition can harden to form a film, preventing the majority of the composition from coming into contact with water. In this respect, volume curing of the composition can occur even after the two substrates have come into contact.

[0022] In a method for bonding substrates submerged in water, one or both substrates may be metal; for example, one or both substrates may be steel.

[0023] In a method for bonding substrates in water, at least one substrate may include a material selected from the group including steel, aluminum, wood, plastic, fiberglass, building materials including aggregates, sand, concrete / cement materials including ferrocement, and fiber-reinforced plastics.

[0024] Appropriately, both substrates may independently include materials selected from the group including building materials such as steel, aluminum, wood, plastics, fiberglass, and aggregates, concrete / cement materials such as sand and ferrocement, and fiber-reinforced plastics.

[0025] In a method for bonding substrates submerged in water, at least one substrate may be a vessel such as a boat or ship, or a part thereof. This method can be used to attach articles to a boat or ship, for example, to attach sensors or replacement parts, or to perform repairs on a boat or ship. Using the method of the present invention, this can be done without the need to return the boat or ship to land to remove it from the water.

[0026] In a method for bonding substrates in water, at least one substrate may be a structure located in water, or part of a structure extending underwater, such as a bridge, oil or gas rig, pipeline, dam, or wind turbine. Such structures cannot be removed from the water, and therefore it is beneficial to be able to attach or repair items, such as accessories, sensors, or replacement parts, while they are submerged.

[0027] In a method for bonding substrates submerged in water, one or both substrates may be metal. In a method for bonding substrates submerged in water, one or both substrates may be plastic material.

[0028] In a method for bonding substrates submerged in water, the nozzle life can be at least 4 minutes, for example, at least 5 minutes. Since the composition does not cure faster than usual and clog the nozzle, the dispensing nozzle has excellent nozzle life. This is surprising, as compositions containing cyanoacrylate typically experience rapid curing when exposed to moisture, for example, in water. Beneficial, the nozzle life is increased, and therefore, more compositions can be applied before the nozzle needs to be replaced.

[0029] Methods for bonding substrates in water can be carried out in water containing varying amounts of salt and / or inorganic substances. For example, the method can be carried out in distilled water or treated water, such as that found in public water / tap water supplies. The method can be carried out in freshwater, such as in wells, rivers, or lakes. The method can be carried out in saltwater, such as seawater, for example, in water with a salt content of approximately 30 g / L to approximately 50 g / L.

[0030] The method for bonding substrates in water can be carried out in water having a pH in the range of approximately 6 to 9, for example, approximately 6.5 to 8 or approximately 7.5 to 8.5.

[0031] In a method for bonding substrates in water, the peroxide catalyst may contain perbenzoic acid.

[0032] The present invention further relates to the use of a cyanoacrylate composition for underwater adhesion of a substrate, wherein the composition is A first part comprising a cyanoacrylate component and t-butyl perbenzoate as a peroxide catalyst, present in an amount of about 0.01% to about 10% relative to the weight of the cyanoacrylate component; and Second part containing free radical-curable components and transition metals Includes, The cyanoacrylate component comprises H2C=C(CN)-COOR [wherein R is selected from alkyl, alkoxyalkyl, cycloalkyl, alkenyl, aralkyl, aryl, allyl, and haloalkyl], and when mixed together, the peroxide catalyst initiates the curing of the free radical curable component, and the transition metal initiates the curing of the cyanoacrylate component, thereby providing a suitable application.

[0033] The present invention relates to an assembly comprising two underwater substrates bonded together by a cyanoacrylate composition, wherein the cyanoacrylate composition is A first part comprising a cyanoacrylate component and t-butyl perbenzoate as a peroxide catalyst, present in an amount of about 0.01% to about 10% relative to the weight of the cyanoacrylate component; and Second part containing free radical-curable components and transition metals Includes, The cyanoacrylate component comprises H2C=C(CN)-COOR, where R is selected from alkyl, alkoxyalkyl, cycloalkyl, alkenyl, aralkyl, aryl, allyl, and haloalkyl groups, and also provides an assembly in which, when mixed together, the peroxide catalyst initiates the curing of the free radical curable component, and the transition metal initiates the curing of the cyanoacrylate component. The assembly will be understood to comprise two substrates bonded together by curing the cyanoacrylate composition.

[0034] In the assembly of the present invention, one or both base materials may be metal. One or both base materials may be steel.

[0035] In the assembly of the present invention, one or both of the base materials may be made of plastic material. [Modes for carrying out the invention]

[0036] This method for bonding substrates in water comprises applying at least one of the compositions disclosed herein to a substrate in water, and curing the composition.

[0037] The nozzle life may be at least 4 minutes, for example, at least 5 minutes. This means that within this time, the composition will not harden while it is being applied in the nozzle used for dispensing. A thin layer of the composition may harden at the nozzle tip where the composition is in contact with water. The main body of the composition in the nozzle body that is not in contact with water remains unhardened. Since the composition has an excellent nozzle life in water, it will still be possible to dispense the composition from the nozzle.

[0038] Beneficially, the composition may be exposed to water for up to 45 seconds (for example, immersed in water) before bonding the surface of the second substrate to the coated surface of the first substrate, and the composition can remain in an uncured state and form adhesion between the substrates.

[0039] This method involves curing a composition in water. The composition is not removed from the water for curing. Once cured, the formed adhesion is strong. Once cured, the formed adhesion maintains its strength over a long period, making the method of the present invention suitable for long-term bonding of substrates.

[0040] <Part A of the composition> The cyanoacrylate component contains a cyanoacrylate monomer. The cyanoacrylate component may contain H2C=C(CN)-COOR, where R is selected from alkyl, alkoxyalkyl, cycloalkyl, alkenyl, aralkyl, aryl, allyl, and haloalkyl groups, for example, where R is C 1~15 Alkyl, C 2~15 Alkoxyalkyl, C 3~15 Cycloalkyl, C 2~15 Alkenil, C 7~15 Aralquil, C 6~15 Ariel, C 3~15Allyl and C 1~15 The monomer is selected from haloalkyl groups. Preferably, the cyanoacrylate monomer is selected from methyl cyanoacrylate, ethyl-2-cyanoacrylate ("ECA"), propyl cyanoacrylate, butyl cyanoacrylate (such as n-butyl-2-cyanoacrylate), octyl cyanoacrylate, allyl cyanoacrylate, β-methoxyethyl cyanoacrylate, and combinations thereof. Ethyl-2-cyanoacrylate is particularly preferred.

[0041] The cyanoacrylate component may be included in partial composition A in an amount ranging from about 50% to about 99.98% by weight, for example, about 90% to about 99% by weight is preferred, and about 92% to about 97% by weight of partial composition A is particularly preferred.

[0042] t-butyl perbenzoate can be used as the peroxide catalyst to be included in the partial A composition of the two-component adhesive system.

[0043] Typically, the amount of peroxide catalyst should be in the range of about 0.001% to about 10.00% by weight of the composition, preferably about 0.01% to about 5.00% by weight of the composition, for example, in the range of about 0.50 to 2.50% by weight of the composition.

[0044] Additives may be included in the partial A composition of the adhesive system to modify physical properties such as improved setting speed, improved shelf life stability, flexibility, thixotropy, increased viscosity, color, and improved toughness. Such additives may be selected from accelerators, free radical stabilizers, anionic stabilizers, gelling agents, thickeners [such as PMMA], thixotropy imparters (such as fumed silica), dyes, toughening agents, plasticizers, and combinations thereof.

[0045] To promote the curing of the cyanoacrylate component, one or more accelerators may also be used in the adhesive system, particularly in the Part A composition. Such accelerators may be selected from calixarenes and oxacalixarenes, sila-crowns, crown ethers, cyclodextrins, poly(ethylene glycol) di(meth)acrylate, ethoxylated hydroxyl-containing compounds, and combinations thereof.

[0046] Many calixarenes and oxacalixarenens are known and reported in the patent literature. See, for example, U.S. Patent Nos. 4,556,700, 4,622,414, 4,636,539, 4,695,615, 4,718,966, and 4,855,461. The disclosures of each of these are expressly incorporated herein by reference.

[0047] For example, with respect to calixarenes, those having the structure below are useful herein.

Chemical Formula

[0048] One particularly desirable calixarene is tetrabutyltetra[2-ethoxy-2-oxoethoxy]calix-4-arene.

[0049] Numerous crown ethers are known. For example, examples that may be used individually or in combination herein include 15-crown-5, 18-crown-6, dibenzo-18-crown-6, benzo-15-crown-5-dibenzo-24-crown-8, dibenzo-30-crown-10, tribenzo-18-crown-6, asym-dibenzo-22-crown-6, dibenzo-14-crown-4, dicyclohexyl-18-crown-6, dicyclohexyl-24-crown-8, cyclohexyl-12-crown-4, and 1,2-decalyl-15-crown-5. Examples include 1,2-naphtho-15-crown-5, 3,4,5-naphthyl-16-crown-5, 1,2-methyl-benzo-18-crown-6, 1,2-methylbenzo-5,6-methylbenzo-18-crown-6, 1,2-t-butyl-18-crown-6, 1,2-vinylbenzo-15-crown-5, 1,2-vinylbenzo-18-crown-6, 1,2-t-butyl-cyclohexyl-18-crown-6, asym-dibenzo-22-crown-6, and 1,2-benzo-1,4-benzo-5-oxygen-20-crown-7. See U.S. Patent No. 4,837,260 (Sato), whose disclosure is expressly incorporated herein by reference.

[0050] Many of the sila crowns are also known and reported in the literature. For example, a typical sila crown can be represented in the following structure. [ka] In the formula, R 3 and R 4 R is an organic group that does not itself cause polymerization of cyanoacrylate monomers. 5 is H or CH3, and n is an integer from 1 to 4. Suitable R 3 and R 4 Examples of groups include the R group, alkoxy groups such as methoxy, and aryloxy groups such as phenoxy. 3 and R 4 The group may contain halogens or other substituents, for example, trifluoropropyl. However, R4 and R 5 Groups that are not suitable as bases are basic groups such as amino, substituted amino, and alkylamino groups.

[0051] Specific examples of silacrown compounds useful in the compositions of the present invention include the following: [ka] Dimethylsila-11-crown-4; [ka] Dimethylsila-14-crown-5; [ka] and dimethylsila-17-crown-6. See, for example, U.S. Patent No. 4,906,317 (Liu), whose disclosure is expressly incorporated herein by reference.

[0052] Many cyclodextrins can be used in connection with the present invention. For example, the claimed cyclodextrins described in U.S. Patent No. 5,312,864 (Wenz), whose disclosure is expressly incorporated herein by reference, as hydroxyl group derivatives of α, β, or γ-cyclodextrins (alpha-, beta-, or gamma-cyclodextrins) that are at least partially soluble in cyanoacrylates, would be a suitable choice for use herein as an accelerating component.

[0053] Furthermore, poly(ethylene glycol) di(meth)acrylates suitable for use in this specification include those with the following structures: [ka] In the formula, n is greater than 3, for example, in the range of 3 to 12, and n is particularly preferred to be 9. More specific examples include PEG200 DMA (n is approximately 4), PEG400 DMA (n is approximately 9), PEG600 DMA (n is approximately 14), and PEG800 DMA (n is approximately 19), where the number (e.g., 400) represents the average molecular weight of the glycol portion of the molecule excluding the two methacrylate groups, expressed in grams / moles (i.e., 400 g / mol). A particularly preferred PEG DMA is PEG cC400 DMA.

[0054] Furthermore, suitable ethoxylated hydroxyl-containing compounds (or ethoxylated fatty alcohols that can be used) may be selected from those with the following structures. [ka] In the formula, C m can be a linear or branched alkyl or alkenyl chain, m is an integer from 1 to 30, e.g., 5 to 20, n is an integer from 2 to 30, e.g., 5 to 15, and R is H or alkyl, e.g., C 1~6 It can be alkyl.

[0055] Furthermore, accelerators are contained within the following structure. [ka] In the formula, R is hydrogen, C 1~6 Alkyl, C 1~6 Alkyloxy, alkylthioether, haloalkyl, carboxylic acids and their esters, sulfinic acid, sulfonic acid and sulfite and their esters, phosphinic acid, phosphonic acid and phosphorous acid and their esters, where Z is a polyether bond, n is 1 to 12, p is 1 to 3 as defined above, R' is the same as R, and g is the same as n.

[0056] The following chemicals are particularly desirable as accelerator components within this class: [ka] In the formula, the combined values ​​of n and m are 12 or greater.

[0057] The accelerator may be included in the composition in an amount ranging from about 0.01% to about 10% by weight, preferably in the range of about 0.1% to about 0.5% by weight, and particularly preferably about 0.4% by weight of the total composition.

[0058] Useful stabilizers in adhesive-based partial composition A include free radical stabilizers, anionic stabilizers, and stabilizer packages containing combinations thereof. The types and amounts of such stabilizers are well known to those skilled in the art. See, for example, U.S. Patents 5,530,037 and 6,607,632, the disclosures of which are incorporated herein by reference. Commonly used free radical stabilizers include hydroquinone, and commonly used anionic stabilizers include boron trifluoride, boron trifluoride etherate, sulfur trioxide (and its hydrolysis products), and methanesulfonic acid.

[0059] <Part B of the composition> Examples of free radical-curable monomers for use in the adhesive system's partial B composition include (meth)acrylate monomers, maleimide-containing compounds, itaconamide-containing compounds, or nadiimide-containing compounds, and combinations thereof.

[0060] Numerous (meth)acrylate monomers are available for use in part B of the adhesive composition, some of which are aromatic, others aliphatic, and still others alicyclic. Examples of such (meth)acrylate monomers include polyethylene glycol di(meth)acrylate, tetrahydrofuran (meth)acrylate and di(meth)acrylate, hydroxypropyl (meth)acrylate ("HPMA"), hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate ("TMPTMA"), diethylene glycol dimethacrylate, triethylene glycol dimethacrylate ("TRIEGMA"), benzyl methacrylate, tetraethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, and di(pentamethylene glycol). Examples include difunctional or trifunctional (meth)acrylates such as dimethacrylate, tetraethylenediglycol diacrylate, diglycerol tetramethacrylate, tetramethylene dimethacrylate, ethylenedimethacrylate, neopentyl glycol diacrylate, and trimethylolpropane triacrylate, as well as bisphenol A mono and di(meth)acrylates such as ethoxylated bisphenol A (meth)acrylate ("EBIPMA"), bisphenol F mono and di(meth)acrylates such as ethoxylated bisphenol F (meth)acrylate, and methacrylate-functional urethanes.

[0061] Examples of maleimides, nadiimides, and itaconimides include compounds having the following structures I, II, and III, respectively. [ka] During the ceremony: m=1~15, p=0~15, Each R 2 These are independently selected from hydrogen or lower alkyl groups. J is a monovalent or polyvalent moiety that includes an organic group or an organosiloxane group, and two or more combinations thereof.

[0062] More specific representations of maleimides, itaconimides, and nadiimides correspond to structures I, II, or III, where m=1 to 6, p=0, and R 2J is independently selected from hydrogen or lower alkyl, and J is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, substituted heteroatom-containing hydrocarbylene, polysiloxane, polysiloxane-polyurethane block copolymer and two or more combinations thereof, covalently bonded, -O -, -S-, -NR-, -OC(O)-, -OC(O)-O-, -OC(O)-NR-, -NR-C(O)-, -NR-C(O)-O-, -NR-C(O)-NR-, -SC(O)-, -SC(O)-O-, -SC(O)-NR- , -S(O)-, -S(O)2-, -OS(O)2-, -OS(O)2-O-, -OS(O)2-NR-, -OS(O)-, -OS(O)-O-, -OS(O)-NR-, -O-NR-C(O)-, -O-NR-C(O)-O-, -O-NR-C(O)-NR-, -NR-OC(O)-, -NR-OC(O)-O-, -NR-OC(O)-NR-, -O-NR-C(S)-, -O-NR-C(S)-O-, -O-NR-C(S)-NR-, -NR-OC(S) -, -NR-OC(S)-O-, -NR-OC(S)-NR-, -OC(S)-, -OC(S)-O-, -OC(S)-NR-, -NR-C(S)-, -NR-C(S)-O-, -NR-C(S)-NR-, -SS(O)2-, - SS(O)2-O-, -SS(O)2-NR-, -NR-OS(O)-, -NR-OS(O)-O-, -NR-OS(O)-NR-, -NR-OS(O)2-, -NR-OS(O)2-O-, -NR-OS(O)2-NR-, -O -NR-S(O)-, -O-NR-S(O)-O-, -O-NR-S(O)-NR-, -O-NR-S(O)2-O-, -O-NR-S(O)2-NR-, -O-NR-S(O)2-, -OP(O)R2-, -SP(O)R2-, A monovalent or polyvalent group optionally containing one or more linkers selected from -NR-P(O)R2-, where each R is independently hydrogen, alkyl or substituted alkyl, or any two or more combinations thereof.

[0063] If one or more of the above monovalent or polyvalent groups contain one or more of the above linkers to form a "J" appendage of a maleimide, nadiimide, or itaconimide group, as will be readily apparent to those skilled in the art, for example, oxyalkyl, thioalkyl, aminoalkyl, carboxyalkyl, oxyalkenyl, thioalkenyl, aminoalkenyl, carboxyalkenyl, oxyalkynyl, thioalkynyl, aminoalkynyl, carboxyalkynyl, oxycycloalkyl, thiocycloalkyl, aminocycloalkyl, carboxycycloalkyl, oxychloroalkenyl, thiocycloalkenyl, aminocycloalkenyl, carboxycycloalkenyl, heterocyclic, oxyheterocyclic, thioheterocyclic, aminoheterocyclic, carboxyheterocyclic, oxyaryl, thioaryl, aminoaryl, carboxyaryl, heteroaryl, oxyheteroaryl, thioheteroaryl, aminoheteroaryl, carboxyheteroaryl, oxyalkylaryl, thioalkylaryl, aminoalkylaryl, carboxyalkylaryl, oxyarylalkyl, thioalkylaryl Oarylalkyl, aminoarylalkyl, carboxyarylalkyl, oxyarylalkenyl, thioarylalkenyl, aminoarylalkenyl, carboxyarylalkenyl, oxyalkenylaryl, thioalkenylaryl, aminoalkenylaryl, carboxyalkenylaryl, oxyarylalkynyl, thioarylalkynyl, aminoarylalkynyl, carboxyarylalkynyl, oxyalkynylaryl, thioalkynylaryl, aminoalkynylaryl or carboxyalkynylaryl, oxyalkylene, thioalkylene, aminoalkylene, carboxyalkylene, oxyalkenylene, thioalkenylene, aminoalkenylene, carboxyalkenylene, oxyalkylynylene, thioalkylynylene, aminoalkylynylene, carboxyalkylynylene, oxycycloalkylene, thiocycloalkylene, aminocycloalkylene, carboxycycloalkylene, oxycycloalkenylene, thiocycloalkenyl, aminocycloalkenylene, carboxycycloalkenylene, oxyarylene, thioarylene, aminoarylene,Carboxyaryl arylene, oxyalkyl arylene, thioaryl alkyl arylene, thioalkyl arylene, aminoalkyl arylene, carboxyalkyl arylene, oxyaryl alkyl arylene, thioaryl alkyl arylene, aminoaryl alkyl arylene, carboxyaryl alkyl arylene, oxyaryl alkenylene, thioaryl alkenylene, aminoaryl alkenylene, carboxyaryl alkenylene, oxyalkenyl arylene, thioalkenyl arylene, aminoalkenyl arylene, carboxyalkenyl arylene, oxyaryl alkyl arylene, thioaryl alkyl arylene, aminoaryl alkyl A wide variety of linkers can be produced, including nylene, carboxyarylalkylnylene, oxyalkylnylarylene, thioalkylnylarylene, aminoalkylnylarylene, carboxyalkylnylarylene, heteroarylene, oxyheteroarylene, thioheteroarylene, aminoheteroarylene, carboxyheteroarylene, heteroatom-containing divalent or polyvalent cyclic moieties, oxyheteroatom-containing divalent or polyvalent cyclic moieties, thioheteroatom-containing divalent or polyvalent cyclic moieties, aminoheteroatom-containing divalent or polyvalent cyclic moieties, carboxyheteroatom-containing divalent or polyvalent cyclic moieties, disulfides, and sulfonamides.

[0064] In another embodiment, the maleimides, nadiimides, and itaconimides intended for use in the implementation of the present invention have structures I, II, and III, where m=1 to 6, p=0 to 6, J is a saturated linear or branched alkyl, optionally comprising an aryl moiety as a substituent on the alkyl chain or as part of the alkyl chain's skeleton, and the alkyl chain has a maximum of about 20 carbon atoms; structure: -(C(R 3 )2) d -[Si(R 4 )2-O] f -Si(R 4 )2-(C(R 3 )2) e -,-(C(R 3 )2)d -C(R 3 )-C(O)O-(C(R 3 )2) d -[Si(R 4 )2-O] f -Si(R 4 )2-(C(R 3 )2) e -O(O)C-(C(R 3 )2) e -, or -(C(R 3 )2) d -C(R 3 )-O(O)C-(C(R 3 )2) d -[Si(R 4 )2-O] f -Si(R 4 )2-(C(R 3 )2) e -C(O)O-(C(R 3 )2) e - A siloxane having, where each R 3 R is independently hydrogen, alkyl, or substituted alkyl, and each R 4 These are independently hydrogen, a lower alkyl, or an aryl, with d=1-10, e=1-10, and f=1-50; structure: [(CR2) r -O-] f -(CR2) s - A polyalkylene oxide having , where each R is independently hydrogen, alkyl, or substituted alkyl, r=1 to 10, s=1 to 10, and f is as defined above; structure: [ka] An aromatic group having, where each Ar is a monosubstituted, disubstituted, or trisubstituted aromatic ring or heteroaromatic ring having 3 to 10 carbon atoms, Z is a saturated linear or branched alkylene, which optionally contains a saturated cyclic moiety as a substituent on the alkylene chain or as part of the alkylene chain's skeleton; or structure: -[(CR2) r -O-] q -(CR2) s - A polyalkylene oxide having (wherein each R is independently hydrogen, alkyl, or substituted alkyl, r and s are defined as above, respectively, and q is in the range of 1 to 50); structure: [ka] A disubstituted or trisubstituted aromatic moiety having, where each R is independently hydrogen, alkyl, or substituted alkyl, t is in the range of 2 to 10, u is in the range of 2 to 10, and Ar is as defined above; structure: [ka] Aromatic groups having, where each R is independently hydrogen, alkyl, or substituted alkyl, t=2-10, k=1, 2, or 3, g=1-approximately 50, each Ar is as defined above, and E is -O- or -NR 5 - and in the formula, R 5 is hydrogen or a lower alkyl; and W is a linear or branched alkyl, alkylene, oxyalkylene, alkenyl, alkenylene, oxyalkenylene, ester or polyester, structure-(C(R 3 )2) d -[Si(R 4 )2-O] f -Si(R 4 )2-(C(R 3 )2) e -,-(C(R 3 )2) d -C(R 3 )-C(O)O-(C(R 3 )2) d -[Si(R 4 )2-O] f -Si(R 4 )2-(C(R 3 )2) e -O(O)C-(C(R3 )2) e - or -(C(R 3 )2) d -C(R 3 )-C(O)O-(C(R 3 )2) d -[Si(R 4 )2-O] f -Si(R 4 )2-(C(R 3 )2) e -C(O)O-(C(R 3 )2) e siloxane having - (wherein each R 3 is independently hydrogen, alkyl or substituted alkyl, and each R 4 is independently hydrogen, lower alkyl or aryl, d=1 to 10, e=1 to 10, and f=1 to 50); Structure: -[(CR2) r -O-] f -(CR2) s - polyalkylene oxide having, wherein each R is independently hydrogen, alkyl or substituted alkyl, r=1 to 10, s=1 to 10, and f is as defined above, and optionally comprises a substituent selected from hydroxy, alkoxy, carboxy, nitrile, cycloalkyl or cycloalkenyl; Structure: R 7 -U-C(O)-NR 6 -R 8 -NR 6 -C(O)-(O-R 8 -O-C(O)-NR 6 -R 8 -NR 6 -C(O)) v -U-R 8 - urethane group having, wherein each R 6 is independently hydrogen or lower alkyl, each R 7 is independently an alkyl, aryl or arylalkyl group having 1 to 18 carbon atoms, each R 8is an alkyl or alkyloxy chain optionally substituted with Ar, having up to approximately 100 atoms in the chain, and U is -O-, -S-, -N(R)-, or -P(L) 1,2 - (wherein R is as defined above, and each L is independently =O, =S, -OR, or -R, and v = 0 to 50); Selected from polycyclic alkenyls; or any mixture of two or more thereof.

[0065] In the more specific descriptions of such maleimide-containing compounds, nadiimide-containing compounds, and itaconimide-containing compounds of structures I, II, and III, respectively, each R is independently hydrogen or a lower alkyl (C 1~4 (etc.), and -J- comprises branched alkyl, alkylene, alkylene oxide, alkylene carboxyl or alkyleneamide species having sufficient length and branching to liquefy maleimide, nadiimide and / or itaconimide compounds, and m is 1, 2 or 3.

[0066] Particularly desirable maleimide-containing compounds include those having two maleimide groups with an aromatic group between them, such as phenyl, biphenyl, bisphenyl, or naphthyl bonds.

[0067] In addition to free radical-curable components, part B also includes transition metal compounds. A non-exhaustive list of typical examples of transition metal compounds includes copper, vanadium, cobalt, and iron compounds. For example, with respect to copper compounds, it is desirable that copper has a valence state of 1+ or 2+. A non-exhaustive list of such copper(I) and (II) compounds includes copper(II) 3,5-diisopropyl salicylate hydrate, bis(2,2,6,6-tetramethyl-3,5-heptanedionate)copper, copper(II) hydroxide phosphate, copper(II) chloride, copper(II) acetate monohydrate, tetrakis(acetonitrile)copper(I) hexafluorophosphate, copper(II) formate hydrate, tetrakisacetonitrile copper(I) triflate, copper(II) tetrafluoroborate, copper(II) perchlorate, tetrakis(acetonitrile)copper(I) tetrafluoroborate, copper(II) hydroxide, copper(II) hexafluoroacetylacetonate hydrate, and copper(II) carbonate. These copper(I) and (II) compounds can be used in amounts such that, when dissolved or suspended in a carrier vehicle such as (meth)acrylate, concentrations of about 100 ppm to about 5,000 ppm, for example, about 500 ppm to about 2,500 ppm, for example, about 1,000 ppm, are present in the solution or suspension.

[0068] Regarding vanadium compounds, those in which vanadium is in the 2+ and 3+ valence states are preferred. Examples of such vanadium(III) compounds include vanadium naphthenate and vanadylacetylacetonate. These vanadium(III) compounds can be used in amounts ranging from 50 ppm to about 5,000 ppm, for example, from about 500 ppm to about 2,500 ppm, for example, about 1,000 ppm.

[0069] Regarding cobalt compounds, those in which cobalt has a valence state of 2+ are preferred. Examples of such cobalt(II) compounds include cobalt naphthenate, cobalt tetrafluoroborate, and cobalt acetylacetonate. These cobalt(II) compounds can be used in amounts ranging from approximately 100 ppm to approximately 1000 ppm.

[0070] Regarding iron compounds, those in which iron is in a valence state of 3+ are preferred. Examples of such iron(III) compounds include iron acetate, iron acetylacetonate, iron tetrafluoroborate, iron perchlorate, and iron chloride. These iron compounds can be used in amounts ranging from approximately 100 ppm to approximately 1000 ppm.

[0071] As described above, additives may be included in either or both of the Part A or Part B composition in order to affect various performance characteristics.

[0072] Examples of fillers that may be used include aluminum nitride, boron nitride, silicon carbide, diamond, graphite, beryllium oxide, magnesia, silica (such as fumed silica or fused silica), alumina, perfluorocarbon polymers (i.e., TEFLON®), thermoplastic polymers, thermoplastic elastomers, mica, and glass powder. Preferably, the particle size of these fillers is about 20 microns or less.

[0073] Regarding silica, silica may have an average particle size of nanoparticle size, i.e., 10 -9 The average particle size is approximately 1 meter. Silica nanoparticles can be pre-dispersed in epoxy resins and can be selected from those available from Nanoresins, Germany, under the trade name NANOCRYL. NANOCRYL is the trade name for a family of silica nanoparticle-enhanced (meth)acrylate products. The silica phase consists of surface-modified synthetic SiO2 nanospheres with a diameter of less than 50 nm and an extremely narrow particle size distribution. The SiO2 nanospheres are weak aggregate dispersions in the (meth)acrylate matrix and result in low viscosity for resins containing up to 50 wt% silica.

[0074] The silica component may be present in an amount ranging from about 1% to about 60% by weight, for example, about 3% to about 30% by weight, preferably about 5% to about 20% by weight, based on the total weight of the composition.

[0075] Toughening agents particularly intended for use in partial A composition include elastomer polymers selected from (i) acrylic acid esters, (ii) methacrylic acid esters, or (iii) vinyl acetate elastomer copolymers of lower alkene monomers, such as acrylic rubber; polyester urethane; ethylene-vinyl acetate; fluororubber; isoprene-acrylonitrile polymers; chlorosulfinized polyethylene; and polyvinyl acetate homopolymers, which have been found to be particularly useful [see U.S. Patent No. 4,440,910 (O'Connor), the disclosures of each of these are expressly incorporated herein by reference]. Elastomer polymers are described in the '910 patent as homopolymers of alkyl esters of acrylic acid; copolymers of alkyl or alkoxy esters of acrylic acid with other polymerizable monomers such as lower alkenes; and copolymers of alkyl or alkoxy esters of acrylic acid. Other unsaturated monomers that can be copolymerized with alkyl and alkoxy esters of acrylic include dienes, reactive halogen-containing unsaturated compounds, and other acrylic monomers such as acrylamide.

[0076] For example, one group of such elastomer polymers is the copolymer of methyl acrylate and ethylene, manufactured by DuPont under the name VAMAC, such as VAMAC N123 and VAMAC B-124. VAMAC N123 and VAMAC B-124 are reported by DuPont to be masterbatches of ethylene / acrylic elastomers. DuPont material VAMAC G is a similar copolymer, but does not contain fillers or stabilizers for coloring. VAMAC VCS rubber appears to be the base rubber from which the rest of the VAMAC product line is made. VAMAC VCS (also known as VAMAC MR) is a reaction product of a combination of monomers having ethylene, methyl acrylate, and carboxylic acid curing sites, and once formed, is substantially free of processing aids (such as the mold release agent octadecylamine, complex organophosphates, and / or stearic acid) and antioxidants (such as substituted diphenylamine).

[0077] DuPont offers rubbers manufactured from ethylene and methyl acrylate under the trade names VAMAC VMX 1012 and VCD 6200. VAMAC VMX 1012 rubber is considered to have little to no carboxylic acids in its polymer backbone. Similar to VAMAC VCS rubber, VAMAC VMX 1012 and VCD 6200 rubbers are substantially free of the mold release agents described above, such as octadecylamine, complex organophosphates and / or stearic acid, as well as antioxidants such as substituted diphenylamine. All of these VAMAC elastomer polymers are useful herein.

[0078] Furthermore, vinylidene chloride-acrylonitrile copolymer [see U.S. Patent No. 4,102,945 (Gleave)] and vinyl chloride / vinyl acetate copolymer [see U.S. Patent No. 4,444,933 (Columbus)] may be included in Part A composition. Of course, the disclosures of each of these U.S. patents are incorporated herein by reference in their entirety.

[0079] A copolymer of polyethylene and polyvinyl acetate, marketed under the trade name LEVAMELT by LANXESS Limited, is useful.

[0080] Various LEVAMELT brand copolymers are available, such as LEVAMELT 400, LEVAMELT 600, and LEVAMELT 900. LEVAMELT products differ in the amount of vinyl acetate present. For example, LEVAMELT 400 contains an ethylene-vinyl acetate copolymer with 40% by weight vinyl acetate. LEVAMELT products are supplied in granular form. The granules are nearly colorless and coated with silica and talc. LEVAMELT consists of methylene units that form a saturated backbone with pendant acetate groups. The presence of a fully saturated backbone is an indicator of the particular stability of LEVAMELT brand copolymers; LEVAMELT brand copolymers do not contain reactive double bonds that make conventional rubber susceptible to degradation reactions, ozone, and UV light. The saturated backbone has been reported to make the polymer robust.

[0081] Interestingly, the solubility of these LEVAMELT elastomers varies depending on the polyethylene / polyvinyl acetate ratio, and the toughening ability also changes as a result of the solubility.

[0082] LEVAMELT elastomers are available in pellet form and are easier to formulate than other known elastomer toughening agents.

[0083] VINNOL surface coating resins, marketed by Wacker Chemie AG in Munich, Germany, represent a broad range of vinyl chloride-derived copolymers and terpolymers advertised for use in various industrial applications. The main components of these polymers are vinyl chloride and vinyl acetate in different compositions. The terpolymers in the VINNOL product line further contain carboxyl or hydroxyl groups. These vinyl chloride / vinyl acetate copolymers and terpolymers can also be used.

[0084] VINNOL surface coating resins containing carboxyl groups are terpolymers of vinyl chloride, vinyl acetate, and dicarboxylic acid, which vary in molar composition, degree of polymerization, and process. These terpolymers have been reported to exhibit excellent adhesion, particularly on metal substrates.

[0085] VINNOL surface coating resins containing hydroxyl groups are copolymers and terpolymers of vinyl chloride, hydroxyacrylate, and dicarboxylate, and their composition and degree of polymerization vary.

[0086] The functional group-free VINNOL surface coating resin is a copolymer of vinyl chloride and vinyl acetate with a variable molar composition and degree of polymerization.

[0087] Rubber particles, particularly those having a relatively small average particle size (e.g., less than about 500 nm or less than about 200 nm), may also be included in the partial B composition. The rubber particles may or may not have a shell common to known core-shell structures.

[0088] In the case of rubber particles having a core-shell structure, such particles generally have a core made of a polymer material having elastomer properties or rubber properties (i.e., a glass transition temperature below about 0°C, e.g., below about -30°C) surrounded by a shell made of a non-elastomer polymer material (i.e., a thermoplastic or thermosetting / crosslinked polymer having a glass transition temperature higher than ambient temperature, e.g., above about 50°C). For example, the core may be made of a diene homopolymer or copolymer (e.g., a homopolymer of butadiene or isoprene, a copolymer of butadiene or isoprene with one or more ethylenically unsaturated monomers such as vinyl aromatic monomers, (meth)acrylonitrile, (meth)acrylate), while the shell may be made of a polymer or copolymer of one or more monomers having a sufficiently high glass transition temperature, such as (meth)acrylate (e.g., methyl methacrylate), vinyl aromatic monomers (e.g., styrene), vinyl cyanides (e.g., acrylonitrile), unsaturated acids and anhydrides (e.g., acrylic acid), (meth)acrylamide, etc. Other rubbery polymers, including butyl polyacrylate or polysiloxane elastomers (e.g., polydimethylsiloxane, particularly crosslinked polydimethylsiloxane), can also be appropriately used for the core.

[0089] Typically, the core makes up about 50 to 95% by weight of the rubber particles, while the shell makes up about 5 to 50% by weight of the rubber particles.

[0090] Preferably, the size of the rubber particles is relatively small. For example, the average particle size may be about 0.03 to about 2 microns or about 0.05 to about 1 micron. The rubber particles may have an average diameter of less than about 500 nm, for example, less than about 200 nm. For example, core-shell rubber particles may have an average diameter in the range of about 25 to about 200 nm.

[0091] When used, these core-shell rubbers allow toughening to occur in a predictable manner with respect to temperature neutrality to curing, often due to the substantial uniform dispersion that typically occurs in core-shell rubbers such as those available commercially.

[0092] In the case of rubber particles that do not have such a shell, the rubber particles may be based on a core with such a structure.

[0093] Preferably, the size of the rubber particles is relatively small. For example, the average particle size may be about 0.03 to about 2 μm or about 0.05 to about 1 μm. In certain embodiments of the present invention, the rubber particles have an average diameter of less than about 500 nm. In other embodiments, the average particle size is less than about 200 nm. For example, the rubber particles may have an average diameter in the range of about 25 to about 200 nm or about 50 to about 150 nm.

[0094] As described above, the rubber particles may be used in a dry form or dispersed in a matrix.

[0095] Typically, the composition may contain about 5 to about 35% by weight of rubber particles.

[0096] Different combinations of rubber particles can be advantageously used in the present invention. The rubber particles may differ, for example, in particle size, glass transition temperature of each material, the extent and by what the material is functionalized, and whether and how the surface of the rubber particles is treated.

[0097] Rubber particles suitable for use in the present invention are available from commercial sources. For example, rubber particles supplied by Eliokem, Inc., such as NEP R0401 and NEP R401S (both based on acrylonitrile / butadiene copolymer); NEP R0501 (based on carboxylated acrylonitrile / butadiene copolymer; CAS number 9010-81-5); NEP R0601A (based on hydroxy-terminated polydimethylsiloxane; CAS number 70131-67-8); and NEP R0701 and NEP 0701S (based on butadiene / styrene / 2-vinylpyridine copolymer; CAS number 25053-48-9), may be used. Additionally, products are available from Dow Chemical Co. in Philadelphia, Pennsylvania, under the brand names PARALOID 2314, PARALOID 2300, and PARALOID 2600, as well as from Ganz Chemical Co., Ltd. in Osaka, Japan, under the brand name STAPHYLOID AC-3832.

[0098] For example, rubber particles treated with reactive gases or other reagents to modify the outer surface of the particles by creating polar groups (e.g., hydroxyl groups, carboxylic acid groups) on the particle surface are also suitable for use herein. Examples of reactive gases include, for example, ozone, Cl2, F2, O2, SO3, and oxidizing gases. Methods for surface-modifying rubber particles using such reagents are known in the Art and are described, for example, in U.S. Patent Nos. 5,382,635; 5,506,283; 5,693,714; and 5,969,053, each of which is expressly incorporated herein in whole by reference. Suitable surface-modified rubber particles are also available from commercial sources such as rubber sold by Exousia Corporation under the trade name VISTAMER.

[0099] If the rubber particles are initially supplied in a dry form, it may be advantageous to ensure that such particles are sufficiently dispersed in the adhesive composition before the adhesive composition is cured. That is, weak aggregates of rubber particles are preferably divided to provide discrete individual rubber particles, which can be achieved by homogeneously and completely mixing the dry rubber particles with the other components of the adhesive composition.

[0100] Thickening agents may also be useful.

[0101] Stabilizers and inhibitors may also be used to suppress and prevent the decomposition and polymerization of peroxides that occur more rapidly than naturally would occur. Inhibitors may be selected from hydroquinones, benzoquinones, naphthoquinones, phenanthroquinones, anthraquinones, and their substituted compounds. Various phenols, such as 2,6-di-tert-butyl-4-methylphenol, may also be used as inhibitors. Inhibitors may be used in amounts of about 0.1% to about 1.0% of the total composition weight without adversely affecting the curing rate of the polymerizable adhesive composition.

[0102] At least one of the first or second portion is about 12 pK a Organic acids having the following properties may also be included, such as sulfimides, sulfonamides, citric acid, maleic acid, succinic acid, phthalic acid, dicarboxylic acids, maleic anhydride, maleic acid dianhydride, succinic anhydride, and phthalic anhydride.

[0103] In practice, each of the Part A and Part B compositions is housed in separate containers within the apparatus before use, and at the time of use, the two parts are removed from the containers, mixed, and applied to the substrate surface. The container may be a two-chambered cartridge, and the separate parts are advanced through the chambers by a plunger through an opening (which may be common or adjacent) and then through a mixing and dispensing nozzle. Alternatively, the container may be coaxial or parallel pouches, which may be cut or torn, and their contents may be mixed and applied to the substrate surface.

[0104] The present invention will be more easily understood by carefully reading the following examples. [Examples]

[0105] <Method> In short, the bonding of the components to be tested was carried out as follows: The bonding was prepared in several ways: (a) extruded on a workbench and cured; (b) extruded on a workbench and cured in water; (c) extruded in water and cured on a workbench; (d) extruded in water and cured. All methods were carried out at room temperature.

[0106] If the bonding was partially or entirely performed underwater, the component was immersed in water so that water was in contact with all surfaces of the component. The component was completely submerged. The component was not removed from the water before the application of the adhesive.

[0107] The adhesive was dispensed from the container and applied to the first component. The second component was overlapped by 0.5 inches (1.27 cm), and the components were sandwiched together to allow the adhesive to cure and form a bond between them. The time from dispensing from the container until the second component was overlapped was defined as the open time. Both the application and curing of the adhesive were performed in water. When dry components were tested, they were not placed in water. The components were dry when the adhesive was applied and when the adhesive was cured; i.e., no surface moisture was present.

[0108] The following substrates were tested: stainless steel, aluminum, mild steel, PC, PVC, and ABS.

[0109] <Result> Table 1 shows the tensile strength achieved using various substrates and bonding conditions according to the above methods (a) to (d). [Table 1]

[0110] Furthermore, the performance of the adhesive cartridge suitable for use in the present invention was confirmed after storage in water (Tables 2 and 3). After 7 days in water, no signs of polymerization were observed inside or around the cartridge, and the performance was unaffected.

[0111] [Table 2]

[0112] [Table 3]

[0113] Furthermore, the performance of nuts and bolts bonded according to the present invention was tested. The base material was prepared as described above. The results are shown in Table 4. [Table 4]

[0114] Tensile strength was measured according to ASTM D1002-10 (2019) for metal-to-metal wrap shear and according to ASTM D3163-01 (2023) for plastic-to-plastic wrap shear.

[0115] Stainless steel bolts have an outer diameter of 9.968 to 9.732 mm, a root diameter of 8.619 to 8.272 mm, and a pitch circle diameter of 8.994 to 8.862 mm. Stainless steel nuts have a thickness of 7.64 to 8.00 mm, a width of 16.73 to 17.00 mm, a minimum outer diameter of 10.0 mm, a root diameter of 8.376 to 8.676 mm, and a pitch circle diameter of 9.026 to 9.206 mm.

[0116] BOMS (black oxide mild steel) refers to black oxide mild steel. The mild steel bolts were coated with black oxide. The mild steel nuts used were not coated with black oxide. The torque values ​​in the last two columns of Table 4 are the release torque (or break torque) and prevailing torque (or prevail torque), respectively, and all values ​​were measured according to ASTM D5649-15, titled "Torque Strength of Adhesives used on Threaded Fasteners".

[0117] Blackened mild steel bolts have an outer diameter of 9.96 to 9.73 mm, a root diameter of 8.08 to 7.98 mm, and a pitch circle diameter of 8.99 to 8.86 mm. Mild steel nuts have a thickness of 8 ± 0.2 mm, a width of 14.0 to 14.3 mm, a minimum outer diameter of 10.0 mm, a root diameter of 8.38 to 8.28 mm, and a pitch circle diameter of 9.20 to 9.03 mm.

[0118] The terms “comprises / comprising” and “having / including,” when used herein in reference to the present invention, are used to identify the presence of a described feature, integer, process, or component, but do not preclude the presence or addition of one or more other features, integers, processes, components, or groups thereof.

[0119] For clarity, it is understood that certain features of the invention described in the context of a separate embodiment may also be provided in combination in a single embodiment. Conversely, for brevity, various features of the invention described in the context of a single embodiment may also be provided separately or in any suitable subcombination.

Claims

1. A method for bonding substrates submerged in water, (a) Applying the cyanoacrylate composition to at least one substrate in water, Here, the cyanoacrylate composition is i. A first part comprising a cyanoacrylate component and a peroxide catalyst; and ii. Second part containing free radical curable components and transition metals Includes, When mixed together, the peroxide catalyst initiates the curing of the free radical curable component, and the transition metal initiates the curing of the cyanoacrylate component. (b) The composition is cured in water. Methods that include...

2. The cyanoacrylate component is H ２ The method according to claim 1, comprising C=C(CN)-COOR [wherein R is selected from alkyl, alkoxyalkyl, cycloalkyl, alkenyl, aralkyl, aryl, allyl and haloalkyl].

3. The method according to claim 1 or 2, wherein the peroxide catalyst comprises perbenzoic acid.

4. The method according to any one of claims 1 to 3, wherein the peroxide catalyst is t-butyl perbenzoate.

5. At least one of the first or second portion has a pK of about 12 or less. ａ The method according to any one of claims 1 to 4, further comprising a member selected from the group consisting of organic acids having a property, such as sulfimides, sulfonamides, citric acid, maleic acid, succinic acid, phthalic acid, dicarboxylic acid, maleic anhydride, maleic acid dianhydride, succinic anhydride, and phthalic anhydride, or combinations thereof.

6. The method according to any one of claims 1 to 5, wherein the peroxide catalyst is present in an amount of about 0.01% to about 10% relative to the weight of the cyanoacrylate component.

7. The method according to any one of claims 1 to 6, wherein the free radical curable component of the composition is selected from a (meth)acrylate component, a maleimide-containing compound, an itaconamide-containing compound, or a nadiimide-containing compound, and combinations thereof.

8. The method according to any one of claims 1 to 7, wherein the free radical curable component of the composition is a (meth)acrylate component selected from the group consisting of polyethylene glycol di(meth)acrylate, tetrahydrofuran (meth)acrylate and di(meth)acrylate, hydroxypropyl (meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, benzyl methacrylate, tetraethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, di(pentamethylene glycol) dimethacrylate, tetraethylene diglycol diacrylate, diglycerol tetramethacrylate, tetramethylene dimethacrylate, ethylene dimethacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, and bisphenol-A mono and di(meth)acrylate.

9. The method according to any one of claims 1 to 8, wherein the transition metal in the composition comprises a member selected from the group consisting of copper, vanadium, cobalt, and iron.

10. The method according to any one of claims 1 to 9, wherein the first portion of the composition is housed in the first chamber of a two-chamber syringe, and the second portion of the composition is housed in the second chamber of the two-chamber syringe.

11. The method according to any one of claims 1 to 10, wherein the second portion of the composition further comprises at least one plasticizer and a filler.

12. The method according to any one of claims 1 to 11, wherein the second portion of the composition further comprises a toughening agent, optionally the toughening agent being a member selected from the group consisting of (a) a reaction product of a combination of monomers having ethylene, methyl acrylate and carboxylic acid curing sites, (b) a dipolymer of ethylene and methyl acrylate, (c) a combination of (a) and (b), (4) a vinylidene chloride-acrylonitrile copolymer, (5) a vinyl chloride / vinyl acetate copolymer, (6) a copolymer of polyethylene and polyvinyl acetate, and combinations thereof.

13. The method according to any one of claims 1 to 12, wherein the first portion of the composition and the second portion of the composition are present in a ratio of about 1:1 by volume.

14. The method according to any one of claims 1 to 13, wherein the first portion of the composition and the second portion of the composition are each housed in separate chambers of a two-chambered container.

15. The method according to any one of claims 1 to 14, wherein at least one of the first part of the composition or the second part of the composition further comprises a member selected from the group consisting of sulfimides, sulfonamides, citric acid, maleic acid, succinic acid, phthalic acid, dicarboxylic acid, maleic anhydride, maleic acid dianhydride, succinic anhydride, phthalic anhydride, and combinations thereof.

16. The method according to any one of claims 1 to 15, wherein the free radical curable component is a (meth)acrylate component selected from the group consisting of ethoxylated bisphenol A (meth)acrylate, ethoxylated bisphenol F (meth)acrylate, methacrylate-functionalized urethane, and combinations thereof.

17. The method according to any one of claims 1 to 16, wherein the transition metal comprises copper in the form of a component selected from the group consisting of copper(II) 3,5-diisopropyl salicylate hydrate, copper bis(2,2,6,6-tetramethyl-3,5-heptanedione), copper(II) hydroxide phosphate, copper(II) chloride, copper(II) acetate monohydrate, tetrakis(acetonitrile) copper(I) hexafluorophosphate, copper(II) formate hydrate, tetrakisacetonitrile copper(I) triflate, copper(II) tetrafluoroborate, copper(II) perchlorate, tetrakis(acetonitrile) copper(I) tetrafluoroborate, copper(II) hydroxide, copper(II) hexafluoroacetylacetonate hydrate, and copper(II) carbonate.

18. The method according to any one of claims 1 to 17, comprising exposing the composition to water for up to 45 seconds before bonding the surface of the second substrate to the coated surface of the first substrate.

19. The method according to any one of claims 1 to 18, wherein one or both substrates are metal, for example, one or both substrates are steel.

20. The method according to any one of claims 1 to 19, wherein one or both substrates are made of plastic material.

21. The use of a cyanoacrylate composition for underwater adhesion of a substrate, wherein the composition is i. A first portion comprising a cyanoacrylate component and t-butyl perbenzoate present as a peroxide catalyst in an amount of about 0.01% to about 10% relative to the weight of the cyanoacrylate component; and ii. Second part containing free radical curable components and transition metals Includes, The cyanoacrylate component is H ２ The formula comprises C=C(CN)-COOR [wherein R is selected from alkyl, alkoxyalkyl, cycloalkyl, alkenyl, aralkyl, aryl, allyl, and haloalkyl], and when mixed together, the peroxide catalyst initiates the curing of the free radical curable component, and the transition metal initiates the curing of the cyanoacrylate component.

22. An assembly comprising two underwater substrates bonded together by a cyanoacrylate composition, wherein the cyanoacrylate composition is i. A first portion comprising a cyanoacrylate component and t-butyl perbenzoate present as a peroxide catalyst in an amount of about 0.01% to about 10% relative to the weight of the cyanoacrylate component; and ii. Second part containing free radical curable components and transition metals Includes, The cyanoacrylate component is H ２ An assembly comprising C=C(CN)-COOR [wherein R is selected from alkyl, alkoxyalkyl, cycloalkyl, alkenyl, aralkyl, aryl, allyl and haloalkyl], wherein when mixed together, the peroxide catalyst initiates the curing of the free radical curable component and the transition metal initiates the curing of the cyanoacrylate component.

23. The assembly according to claim 22, wherein one or both of the base materials are metal.

24. The assembly according to claim 22, wherein one or both of the base materials are made of plastic material.

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