Anaerobically curable adhesive composition

Abstract

An anaerobically curable adhesive composition comprising: an anaerobically curable component; a cure-inducing component; and a stabilizer component comprising one or both of the following compounds: glutamic acid diacetic acid tetrasodium salt (Na4GLDA); and / or methylglycine N,N-diacetic acid trisodium salt (Na3MGDA). This stabilizer component, alone or in combination, functions as an effective metal ion chelator in anaerobic formulations at levels significantly lower than would normally be effective for Na4EDTA.

Description

Technical Field

[0001] This invention relates to anaerobic curable adhesive compositions, methods for anaerobic curing such compositions, and cured products thereof. Background Technology

[0002] Anaerobic curable compositions are well known. Anaerobic curable compositions remain uncured when exposed to air (oxygen) and cure under suitable anaerobic conditions. The applications of anaerobic curable compositions are wide-ranging and continuously evolving. For example, they can be used as threadlockers, for gasket sealing, for adhesion to oily substrates, as pipe sealants, and for joint repair.

[0003] Typically, anaerobic adhesive compositions are mixtures of polymerizable acrylate monomers and their peroxy polymerization initiators. Preferably, at least a portion of the acrylate monomers is diacrylate or other polyacrylates. Suitable polyacrylate monomers are di, tri, and tetraethylene glycol dimethacrylate; dipropylene glycol dimethacrylate; polyethylene glycol dimethacrylate; polypropylene glycol dimethacrylate; bis(pentamethylene glycol) dimethacrylate; tetraethylene glycol dimethacrylate; tetraethylene glycol di(chloroacrylate); diglycerol diacrylate; diglycerol tetramethacrylate; tetramethylene dimethacrylate; ethylene glycol dimethacrylate; butanediol dimethacrylate; neopentyl glycol diacrylate; and trimethylolpropane triacrylate.

[0004] Monofunctional acrylates (esters containing one acrylate group) can also be used in anaerobic adhesives, and preferably, the esters are those with a relatively polar alcohol moiety. Typical examples of this class of compounds are cyclohexyl methacrylate; tetrahydrofurfuryl methacrylate; hydroxyethyl acrylate; hydroxypropyl methacrylate; tert-butylaminoethyl methacrylate; ethyl cyanoacrylate; and chloroethyl methacrylate.

[0005] Another class of polyacrylate monomers used in anaerobic adhesive compositions are isocyanate monoacrylate reaction products described in U.S. Patent No. 3,424,988 (Toback / Gorman).

[0006] It is generally known that anaerobic curable compositions can be unstable and lose their adhesive properties over time. Therefore, stabilizers are often used in the composition to obtain anaerobic curable compositions with increased stability. However, these stabilizers can degrade the properties of the anaerobic curable composition.

[0007] All anaerobic binders are sensitive to the presence of metal ions, particularly Cu and Fe metal ion contaminants, in their formulations. Low (ppm) levels of these metal ions are typically present in the raw material components or acquired through the processing of the formulation. Therefore, a key component in all anaerobic formulations is a stabilizer, which chelates these metal ions before they begin to destabilize the anaerobic binder itself. This stabilizer is called a metal chelating agent. Currently, commercially available anaerobic curable compositions use tetrasodium EDTA (ethylenediaminetetraacetic acid) (hereinafter referred to as Na4EDTA) as a stabilizer, as follows: .

[0008] European patent application number EP 0 282 292 describes a metal ion chelating agent, trisodium N-hydroxyethylenediamine triacetate (HEDTA Na3), for use in anaerobic acrylate sealants or adhesives.

[0009] Despite the existence of existing metal ion chelating agents, alternatives are still needed. Ideally, such alternatives would be good stabilizers. Of particular interest are alternative stabilizers capable of stabilizing anaerobic compositions. Furthermore, it is desirable that such stabilizers be effective at low concentrations, for example, even lower than that of stabilizers such as Na4EDTA. Of course, it is also desirable that any such alternative stabilizer will not adversely affect the curing of the anaerobic adhesive, for example, by not hindering the curing rate or affecting the bond strength, such as tensile bond strength.

[0010] Therefore, one object of the present invention is to provide a metal ion chelating agent for anaerobic adhesives, which is soluble in anaerobic adhesive compositions and can effectively chelate and deactivate contaminating metals without substantially interfering with the curing properties or post-curing properties of such adhesives. Summary of the Invention

[0011] In one aspect, the present invention provides an anaerobic curable adhesive composition comprising: (i) Components that can be anaerobically cured; (ii) Curing-inducing components; and (iii) Stabilizer components with the following structures: N-[C(R1)(R2)-COOM] n (R a ) m R1 and R2 are each independently selected from H, OH, straight-chain or branched C1-C6 alkyl, straight-chain or branched C1-C6 alkoxy, straight-chain or branched C2-C6 alkenyl, straight-chain or branched C2-C6 alkynyl, C5-C9 aryl, C3-C9 cycloalkyl, C4-C9 cycloalkenyl, C4-C9 cycloalkynyl, C5-C9 heteroaryl, C3-C9 heterocycloalicyclic, C6-C 12Aryl group, C6-C 12 Heteroalkyl, C6-C 12 (Heterocyclic)alkyl, C2-C6 alkoxy, C5-C9 aryloxy, C2-C6 acyl, carboxyl, ester, mercapto, alkylthio, arylthio, cyano, halogen, carbonyl, thiocarbonyl, O-carbamoyl, N-carbamoyl, O-thiocarbamoyl, N-thiocarbamoyl, C-amide, N-amide, S-sulfonamide, N-sulfonamide, C-carboxyl, O-carboxyl, isocyanate, thiocyanate, isothiocyanate, nitro, silyl, sulfenyl, sulfinyl, sulfonyl, haloalkyl, haloalkoxy, trihalomethanesulfonyl and trihalomethanesulfonamide; M is a cation such as H+ or a metal cation, such as Na. + Li + or K + ; n is an integer selected from 1, 2, or 3; R a It can be selected from H, OH, straight-chain or branched C1-C6 alkyl, straight-chain or branched C1-C6 alkoxy, straight-chain or branched C2-C6 alkenyl, straight-chain or branched C2-C6 alkynyl, C5-C9 aryl, C3-C9 cycloalkyl, C4-C9 cycloalkenyl, C4-C9 cycloalkynyl, C7-C 12 Aryl group, C2-C6 alkoxy group, C5-C9 aryloxy group, C2-C6 acyl group, carboxyl group, ester group or carbonyl group; m is an integer selected from 3 to n. Therefore, when n is less than 3, one or two substituents of N can be selected from H, OH, straight-chain or branched C1-C6 alkyl, straight-chain or branched C1-C6 alkoxy, straight-chain or branched C2-C6 alkenyl, straight-chain or branched C2-C6 alkynyl, C5-C9 aryl, C3-C9 cycloalkyl, C4-C9 cycloalkenyl, C4-C9 cycloalkynyl, C7-C 12 Aryl, C2-C6 alkoxy, C5-C9 aryloxy, C2-C6 acyl, carboxyl, ester or carbonyl.

[0012] In this document, carbonyl refers to any functional group containing a carbonyl group, which may include, but is not limited to, aldehydes, ketones, carboxylic acids, and amides. Thiocarbonyl refers to any functional group containing a thiocarbonyl group, which may include, but is not limited to, thioaldehydes and thioketones.

[0013] The anaerobic curable adhesive composition may contain: (i) Components that can be anaerobically cured; (ii) Curing-inducing components; and (iii) Stabilizer components with the following structures: N-[C(R1)(R2)-COOM]n (R a ) m R1 and R2 are each independently selected from H, OH, straight-chain or branched C1-C6 alkyl, straight-chain or branched C1-C6 alkoxy, straight-chain or branched C2-C6 alkenyl, straight-chain or branched C2-C6 alkynyl, C5-C9 aryl, C3-C9 cycloalkyl, C4-C9 cycloalkenyl, C4-C9 cycloalkynyl, C5-C9 heteroaryl, C3-C9 heterocycloalicyclic, C6-C 12 Aryl group, C6-C 12 Heteroalkyl, C6-C 12 (Heterocyclic)alkyl, C2-C6 alkoxy, C5-C9 aryloxy, C2-C6 acyl, straight-chain or branched C1-C6 carboxylic acid ester, ester, mercapto, alkylthio, arylthio, cyano, halogen, carbonyl, thiocarbonyl, O-carbamoyl, N-carbamoyl, O-thiocarbamoyl, N-thiocarbamoyl, C-amide, N-amide, S-sulfonamide, N-sulfonamide, C-carboxyl, O-carboxyl, isocyanate, thiocyanate, isothiocyanate, nitro, silyl, sulfenyl, sulfinyl, sulfonyl, haloalkyl, haloalkoxy, trihalomethanesulfonyl and trihalomethanesulfonamide; M is a cation such as H+ or a metal cation, such as Na. + Li + or K + ; n is an integer selected from 1, 2, or 3; R a It can be selected from H, OH, straight-chain or branched C1-C6 alkyl, straight-chain or branched C1-C6 alkoxy, straight-chain or branched C2-C6 alkenyl, straight-chain or branched C2-C6 alkynyl, C5-C9 aryl, C3-C9 cycloalkyl, C4-C9 cycloalkenyl, C4-C9 cycloalkynyl, C7-C 12 Aryl group, C2-C6 alkoxy group, C5-C9 aryloxy group, C2-C6 acyl group, straight-chain or branched C1-C6 carboxylic acid ester group, ester group or carbonyl group; m is an integer selected from 3 to n. Therefore, when n is less than 3, one or two substituents of N can be selected from H, OH, straight-chain or branched C1-C6 alkyl, straight-chain or branched C1-C6 alkoxy, straight-chain or branched C2-C6 alkenyl, straight-chain or branched C2-C6 alkynyl, C5-C9 aryl, C3-C9 cycloalkyl, C4-C9 cycloalkenyl, C4-C9 cycloalkynyl, C7-C 12 Aryl group, C2-C6 alkoxy group, C5-C9 aryloxy group, C2-C6 acyl group, straight-chain or branched C1-C6 carboxylic acid ester group, ester group or carbonyl group.

[0014] Possible alternatives to the C(R1)(R2)-COOM shown in the above structure include: Where M is a cation such as H+ or a metal cation, such as Na. + Li + K + ;and R1 and R2 are defined independently as described above.

[0015] The present invention also provides an anaerobic curable adhesive composition, wherein the stabilizer component may comprise one or both of the following compounds: (i) The following structure of tetrasodium glutamate diacetate (Na4GLDA): and / or (ii) The following structure of methylglycine N,N-diacetic acid trisodium salt (Na3MGDA):

[0016] Tetrapotassium glutamate diacetate (K4GLDA) is also within the scope of this invention.

[0017] Methylglycine N,N-diacetic acid tripotassium salt (K3MGDA) is also within the scope of this invention.

[0018] Advantageously, the stabilizer component Na4GLDA is bio-based, for example derived from manufacturers such as Nouryon. TM The disclosed component is monosodium glutamate (MSG), a common food ingredient. The stabilizer component, Na3MGDA, is biodegradable, as disclosed by the manufacturer, Nouryon. Therefore, both stabilizer components provide an environmentally sustainable alternative for the solidification of anaerobic products.

[0019] Advantageously, the compositions of the present invention exclude (must have) Na4EDTA as a component of the composition.

[0020] Suitablely, stabilizer components, such as tetrasodium glutamate diacetate (Na4GLDA) and / or trisodium methylglycine N,N-diacetate (Na3MGDA), are added to the adhesive composition in the form of a diluted mixture or premix.

[0021] Suitably, the stabilizer component is in solution form, wherein the concentration of the stabilizer component in the solution is from about 2% to about 10%, for example, about 3.5%, before it is added to the adhesive composition.

[0022] Suitablely, the stabilizer component can be used in the adhesive composition at a variety of concentrations, said concentration being from about 2 ppm to about 1000 ppm, for example from about 5 ppm to 500 ppm or from about 10 ppm to 1000 ppm, for example from about 10 ppm to about 100 ppm.

[0023] Surprisingly, the stabilizer components of this invention (alone or in combination) act as potent metal ion chelators in anaerobic formulations at levels significantly lower than those typically effective for Na4EDTA.

[0024] In another aspect, the present invention provides a method for anaerobic curing an anaerobic curable adhesive composition, comprising the following steps: (A) Provides an anaerobic curable adhesive composition comprising: (a) Components that can be anaerobically cured; (b) Curing-inducing components; (c) Stabilizer components with the following structures: N-[C(R1)(R2)-COOM] n (R a ) m R1 and R2 are each independently selected from H, OH, straight-chain or branched C1-C6 alkyl, straight-chain or branched C1-C6 alkoxy, straight-chain or branched C2-C6 alkenyl, straight-chain or branched C2-C6 alkynyl, C5-C9 aryl, C3-C9 cycloalkyl, C4-C9 cycloalkenyl, C4-C9 cycloalkynyl, C5-C9 heteroaryl, C3-C9 heterocycloalicyclic, C6-C 12 Aryl group, C6-C 12 Heteroalkyl, C6-C 12 (Heterocyclic)alkyl, C2-C6 alkoxy, C5-C9 aryloxy, C2-C6 acyl, carboxyl, ester, mercapto, alkylthio, arylthio, cyano, halogen, carbonyl, thiocarbonyl, O-carbamoyl, N-carbamoyl, O-thiocarbamoyl, N-thiocarbamoyl, C-amide, N-amide, S-sulfonamide, N-sulfonamide, C-carboxyl, O-carboxyl, isocyanate, thiocyanate, isothiocyanate, nitro, silyl, sulfenyl, sulfinyl, sulfonyl, haloalkyl, haloalkoxy, trihalomethanesulfonyl and trihalomethanesulfonamide; M is a cation such as H+ or a metal cation, such as Na. + Li + or K + ; n is an integer selected from 1, 2, or 3; R aIt can be selected from H, OH, straight-chain or branched C1-C6 alkyl, straight-chain or branched C1-C6 alkoxy, straight-chain or branched C2-C6 alkenyl, straight-chain or branched C2-C6 alkynyl, C5-C9 aryl, C3-C9 cycloalkyl, C4-C9 cycloalkenyl, C4-C9 cycloalkynyl, C7-C 12 Aryl group, C2-C6 alkoxy group, C5-C9 aryloxy group, C2-C6 acyl group, carboxyl group, ester group or carbonyl group; m is an integer selected from 3 to n; and (B) The time required to expose the anaerobic curable adhesive composition to an anaerobic environment for curing the composition.

[0025] The present invention also provides a method for anaerobic curing an anaerobic curable adhesive composition, comprising the following steps: (A) Provides an anaerobic curable adhesive composition comprising: (a) Components that can be anaerobically cured; (b) Curing-inducing components; (c) Stabilizer components with the following structures: N-[C(R1)(R2)-COOM] n (R a ) m R1 and R2 are each independently selected from H, OH, straight-chain or branched C1-C6 alkyl, straight-chain or branched C1-C6 alkoxy, straight-chain or branched C2-C6 alkenyl, straight-chain or branched C2-C6 alkynyl, C5-C9 aryl, C3-C9 cycloalkyl, C4-C9 cycloalkenyl, C4-C9 cycloalkynyl, C5-C9 heteroaryl, C3-C9 heterocycloalicyclic, C6-C 12 Aryl group, C6-C 12 Heteroalkyl, C6-C 12 (Heterocyclic)alkyl, C2-C6 alkoxy, C5-C9 aryloxy, C2-C6 acyl, straight-chain or branched C1-C6 carboxylic acid ester, ester, mercapto, alkylthio, arylthio, cyano, halogen, carbonyl, thiocarbonyl, O-carbamoyl, N-carbamoyl, O-thiocarbamoyl, N-thiocarbamoyl, C-amide, N-amide, S-sulfonamide, N-sulfonamide, C-carboxyl, O-carboxyl, isocyanate, thiocyanate, isothiocyanate, nitro, silyl, sulfenyl, sulfinyl, sulfonyl, haloalkyl, haloalkoxy, trihalomethanesulfonyl and trihalomethanesulfonamide; M is a cation such as H+ or a metal cation, such as Na. + Li + or K + ; n is an integer selected from 1, 2, or 3; R a It can be selected from H, OH, straight-chain or branched C1-C6 alkyl, straight-chain or branched C1-C6 alkoxy, straight-chain or branched C2-C6 alkenyl, straight-chain or branched C2-C6 alkynyl, C5-C9 aryl, C3-C9 cycloalkyl, C4-C9 cycloalkenyl, C4-C9 cycloalkynyl, C7-C 12 Aryl group, C2-C6 alkoxy group, C5-C9 aryloxy group, C2-C6 acyl group, straight-chain or branched C1-C6 carboxylic acid ester group, ester group or carbonyl group; m is an integer selected from 3 to n; and (B) The time required to expose the anaerobic curable adhesive composition to an anaerobic environment for curing the composition.

[0026] More specifically, in this respect, the present invention provides a method for anaerobic curing an anaerobic curable adhesive composition, comprising the following steps: (A) Provides an anaerobic curable adhesive composition comprising: (a) Components that can be anaerobically cured; (b) Curing-inducing components; (c) A stabilizer component comprising one or both of the following compounds: (i) The following structure of tetrasodium glutamate diacetate (Na4GLDA): and / or (ii) The following structure of methylglycine N,N-diacetic acid trisodium salt (Na3MGDA): as well as; (B) The time required to expose the anaerobic curable adhesive composition to an anaerobic environment for curing the composition.

[0027] In another aspect, the present invention provides cured / cured products formed by curing the anaerobic curable adhesive composition of the present invention.

[0028] In another aspect, the present invention provides an adhesive assembly comprising a first substrate bonded to a second substrate by means of a cured / cured product, said cured / cured product being formed by curing the anaerobic curable adhesive composition of the present invention.

[0029] The present invention also relates to the use of stabilizer components with the following structures as stabilizers for anaerobic curable adhesive compositions: N-[C(R1)(R2)-COOM] n (R a ) m R1 and R2 are each independently selected from H, OH, straight-chain or branched C1-C6 alkyl, straight-chain or branched C1-C6 alkoxy, straight-chain or branched C2-C6 alkenyl, straight-chain or branched C2-C6 alkynyl, C5-C9 aryl, C3-C9 cycloalkyl, C4-C9 cycloalkenyl, C4-C9 cycloalkynyl, C5-C9 heteroaryl, C3-C9 heterocycloalicyclic, C6-C 12 Aryl group, C6-C 12 Heteroalkyl, C6-C 12 (Heterocyclic)alkyl, C2-C6 alkoxy, C5-C9 aryloxy, C2-C6 acyl, carboxyl, ester, mercapto, alkylthio, arylthio, cyano, halogen, carbonyl, thiocarbonyl, O-carbamoyl, N-carbamoyl, O-thiocarbamoyl, N-thiocarbamoyl, C-amide, N-amide, S-sulfonamide, N-sulfonamide, C-carboxyl, O-carboxyl, isocyanate, thiocyanate, isothiocyanate, nitro, silyl, sulfenyl, sulfinyl, sulfonyl, haloalkyl, haloalkoxy, trihalomethanesulfonyl and trihalomethanesulfonamide; M is a cation such as H+ or a metal cation, such as Na. + Li + or K + ; n is an integer selected from 1, 2, or 3; R a It can be selected from H, OH, straight-chain or branched C1-C6 alkyl, straight-chain or branched C1-C6 alkoxy, straight-chain or branched C2-C6 alkenyl, straight-chain or branched C2-C6 alkynyl, C5-C9 aryl, C3-C9 cycloalkyl, C4-C9 cycloalkenyl, C4-C9 cycloalkynyl, C7-C 12 Aryl group, C2-C6 alkoxy group, C5-C9 aryloxy group, C2-C6 acyl group, carboxyl group, ester group or carbonyl group; m is an integer selected from 3 to n.

[0030] The present invention also relates to the use of stabilizer components with the following structures as stabilizers for anaerobic curable adhesive compositions: N-[C(R1)(R2)-COOM] n (R a ) m R1 and R2 are each independently selected from H, OH, straight-chain or branched C1-C6 alkyl, straight-chain or branched C1-C6 alkoxy, straight-chain or branched C2-C6 alkenyl, straight-chain or branched C2-C6 alkynyl, C5-C9 aryl, C3-C9 cycloalkyl, C4-C9 cycloalkenyl, C4-C9 cycloalkynyl, C5-C9 heteroaryl, C3-C9 heterocycloalicyclic, C6-C12 Aryl group, C6-C 12 Heteroalkyl, C6-C 12 (Heterocyclic)alkyl, C2-C6 alkoxy, C5-C9 aryloxy, C2-C6 acyl, straight-chain or branched C1-C6 carboxylic acid ester, ester, mercapto, alkylthio, arylthio, cyano, halogen, carbonyl, thiocarbonyl, O-carbamoyl, N-carbamoyl, O-thiocarbamoyl, N-thiocarbamoyl, C-amide, N-amide, S-sulfonamide, N-sulfonamide, C-carboxyl, O-carboxyl, isocyanate, thiocyanate, isothiocyanate, nitro, silyl, sulfenyl, sulfinyl, sulfonyl, haloalkyl, haloalkoxy, trihalomethanesulfonyl and trihalomethanesulfonamide; M is a cation such as H+ or a metal cation, such as Na. + Li + or K + ; n is an integer selected from 1, 2, or 3; R a It can be selected from H, OH, straight-chain or branched C1-C6 alkyl, straight-chain or branched C1-C6 alkoxy, straight-chain or branched C2-C6 alkenyl, straight-chain or branched C2-C6 alkynyl, C5-C9 aryl, C3-C9 cycloalkyl, C4-C9 cycloalkenyl, C4-C9 cycloalkynyl, C7-C 12 Aryl group, C2-C6 alkoxy group, C5-C9 aryloxy group, C2-C6 acyl group, straight-chain or branched C1-C6 carboxylic acid ester group, ester group or carbonyl group; m is an integer selected from 3 to n.

[0031] In this respect, the stabilizer component may include at least one of the following as a stabilizer for an anaerobic curable adhesive composition: The following is a tetrasodium salt of glutamate diacetate (Na4GLDA): Or the following structure: trisodium methylglycine N,N-diacetate (Na3MGDA): .

[0032] As discussed above, stabilizer components can be used in combination. Other stabilizers can be used, as described below.

[0033] The present invention also relates to a method for stabilizing an anaerobic curable adhesive composition by providing an effective amount of a stabilizer component with the following structure: N-[C(R1)(R2)-COOM] n (R a ) m R1 and R2 are each independently selected from H, OH, straight-chain or branched C1-C6 alkyl, straight-chain or branched C1-C6 alkoxy, straight-chain or branched C2-C6 alkenyl, straight-chain or branched C2-C6 alkynyl, C5-C9 aryl, C3-C9 cycloalkyl, C4-C9 cycloalkenyl, C4-C9 cycloalkynyl, C5-C9 heteroaryl, C3-C9 heterocycloalicyclic, C6-C 12 Aryl group, C6-C 12 Heteroalkyl, C6-C 12 (Heterocyclic)alkyl, C2-C6 alkoxy, C5-C9 aryloxy, C2-C6 acyl, carboxyl, ester, mercapto, alkylthio, arylthio, cyano, halogen, carbonyl, thiocarbonyl, O-carbamoyl, N-carbamoyl, O-thiocarbamoyl, N-thiocarbamoyl, C-amide, N-amide, S-sulfonamide, N-sulfonamide, C-carboxyl, O-carboxyl, isocyanate, thiocyanate, isothiocyanate, nitro, silyl, sulfenyl, sulfinyl, sulfonyl, haloalkyl, haloalkoxy, trihalomethanesulfonyl and trihalomethanesulfonamide; M is a cation such as H+ or a metal cation, such as Na. + Li + or K + ; n is an integer selected from 1, 2, or 3; R a It can be selected from H, OH, straight-chain or branched C1-C6 alkyl, straight-chain or branched C1-C6 alkoxy, straight-chain or branched C2-C6 alkenyl, straight-chain or branched C2-C6 alkynyl, C5-C9 aryl, C3-C9 cycloalkyl, C4-C9 cycloalkenyl, C4-C9 cycloalkynyl, C7-C 12 Aryl group, C2-C6 alkoxy group, C5-C9 aryloxy group, C2-C6 acyl group, carboxyl group, ester group or carbonyl group; m is an integer selected from 3 to n.

[0034] The present invention also relates to a method for stabilizing an anaerobic curable adhesive composition by providing an effective amount of a stabilizer component with the following structure: N-[C(R1)(R2)-COOM] n (R a ) m R1 and R2 are each independently selected from H, OH, straight-chain or branched C1-C6 alkyl, straight-chain or branched C1-C6 alkoxy, straight-chain or branched C2-C6 alkenyl, straight-chain or branched C2-C6 alkynyl, C5-C9 aryl, C3-C9 cycloalkyl, C4-C9 cycloalkenyl, C4-C9 cycloalkynyl, C5-C9 heteroaryl, C3-C9 heterocycloalicyclic, C6-C12 Aryl group, C6-C 12 Heteroalkyl, C6-C 12 (Heterocyclic)alkyl, C2-C6 alkoxy, C5-C9 aryloxy, C2-C6 acyl, straight-chain or branched C1-C6 carboxylic acid ester, ester, mercapto, alkylthio, arylthio, cyano, halogen, carbonyl, thiocarbonyl, O-carbamoyl, N-carbamoyl, O-thiocarbamoyl, N-thiocarbamoyl, C-amide, N-amide, S-sulfonamide, N-sulfonamide, C-carboxyl, O-carboxyl, isocyanate, thiocyanate, isothiocyanate, nitro, silyl, sulfenyl, sulfinyl, sulfonyl, haloalkyl, haloalkoxy, trihalomethanesulfonyl and trihalomethanesulfonamide; M is a cation such as H+ or a metal cation, such as Na. + Li + or K + ; n is an integer selected from 1, 2, or 3; R a It can be selected from H, OH, straight-chain or branched C1-C6 alkyl, straight-chain or branched C1-C6 alkoxy, straight-chain or branched C2-C6 alkenyl, straight-chain or branched C2-C6 alkynyl, C5-C9 aryl, C3-C9 cycloalkyl, C4-C9 cycloalkenyl, C4-C9 cycloalkynyl, C7-C 12 Aryl group, C2-C6 alkoxy group, C5-C9 aryloxy group, C2-C6 acyl group, straight-chain or branched C1-C6 carboxylic acid ester group, ester group or carbonyl group; m is an integer selected from 3 to n.

[0035] More specifically, the method for stabilizing the anaerobic curable adhesive composition provides an effective amount of at least one of the following as a stabilizer component of the anaerobic curable adhesive composition: (a) The following structure of tetrasodium glutamate diacetate (Na4GLDA): or (b) The following structure of methylglycine N,N-diacetic acid trisodium salt (Na3MGDA): .

[0036] Therefore, the present invention offers significant advantages over the prior art, including being biodegradable, harmless and / or bio-based, and exhibiting better stability at significantly lower concentrations.

[0037] Suitable anaerobic curable adhesive compositions may include one or two of the stabilizer components described above, comprising those components (including those discussed under the "Background Art") and those components described below.

[0038] This invention includes a monoaminopolycarboxylic acid / salt as a stabilizer component in an anaerobic curable adhesive composition. Ideally, the monoaminopolycarboxylic acid / salt stabilizer component contains 3 or 4 carboxylic acid / salt groups. Optionally, the monoaminopolycarboxylic acid salt is a potassium or sodium salt. Polymerizable (meth)acrylate monomers

[0039] (Meth)acrylate monomers can be used as anaerobic curable components. The (meth)acrylate monomers suitable for the anaerobic curable adhesive compositions described herein can be selected from a variety of materials, such as those derived from H₂C═CGCO₂R. 4 Those indicated, wherein G is hydrogen, halogen, or an alkyl group having 1 to about 4 carbon atoms, and R 4 Selected from C1-C6 alkyl, C3-C9 cycloalkyl, alkenyl, C4-C9 cycloalkenyl, and C6-C5 groups having 1 to 16 carbon atoms. 12 Alkyl, C6-C 12 Aryl or C3-C9 aryl, any of which may optionally be substituted or interrupted by silane, silicon, oxygen, halogen, carbonyl, hydroxyl, ester, carboxyl, urea, urethane, carbonate, amino, amide, sulfur, sulfonate, sulfone, etc.

[0040] One class of monomers suitable for use in this invention includes polyacrylates represented by the following formula: Where R is located 4 The group is selected from hydrogen, halogens, or alkyl groups having 1 to about 4 carbon atoms; q is an integer equal to at least 1, and preferably equal to about 4; and X is an organic group containing at least two carbon atoms and having a total bonding capacity of q+1. Regarding the upper limit of the number of carbon atoms in X, monomers can be used in virtually any value. However, in practice, the general upper limit is about 50 carbon atoms, preferably 30, and most preferably about 20.

[0041] For example, X can be an organic group of the following formula: In this Y 1 and Y 2 Each of them is an organic group containing at least 2 carbon atoms, preferably 2 to about 10 carbon atoms, preferably a hydrocarbon group, and Z is an organic group containing at least 1 carbon atom, preferably 2 to about 10 carbon atoms, preferably a hydrocarbon group.

[0042] Other types of useful monomers are reaction products of dialkylolamines or trialkylolamines (e.g., ethanolamine or propanolamine) with acrylic acid, as disclosed in French Patent No. 1,581,361.

[0043] Useful examples of acrylate oligomers include those having the following general formula: Where R is located 5 A group representing a group selected from hydrogen, lower alkyl groups of 1 to 4 carbon atoms, hydroxyalkyl groups of 1 to 4 carbon atoms, and... Where R is located 4 It is a group selected from hydrogen, halogens, or lower alkyl groups with 1 to 4 carbon atoms; R 6 It is a group selected from hydrogen, hydroxyl, or the following: m is an integer equal to at least 1, for example, from 1 to about 15 or higher, and preferably from 1 to about 8; n is an integer equal to at least 1, for example, from 1 to about 40 or higher, and preferably from about 2 to about 10; and p is 0 or 1.

[0044] Typical examples of (meth)acrylate oligomers corresponding to the above general formula include di-, tri-, and tetraethylene glycol dimethacrylate; bis(pentamethylene glycol) dimethacrylate; tetraethylene glycol diacrylate; tetraethylene glycol di(chloroacrylate); diglycerol diacrylate; diglycerol tetramethacrylate; butanediol dimethacrylate; neopentyl glycol diacrylate; and trimethylolpropane triacrylate.

[0045] While diacrylates and other polyacrylates, particularly those described in the preceding paragraphs, may be desirable, monofunctional acrylates (esters containing one acrylate group) can also be used. When processing monofunctional acrylates, esters with a relatively polar alcohol moiety are highly preferred. Such materials are less volatile than low molecular weight alkyl esters, and more importantly, the polar groups tend to provide intermolecular attraction during and after curing, resulting in more desirable cured properties and more durable sealants or adhesives. Ideally, the polar groups are selected from unstable hydrogen, heterocyclic, hydroxyl, amino, cyano, and halogen polar groups. Typical examples of such compounds are cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, tert-butylaminoethyl methacrylate, ethyl cyanoacrylate, and chloroethyl methacrylate.

[0046] Another class of useful monomers is prepared by reacting monofunctional substituted alkyl or aryl (meth)acrylates containing active hydrogen atoms on their functional substituents. Such monofunctional (meth)acrylate-terminated materials react with organic polyisocyanates in suitable proportions to convert all isocyanate groups into urethane or urea groups. The monofunctional alkyl and aryl acrylates are preferably acrylates and methacrylates containing hydroxyl or amino functional groups on their non-acrylate moieties. Suitable acrylates have the following formula: Here, X is selected from --O-- or --O-- And R 9 Selected from hydrogen or lower alkyl groups with 1 to 7 carbon atoms; R 7 Selected from hydrogen, chloro, or methyl and ethyl; and R 8 These are divalent organic groups selected from lower alkylene, phenylene, or naphthyl groups having 1 to 8 carbon atoms. Upon appropriate reaction with polyisocyanates, these groups yield monomers of the following general formula: Where n is an integer from 2 to 6; B is a polyvalent organic group selected from (both substituted and unsubstituted) alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, aralkyl, alkylaryl, or heterocyclic groups; and R 7 R 8 X has the meanings given above in this paragraph.

[0047] Examples of suitable hydroxy-functionalized (meth)acrylates include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate (“HEMA”), hydroxypropyl methacrylate (“HPMA”), hydroxybutyl methacrylate, and mixtures thereof. Other examples of suitable hydroxy-functionalized (meth)acrylates include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate (“HEMA”), pentaerythritol triacrylate (“PETA”), and 4-hydroxybutyl acrylate.

[0048] Hydroxyl-functional (meth)acrylates may have a number average molecular weight of about 80 to about 1,000 g / mol, or about 100 to about 800 g / mol, or about 110 to about 600 g / mol.

[0049] Of course, this combination of (meth)acrylate monomers can also be used.

[0050] Other (meth)acrylate monomers that may be used herein include silicone (meth)acrylate moieties (“SiMA”), such as those taught and claimed in U.S. Patent No. 5,605,999 (Chu).

[0051] Based on the total weight of the composition, the polymerizable (meth)acrylate monomer may be present in the composition in an amount of about 10% by weight to about 90% by weight, suitably about 30% by weight to about 70% by weight.

[0052] Compositions that induce anaerobic curing typically include free radical initiators, co-promoters and free radical inhibitors, as well as metal catalysts.

[0053] Many well-known free radical initiators can be used, including but not limited to peroxide compounds such as hydroperoxides, such as cumene hydroperoxide (“CHP”), p-menthol hydroperoxide, tert-butyl hydroperoxide (“TBH”), dicumene hydroperoxide, and tert-butyl perbenzoate. Other useful peroxides include benzoyl peroxide, dibenzoyl peroxide, 1,3-bis(tert-butylperoxyisopropyl)benzene, diacetyl peroxide, butyl 4,4-bis(tert-butylperoxy)valerate, p-chlorobenzoyl peroxide, tert-butyl peroxide, tert-butyl perbenzoate, di-tert-butyl peroxide, dicumene peroxide, 2,5-dimethyl-2,5-di-tert-butylperoxyhexane, 2,5-dimethyl-2,5-di-tert-butyl-peroxyhexane, 4-methyl-2,2-di-tert-butylperoxypentane, and combinations thereof.

[0054] Based on the total weight of the composition, such peroxide compounds are typically used in the present invention at about 0.1% to about 10% by weight, of which about 1% to about 5% by weight is desired.

[0055] As described above, conventional accelerators for free radical polymerization can also be used in conjunction with the curing accelerators used in this invention, although in smaller amounts than previously used. Such accelerators (referred to herein as co-accelerators) are typically hydrazine-based (e.g., APH), as disclosed in U.S. Patent Nos. 4,287,350 (Rich) and 4,321,349 (Rich). When APH is selected as the co-accelerator used herein, maleic acid is typically also added. One advantage of this invention is that the anaerobic curing accelerator eliminates the need for such acids in the preparation of anaerobic adhesive compositions.

[0056] Other co-accelerators may also be used in the compositions of the present invention, including but not limited to organic amides and imides, such as o-sulfonylbenzeneimide (also known as saccharin) (see U.S. Patent No. 4,324,349). Of course, THQ can also be used as a co-accelerator. Redox Active Metal Catalysts

[0057] Furthermore, when the anaerobic curable adhesive composition is contacted with a plastic substrate under anaerobic conditions, the curing inducing component / reagent of the anaerobic curable adhesive composition can be a redox-active metal catalyst containing a transition metal. Redox-active metal catalysts enhance the curing strength, curing rate, and combinations thereof of the compositions described herein.

[0058] The transition metal contained in the redox active metal catalyst can be titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, vanadium, molybdenum, ruthenium, and combinations thereof. Furthermore, the transition metal can be provided in the form of salts. For example, transition metal salts can be selected from cobalt(II) naphthenate; copper carbonate; copper(II) acetylacetonate; silver nitrate; vanadium(III) acetylacetonate, and combinations thereof. Suitably, the redox active metal catalyst is iron(II) naphthenate, disodium copper(II) ethylenediaminetetraacetate (EDTA.2Na.Cu(II)) or copper naphthenate, vanadium acetylacetonate, vanadium acetylacetonate oxyacetate, iron(II) acetate, or combinations thereof.

[0059] Based on the total weight of the composition, the redox active metal catalyst may be included in the composition in an amount of about 0.0001 wt% to about 2 wt%, suitably about 0.0002 wt% to about 0.5 wt%. stabilizer components

[0060] Stabilizers and inhibitors (such as phenols, including hydroquinone and quinone) can be used to control and prevent premature decomposition and polymerization of the compositions of the present invention.

[0061] In addition to the stabilizer components described above, the compositions of the present invention may optionally include one or more additional stabilizers. Such additional stabilizers may include benzoyl-functionalized compounds. Benzoyl-functionalized compounds in the compositions of the present invention are desirable because their inclusion stabilizes the composition, for example, it can stabilize redox-active metal catalysts.

[0062] Benzoyl-functionalized compounds can be photoinitiators. For example, they can be found at BASF Chemical, Germany under the name "IRGACURE". TM "and "DAROCUR TM "The photoinitiators purchased under the brand name are ideal, especially 'IRGACURE'." TM"184 (1-hydroxycyclohexylphenyl ketone), 907 (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylprop-1-one), 369 (2-benzyl-2-N,N-dimethylamino-1-(4-morpholinylphenyl)-1-butanone), 500 (a combination of 1-hydroxycyclohexylphenyl ketone and benzophenone), 651 (2,2-dimethoxy-2-phenylacetophenone), 1700 (a combination of bis(2,6-dimethoxybenzoyl-2,4,4-trimethylpentylphosphine oxide and 2-hydroxy-2-methyl-1-phenyl-prop-1-one) and "DAROCUR" TM "1173 (2-hydroxy-2-methyl-1-phenyl-1-propane) and 4265 (a combination of 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 2-hydroxy-2-methyl-1-phenyl-prop-1-one). Of course, combinations of these materials can also be used herein. The structures of preferred photoinitiators are shown below."

[0063] Irgacure TM 651

[0064] Irgacure TM 184

[0065] Irgacure TM 127

[0066] Irgacure TM 819

[0067] Irgacure TM 369

[0068] Based on the total weight of the composition, the benzoyl-functionalized compound may be included in the composition in an amount of about 0.1 to about 5% by weight, suitably about 0.5 to about 2% by weight. Ideally, the benzoyl-functionalized compound is present in an excess amount relative to the redox active metal catalyst. For example, the benzoyl-functionalized compound is ideally present in an excess amount relative to the redox active metal catalyst at a ratio of at least about 3:1, for example at least about 4:1, for example at least about 5:1. Optional components

[0069] Additional / optionally present components may be included in the anaerobic curable adhesive compositions disclosed herein, such that such additional components do not interfere with the function of the aforementioned components.

[0070] For example, based on the total weight of the composition, acrylic acid may be included in the composition in an amount of about 0% to about 20% by weight, suitably about 1% to about 10% by weight, to enhance curing and adhesion.

[0071] (Meth)acrylate oligomers may be further optionally included in the composition. (Meth)acrylate oligomers may be included to improve the full-cured peel strength of the compositions described herein. For example, (meth)acrylate-terminated polyurethane oligomers may be included. A variety of commercially available urethane (meth)acrylate oligomer resins are known. Suitably, the component is or includes a block resin, such as the block resin described in U.S. Patent No. 4,309,526, which comprises at least one polyether block derived from a polyether polyol and at least one hard block derived from an aromatic or alicyclic diisocyanate and an aromatic or alicyclic polyol. Particularly preferred are resins in which the polyether polyol is an aliphatic polyether with a number average molecular weight of about 400 to about 10,000, more preferably about 700 to about 3,500.

[0072] If included, the (meth)acrylate oligomer may be present in the anaerobic curable adhesive composition in an amount of about 5% to about 90% by weight, suitably about 10% to about 50% by weight, based on the total weight of the composition.

[0073] Amines may optionally be included in the composition to polymerize the monomers in the absence of oxygen and to prevent the monomers from polymerizing in the presence of oxygen.

[0074] The nature of the amine is not critical to the purpose of the anaerobic curable adhesive compositions disclosed herein; that is, primary, secondary, tertiary, aliphatic, or aromatic amines can be used. For example, aliphatic primary amines such as ethyl, n-butyl, n-propyl, isopropyl, n-hexyl, and tert-butylamine can be conveniently used. Aromatic primary amines such as aniline, p-toluidine or p-naphthylamine, xyleneamine, benzylamine, or p-benzylaniline can also be used. Aliphatic or aromatic secondary amines can also be used. Typical examples of acceptable secondary amines are diethylamine, dipropylamine, diisopropylamine, diphenylamine, N-phenylbenzylamine, and N-allylaniline.

[0075] Tertiary amines are organic amines in which all three valences of the nitrogen atom are satisfied by the carbon atom. Tertiary amines are also suitable for the compositions described herein. The carbon atom in a tertiary amine may be part of an unsubstituted or hydroxylated alkyl, carbocyclic, or heterocyclic group. Generally, trialkylamines and dialkylanilines are most suitable. However, alkaloids and other compounds within the above-defined scope are also suitable for this invention. Examples of various tertiary amines that can be used are triethylamine, tripropylamine, tributylamine, tripentylamine, triphenylamine, dimethylaniline, ethyldiethanolamine, triethanolamine, and piperidine.

[0076] Generally, amines suitable for the compositions described herein can be represented by the formula R”-R-NH, wherein R” is a hydrocarbon group containing up to about 14 carbon atoms, suitably an aliphatic or aromatic hydrocarbon group containing up to about 8 carbon atoms, and R is hydrogen or R. Naturally, R” or R can contain any substituents or bonds, hydrocarbons or others, which will not adversely affect the condensation product for the purposes disclosed herein.

[0077] One or more amines used in the compositions described herein are suitably liquid at room temperature for ease of handling and mixing, although gaseous and solid compounds may be used by dispersing them in monomers.

[0078] The anaerobic curable adhesive compositions disclosed herein may include various organic secondary and tertiary amines, preferably aromatic secondary amines.

[0079] Based on the total weight of the composition, the amine (suitably an aromatic secondary amine) may be included in the composition in an amount of up to about 5% by weight, preferably from about 0.001% to about 2% by weight.

[0080] Silica and inorganic fillers may also optionally be included in the composition. Such fillers can be added to make the composition more viscous, i.e., thixotropic. This is beneficial for non-flowing and non-sagging properties, for example, for gasket seals. Suitably, when silica and / or inorganic fillers are included in the composition, their content is at most about 10% by weight, suitably at most about 5% by weight, based on the total weight of the composition.

[0081] Additional resins may optionally be included in the composition. Such additional resins may include, but are not limited to, polyesters and polyurethanes. Based on the total weight of the composition, such resins may be included in the composition in an amount of up to about 50% by weight, suitably up to about 20% by weight.

[0082] Some components already included in conventional anaerobic adhesives may also be added to the anaerobic adhesive compositions of the present invention to alter the physical properties of the formulation or its reaction products. For example, one or more of the following may be included: maleimide components, heat-contributing co-reactants, diluent components reactive under elevated temperature conditions, monohydroxy or polyhydroxy alkanes, polymer plasticizers, and other chelating agents (see U.S. Patent No. 6,391,993, which is incorporated herein by reference) to alter the physical properties of the formulation and / or the curing profile and / or the strength or temperature resistance of the cured adhesive.

[0083] When used, maleimide, co-reactant, reactive diluent, plasticizer and / or monohydroxyalkane or polyhydroxyalkane may be present in amounts from about 1% to about 30% by weight, based on the total weight of the composition.

[0084] Other additives, such as thickeners, non-reactive plasticizers, fillers, toughening agents (such as elastomers and rubbers), and other well-known additives, may be used in the compositions of the present invention where those skilled in the art deem it desirable to do so. Detailed Implementation

[0085] The experimental details given below are examples of anaerobic curable adhesive compositions according to the present invention.

[0086] As described below, the curing properties of stabilizer components at different concentration levels in anaerobic adhesives were tested.

[0087] Na4GLDA and Na3MGDA are each available from Nouryon of 1101 BZ, Amsterdam, The Netherlands.

[0088] Solutions of Na4GLDA and Na3MGDA, each in a 1:3 volume ratio of water / propylene glycol, were prepared to facilitate their addition to adhesive formulations. Equivalent formulations using Na4EDTA were used for direct comparison testing.

[0089] Adhesive compositions that can be anaerobically cured using raw materials having the compositions listed in Table 1: Table 1 *Through the reaction of a diol and a carboxylic acid used to form a polyester diol, followed by a reaction with toluene diisocyanate, finally... It was prepared in a continuous process by end capping with (meth)acrylate. See, for example, U.S. Patent Nos. 3,425,988 and 4,309,526.

[0090] A control formulation of an anaerobic curable adhesive composition based on the raw materials in Table 1, without stabilizers, is prepared. This is included in Table 2 below.

[0091] A comparative formulation containing Na4EDTA was also prepared based on the anaerobic curable adhesive compositions of the raw materials in Table 1 to obtain the compositions shown in Table 2 below.

[0092] Na4GLDA and Na3MGDA were each converted into 3.5% by weight solutions in a 1:3 volume ratio of water / propylene glycol. These solutions were then mixed with the anaerobic curable adhesive compositions from Table 1 to obtain the compositions shown in Table 2 below. Table 2

[0093] The thermal stability (82°C in 10mm × 75mm test tubes and / or 55°C in 25ml glass jars with lids), shear strength, and torque strength (tested according to standard ASTM D5649) of the formulations in Table 2 containing Na4EDTA (control) or Na4GLDA / Na3MGDA were tested separately. The thermal stability test results best indicate the presence and performance of the chelating stabilizer in the formulation.

[0094] In the absence of a stabilizer, it was found that the control formulation (A1) gelled in less than 10 minutes when exposed to 82°C in test tubes.

[0095] In the presence of EDTA (A2) or the stabilizer components of the present invention (A3-A10), this was extended to more than 7 days under the same conditions, and no gelation time was observed as an endpoint.

[0096] Similarly, for the 55°C covered glass jar test, no gelation was observed in any of the samples A3 to A10 after 6 weeks. This indicates a highly stable product in the glass jar, exceeding the target specifications of >3 hours at 82°C or >3 days at 55°C.

[0097] Adhesive properties of all formulations were measured according to test standards ASTM D4562 and ASTM D5649 (shear strength at 1h and 24h, and torque strength at 1h, 4h and 24h).

[0098] For formulations prepared using Na4GLDA and Na3MGDA at concentrations of 236, 315, 394, and 473 ppm (A3 to A10), a clear trend emerged: cured strength decreased with increasing stabilizer content. This indicates that over-stabilized formulations, containing a large amount of metal chelating agents, can compete with the binder for the metal substrate, leading to reduced cured strength. These two new stabilizer components are extremely strong chelating agents.

[0099] The two new stabilizer components, Na4GLDA and Na3MGDA, were highly effective in stabilizing the composition of Table 1 at all the concentrations examined. Curing performance indicates that these should be considered at lower concentrations, as they are potent stabilizer components and can be effective at levels far below the control material, Na4EDTA. The tests were then repeated using an anaerobic curable adhesive composition with the raw materials shown in Table 3: Table 3 *Through the reaction of a diol and a carboxylic acid used to form a polyester diol, followed by a reaction with toluene diisocyanate, finally... It was prepared in a continuous process by end capping with (meth)acrylate. See, for example, U.S. Patent Nos. 3,425,988 and 4,309,526.

[0100] A comparative formulation containing Na4EDTA was also prepared based on the anaerobic curable adhesive composition of the raw materials in Table 3 to obtain composition B1 shown in Table 4 below.

[0101] Na4GLDA and Na3MGDA were each converted into 3.5% by weight solutions in a 1:3 volume ratio of water / propylene glycol. These solutions were then mixed with the anaerobic curable adhesive compositions from Table 3 to obtain the compositions shown in Table 4 below. Table 4

[0102] Both stabilizer components are effective in the range of about 5 ppm to about 1000 ppm, for example about 10 ppm to about 300 ppm, for example about 15 ppm to about 100 ppm.

[0103] The repeat tests confirmed that Na4GLDA and Na3MGDA are effective metal ion chelators in anaerobic formulations at levels significantly lower than those typically effective for Na4EDTA. See Table 5 below, which shows the concentration ranges for Na4GLDA and Na3MGDA tests and the achieved results for thermal stability and adhesive properties. Table 5

[0104] The results confirmed that these stabilizer components are effective in chelating metal ions and stabilizing binder formulations at much lower ppm levels than the standard stabilizer Na4EDTA.

[0105] When used herein with reference to the present invention, the terms “comprising / including” and “having / including” are used to specify the presence of the said feature, integer, step, or component, but do not exclude the presence or addition of one or more other features, integers, steps, components, or combinations thereof.

[0106] It should be understood that, for clarity, certain features of the invention described in the context of individual embodiments may also be provided in combination in a single embodiment. Conversely, for brevity, various features of the invention described in the context of individual embodiments may also be provided individually or in any suitable sub-combination.

Claims

1. An anaerobic curable adhesive composition comprising: (a) Components that can be anaerobically cured; (b) Curing-inducing components; and (c) Stabilizer components with the following structures: N-[C(R1)(R2)-COOM] n (R a ) m R1 and R2 are each independently selected from H, OH, straight-chain or branched C1-C6 alkyl, straight-chain or branched C1-C6 alkoxy, straight-chain or branched C2-C6 alkenyl, straight-chain or branched C2-C6 alkynyl, C5-C9 aryl, C3-C9 cycloalkyl, C4-C9 cycloalkenyl, C4-C9 cycloalkynyl, C5-C9 heteroaryl, C3-C9 heterocycloalicyclic, C6-C 12 Aryl group, C6-C 12 Heteroalkyl, C6-C 12 (Heterocyclic)alkyl, C2-C6 alkoxy, C5-C9 aryloxy, C2-C6 acyl, straight-chain or branched C1-C6 carboxylic acid ester, ester, mercapto, alkylthio, arylthio, cyano, halogen, carbonyl, thiocarbonyl, O-carbamoyl, N-carbamoyl, O-thiocarbamoyl, N-thiocarbamoyl, C-amide, N-amide, S-sulfonamide, N-sulfonamide, C-carboxyl, O-carboxyl, isocyanate, thiocyanate, isothiocyanate, nitro, silyl, sulfenyl, sulfinyl, sulfonyl, haloalkyl, haloalkoxy, trihalomethanesulfonyl and trihalomethanesulfonamide; M is a cation such as H+ or a metal cation, such as Na. + Li + or K + ; n is an integer selected from 1, 2, or 3; R a It can be selected from H, OH, straight-chain or branched C1-C6 alkyl, straight-chain or branched C1-C6 alkoxy, straight-chain or branched C2-C6 alkenyl, straight-chain or branched C2-C6 alkynyl, C5-C9 aryl, C3-C9 cycloalkyl, C4-C9 cycloalkenyl, C4-C9 cycloalkynyl, C7-C 12 Aryl group, C2-C6 alkoxy group, C5-C9 aryloxy group, C2-C6 acyl group, straight-chain or branched C1-C6 carboxylic acid ester group, ester group or carbonyl group; m is an integer selected from 3 to n.

2. The anaerobic curable adhesive composition according to claim 1, wherein C(R1)(R2)-COOM is selected from... Where M is a cation such as H+ or a metal cation; and R1 and R2 are each independently as defined above.

3. The anaerobic curable adhesive composition according to any one of the preceding claims, wherein the stabilizer component comprises one or both of the following compounds: (i) Tetrasodium glutamate diacetate (Na4GLDA) having the following structure: (ii) Trisodium methylglycine N,N-diacetic acid (Na3MGDA) having the following structure: 。 4. The anaerobic curable adhesive composition according to any one of the preceding claims, wherein the stabilizer component is present in the curable adhesive composition in an amount of about 10 ppm to 1000 ppm.

5. The anaerobic curable adhesive composition according to any one of the preceding claims, wherein the stabilizer component is present in the curable adhesive composition in an amount of about 10 ppm to 100 ppm.

6. The anaerobic curable adhesive composition according to any one of the preceding claims, wherein the stabilizer component acts as a metal ion chelating agent.

7. A method for anaerobic curing an anaerobic curable adhesive composition according to any one of claims 1 to 5, comprising the following steps: (A) Provides an anaerobic curable adhesive composition comprising: (a) Components that can be anaerobically cured; (b) Curing-inducing components; and (c) Stabilizer components with the following structures: N-[C(R1)(R2)-COOM] n (R a ) m R1 and R2 are each independently selected from H, OH, straight-chain or branched C1-C6 alkyl, straight-chain or branched C1-C6 alkoxy, straight-chain or branched C2-C6 alkenyl, straight-chain or branched C2-C6 alkynyl, C5-C9 aryl, C3-C9 cycloalkyl, C4-C9 cycloalkenyl, C4-C9 cycloalkynyl, C5-C9 heteroaryl, C3-C9 heterocycloalicyclic, C6-C 12 Aryl group, C6-C 12 Heteroalkyl, C6-C 12 (Heterocyclic)alkyl, C2-C6 alkoxy, C5-C9 aryloxy, C2-C6 acyl, straight-chain or branched C1-C6 carboxylic acid ester, ester, mercapto, alkylthio, arylthio, cyano, halogen, carbonyl, thiocarbonyl, O-carbamoyl, N-carbamoyl, O-thiocarbamoyl, N-thiocarbamoyl, C-amide, N-amide, S-sulfonamide, N-sulfonamide, C-carboxyl, O-carboxyl, isocyanate, thiocyanate, isothiocyanate, nitro, silyl, sulfenyl, sulfinyl, sulfonyl, haloalkyl, haloalkoxy, trihalomethanesulfonyl and trihalomethanesulfonamide; M is a cation such as H+ or a metal cation, such as Na. + Li + or K + ; n is an integer selected from 1, 2, or 3; R a It can be selected from H, OH, straight-chain or branched C1-C6 alkyl, straight-chain or branched C1-C6 alkoxy, straight-chain or branched C2-C6 alkenyl, straight-chain or branched C2-C6 alkynyl, C5-C9 aryl, C3-C9 cycloalkyl, C4-C9 cycloalkenyl, C4-C9 cycloalkynyl, C7-C 12 Aryl group, C2-C6 alkoxy group, C5-C9 aryloxy group, C2-C6 acyl group, straight-chain or branched C1-C6 carboxylic acid ester group, ester group or carbonyl group; m is an integer selected from 3 to n; as well as (B) The time required to expose the anaerobic curable adhesive composition to an anaerobic environment for curing the composition.

8. The method of claim 7, wherein the stabilizer component comprises one or both of the following compounds: (i) Tetrasodium glutamate diacetate (Na4GLDA) having the following structure: (ii) Trisodium methylglycine N,N-diacetic acid (Na3MGDA) having the following structure: 。 9. A cured product formed by curing an anaerobic curable adhesive composition according to any one of claims 1 to 5.

10. An adhesive assembly comprising a first substrate bonded to a second substrate by a cured product, said cured product being formed by curing an anaerobic curable adhesive composition according to any one of claims 1 to 5.

11. The following stabilizer components are used as stabilizer components in anaerobic curable compositions: N-[C(R1)(R2)-COOM] n (R a ) m R1 and R2 are each independently selected from H, OH, straight-chain or branched C1-C6 alkyl, straight-chain or branched C1-C6 alkoxy, straight-chain or branched C2-C6 alkenyl, straight-chain or branched C2-C6 alkynyl, C5-C9 aryl, C3-C9 cycloalkyl, C4-C9 cycloalkenyl, C4-C9 cycloalkynyl, C5-C9 heteroaryl, C3-C9 heterocycloalicyclic, C6-C 12 Aryl group, C6-C 12 Heteroalkyl, C6-C 12 (Heterocyclic)alkyl, C2-C6 alkoxy, C5-C9 aryloxy, C2-C6 acyl, straight-chain or branched C1-C6 carboxylic acid ester, ester, mercapto, alkylthio, arylthio, cyano, halogen, carbonyl, thiocarbonyl, O-carbamoyl, N-carbamoyl, O-thiocarbamoyl, N-thiocarbamoyl, C-amide, N-amide, S-sulfonamide, N-sulfonamide, C-carboxyl, O-carboxyl, isocyanate, thiocyanate, isothiocyanate, nitro, silyl, sulfenyl, sulfinyl, sulfonyl, haloalkyl, haloalkoxy, trihalomethanesulfonyl and trihalomethanesulfonamide; M is a cation such as H+ or a metal cation, such as Na. + Li + or K + ; n is an integer selected from 1, 2, or 3; R a It can be selected from H, OH, straight-chain or branched C1-C6 alkyl, straight-chain or branched C1-C6 alkoxy, straight-chain or branched C2-C6 alkenyl, straight-chain or branched C2-C6 alkynyl, C5-C9 aryl, C3-C9 cycloalkyl, C4-C9 cycloalkenyl, C4-C9 cycloalkynyl, C7-C 12 Aryl group, C2-C6 alkoxy group, C5-C9 aryloxy group, C2-C6 acyl group, straight-chain or branched C1-C6 carboxylic acid ester group, ester group or carbonyl group; m is an integer selected from 3 to n.

12. The use according to claim 11, wherein the stabilizer component is at least one of the following: (i) Tetrasodium glutamate diacetate (Na4GLDA) having the following structure: ;or (ii) Trisodium methylglycine N,N-diacetic acid (Na3MGDA) having the following formula: 。 13. A method for stabilizing an anaerobic curable adhesive composition by providing an effective amount of a stabilizer component with the following structure: N-[C(R1)(R2)-COOM] n (R a ) m R1 and R2 are each independently selected from H, OH, straight-chain or branched C1-C6 alkyl, straight-chain or branched C1-C6 alkoxy, straight-chain or branched C2-C6 alkenyl, straight-chain or branched C2-C6 alkynyl, C5-C9 aryl, C3-C9 cycloalkyl, C4-C9 cycloalkenyl, C4-C9 cycloalkynyl, C5-C9 heteroaryl, C3-C9 heterocycloalicyclic, C6-C 12 Aryl group, C6-C 12 Heteroalkyl, C6-C 12 (Heterocyclic)alkyl, C2-C6 alkoxy, C5-C9 aryloxy, C2-C6 acyl, straight-chain or branched C1-C6 carboxylic acid ester, ester, mercapto, alkylthio, arylthio, cyano, halogen, carbonyl, thiocarbonyl, O-carbamoyl, N-carbamoyl, O-thiocarbamoyl, N-thiocarbamoyl, C-amide, N-amide, S-sulfonamide, N-sulfonamide, C-carboxyl, O-carboxyl, isocyanate, thiocyanate, isothiocyanate, nitro, silyl, sulfenyl, sulfinyl, sulfonyl, haloalkyl, haloalkoxy, trihalomethanesulfonyl and trihalomethanesulfonamide; M is a cation such as H+ or a metal cation, such as Na. + Li + or K + ; n is an integer selected from 1, 2, or 3; R a It can be selected from H, OH, straight-chain or branched C1-C6 alkyl, straight-chain or branched C1-C6 alkoxy, straight-chain or branched C2-C6 alkenyl, straight-chain or branched C2-C6 alkynyl, C5-C9 aryl, C3-C9 cycloalkyl, C4-C9 cycloalkenyl, C4-C9 cycloalkynyl, C7-C 12 Aryl group, C2-C6 alkoxy group, C5-C9 aryloxy group, C2-C6 acyl group, straight-chain or branched C1-C6 carboxylic acid ester group, ester group or carbonyl group; m is an integer selected from 3 to n.

14. The method of claim 13, wherein the stabilizer component is at least one of the following, as a component of the anaerobic curable composition: (i) Tetrasodium glutamate diacetate (Na4GLDA) having the following structure: ;or (ii) Trisodium methylglycine N,N-diacetic acid (Na3MGDA) having the following structure: 。

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