ANAEROBICALLY CURABLE COMPOSITIONS

Abstract

An anaerobically curable composition comprising a hydroxy-functionalized mono(meth)acrylate compound, an aromatic mono(meth)acrylate compound which is not the same as the hydroxy-functionalized mono(meth)acrylate compound, a (meth)acrylate functionalised polyurethane resin, and an anaerobic cure inducing component.

Claims

1. An anaerobically curable composition comprising: (i) a hydroxy-functionalized mono(meth)acrylate compound, (ii) an aromatic mono(meth)acrylate compound which is not the same compound as the hydroxy-functionalized mono(meth)acrylate compound, (iii) a (meth)acrylate functionalised polyurethane resin, and (iv) an anaerobic cure inducing component.

2. The composition of claim 1 wherein the hydroxy-functionalized mono(meth)acrylate compound comprises hydroxyethyl methacrylate.

3. The composition of claim 1 wherein the hydroxy-functionalized mono(meth)acrylate compound is present in an amount from about 5% to about 30% by weight based on the total weight of the composition.

4. The composition of claim 1 wherein the hydroxy-functionalized mono(meth)acrylate compound is present in an amount from about 7% to about 15% by weight based on the total weight of the composition.

5. The composition of claim 1 wherein the hydroxy-functionalized mono(meth)acrylate compound has a molecular weight below about 1000 g/mol, or below about 800 g/mol, or below about 600 g/mol, or below about 400 g/mol, or below about 200 g/mol.

6. The composition of claim 1 wherein the hydroxy-functionalized mono(meth)acrylate compound has a molecular weight of from about 100 g/mol to about 150 g/mol.

7. The composition of claim 1 wherein the aromatic mono(meth)acrylate compound comprises benzyl methacrylate, tetrahydrofurfuryl methacrylate or combinations thereof.

8. The composition of claim 1 wherein the aromatic mono(meth)acrylate compound is present in an amount from about 5% to about 60% by weight based on the total weight of the composition.

9. The composition of claim 1 wherein the aromatic mono(meth)acrylate compound is present in an amount from about 25% to about 40% by weight based on the total weight of the composition.

10. The composition of claim 1 wherein the aromatic mono(meth)acrylate compound has a molecular weight below about 1000 g/mol, or below about 800 g/mol, or below about 600 g/mol, or below about 400 g/mol, or below about 200 g/mol.

11. The composition claim 1 wherein the aromatic mono(meth)acrylate compound has a molecular weight of from about 150 g/mol to about 200 g/mol.

12. The composition of claim 1 wherein the (meth)acrylate functionalised polyurethane resin is present in an amount from about 20% to about 50% by weight based on the total weight of the composition.

13. The composition of claim 1 wherein the (meth)acrylate functionalised polyurethane resin is present in an amount from about 25% to about 40% by weight based on the total weight of the composition.

14. The composition of claim 1 wherein the (meth)acrylate functionalised polyurethane resin has a molecular weight of from about 5000 to about 7000 g/mol, or a molecular weight from about 5500 to about 6000 g/mol.

15. The composition of claim 1 wherein the composition further comprises a polyethylene filler.

16. The composition of claim 15 wherein the polyethylene filler is present in an amount from about 5% to about 15% by weight based on the total weight of the composition.

17. The composition of claim 1 wherein the composition further comprises a hydrophobic silica.

18. The composition of claim 1 wherein the composition is thixotropic.

19. The composition of claim 1 wherein the composition has a viscosity of about 500 mPas to about 3000 mPas as measured at 25° C. using BS EN 125092:2001.

20. A cure product formed by anaerobic cure of a composition according to claim 1.

21. A method of sealing a joint between a male and a female mating parts comprising: (i) viding a composition according to claim 1; (ii) applying the composition to at least one mating part; (iii) joining the mating parts so as to form a joint between the male and female mating parts; (iv) and curing the composition so that the joint between the male and female mating parts is sealed by the cured composition; optionally wherein one of the male or female mating parts is formed from a metal and the other is formed from a plastics material.

22. A sealed joint assembly comprising a male mating part and a female mating part mated together and forming a joint and the cure product of a composition according to claim 1 forming a seal for the joint.

Description

DETAILED DESCRIPTION

[0058] It should be readily apparent to one of ordinary skill in the art that the examples disclosed herein below represent illustrative examples only, and that other arrangements and methods capable of reproducing the invention are possible and are embraced by the present invention.

EXPERIMENTAL

[0059] The components of a representative composition according to the invention are listed in Table 1:

TABLE-US-00001 Wt % (based on total weight of Material the composition) Hydroxyethyl methacrylate  5-30 Benzyl methacrylate  5-40 Methacrylate functionalised 20-50 polyurethane resin PVA beads  0-15 Carboxyethyl acrylate 1-8 Acetyl Phenyl Hydrazine 0.1-1   Acid Saccharin 0.1-3   Stabiliser 1 0.01-0.15 Stabiliser 2 0.01-0.25 Polypropylene filler  5-15 Aerosil 380 Hydrophilic 1-3 Aerosil R202 Hydrophobic 1-2 Aerosil P972 2-4 Tert-butyl peroxybenzoate 0.5-3   Polyethylene glycol monooleate  0-15 Thixatrol ST 0-2 Yellow dye   0-0.5 Aerosil: Fumed silica available from Evonik Industries; Thixatrol ST: Hydroxy modified aliphatic hydrocarbon available from Elementis Specialities.

[0060] The anaerobic composition is prepared by mixing the materials in Table 1 at room temperature.

[0061] Lap shear strength was assessed for various substrates using various compositions within the ranges set forth in Table 1.

Examples

[0062] The following compositions were prepared:

TABLE-US-00002 Sample 1 Sample 2 Material Wt % (based on total weight of the composition) Hydroxyethyl methacrylate 13 19.5 Benzyl methacrylate 32 19.5 Methacrylate functionalised 36 32 polyurethane resin PVA beads 0 6.2 Carboxyethyl acrylate 2.6 2.5 Acetyl Phenyl Hydrazine 0.5 0.5 Acid Saccharin 0.5 0.5 Stabiliser 1 0.1 0.1 Stabiliser 2 0.1 0.1 Polypropylene filler 10 8 Aerosil 380 Hydrophilic 0 1.8 Aerosil R202 Hydrophobic 0 0.6 Aerosil P972 3 0 Tert-butyl peroxybenzoate 2.2 2.2 Polyethylene glycol monooleate 0 5 Thixatrol ST 0 1.3 UK yellow dye 0 0.2

[0063] The sample compositions according to the invention were tested to determine the lap shear strength. The sample compositions were compared to Loctite 577, Loctite 603, Loctite 638, Loctite 648, Loctite 620, and Loctite 6300 from Henkel.

TABLE-US-00003 Comparative compositions Description Loctite 577 Thread sealant comprising of dimethacrylate monomers/oligomers/resins with standard anaerobic cure systems Loctite 603 Retaining products comprising of dimethacrylate monomers/oligomers/resins and standard anaerobic cure systems Loctite 638 Retaining products comprising of dimethacrylate monomers/oligomers/resins and standard anaerobic cure systems Loctite 620 Retaining products comprising of dimethacrylate monomers/oligomers/resins and standard anaerobic cure systems Loctite 6300 Retaining products comprising of dimethacrylate monomers/oligomers/resins and standard anaerobic cure systems

Lap Strength Testing

[0064] Lap strength testing was performed according to ASTM D1002-05 (Oct. 1, 2005).

Break Torque Testing

[0065] Break torque testing was performed according to ASTM D5649.

Metal to PVC Bonding

[0066] Polyvinyl chloride (PVC) bonding to stainless was tested for sample 2. The bonded parts were cured were heat treated at 80° C. for 60 minutes prior to curing for 18 hours at room temperature. 5 independent replicates (N=5) were carried out. The composition of the present invention provided greatly improved bonding of PVC to stainless steel in comparison a known composition. The results were:

TABLE-US-00004 Sample N1 N2 N3 N4 N5 Mean σ Max Min Lap shear strength (N/mm.sup.2) Loctite 577 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Sample 2 3.2 4.3 6.1 4.8 4.4 4.5 1.1 6.1 3.2

Metal to Nylon Bonding

[0067] Nylon bonding to stainless and mild steel was tested for sample 1. The bonded parts were cured for 24 hours at room temperature or were heat treated at 80° C. for 45 minutes prior to curing for 24 hours at room temperature. The results were:

TABLE-US-00005 Sample Loctite 603 Loctite 638 Loctite 648 Loctite 620 Loctite 6300 Sample 1 Lap shear strength 24 hours stainless steel 0.9 0.0 2.2 0.0 0.0 5.5 Lap shear strength 24 hours mild steel 0.0 0.0 0.0 0.0 0.0 3.0 Lap shear strength 80° C. for 45 minutes and 24 0.9 0.0 1.2 0.7 0.0 5.9 hours stainless steel Lap shear strength 80° C. for 45 minutes and 24 1.0 0.8 1.3 0.0 0.0 6.7 hours mild steel

[0068] Nylon bonding to stainless was tested for sample 2. The bonded parts were cured for 24 hours or heat treated for 45 minutes at 80° C. followed by cure for 18 hours at room temperature. 5 independent replicates (N=5) were carried out for each time point. The results were:

TABLE-US-00006 Sample N1 N2 N3 N4 N5 Mean σ Max Min Break torque (Nm) 24 hours Loctite 0.6 0.5 0.0 0.0 0.3 0.3 0.3 0.6 0.0 577 Sample 3.7 2.8 3.3 2.9 3.4 3.2 0.4 3.7 2.8 2 45 minutes Loctite 0.4 0.5 0.4 0.6 0.1 0.4 0.2 0.6 0.1 at 80° C. and 577 18 hours at Sample 5.6 5.5 5.8 5.6 5.8 5.7 0.1 5.8 5.5 RT 2

[0069] Nylon bonding to stainless steel was tested for sample 2 after humidity resistance. The bonded parts were cured for 45 minutes at 80° C. followed by 18 hours at room temperature, followed by 72 hours at 40° C. at 98% relative humidity. 5 independent replicates (N=5) were carried out for each time point. The results were:

TABLE-US-00007 Sample N1 N2 N3 N4 N5 Mean σ Max Min Break torque (Nm) Loctite 577 1.3 1.2 0.7 1.5 0.8 1.1 0.3 1.5 0.7 Sample 2 4.9 4.8 4.7 4.7 4.9 4.8 0.1 4.9 4.7

[0070] The compositions of the present invention provided greatly improved lap shear strength and break torque of nylon to both stainless steel (inactive metal) and mild steel (active metal) in comparison with known compositions. The composition of the present invention had greatly improved resistance to humidity stress.

Metal to Polyphenylene Sulfide Bonding

[0071] Polyphenylene sulfide bonding to stainless and mild steel was tested for sample 1. The bonded parts were cured for 24 hours at room temperature or were heat treated at 80° C. for 45 minutes prior to curing for 24 hours at room temperature. The compositions of the present invention provided greatly improved lap shear strength bonding of polyphenylene sulfide to both stainless steel (inactive metal) and mild steel (active metal) in comparison with known compositions. The results were:

TABLE-US-00008 Sample Loctite 603 Loctite 638 Loctite 648 Loctite 620 Loctite 6300 Sample 1 Lap shear strength 24 hours stainless steel 2.0 0.8 0.9 0.0 0.0 5.1 Lap shear strength 24 hours mild steel 0.0 0.0 0.0 0.0 0.0 1.9 Lap shear strength 80° C. for 45 minutes and 24 3.8 4.5 3.7 2.5 2.3 6.4 hours stainless steel Lap shear strength 80° C. for 45 minutes and 24 4.1 3.0 3.3 1.0 0.0 8.3 hours mild steel

Metal to Phenolic Bonding

[0072] Phenolic bonding to stainless and mild steel was tested for sample 1. The bonded parts were cured for 24 hours at room temperature or were heat treated at 80° C. for 45 minutes prior to curing for 24 hours at room temperature. The compositions of the present invention provided greatly improved lap shear strength bonding of phenolic to both stainless steel (inactive metal) and mild steel (active metal) in comparison with known compositions. The results were:

TABLE-US-00009 Loctite Loctite Loctite Loctite Loctite Sample Sample 603 638 648 620 6300 1 Lap shear strength 24 hours stainless steel 2.4 0.0 1.1 0.3 0.0 5.9 Lap shear strength 24 hours mild steel 0.7 0.0 0.0 0.0 0.0 4.4 Lap shear strength 80° C. for 45 minutes and 24 5.1 4.7 3.9 3.0 0.0 9.6 hours stainless steel Lap shear strength 80° C. for 45 minutes and 24 7.4 6.0 8.1 4.4 0.0 9.2 hours mild steel

Metal to Acrylonitrile Butadiene Styrene Bonding

[0073] Acrylonitrile butadiene styrene bonding to stainless and mild steel was tested for sample 1. The bonded parts were cured for 24 hours at room temperature or were heat treated at 80° C. for 45 minutes prior to curing for 24 hours at room temperature. The compositions of the present invention provided greatly improved lap shear strength bonding of ABS to both stainless steel (inactive metal) and mild steel (active metal) in comparison with known compositions. The results were:

TABLE-US-00010 Loctite Loctite Loctite Loctite Loctite Sample Sample 603 638 648 620 6300 1 Lap shear strength 24 hours stainless 0.0 0.0 0.0 0.0 0.0 4.2 steel Lap shear strength 24 hours mild steel 0.0 0.0 0.0 0.0 0.0 0.0 Lap shear strength 80° C. for 45 minutes 1.5 0.1 0.6 2.8 0.2 6.6 and 24 hours stainless steel Lap shear strength 80° C. for 45 minutes 0.6 0.9 2.2 1.4 2.1 5.5 and 24 hours mild steel

Metal to Metal Bonding

[0074] Stainless steel bonding to stainless steel was tested for sample 2. The bonded parts were cured for 24 hours at room temperature or were heat treated at 80° C. for 45 minutes prior to curing for 24 hours at room temperature. The compositions of the present invention provided greatly improved break torque bonding of stainless steel to stainless steel (inactive metals) in comparison with known compositions. The results were:

TABLE-US-00011 Sample N1 N2 N3 N4 N5 Mean σ Max Min Break torque (Nm) 1 hour Loctite 1.3 0.6 0.7 0.7 0.2 0.7 0.4 1.3 0.2 577 Sample 2 1.3 0.4 0.9 0.8 1.4 1.0 0.4 1.4 0.4 18 hours Loctite 7.1 8.6 4.0 8.7 6.8 7.0 1.9 8.7 4.0 577 Sample 2 11.1 11.3 11.7 10.6 10.1 11.0 0.6 11.7 10.1 168 hours Loctite 16.1 147 12.0 13.0 13.1 13.8 1.6 16.1 12.0 577 Sample 2 12.5 12.9 13.8 13.2 12.2 12.9 0.6 13.8 12.2

[0075] The words “comprises/comprising” and the words “having/including” when used herein with reference to the present invention are used to specify the presence of stated features, integers, steps or components but do not preclude the presence or addition of one or more other features, integers, steps, components or groups thereof.

[0076] It is appreciated that certain features of the invention, which are, for clarity, described in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable sub-combination.