Improved adhesive composition for bonding rubber to metal
US-2019112509-A1 · Apr 18, 2019 · US
US11987730B2 · US · B2
| Field | Value |
|---|---|
| Publication number | US-11987730-B2 |
| Application number | US-201916978982-A |
| Country | US |
| Kind code | B2 |
| Filing date | Mar 12, 2019 |
| Priority date | Apr 23, 2018 |
| Publication date | May 21, 2024 |
| Grant date | May 21, 2024 |
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Disclosed is an aqueous adhesive composition which comprises an admixture of: (a) a first aqueous composition comprising, (i) one or more film forming polymers, (ii) one or more lower crystallinity polynitroso compounds, (iii) one or more higher crystallinity polynitroso compounds, and (iv) one or more bismaleimide-containing monomers; and (b) a second aqueous composition comprising (i) an aqueous dispersion of at least one phenolic resin which is a condensation product of a phenol and formaldehyde, wherein the aqueous dispersion is stabilized by at least one polyacrylate; (b) one or more latices formed from one or more halogenated polyolefins; and (c) one or more metal oxides.
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What is claimed is: 1. An aqueous adhesive composition which comprises an admixture of: (a) a first aqueous composition comprising, (i) one or more film forming polymers, (ii) one or more lower crystallinity polynitroso compounds, (iii) one or more higher crystallinity polynitroso compounds, and (iv) one or more bismaleimide-containing monomers; and (b) a second aqueous composition comprising (i) an aqueous dispersion of at least one phenolic resin which is a condensation product of a phenol and formaldehyde, wherein the aqueous dispersion is stabilized by at least one polyacrylate derived from a monomer represented by Formula I: wherein R 1 is H, CH 3 , C 2 to C 4 alkyl or C 6 to C 12 aryl; R 2 is H, OH, CN, CH 3 , C 2 to C 8 alkyl, or a halogen; and R 3 and R 4 are each independently H, CH 3 , C 2 to C 8 alkyl, C 6 to C 12 aryl, O—CH 3 , O—C 2 to C 8 alkyl, and O-aryl; (b) one or more latices formed from one or more halogenated polyolefins; and (c) one or more metal oxides. 2. The aqueous adhesive composition according to claim 1 , wherein the one or more film forming polymers are a halogenated olefin polymer. 3. The aqueous adhesive composition according to claim 1 , wherein the one or more film forming polymers are a halogenated substituted polydiene polymer. 4. The aqueous adhesive composition according to claim 1 , wherein the one or more lower crystallinity polynitroso compounds has a crystallinity of less than 30% by weight as determined by X-ray diffraction and the one or more higher crystallinity polynitroso compounds has crystallinity of greater than 40% by weight as determined by X-ray diffraction. 5. The aqueous adhesive composition according to claim 4 , wherein the one or more lower crystallinity polynitroso compounds and the one or more higher crystallinity polynitroso compounds are poly-(1,4-phenylyenazine-N,N-dioxide). 6. The aqueous adhesive composition according to claim 1 , wherein a weight ratio of the one or more lower crystallinity polynitroso compounds to the one or more higher crystallinity polynitroso compounds is 1:2 to 2:1. 7. The aqueous adhesive composition according to claim 1 , wherein the one or more bismaleimide-containing monomers are represented by the formula: wherein R is a alkylene, cycloalkylene, heterocyclic, arylene, mixtures thereof. 8. The aqueous adhesive composition according to claim 1 , wherein the first aqueous composition comprises: (i) 2 wt. % to 75 wt. %, based on the total weight of the first aqueous composition, of the one or more film forming polymers, (ii) 2 wt. % to 30 wt. %, based on the total weight of the first aqueous composition, of the one or more lower crystallinity polynitroso compounds, (iii) 3 wt. % to 30 wt. %, based on the total weight of the first aqueous composition, of the one or more higher crystallinity polynitroso compounds, and (iv) 0.1 wt. % to 15 wt. %, based on the total weight of the first aqueous composition, of the one or more bismaleimide-containing monomers. 9. The aqueous adhesive composition according to claim 1 , wherein the polyacrylate is an alkali or ammonium salt of a polyacrylic acid and/or a substituted polyacrylic acid. 10. The aqueous adhesive composition according to claim 1 , wherein the one or more latices formed from one or more halogenated polyolefins comprises an emulsion copolymer of a chlorinated polyolefin with an ethylenically unsaturated monomer. 11. The aqueous adhesive composition according to claim 1 , wherein the second aqueous composition comprises: (i) 2 wt. % to 30 wt. %, based on the total weight of the second aqueous composition, of the aqueous dispersion of at least one phenolic resin, (ii) 5 wt. % to 40 wt. %, based on the total weight of the second aqueous composition, of the one or more latices formed from one or more halogenated polyolefins, and (iii) 3 wt. % to 30 wt. %, based on the total weight of the second aqueous composition, of the one or more metal oxides. 12. The aqueous adhesive composition according to claim 1 , further comprising a surfactant and carbon black. 13. The aqueous adhesive composition according to claim 1 , wherein the first aqueous composition and second aqueous composition are admixed in a volume ratio of the first aqueous composition to the second aqueous composition of 10:0.5 to 0.5:10. 14. The aqueous adhesive composition according to claim 1 , having a Brookfield viscosity of from 10 to 1500 cPs at 20° C. 15. A bonded assembly comprising; (a) a rigid substrate having an interfacial bond area, (b) an unvulcanized rubber; and (c) an aqueous adhesive composition bonding the rigid substrate to the unvulcanized rubber; wherein the aqueous adhesive composition comprises an admixture of: (i) a first aqueous composition comprising, (1) one or more film forming polymers, (2) one or more lower crystallinity polynitroso compounds, (3) one or more higher crystallinity polynitroso compounds, and (4) one or more bismaleimide-containing monomers; and (ii) a second aqueous composition comprising (1) an aqueous dispersion of at least one phenolic resin which is a condensation product of a phenol and formaldehyde, wherein the aqueous dispersion is stabilized by at least one polyacrylate derived from a monomer represented by Formula I: wherein R 1 is H, CH 3 , C 2 to C 4 alkyl or C 6 to C 12 aryl; R 2 is H, OH, CN, CH 3 , C 2 to C 8 alkyl, or a halogen; and R 3 and R 4 are each independently H, CH 3 , C 2 to C 8 alkyl, C 6 to C 12 aryl, O—CH 3 , O—C 2 to C 8 alkyl, and O-aryl; (2) one or more latices formed from one or more halogenated polyolefins; and (3) one or more metal oxides. 16. The bonded assembly according to claim 15 , wherein the rigid substrate is steel. 17. The bonded assembly according to claim 15 , wherein the first aqueous composition and second aqueous composition are admixed in a volume ratio of the first aqueous composition to the second aqueous composition of 10:0.5 to 0.5:10. 18. The bonded assembly according to claim 15 , after heating the bonding assembly to a vulcanization temperature and under pressure for a time sufficient to vulcanize the unvulcanized rubber and the aqueous adhesive composition thereby bonding the rubber to the rigid substrate. 19. A method for bonding rubber to a rigid substrate, the method comprising: (a) interposing an aqueous adhesive composition between at least a portion of a rigid substrate and an unvulcanized rubber to form an assemblage, wherein the aqueous adhesive composition comprises: (i) a first aqueous composition comprising, (a) one or more film forming polymers, (2) one or more lower crystallinity polynitroso compounds, (3) one or more higher crystallinity polynitroso compounds, and (4) one or more bismaleimide-containing monomers; and (ii) a second aqueous composition comprising (1) an aqueous dispersion of at least one phenolic resin which is a condensation product of a phenol and formaldehyde, wherein the aqueous dispersion is stabilized by at least one polyacrylate derived from a monomer represented by Formula I: wherein R 1 is H, CH 3 , C 2 to C 4 alkyl or
Latex · CPC title
Aqueous adhesives · CPC title
Carbon · CPC title
of metals · CPC title
Phosphorus-containing compounds · CPC title
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