Granted Patent B2

US 8,178,614 · App. 12/636,216 · Granted May 15, 2012

Abstract

Claims (55)

1. A laminate comprising a backing material having a solvent resistant adhesive composition applied thereto,

the adhesive composition including:

(i) a hydroxyl terminated or urea terminated or hydrocarbon terminated unsaturated polyurethane or polyurethane-urea derived from a polyisocyanate and a hydroxyl-terminated vinyl-containing branched butadiene polymer, wherein the butadiene polymer has a molecular weight (Mn) of from 500 to 10,000, an average content of copolymerized additional monomer of from 0 to 50 weight percent, hydroxyl groups per polymer of from 2.4 to 2.8 and terminal hydroxyl groups bonded to carbon atoms adjacent to double bonded carbon atoms, and

(ii) a peroxide capable of generating free radicals or a silicone hydride providing SiH,

wherein components (i) and (ii) are present in amounts sufficient to provide a molar ratio of the unsaturated sites of component (i) relative to the SiH or the free radicals of component (ii) between 514 and 824

wherein the silicone hydride of component (ii) is a substantially linear hydrogen siloxane having a formula selected from the group consisting of MD e D′ f M, MD′ f M, MD e D′ f M′, M′D e D′ f M′ and M′D e M′, wherein

M is defined as R 3 SiO 1/2

M′ is defined as H g R 3-g SiO 1/2

D=RRSiO 2/2 , and

D′=RHSiO 2/2

where each R is independently a monovalent hydrocarbon radical of from about 1 to 40 carbon atoms, the subscripts e and f may be zero or positive wherein the sum of e and f ranges from about 10 to about 100, with the proviso that the sum of f and g is at least 2; and

wherein the peroxide is one or more compound selected from the groups consisting of di-tert-butyl peroxide, dicumyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, tert-butyl perbenzoate, tert-butyl per-3,5,5-trimethylhexanoate, tert-butyl per-2-ethylhexanoate, and benzoyl peroxide.

2. The laminate of claim 1 wherein the unsaturated polyurethane or polyurethane-urea is hydroxyl terminated.

3. The laminate of claim 1 wherein the unsaturated polyurethane or polyurethane-urea is urea terminated.

4. The laminate of claim 1 wherein the unsaturated polyurethane or polyurethane-urea is hydrocarbon terminated.

5. The laminate of claim 1 wherein the unsaturated polyurethane or polyurethane-urea is crosslinked with the peroxide.

6. The laminate of claim 1 wherein the unsaturated polyurethane or polyurethane-urea is crosslinked with the silicone hydride in the presence of a hydrosilylation catalyst.

7. The laminate of claim 1 wherein the unsaturated polyurethane or polyurethane-urea is crosslinked with the silicone hydride in the presence of a hydrosilylation catalyst and a hydrosilylation inhibitor.

8. The laminate of claim 1 wherein the hydroxyl-terminated polybutadiene is copolymerized with a comonomer selected from the group consisting of ethylene, propylene, 1-butene, isoprene, chloroprene, 2,3-methyl-1,3-butadiene, 1,4-pentadiene, acrylonitrile, methacrylonitrile, methylstyrene, methyl acrylate, methyl methacrylate, vinyl acetate, 1,2-epoxides and e-caprolactone.

9. The laminate of claim 1 wherein the polyisocyanate is selected from the group consisting of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4′ diphenyl-methanediisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate and liquid diphenylmethane-diisocyantes containing a mixture of 2,4- and 4,4′ isomers.

10. The laminate of claim 1 wherein R includes substituted or unsubstituted aryl, alkaryl or alkyl radicals.

11. The laminate of claim 1 wherein M′ is a dimethylstyrylsiloxy group.

12. The laminate of claim 1 wherein R is styryl.

13. The laminate of claim 1 wherein the adhesive composition contains at least one additional component selected from the group consisting of filler, tackifier, adhesion promoter, plasticizer, solvent, thixotropic agent, UV stabilizer and antioxidant.

14. The laminate of claim 1 wherein the adhesive composition further includes a tackifier comprising one or more compounds selected from the group consisting of MQ silicone resins, terpene oligomers, coumarone/indene resins, aliphatic petrochemical resins and modified phenolic resins.

15. The laminate of claim 1 wherein the adhesive composition further includes a filler selected from the group consisting of one or more compounds selected from the group consisting of fumed silica, precipitated silica and calcium carbonates.

16. An article having a surface to which the laminate of claim 1 is attached.

17. The article of claim 16 wherein the article is an aircraft.

18. A method for making a laminate comprising the steps of:

a) providing an adhesive composition including (i) a hydroxyl terminated, urea terminated or hydrocarbon terminated unsaturated polyurethane or polyurethane-urea derived from a polyisocyanate and a hydroxyl-terminated vinyl-containing branched butadiene polymer, wherein the butadiene polymer has a molecular weight (Mn) of from 500 to 10,000, an average e content of copolymerized additional monomer of from 0 to 50 weight percent, hydroxyl groups per polymer of from 2.4 to 2.8 and terminal hydroxyl groups bonded to carbon atoms adjacent to double bonded carbon atoms and (ii) a peroxide capable of generating free radicals or a silicone hydride;

b) applying the adhesive composition to a backing material; and

c) crosslinking the unsaturated polyurethane or polyurethane-urea with the peroxide or the silicone hydride to provide an adhesive layer, thereby making the laminate,

wherein components (i) and (ii) are present in amounts sufficient to provide a molar ratio of the unsaturated sites of component (i) relative to the SiH or the free radicals of component (ii) between 514 and 824

wherein the silicone hydride of component (ii) is a substantially linear hydrogen siloxane having a formula selected from the group consisting of MD e D′ f M, MD′ f M, MD e D′ f M′, M′D e D′ f M′ and M′D e M′, wherein

M is defined as R 3 SiO 1/2

M′ is defined as H g R 3-g SiO 1/2

D=RRSiO 2/2 , and

D′=RHSiO 2/2

where each R is independently a monovalent hydrocarbon radical of from about 1 to 40 carbon atoms, the subscripts e and f may be zero or positive wherein the sum of e and f ranges from about 10 to about 100, with the proviso that the sum of f and g is at least 2; and

wherein the peroxide is one or more compound selected from the groups consisting of di-tert-butyl peroxide, dicumyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, tert-butyl perbenzoate, tert-butyl per-3,5,5-trimethylhexanoate, tert-butyl per-2-ethylhexanoate, and benzoyl peroxide .

19. The method of claim 18 further comprising applying a release liner to the adhesive layer, the release liner being removable from the laminate.

20. A method of applying a laminate to a surface of a substrate comprising the steps of:

(a) providing a laminate comprising a backing material with a layer of an adhesive composition in contact with at least one side of the backing material, the laminate having a release liner disposed on the layer of the adhesive composition; the adhesive composition comprising a component obtained by the crosslinking of (i) a hydroxyl terminated or urea terminated or hydrocarbon terminated unsaturated polyurethane or polyurethane-urea with (ii) a peroxide capable of generating free radicals or a silicone hydride providing SiH;

(b) removing the release liner;

(c) applying the laminate to the surface of the substrate such that the layer of adhesive composition of the laminate contacts and adheres to the surface of the substrate,

wherein the hydroxyl terminated, urea terminated or hydrocarbon terminated unsaturated polyurethane or polyurethane-urea is derived from a polyisocyanate and a hydroxyl-terminated vinyl-containing branched butadiene polymer, wherein the butadiene polymer has a molecular weight (Mn) of from 500 to 10,000, an average content of copolymerized additional monomer of from 0 to 50 weight percent, hydroxyl groups per polymer of from 2.4 to 2.8 and terminal hydroxyl groups bonded to carbon atoms adjacent to double bonded carbon atoms;

wherein components (i) and (ii) are present in amounts sufficient to provide a molar ratio of the unsaturated sites of component (i) relative to the SiH or the free radicals of component (ii) between 514 and 824;

wherein the silicone hydride of component (ii) is a substantially linear hydrogen siloxane having a formula selected from the group consisting of MD e D′ f M, MD′ f M, MD e D′ f M′, M′D e D′ f M′ and M′D e M′, wherein

M is defined as R 3 SiO 1/2

M′ is defined as H g R 3-g SiO 1/2

D=RRSiO 2/2 , and

D′=RHSiO 2/2

where each R is independently a monovalent hydrocarbon radical of from about 1 to 40 carbon atoms, the subscripts e and f may be zero or positive wherein the sum of e and f ranges from about 10 to about 100, with the proviso that the sum of f and g is at least 2; and

wherein the peroxide is one or more compound selected from the groups consisting of di-tert-butyl peroxide, dicumyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, tert-butyl perbenzoate, tert-butyl per-3,5,5-trimethylhexanoate, tert-butyl per-2-ethylhexanoate, and benzoyl peroxide.

21. The method of claim 20 wherein the surface of the substrate comprises a surface of an aircraft component.

Assignments (21)