Two-part cyanoacrylate curable adhesive system

Patent metadata

Field	Value
Publication number	US-12103997-B2
Application number	US-202117158989-A
Country	US
Kind code	B2
Filing date	Jan 26, 2021
Priority date	Aug 13, 2018
Publication date	Oct 1, 2024
Grant date	Oct 1, 2024

Abstract

Two-part cyanoacrylate/cationically curable adhesive systems are provided.

First claim

The invention claimed is:

1. A two-part curable composition comprising:
a. a first part comprising a cyanoacrylate component, and a cationic curing catalyst;
b. a second part comprising a cationic curable component, an initiator component, and a cyclic carbonate;
wherein the two-part composition further comprises core-shell rubber particles having an average particle size of from about 50 μm to about 300 μm;
wherein when mixed together, the cationic curing catalyst initiates cure of the cationic curable component.

2. The composition of claim 1 , wherein the cyclic carbonate has the following structure:

n is 1 to 3;
each R is independently selected from hydrogen, C 1 -C 12 aliphatic, or C 3 -C 10 cycloaliphatic; or together at least two R form a ring system comprising from 4 to 12 carbon atoms, said ring system optionally including one or more nitrogen, oxygen or sulfur atoms;
each R can independently be unsubstituted or substituted with at least one of a halogen, a hydroxyl, an amino group, a sulfonyl group, a sulphonamide group, a thiol, a C 1 -C 6 alkyl, a C 1 -C 6 alkoxy, a C 1 -C 6 ether, a C 1 -C 6 thioether, a C 1 -C 6 ester, a C 1 -C 6 ketone, a C 1 -C 6 ketimine, a C 1 -C 6 sulfone, a C 1 -C 6 sulfoxide, a C 1 -C 6 primary amide, a C 1 -C 6 secondary amide, a halo C 1 -C 6 alkyl, a carboxyl group, a cyano group, a nitro group, a nitroso group, —C(O)O—C 1 -C 6 alkyl, —OC(O)O—C 1 -C 6 alkyl, —OC(O)NR′R′, —N(R′)C(O)NR′R′, —N(R′)C(O)O—C 1 -C 6 alkyl, oxo, C 3 -C 6 cycloalkyl, C 3 -C 6 heterocyclyl, C 2 -C 5 heteroaryl and C 6 -C 10 aryl; wherein each R′ is independently selected, from the group consisting of hydrogen and C 1 -C 6 alkyl.

3. The composition of claim 2 , wherein n is 1 or 2.

4. The composition of claim 2 , wherein R is C 1 -C 12 aliphatic optionally substituted with one or more hydroxyl, C 1 -C 6 alkyl or C 1 -C 6 alkoxy.

5. The composition of claim 1 , wherein the cyclic carbonate has the following structure:

wherein n is 1 or 2, and each R is independently selected from H or C 1 -C 12 aliphatic aliphatic optionally substituted with one or more hydroxyl, C 1 -C 6 alkyl or C 1 -C 6 alkoxy.

6. The composition of claim 1 , wherein the cyclic carbonate has the following structure:

wherein R is selected from H or C 1 -C 12 aliphatic aliphatic optionally substituted with one or more hydroxyl, C 1 -C 6 alkyl or C 1 -C 6 alkoxy.

7. The composition of claim 6 , where R is C 1 -C 12 alkyl optionally substituted with one or more hydroxyl, C 1 -C 6 alkyl or C 1 -C 6 alkoxy.

8. The composition of claim 1 , wherein the cyclic carbonate is present in an amount of from about 5 wt % to about 35 wt % based on the total weight of the second part, based on the total weight of the second part.

9. The composition of claim 1 , wherein the cyclic carbonate is a liquid at room temperature.

10. The composition of claim 1 , wherein the core-shell rubber particles comprise acrylonitrile butadiene-styrene copolymer and/or methyl methacrylate butadiene styrene copolymer.

11. The composition of claim 1 , wherein the core-shell rubber particles are present in an amount of from about 10 wt % to 15 wt %, in the second part of the composition, based on the total weight of the second part of the composition.

12. The composition of claim 1 , further comprising a thermoplastic resin.

13. The composition of claim 12 , wherein the thermoplastic resin comprises a thermoplastic acrylic resin.

14. The composition of claim 12 , wherein the thermoplastic resin is composed of a methyl methacrylate and butyl methacrylate copolymer.

15. The composition of claim 12 , wherein the thermoplastic resin is present in an amount of from about 1.5 wt % to about 15 wt % based on the total weight of the composition.

16. The composition of claim 12 , wherein the thermoplastic resin is present in an amount of from about 5 wt % to about 15 wt % based on the total weight of the second part.

17. The composition of claim 1 , wherein the cyanoacrylate component comprises H 2 C═C(CN)—COOR, wherein R is selected from alkyl, alkoxyalkyl, cycloalkyl, alkenyl, aralkyl, aryl, allyl and haloalkyl groups.

18. The composition of claim 1 , wherein the cationic curing catalyst comprises salts of lithium and metals from Group II of the Periodic Table, and non-nucleophilic acids.

19. The composition of claim 1 , wherein the cationic curing catalyst is a non-nucleophilic acid having a pH of less than 1.0 when measured as a 10% by weight solution in water.

20. The composition of claim 1 , wherein the cationic curing catalyst is a member selected from the group consisting of fluoroboric, fluoroarsenic, fluoroantimonic and fluorophosphoric acids; lithium tetrafluoroborate, calcium di-tetrafluoroborate, magnesium di-tetrafluoroborate, lithium hexaflourophosphate, calcium di-hexaflourophosphate, magnesium di-hexaflourophosphate, lithium hexaflouroantimonate and lithium hexaflouroarsenate; lanthanide triflate salts, aryl iodonium salts, aryl sulfonium salts, lanthanum triflate, ytterbium triflate, trimethoxyboroxine, trimethoxyboroxine-aluminum acetyl acetonate, amine-boron trihalide complexes, quaternary ammonium salts, quaternary phosphonium salts, tri-aryl sulfonium salts, di-aryl iodonium salts, and diazonium salts; trialkoxyboroxine curing agents; and combinations thereof.

21. The composition of claim 1 , wherein the cationic curable component is selected from an epoxy component, an episulfide component, an oxetane component, a vinyl ether component and combinations thereof.

22. The composition of claim 1 , wherein the cationic curable component is an epoxy component selected from the group consisting of cycloaliphatic epoxy, aromatic epoxy, aliphatic epoxy and hydrogenated aromatic epoxy.

23. The composition of claim 22 , wherein the epoxy component comprises a cycloaliphatic epoxy selected from the group consisting of: 2-(3,4-epoxy)cyclohexyl-5,5-spiro-(3,4-epoxy)cyclohexane-m-dioxane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate,3,4-epoxy-6-methylcyclohexylnnethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, vinyl cyclohexanedioxide, bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, exo-exo bis(2,3-epoxycyclopentyl) ether, endo-exo bis(2,3-epoxycyclopentyl) ether, 2,2-bis(4-(2,3-epoxypropoxy)cyclohexyl)propane, 2,6-bis(2,3-epoxypropoxycyclohexyl-p-dioxane), 2,6-bis(2,3-epoxypropoxy)norbornene.

24. The composition of claim 22 , wherein the epoxy component is a member selected from the group consisting of epoxy-functionalized hydrogenated bisphenol-A, bisphenol-F, bisphenol-E, bisphenol-S and biphenyl.

25. The composition of claim 1 , wherein the first part is housed in a first chamber of a dual chamber syringe and the second part is housed in a second chamber of the dual chamber syringe.

26. The composition of claim 1 , wherein the first part further comprises phosphoric acid.

27. The composition of claim 1 , wherein the second part further comprises at least one of a plasticizer, a filler and a toughener.

Assignees

• Henkel Ag & Co Kgaa

Inventors

• Shah Jayesh P
• Singh Sangita
• Tale Nishant
• Trivedi Krunal

Classifications

• C09J4/06

  {Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond} in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00 · CPC title

• C08L2207/53

  Core-shell polymer · CPC title

• C08L55/02

  ABS [Acrylonitrile-Butadiene-Styrene] polymers · CPC title

• C08L25/10

  with conjugated dienes · CPC title

• C08K2201/005

  Additives being defined by their particle size in general · CPC title