Curable compositions comprising acetoacetylated resins, aldehydes and certain amines

Patent metadata

Field	Value
Publication number	US-11530342-B2
Application number	US-201916705351-A
Country	US
Kind code	B2
Filing date	Dec 6, 2019
Priority date	Dec 11, 2018
Publication date	Dec 20, 2022
Grant date	Dec 20, 2022

Abstract

This invention relates to a curable composition comprising:I. a first component comprising a resin having at least one functional group selected from the group consisting of β-ketoester and malonate functional groups,II. a second component comprising at least one curing agent having at least one aldehyde functional group, andIII. a third component comprising at least one primary amine or at least one secondary amine, salts thereof, or combinations thereof.

First claim

What is claimed is:

1. A curable composition comprising:
I. a first component comprising at least one resin having at least one functional group selected from the group consisting of β-ketoester and malonate functional groups,
II. a second component comprising at least one curing agent having at least one aldehyde functional group, and
III. a third component comprising at least one primary amine or at least one secondary amine, salts thereof, or combinations thereof;
wherein said amine is present in an amount ranging from 0.5 to 2 phr based on the total weight of the resin.

2. The composition of claim 1 wherein at least one resin is selected from amorphous polyesters, semi-crystalline polyesters, or polyethers or combinations thereof.

3. The composition of claim 1 wherein said first component is at least one acetoacetate functional polyester resin comprising the residues of
a. a hydroxyl component comprising:
(i) a diol in an amount ranging from 60 to 90 mole %, based on the total moles of (i) and (ii) equaling 100 mole %; and
(ii) a polyol in an amount ranging from 10 to 40 mole %, based on the total moles of (i) and (ii) equaling 100 mole %;

b. a carboxyl component comprising a polycarboxylic acid compound, a derivative of a polycarboxylic acid compound, or a combination thereof; and
c. an alkyl acetoacetate, a diketene, or a combination thereof in an amount ranging from about 5 to about 65 weight %, based on the total weight of (a), (b), and (c) equaling 100 weight %.

4. The composition of claim 3 wherein the diol component (a)(i) is selected from the group consisting of 2,2-dimethyl-1,3-propanediol, 2-methyl-1,3-propanediol, tricyclodecanedimethanol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4-trimethyl-1,3-pentanediol, hydroxypivalyl hydroxypivalate, 2,2,4,4-tetramethylcyclobutane-1,3-diol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, or combinations thereof.

5. The composition of claim 3 wherein the polyol component (a)(ii) is selected from 1,1,1-trimethylolpropane, 1,1,1-trimethylolethane, glycerin, sorbitol, pentaerythritol, or combinations thereof.

6. The composition of claim 3 wherein said carboxyl component (b) is selected from the group consisting of adipic acid, isophthalic acid, dimethyl isophthalate, terephthalic acid, dimethyl terephthalate, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, tetrahydrophthalic anhydride, tetrahydrophthalic acid, hexahydrophthalic anhydride, hexahydrophthalic acid, maleic anhydride, succinic anhydride, phthalic acid, phthalic anhydride, or mixtures thereof.

7. The composition of claim 1 containing essentially no volatile solvents.

8. The composition of claim 2 wherein said polyester has a glass transition temperature (Tg) of about −75° C. to 60° C.

9. The composition of claim 1 further comprising one or more organic solvents.

10. The composition of claim 1 wherein said curing agent comprises an aliphatic, cycloaliphatic, or aromatic, di-, or poly-aldehyde.

11. The composition of claim 10 wherein said curing agent is at least one dialdehyde selected from the group consisting of 1,3-cyclohexanedicarboxaldehyde; 1,4-cyclohexanedicarboxaldehyde; mixtures of 1,3-cyclohexanedicarboxaldehyde and 1,4-cyclohexanedicarboxaldehyde; 2,6-norbornanedicarboxaldehyde; 2,5-norbornanedicarboxaldehyde; cyclododecane-1,4,8-tricarbaldehyde; 3-(4-formylcyclohexyl)propanal; tricyclodecane dialdehyde; o-phthalaldehyde; terephthalaldehyde; isophthalaldehyde; cyclopentane-1,3-dicarbaldehyde; cyclopenta-3,5-diene-1,3-dicarbaldehyde; glutaraldehyde; benzenedipropanal; or any isomers thereof, or mixtures thereof.

12. The composition of claim 1 wherein at least one said primary amine or secondary amine is selected from aliphatic, cycloaliphatic, aliphatic-aromatic or aromatic amines.

13. The composition of claim 1 wherein said primary or secondary amines are selected from at least one of: piperidine; piperazine; morpholine, pyrrolidine; ethylenediamine; diethylenetriamine; triethylenetetramine; tetraethylenepentamine; 2,2,4-trimethylhexamethylenediamine; 1,2-diaminopropane; 1,3-diaminopropane; 1-ethyl-1,3-propanediamine; 2,2-dimethylpropylenediamine; 1,4-diaminobutane; 2-methylpentamethylenediamine; 1,6-hexanediamine; 1,7-diaminoheptane; 1,8-diaminooctane; 1,9-diaminononane; 1,12-diaminododecane; 4-azaheptamethylenediamine; N,N-bis(3-aminopropyl)butane-1,4-diamine; N,N-bis(3-aminopropyl)ethylenediamine; 2,4-toluenediamine; 2,6-toluenediamine; 3-dimethylaminopropylamine; 3-diethylaminopropylamine; 3,3′-iminobispropylamine; 1,2-diaminocyclohexane; 1,3-diaminocyclohexane; 1,4-diamino-2,5-diethylcyclohexane; 1,4-diamino-3,6-diethylcyclohexane; 1,2-diamino-4-ethylcyclohexane; 1,2-diamino-4-cyclohexylcyclohexane; isophorone diamine; norbornanediamine; 4,4′-diaminodicyclohexylmethane; 4,4′-diaminodicyclohexylethane; 4,4′-diaminodicyclohexylpropane; 2,2-bis(4-aminocyclohexyl)propane; 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane; 3-amino-1-(4-aminocyclohexyl)propane; 1,3-bis(aminomethyl)cyclohexane; 1,4-bis(aminomethyl)cyclohexane; 1-cyclohexyl-3,4-diamino-cyclohexane; m-xylylenediamine and its hydrogenation products; p-xylylenediamine and its hydrogenation products; 4,4′-methylenedianiline; 2,4-bis(p-aminobenzyl)aniline; diethyltoluenediamine; m-phenylenediamine; 1,2,4-triazole; alanine; proline; 1,4,8,11-tetraazacyclotetradecane (cyclam); diphenylethylenediamine; 2,2,4,4-tetramethylcyclobutane-1,3-diamine; 2,2-dimethylpropane-1,3-diamine; 2,3-dimethylbutane-2,3-diamine; 1,2-diaminocyclopentane; 1,2,2-trimethylcyclopentane-1,3-diamine; 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-diamine; dioctyl amine; diisopropylamine; and polyetheramines, or isomers thereof.

14. The composition of claim 1 further comprising an adduct having two or more β-ketoester functional groups.

15. The composition of claim 3 wherein the equivalent ratio of the acetoacetate functional group in the resin to the aldehyde functional group in said composition is from about 4 to about 0.25.

16. The composition according to claim 1 wherein the composition is prepared by a process comprising: (a) mixing at least one component having two or more β-ketoester functional groups, and at least one component having two or more aldehyde functional groups with at least one primary or secondary amine catalyst, and (b) after optional activation, curing the composition at 20° C. or higher in six days or less, and (c) optionally post-curing the composition at or above 20° C.

17. A composition according to claim 1 further comprising at least one additive selected from the group consisting of tackifiers, plasticizers, fillers, pigments, stabilizers, antioxidants, waxes, adhesion promoters, flame retardants, conductive agents, rheology modifiers or mixtures thereof.

18. The composition of claim 1 or 2 wherein the composition is an adhesive composition.

19. A cured adhesive composition obtained by curing the composition of claim 18 .

20. The composition of claim 19 wherein the cured adhesive composition comprises a bond that is maintained after cure at or above about 23° C.

21. An article comprising said composition of claim 1 or 17 selected from at least one of the following:
an adhesive, a laminate, a tape, a label, a tag, a radio frequency identification (RFID) tag, a coating, a sealant, a flexible or non-flexible film, a foam, a potting compound, composite, a dis

Assignees

• Eastman Chem Co

Inventors

• Dougherty Shawn Marie
• Carvagno Terri Roxanne
• Boggs Monika Karin Wiedmann
• Collins Nick Allen
• Sharpe Robert Jacks
• Feng Ke
• Kuo Thauming
• Deng Liu
• Burk Christopher Harlan
• Bhonde Vasudev R

Classifications

• C08G63/914

  derived from polycarboxylic acids and polyhydroxy compounds · CPC title

• C09D167/00 Primary

  Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain (based on polyester-amides C09D177/12; based on polyester-imides C09D179/08); Coating compositions based on derivatives of such polymers · CPC title

• C08J3/24

  Crosslinking, e.g. vulcanising, of macromolecules (mechanical aspects B29C35/00; crosslinking agents C08K) · CPC title

• C08K3/013

  Fillers, pigments or reinforcing additives · CPC title

• C08K5/07

  Aldehydes; Ketones · CPC title