Curable acetoacetylated resin compositions comprising aldehydes and certain basic catalysts

Patent metadata

Field	Value
Publication number	US-11447670-B2
Application number	US-201916705331-A
Country	US
Kind code	B2
Filing date	Dec 6, 2019
Priority date	Dec 11, 2018
Publication date	Sep 20, 2022
Grant date	Sep 20, 2022

Abstract

This invention relates to a curable adhesive composition comprising:
I. Component (I) comprising at least one amorphous or semi-crystalline polyester or at least one polyether or combinations thereof having at least one or at least two functional groups selected from the group consisting of β-ketoester and malonate functional groups, II. Component (II) comprising at least one or at least two aldehyde functional groups or isomers thereof, and III. Component (III) comprising at least one basic catalyst, salts thereof, or combinations thereof.

First claim

What is claimed is:

1. A curable adhesive composition comprising:
I. Component (I) comprising at least one amorphous or semi-crystalline polyester or at least one polyether or combinations thereof having at least one or at least two functional groups selected from the group consisting of β-ketoester and malonate functional groups,
II. Component (II) comprising at least one or at least two aldehyde functional groups or isomers thereof, and
III. Component (III) comprising at least one basic catalyst, salts thereof, or combinations thereof.

2. The adhesive composition of claim 1 wherein said Component (I) is an acetoacetate functional polyester comprising the residues of
a. a hydroxyl component comprising:
i. a diol in an amount ranging from 50 to 95 mole %, based on the total moles of (i) and (ii), and
ii. a polyol in an amount ranging from 5 to 50 mole %, based on the total moles of (i) and (ii);

b. a carboxyl component comprising a polycarboxylic acid compound, a derivative of 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).

3. The adhesive composition of claim 2 , wherein the diol component (a)(i) is in an amount ranging from about 60 to about 90 mole % and the polyol component (a)(ii) is in an amount ranging from about 10 to about 40 mole %.

4. The adhesive composition of claim 2 , wherein the diol component (a)(i) is one or more selected from the group consisting of 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2-methyl-1,3-propanediol, 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, and polyethylene glycol.

5. The adhesive composition of claim 2 , wherein the polyol component (a)(ii) is selected from 1,1,1-trimethylolpropane, 1,1,1-trimethylolethane, glycerin, sorbitol, and pentaerythritol or mixtures thereof.

6. The adhesive composition of claim 2 , wherein the carboxyl component (b) is one or more selected from the group consisting of adipic acid, isophthalic acid (or dimethyl isophthalate), 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, hexahydrophthalic anhydride, maleic anhydride, succinic anhydride, phthalic acid, and phthalic anhydride.

7. The adhesive composition of claim 2 , wherein said alkyl acetoacetate is one or more selected from selected from t-butyl acetoacetate, methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate, n-butyl acetoacetate, isobutyl acetoacetate, t-amyl acetoacetate, diisopropyl carbinol acetoacetate, or mixtures thereof.

8. The adhesive composition of claim 2 , wherein said polyester (I) has a glass transition temperature (Tg) of about −65° C. to about −50° C.

9. The adhesive composition of claim 1 containing essentially no volatile solvents.

10. The adhesive composition of claim 1 wherein said polyester (I) has a glass transition temperature (Tg) of about −45° C. to −10° C.

11. The adhesive composition of claim 1 further comprising one or more organic solvents selected from the group comprising ethyl acetate, butyl acetate, xylene, methyl amyl ketone, methyl ethyl ketone, and toluene.

12. The adhesive composition of claim 1 wherein the curing agent (II) is a dialdehyde.

13. The adhesive composition of claim 1 wherein the basic catalyst is one or more selected from the group consisting of 1,8-diazabicyclo-[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1,1,3,3-tetramethylguanidine, 1,4-diazabicyclo[2.2.2]octane, triethylamine, N,N-dimethylethanolamine, ammonium hydroxide, triphenyl phosphine, and tributyl phosphine.

14. The adhesive composition of claim 1 wherein the basic catalyst is in an amount ranging from 0.5 to 5 weight % based on the total weight of Components (I) and (II).

15. The adhesive composition of claim 1 , wherein said polyester is an acetoacetate functional polyester comprising the residues of
d. 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); and
ii. a polyol in an amount ranging from 10 to 40 mole %, based on the total moles of (i) and (ii);

e. a carboxyl component comprising a polycarboxylic acid compound, a derivative of polycarboxylic acid compound, or a combination thereof; and

an alkyl acetoacetate, a diketene, or a combination thereof in an amount ranging from about 15 to about 30 weight %, based on the total weight of (a), (b), and (c).

16. The adhesive composition of claim 1 wherein the curing agent is selected from the group comprising 1,3-cyclohexanedicarboxaldehyde; 1,4-cyclohexanedicarboxaldehyde; mixtures of 1,3-cyclohexanedicarboxaldehyde; 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; methylfurfural; furfural; or 5-(hydroxymethyl)furan-2-carbaldehyde; benzenedipropanal; or any isomers thereof; or mixtures thereof.

17. The adhesive composition of claim 1 wherein said polyester (I) is an acetoacetate functional polyester, Component (I) (II) is selected from 1,3-cyclohexanedicarboxaldehyde; 1,4-cyclohexanedicarboxaldehyde; mixtures of 1,3-cyclohexanedicarboxaldehyde; 1,4-cyclohexanedicarboxaldehyde; 2,6-norbornanedicarboxaldehyde; terephthalaldehyde, isophthalaldehyde, orthophthalaldehyde, cyclopenta-3,5-diene-1,3-dicarbaldehyde and tricyclodecane dialdehyde, or any isomers thereof or any combinations thereof.

18. The adhesive composition of claim 17 wherein the equivalent ratio of the acetoacetate (AcAc) functionality in the polyester (I) and the aldehyde functionality in the composition is from about 1.3 to about 0.7.

19. The adhesive composition of claim 1 further comprising an adduct having two or more β-ketoester functional groups selected from 2-methyl-1,3-propanediol diacetoacetate, neopentyl glycol diacetoacetate, 2,2,4,4-tetramethylcyclobutane-1,3-diacetoacetate, trimethylolpropane triacetoacetate, or mixtures thereof.

20. The adhesive composition of claim 1 comprising tackifiers, plasticizers, fillers, pigments, stabilizers, antioxidants, adhesion promoters, flame retardants, conductive agents, rheology modifiers and mixtures thereof.

Assignees

• Eastman Chem Co

Inventors

• Kuo Thauming
• Collins Nick Allen
• Carvagno Terri Roxanne

Classifications

• C09J11/08

  Macromolecular additives · 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

• C08G63/916

  Dicarboxylic acids and dihydroxy compounds · CPC title

• C08J2367/02

  Polyesters derived from dicarboxylic acids and dihydroxy compounds; (C08J2367/06 takes precedence) · CPC title

• C08J2323/06

  Polyethene · CPC title