Two-part cyanoacrylate curable adhesive system

Patent metadata

Field	Value
Publication number	US-10100235-B2
Application number	US-201715602473-A
Country	US
Kind code	B2
Filing date	May 23, 2017
Priority date	May 23, 2016
Publication date	Oct 16, 2018
Grant date	Oct 16, 2018

Abstract

Two-part cyanoacrylate compositions, methods for making same, and uses therefor are described. The compositions can be used to bond a variety of substrates including plastics and metals. The compositions remain effective after thermal ageing and humid ageing.

First claim

The invention claimed is:

1. A two-part curable composition comprising:
(a) a first part comprising a cyanoacrylate composition comprising:

a cyanoacrylate component, and
a rubber toughening agent comprised of (i) reaction products of the combination of ethylene, methyl acrylate and monomers having carboxylic acid cure sites, (ii) dipolymers of ethylene and methyl acrylate, and combinations of (i) and (ii); and
(b) a second part comprising:

a 2-substituted benzothiazole or derivative thereof, wherein the 2-substitutent is a C 1-20 alkyl, a C 2-20 alkene, a C 8-20 alkylbenzyl, a C 1-20 alkylamino, a C 1-20 alkoxy, a C 1-20 alkylhydroxy, an ether, a sulfenamide, a C 1-20 thioalkyl or a C 1-20 thioalkoxy group; and
wherein at least one of the first or the second part further comprises one or more of:

a component containing at least two (meth)acrylate functional groups,
at least one benzonitrile compound substituted with at least two or more electron withdrawing groups selected from halo, —NO 2 , or —CN and combinations thereof, and
at least one anhydride component.

2. The two-part curable composition according to claim 1 wherein the cyanoacrylate component is represented by H 2 C═C(CN)—COOR, wherein R is selected from C 1-15 alkyl, C 2-15 alkoxyalkyl, C 3-15 cycloalkyl, C 2-15 alkenyl, C 6-15 aralkyl, C 5-15 aryl, C 3-15 allyl and C 1-15 haloalkyl groups.

3. The two-part curable composition according to claim 2 , wherein the cyanoacrylate component comprises ethyl-2-cyanoacrylate.

4. The two-part curable composition according to claim 1 , wherein the 2-substituted benzothiazole is further substituted with at least one halo, C 1-20 thioalkyl, C 1-20 haloalkyl, C 1-20 alkyl, C 1-20 alkoxy or hydroxyl substituent.

5. The two-part curable composition according to claim 4 , wherein the halo substituent is Cl, F or Br.

6. The two-part curable composition according to claim 1 , wherein the 2-substituted benzothiazole is selected from the group consisting of: 5-chloro-2-methyl benzothiazole, 5-bromo-2-methyl-1,3-benzothiazole, 2-[(tert-butylamino)thio]-1,3-benzothiazol-5-ol, 5,6-dichloro-2-methyl-1,3-benzothiazole, 6-bromo-2-methyl-1,3-benzothiazole, 5-fluoro-2-methyl-1,3-benzothiazole, 6,7-dichloro-2-methyl-1,3-benzothiazole, 2,5-dimethyl-1,3-benzothiazole, 4,5,6,7-tetrafluoro-2-methyl-1,3-benzothiazole, 4,5,6,7-tetrafluoro-2-methyl-1,3-benzothiazole, 2-(allyloxy)-1,3-benzothiazole 2-methyl-5-(methylthio)-1,3-benzothiazole, 2-(ethylthio)-1,3-benzothiazole, 2-(hexyloxy)-1,3-benzothiazole, 2-(1,3-dimethylbutoxy)-1,3-benzothiazole, 2-(Octadecylthio)benzothiazole, 2-(1-ethylbutoxy)-1,3-benzothiazole, 2-(octyloxy)-1,3-benzothiazole, 2-(1-methylbutoxy)-1,3-benzothiazole, 2-(2-phenylethoxy)-1,3-benzothiazole, 2-[(1-methylheptyl)oxy]-1,3-benzothiazole 2-allyl-1,3-benzothiazole, 2-[(1-methylhexyl)oxy]-1,3-benzothiazole, 4-chloro-2-methoxy-1,3-benzothiazole, 2-(3-methylbutoxy)-1,3-benzothiazole, 4-chloro-2-(ethynyloxy)-1,3-benzothiazole, 2,5,6-trimethyl-1,3-benzothiazole, 4-methoxy-2,7-dimethyl-1,3-benzothiazole, 5,6-dimethoxy-2-methyl-1,3-benzothiazole, 2,5,7-trimethyl-1,3-benzothiazole, 2-(butylthio)-1,3-benzothiazole, 5-chloro-2-(ethylthio)-1,3-benzothiazole, 2-methyl-1,3-benzothiazole, 2-(undecylthio)-1,3-benzothiazole, 2-methyl-1,3-benzothiazole 5-methoxy-2-methylbenzothiazole, 2,5-dimethylbenzothiazole 6-methoxy-2-methylbenzothiazole, 2-methyl-5-benzothiazolol, 2-(methylmercapto)-benzothiazole, and 2-[(cyclohexylamino)thio]-benzothiazole).

7. The two-part curable composition according to claim 6 , wherein the 2-substituted benzothiazole is selected from the group consisting of: 5-chloro-2-methyl benzothiazole, 2-methyl-1,3-benzothiazole, 2-(methylmercapto)-benzothiazole, 5-methoxy-2-methylbenzothiazole, 6-methoxybenzothiazole, 2,5-dimethylbenzothiazole and 2-methyl-5-benzothiazolol.

8. The two-part curable composition according to claim 1 , wherein the component containing at least two (meth)acrylate functional groups is represented by the formula:

wherein A is a C 4 to C 30 aliphatic chain which can optionally comprise heteroatoms selected from the group consisting of O, N and S;
wherein said chain is optionally substituted with one or more acrylate or methacrylate functional groups, and/or one or more C 1 -C 10 alkyl groups; and
wherein R 1 and R 2 may be the same or different and are each optionally selected from the group consisting of H and C 1 to C 6 alkyl.

9. The two-part curable composition according to claim 1 , wherein the component containing at least two (meth)acrylate functional groups is selected from the group consisting of hexane diol diacrylate, hexane diol dimethacrylate, and di-trimethylolpropane tetraacrylate and combinations thereof.

10. The two-part curable composition according to claim 1 , wherein the component containing at least two (meth)acrylate functional groups is in the second part (b).

11. The two-part curable composition according to claim 1 , wherein the anhydride component is selected from the group consisting of: phthalic anhydride, tetrahydrophthalic anhydride, 4-methylphthalic anhydride, itaconic anhydride, diphenic anhydride, phenylsuccinic anhydride, 1,8 naphthalic anhydride, bromomaleic anhydride, 2,3-dichloromaleic anhydride, 2-dodecen-1-yl-succinic anhydride, homophthalic anhydride, tetrabromophthalic anhydride, bicyclo[2,2,2]oct-7-ene 2,3,5,6-tetracarboxylic dianhydride, 3-fluorophthalic anhydride, 3,3,4,4-benzophenone tetracarboxylic dianhydride, 3-nitrophthalic anhydride, 3,3,4,4-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 1,4,5,8 naphthalene tetracarboxylic dianhydride, methacrylic anhydride, citraconic anhydride, hexahydro-4-methylphthalic anhydride, maleic anhydride, 2,3-diphenylmaleic anhydride, hexafluoroglutaric anhydride, 2,3-dimethylmaleic anhydride, tetrafluorophthalic anhydride, 1,2-cyclohexanedicarboxylic anhydride, glutaric anhydride, bromomaleic anhydride, 1,4,5,8-napthalenetetracarboxylicacid dianhydride, 1,2,4-benzenetricarboxylic anhydride, Exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, di-O-acetyl-L-tartaric anhydride, 1,2,4,5-benzenetetracarboxylic dianhydride, 1,2,4-benzenetricarboxylic anhydride and combinations thereof.

12. The two-part curable composition according to claim 1 , wherein the benzonitrile compound is selected from the group consisting of: tetrafluoroisophthalonitrile, 3,5-dinitrobenzonitrile; 2-chloro-3,5-dinitrobenzonitrile; pentafluorobenzonitrile; α,α,α-2-tetrafluoro-p-tolunitrile; and tetrachloroterphthalonitrile and combinations thereof.

13. The two-part curable composition according to claim 1 , wherein the benzonitrile compound is present in an amount of from 0.05 to 5 wt %, based on the total weight of the composition.

14. The two-part curable composition according to claim 1 , wherein the anhydride component is present in an amount of from 0.1 to 5 wt %, based on the total weight of the composition.

15. The two-part curable composition according to claim 1 , wherein the component containing at least two (meth)acrylate functional groups is present in an amount of from 1 to 20 wt %, based on the total weight of the composition.

16. The two-part curable composition according to claim 1 , wherein the 2-substituted benzothiazole is 5-chloro-2-methyl benzothiazole, the anhydride is selected from the group consisting of phthalic anhydride, tetrahydrophthalic anhydride, itaconic anhydride or 4-methylphthalic anhydride a

Assignees

• Henkel IP & Holding GmbH

Inventors

• Ward Emer
• Coleman Deborah
• Tully Raymond

Classifications

• C08L33/10

  Homopolymers or copolymers of methacrylic acid esters · CPC title

• C09J5/00

  Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers · CPC title

• C09J133/14 Primary

  of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen · CPC title

• C08F22/32

  Alpha-cyano-acrylic acid; Esters thereof · CPC title

• C08K5/315

  Compounds containing carbon-to-nitrogen triple bonds · CPC title