Adhesives suitable for use in bonding applications

Patent metadata

Field	Value
Publication number	US-9644121-B2
Application number	US-201313796633-A
Country	US
Kind code	B2
Filing date	Mar 12, 2013
Priority date	Apr 29, 2011
Publication date	May 9, 2017
Grant date	May 9, 2017

Abstract

The present invention relates to adhesives that are suitable for use in a broad variety of bonding applications. In particular, the present invention relates to adhesives that are suitable for use in polymer-to-metal, for example elastomer-to-metal, such as rubber-to-metal bonding applications, wherein the adhesives comprise at least one halogenated polyolefin, at least one epoxysilane having at least one terminal alkoxy silane group, at least one bis-silane, and optionally at lease one organic solvent.

First claim

What is claimed is:

1. An article comprising an adhesive layer, comprising:
i) at least one halogenated polyolefin having a weight average molecular weight of 200,000 to 400,000, wherein the halogen content ranges from 55 to 90 percent by weight, present in an amount in the range of 1 to 30 wt.-%, based on the weight of the adhesive;
ii) at least one epoxysilane having at least one terminal alkoxy silane group wherein the epoxysilane is present in an amount of 0.2 to 5 wt.-%, based on the weight of the adhesive;
iii) at least one bis-silane, wherein the bis-silane has two silicon atoms per molecule, wherein the two silicon atoms are linked with each other by a divalent linkage group and each silicon atom carries three additional substituents, wherein at least one of the three additional substituents is an alkyl or alkoxy residue, and the bis-silane is present in an amount of 0.1 to 2 wt.-%, based on the weight of the adhesive;
iv) optionally at least one organic solvent, wherein the weight ratio of epoxysilane to bis-silane in the adhesive is from 1:0.2 to 1:0.8 wherein the adhesive layer is, disposed between (a) a polar elastomeric substrate selected from the group consisting of nitrile butadiene rubber, hydrogenated nitrile butadiene rubber and ethylene acrylic elastomers, and (b) a metallic substrate.

2. The article of claim 1 , wherein the halogenated polyolefin is selected from chlorinated polyolefins.

3. The article of claim 1 , wherein the epoxysilane comprises a single epoxy group and a single terminal alkoxy silane group per molecule.

4. The article of claim 1 , wherein the epoxysilane is represented by formula (I)

wherein R a is a divalent linkage group, comprising 1 to 24 carbon atoms, R and R 3 independently of one another are selected from C 1-24 alkyl, C 2-24 alkenyl, C 1-24 alkoxyl or C 3-24 acyl, and R 2 is selected from C 1-24 alkyl or C 3-24 acyl, A is either

where R, R o and R d independently of one another are hydrogen or C 1-6 alkyl; or

5. The article of claim 1 , wherein the epoxysilane is represented by formula (II),

wherein n is an integer from 1 to 10, m is an integer from 0 to 14, R 1a and R 3a independently of one another are selected from C 1-24 alkyl, C 2-24 alkenyl, C 1-24 alkoxyl or C 3-24 acyl, and R 2a is selected from C 1-24 alkyl or C 3-24 acyl; or
is represented by formula (IIa),

wherein v is an integer from 1 to 10, R 1b and R 3b independently of one another are selected from C 1-24 alkyl, C 2-24 alkenyl, C 1-24 alkoxyl or C 3-24 acyl, and R 2b is selected from C 1-24 alkyl or C 3-24 acyl.

6. The article of claim 1 , wherein the epoxysilane is selected from 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyltri-n-propoxysilane, 3-glycidyloxypropyltri-iso-propoxysilane, 3-glycidyloxypropyltri-n-butoxysilane, 3-glycidyloxypropyltri-iso-butoxysilane, beta-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, beta-(3,4-epoxycyclohexyl)-ethyltriethoxysilane, beta-(3,4-epoxycyclohexyl)-ethyltri-n-propoxysilane, beta-(3,4-epoxycyclohexyl)-ethyltri-iso-propoxysilane, gamma-(3,4-epoxycyclohexyl)-propyltrimethoxysilane, gamma-(3,4-epoxycyclohexyl)-propyltriethoxysilane, gamma-(3,4-epoxycyclohexyl)-propyltri-n-propoxysilane, gamma-(3,4-epoxycyclohexyl)-propyltri-iso-propoxysilane, and/or combinations thereof.

7. The article of claim 1 , wherein the bis-silane is represented by formula (III),
(R 5 O) (3-q) (R 4 ) q Si—B—Si(R 6 ) p (OR 7 ) (3-p)   formula (III)

wherein p is 0 to 3, q is 0 to 3, B represents a divalent linkage group comprising 1 to 24 carbon atoms and at least one heteroatom selected from N, S or O, each R 4 and each R 6 is independently selected from hydrogen, halogen, C 1-24 alkyl, C 2-24 alkenyl, C 1-24 alkoxyl or C 3-24 acyl, and each R 5 and each R 7 is independently selected from C 1-24 alkyl or C 3-24 acyl.

8. The article of claim 1 , wherein the bis-silane is represented by formula (IV),
(R 15 O) 3 Si—(R 14 ) k -D-(R 14 ) k —Si(OR 15 ) 3   formula (IV)

where k is 0 or 1, each R 15 is independently selected from C 1-4 alkyl or C 1-4 acyl, each R 14 is independently selected from C 1-6 alkylene or C 6-12 arylene, and D is selected from one of the following divalent groups:

where R 8a is selected from hydrogen, C 1-24 alkyl or C 6-18 aryl;

where each R 9a is independently selected from hydrogen, C 1-24 alkyl, or C 6-18 aryl, and R 10a is selected from C 1-24 alkylene or C 6-18 arylene;

where Y is selected from O, S or NR 11a , Z is selected from O, S, and NR 12a , wherein R 11a and R 12a independently of one another are selected from hydrogen, C 1-24 alkyl or C 6-18 aryl, and X is the selected from O or S, with the proviso that Y and Z are not both O or S.

9. The article of claim 1 , wherein the bis-silane is selected from bis-(trimethoxysilylethyl)amine, bis-(triethoxysilylethyl)amine, bis-(tri-n-propoxysilylethyl)amine, bis-(tri-iso-propoxysilylethyl)amine, bis-(trimethoxysilylpropyl)amine, bis-(triethoxysilylpropyl)amine, bis-(tri-n-propoxysilylpropyl)amine, bis-(tri-iso-propoxysilylpropyl)amine, bis-(trimethoxysilylethyl)urea, bis-(triethoxysilylethyl)urea, bis-(tri-n-propoxysilylethyl)urea, bis-(tri-iso-propoxysilylethyl)urea, bis-(trimethoxysilylpropyl)urea, bis-(triethoxysilylpropyl)urea, bis-(tri-n-propoxysilylpropyl)urea, bis-(tri-iso-propoxysilylpropyl) urea, and combinations thereof.

10. The article of claim 9 , wherein the adhesive is substantially free of nitroso-containing compounds.

11. The article of claim 1 , wherein the adhesive is a one-part adhesive.

Assignees

• Henkel Ireland Ltd
• Henkel Ag & Co Kgaa
• Henkel IP & Holding GmbH

Inventors

• Nolan Darren
• Fay Nigel
• Fleming Eimear
• Kneafsey Brendan
• Wefringhaus Rainer
• Weimar Wolfgang

Classifications

• B32B9/043

  of natural rubber or synthetic rubber · CPC title

• C08K2201/014

  Additives containing two or more different additives of the same subgroup in C08K · CPC title

• C08K5/5435

  containing oxygen in a ring · CPC title

• Y10T428/31515

  As intermediate layer · CPC title

• B32B9/041

  of metal · CPC title