Polybenzoxazine that can be used for coating metal and for the bonding of same to rubber

Patent metadata

Field	Value
Publication number	US-11306229-B2
Application number	US-201716345310-A
Country	US
Kind code	B2
Filing date	Sep 25, 2017
Priority date	Oct 26, 2016
Publication date	Apr 19, 2022
Grant date	Apr 19, 2022

Abstract

Polybenzoxazine comprises repeat units which comprise at least one unit corresponding to the formulae (I) or (II):

in which Z 1 and Z 2 , which are identical or different, represent an at least divalent, aliphatic, cycloaliphatic or aromatic bonding group comprising at least one carbon atom and optionally at least one heteroatom selected from O, S, N and P. Such a polybenzoxazine may be used as a metal-adhesive layer, in particular for the adhesive bonding of a metal substrate, in particular made of carbon steel, to a rubber.

First claim

The invention claimed is:

1. A polybenzoxazine, the repeat units of which comprise at least one unit corresponding to the formula (I) or (II):

wherein Z 1 and Z 2 are different one of Z 1 and Z 2 represents an aliphatic group comprising from 1 to 20 carbon atoms or a cycloaliphatic group comprising from 3 to 20 carbon atoms, and optionally at least one heteroatom chosen from O, S, N and P, and the other of Z 1 and Z 2 represents an aromatic group comprising from 6 to 30 carbon atoms, and optionally at least one heteroatom chosen from O, S, N and P.

2. The polybenzoxazine according to claim 1 , wherein the one of Z 1 and Z 2 represents an alkylene group comprising from 1 to 20 carbon atoms, and optionally at least one heteroatom chosen from O, S, N and P.

3. A polybenzoxazine, the repeat units of which comprise at least one unit corresponding to the formula (I) or (II):

wherein one of Z 1 and Z 2 comprises a group selected from the group consisting of —(CH 2 ) x —, —CH 2 -Ph-CH 2 —, —(CH 2 —CH 2 —X) n — and —(CH(CH 3 )—CH 2 —X) n —,
wherein x and n are integers from 1 to 20, Ph represents a benzene ring, and X represents at least one heteroatom chosen from oxygen, sulfur, nitrogen and phosphorus, and
wherein the other of Z 1 and Z 2 represents an aromatic group comprising from 6 to 30 carbon atoms, and optionally at least one heteroatom chosen from O, S, N and P.

4. A coating for a substrate, at least the surface of which is at least partially metallic, comprising a polybenzoxazine, the repeat units of which comprise at least one unit corresponding to the formulae (I) or (II):

wherein Z 1 , Z 2 , or both Z 1 and Z 2 , which are identical or different, represent an aromatic group comprising from 6 to 30 carbon atoms, and optionally at least one heteroatom chosen from O, S, N and P, and
wherein, when Z 1 and Z 2 are different, one of Z 1 and Z 2 is as defined above and one of Z 1 and Z 2 represents an at least divalent, aliphatic, cycloaliphatic or aromatic bonding group comprising at least one carbon atom and optionally at least one heteroatom selected from O, S, N and P.

5. A method of bonding metal to rubber comprising:
coating a substrate, at least the surface of which is at least partially metallic, with a substrate coating comprising a polybenzoxazine, the repeat units of which comprise at least one unit corresponding to the formulae (I) or (II):

wherein Z 1 , Z 2 , or both Z 1 and Z 2 , which are identical or different, represent an aromatic group comprising from 6 to 30 carbon atoms, and optionally at least one heteroatom chosen from O, S, N and P, and
wherein, when Z 1 and Z 2 are different, one of Z 1 and Z 2 is as defined above and one of Z 1 and Z 2 represents an at least divalent, aliphatic, cycloaliphatic or aromatic bonding group comprising at least one carbon atom and optionally at least one heteroatom selected from O, S, N and P.

6. A substrate, at least the surface of which is at least partially metallic, wherein the at least partially metallic portion is coated with a polybenzoxazine, the repeat units of which comprise at least one unit corresponding to the formulae (I) or (II):

wherein Z 1 , Z 2 , or both Z 1 and Z 2 , which are identical or different, represent an aromatic group comprising from 6 to 30 carbon atoms, and optionally at least one heteroatom chosen from O, S, N and P, and
wherein, when Z 1 and Z 2 are different, one of Z 1 and Z 2 is as defined above and one of Z 1 and Z 2 represents an at least divalent, aliphatic, cycloaliphatic or aromatic bonding group comprising at least one carbon atom and optionally at least one heteroatom selected from O, S, N and P.

7. The substrate according to claim 6 , wherein the substrate is made of steel.

8. The substrate according to claim 7 , wherein the substrate is made of carbon steel.

9. The substrate according to claim 7 , wherein the steel is a bright steel.

10. The substrate according to claim 7 , wherein the steel is at least partially coated with at least one layer of a second metal selected from the group consisting of aluminium, copper, zinc and alloys of at least one of these metals.

11. The substrate according to claim 10 , wherein the at least one layer of a second metal comprises brass.

Assignees

• Michelin & Cie

Inventors

• Fedurco Milan
• Ribezzo Marco

Classifications

• C09J179/04

  Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors · CPC title

• C08G73/0233

  Polyamines derived from (poly)oxazolines, (poly)oxazines or having pendant acyl groups · CPC title

• B32B15/20

  comprising aluminium or copper {(B32B15/016 and B32B15/017 take precedence)} · CPC title

• B60C2009/0021

  Coating rubbers for steel cords · CPC title

• B32B2255/205

  Metallic coating · CPC title