Metal or metal-plated reinforcement with sulfur polybenzoxazine-coated surface

Patent metadata

Field	Value
Publication number	US-11701922-B2
Application number	US-201816621570-A
Country	US
Kind code	B2
Filing date	Jun 12, 2018
Priority date	Jun 14, 2017
Publication date	Jul 18, 2023
Grant date	Jul 18, 2023

Abstract

A metallic or metallized reinforcer has at least a surface of which is at least partially metallic, the at least partially metallic surface being coated with a polybenzoxazine sulfide whose repeating units include at least one unit corresponding to formula (I) or (II):

in which the two oxazine rings are connected together via a central aromatic group, the benzene ring of which bears one, two, three or four groups of formula —S x —R in which “x” is an integer from 1 to 8 and R represents hydrogen or a hydrocarbon-based group including 1 to 10 carbon atoms and optionally a heteroatom chosen from O, S, N and P. Such a reinforcement can be used for the reinforcement of a rubber article, in particular a motor vehicle tire.

First claim

The invention claimed is:

1. A metallic or metallized reinforcer, at least a surface of which is at least partially metallic, the at least partially metallic surface being coated with a polybenzoxazine sulfide, repeating units of which include at least one unit corresponding to formula (I) or (II):

in which the two oxazine rings are connected together via a central aromatic group, a is an integer from 1 to 4, x is an integer from 1 to 8, R represents hydrogen or a hydrocarbon-based group including 1 to 10 carbon atoms and optionally a heteroatom chosen from O, S, N and P, and *, which may be identical or different, represents any attachment to a carbon atom or to a heteroatom chosen from O, S, N and P.

2. The reinforcer according to claim 1 , wherein a is 2.

3. The reinforcer according to claim 2 , wherein the two groups of formula —S x —R are in the meta-position relative to each other on the central benzene ring.

4. The reinforcer according to claim 1 , wherein x is in a range from 1 to 4.

5. The reinforcer according to claim 1 , wherein R is an alkyl containing from 1 to 5 carbon atoms.

6. The reinforcer according to claim 5 , wherein R represents a methyl or an ethyl.

7. The reinforcer according to claim 1 , wherein x is equal to 1 and R represents a methyl.

8. The reinforcer according to claim 1 , the repeating units of which comprise at least one unit corresponding to formulae (I-bis) or (II-bis):

9. The reinforcer according to claim 8 , the repeating units of which comprise at least one unit corresponding to formulae (I-a) or (II-a):

10. The reinforcer according to claim 1 , wherein the reinforcer is in the form of a yarn, film, tape or cord made of steel.

11. The reinforcer according to claim 10 , wherein the steel is a bright steel.

12. The reinforcer according to claim 10 , wherein the steel is at least partially coated with a second surface metal selected from the group consisting of aluminum, copper, zinc and alloys thereof.

13. The reinforcer according to claim 12 , wherein the second surface metal is brass.

14. A metallic or metallized reinforcer, at least a surface of which is at least partially metallic, the at least partially metallic surface being coated with a polybenzoxazine sulfide, the repeating units of which comprise at least one unit corresponding to formulae (I-a-1), (I-b-1), (II-a-1) or (II-b-1):

wherein *, which may be identical or different, represents any attachment to a carbon atom or to a heteroatom chosen from O, S, N and P.

15. A metallic or metallized reinforcer, at least a surface of which is at least partially metallic, the at least partially metallic surface being coated with a polybenzoxazine sulfide, the repeating units of which correspond to at least one of the formulae (I-1) or (II-1) below:

in which:
X 1 and X 2 , which may be identical or different, represent O or S;
Ar 1 and Ar 2 , which may be identical or different, represent an aromatic group;
Z represents O or (S) n , representing an integer greater than or equal to 1;
a is an integer from 1 to 4;
x is an integer from 1 to 8;
R represents hydrogen or a hydrocarbon-based group including 1 to 10 carbon atoms and optionally a heteroatom chosen from O, S, N and P; and
*, which may be identical or different, represents any attachment to a carbon atom or to a heteroatom chosen from O, S, N and P.

16. The reinforcer according to claim 15 , the repeating units of which correspond to at least one of the formulae (I-1bis) or (II-1bis) below:

17. A rubber article reinforced with at least one metallic or metallized reinforcer, at least a surface of which is at least partially metallic, the at least partially metallic surface being coated with a polybenzoxazine sulfide, repeating units of which include at least one unit corresponding to formula (I) or (II):

in which the two oxazine rings are connected together via a central aromatic group a is an integer from 1 to 4, x is an integer from 1 to 8, R represents hydrogen or a hydrocarbon-based group including 1 to 10 carbon atoms and optionally a heteroatom chosen from O, S, N and P, and *, which may be identical or different, represents any attachment to a carbon atom or to a heteroatom chosen from O, S, N and P.

18. A motor vehicle tire reinforced with at least one metallic or metallized reinforcer, at least a surface of which is at least partially metallic, the at least partially metallic surface being coated with a polybenzoxazine sulfide, repeating units of which include at least one unit corresponding to formula (I) or (II):

in which the two oxazine rings are connected together via a central aromatic group, a is an integer from 1 to 4, x is an integer from 1 to 8, R represents hydrogen or a hydrocarbon-based group including 1 to 10 carbon atoms and optionally a heteroatom chosen from O, S, N and P, and *, which may be identical or different, represents any attachment to a carbon atom or to a heteroatom chosen from O, S, N and P.

Assignees

• Michelin & Cie

Inventors

• Fedurco Milan
• Ribezzo Marco

Classifications

• B60C9/0007 Primary

  Reinforcements made of metallic elements, e.g. cords, yarns, filaments or fibres made from metal · CPC title

• C08G65/4031

  (I) or (II) containing nitrogen · CPC title

• C08G65/4056

  (I) or (II) containing sulfur (as the sulfone group C08G75/23) · CPC title

• C08G73/0233

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

• C08J5/06

  using pretreated fibrous materials · CPC title