Nonaqueous sol-gel for adhesion enhancement of water-sensitive materials

Patent metadata

Field	Value
Publication number	US-11739237-B2
Application number	US-201715827156-A
Country	US
Kind code	B2
Filing date	Nov 30, 2017
Priority date	Jun 30, 2017
Publication date	Aug 29, 2023
Grant date	Aug 29, 2023

Abstract

The present disclosure provides sol-gel films and substrates, such as vehicle components, having a sol-gel film disposed thereon. At least one sol-gel formulation has about 10 wt % or less water content based on the total weight of the sol-gel formulation and comprises an organosilane, a metal alkoxide, an acid stabilizer, and an organic solvent. At least one vehicle component comprises a sol-gel coating system comprising a metal substrate and a sol-gel formulation disposed on the metal substrate. The sol-gel formulation has about 10 wt % or less water content based on the total weight of the sol-gel formulation and comprises an organosilane, a metal alkoxide, an acid stabilizer, and an organic solvent.

First claim

What is claimed is:

1. A sol-gel formulation for an adhesive in contact with a steel substrate, the sol-gel formulation consisting of:
0.7 wt % to 5 wt % of an organosilane based on a total weight of the sol-gel formulation, wherein the organosilane is one or more of 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldiisopropylethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, or 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane;
0.2 wt % to 5 wt % of a zirconium alkoxide based on the total weight of the sol-gel formulation;
15 wt % to 40 wt % of a corrosion inhibitor based on the total weight of the sol-gel formulation, the corrosion inhibitor selected from a group consisting of a compound represented by a formula R 1 —S n —X—R 2 wherein R 1 is an organic group, wherein n is an integer greater than or equal to 1, wherein X is a sulfur or a metal atom, wherein R 2 is an organic group, wherein one or both of the organic groups of R 1 and R 2 is a thiol group;
an acid stabilizer; and
an organic solvent,

wherein:
the sol-gel formulation has from 0 wt % to 1 wt % water content based on the total weight of the sol-gel formulation,
the sol-gel formulation has a pH from 2 to 5, and
a ratio of the zirconium alkoxide to the acid stabilizer is from 1:1 to 3:1.

2. The sol-gel formulation of claim 1 , wherein the acid stabilizer is from 0.1 wt % to 10 wt % based on the total weight of the sol-gel formulation.

3. The sol-gel formulation of claim 1 , wherein the sol-gel formulation has a water content of from 0 wt % to 0.5 wt % based on the total weight of the sol-gel formulation.

4. The sol-gel formulation of claim 1 , wherein the organic solvent is selected from the group consisting of alcohol, ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, an ether, tetrahydrofuran, N-methyl-2-pyrrolidone, dimethyl sulfoxide, and combinations thereof.

5. The sol-gel formulation of claim 1 , wherein the organic solvent is selected from the group consisting of ethanol, n-propanol, isopropanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, and combinations thereof.

6. The sol-gel formulation of claim 1 , wherein the sol-gel formulation has an organic solvent content of from 90 wt % to 95 wt % based on the total weight of the sol-gel formulation.

7. The sol-gel formulation of claim 1 , wherein the zirconium alkoxide is one or more of zirconium (IV) tetramethoxide, zirconium (IV) tetraethoxide, zirconium (IV) tetra-n-propoxide, zirconium (IV) tetra-isopropoxide, zirconium (IV) tetra-n-butoxide, zirconium (IV) tetra-isobutoxide, zirconium (IV) tetra-n-pentoxide, zirconium (IV) tetra-isopentoxide, zirconium (IV) tetra-n-hexoxide, zirconium (IV) tetra-isohexoxide, zirconium (IV) tetra-n-heptoxide, zirconium (IV) tetra-isoheptoxide, zirconium (IV) tetra-n-octoxide, zirconium (IV) tetra-n-isooctoxide, zirconium (IV) tetra-n-nonoxide, zirconium (IV) tetra-n-isononoxide, zirconium (IV) tetra-n-decyloxide, or zirconium (IV) tetra-n-isodecyloxide.

8. The sol-gel formulation of claim 1 , wherein the acid stabilizer is acetic acid.

9. The sol-gel formulation of claim 1 , wherein the steel substrate is a 4130 low alloy steel substrate.

10. The sol-gel formulation of claim 1 , wherein the acid stabilizer is one or more of an organic acid, a glycol, an ethoxyethanol, or H 2 NCH 2 CH 2 OH.

11. The sol-gel formulation of claim 1 , wherein the corrosion inhibitor is represented by formula (III):

12. The sol-gel formulation of claim 1 , wherein the corrosion inhibitor is represented by formula (IV):

13. The sol-gel formulation of claim 1 , wherein the sol-gel formulation has no cloudiness.

14. A sol-gel formulation for an adhesive in contact with a steel substrate, the sol-gel formulation consisting of:
an organosilane represented by formula (II):

wherein R is selected from alkyl, cycloalkyl, ether, and aryl;

0.2 wt % to 5 wt % of a zirconium alkoxide based on a total weight of the sol-gel formulation;
15 wt % to 40 wt % of a corrosion inhibitor based on the total weight of the sol-gel formulation, wherein the corrosion inhibitor is represented by a formula R 1 —S n —X—R 2 wherein R 1 is an organic group, wherein n is an integer greater than or equal to 1, wherein X is a sulfur or a metal atom, wherein R 2 is an organic group, wherein one or both of the organic groups of R 1 and R 2 is a thiol group;
an acid stabilizer; and
an organic solvent, wherein the sol-gel formulation has a water content of 0 wt % based on the total weight of the sol-gel formulation.

15. A sol-gel formulation for an adhesive in contact with a steel substrate, the sol-gel formulation consisting of:
0.3 wt % to 15 wt % of 3-glycidoxypropyltrimethoxysilane, based on a total weight of the sol-gel formulation;
0.2 wt % to 5 wt % of zirconium tetra-n-propoxide based on the total weight of the sol-gel formulation;
15 wt % to 40 wt % of a corrosion inhibitor based on the total weight of the sol-gel formulation, the corrosion inhibitor having a formula R 1 —S n —X—R 2 , wherein:
n is an integer greater than or equal to 1,
R 1 and R 2 are organic groups, and
one or both of the organic groups is a thiol, a polymer, or a combination thereof;

acetic acid;
an organic solvent; and

0 wt % to 0.5 wt % of water based on the total weight of the sol-gel formulation.

16. The sol-gel formulation of claim 15 , wherein the weight percent of 3-glycidoxypropyltrimethoxysilane in the sol-gel formulation is from 0.7 wt % to 5 wt % based on the total weight of the sol-gel formulation.

17. The sol-gel formulation of claim 15 , wherein a weight percent of the organic solvent in the sol-gel formulation is from 90 wt % to 95 wt % based on the total weight of the sol-gel formulation.

18. A sol-gel formulation for an adhesive in contact with a steel substrate the sol-gel formulation consisting of:
0.7 wt % to 5 wt % of an organosilane based on a total weight of the sol-gel formulation, wherein the organosilane is one or more of 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldiisopropylethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, or 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane,
0.2 wt % to 5 wt % of a zirconium alkoxide based on the total weight of the sol-gel formulation;
7 wt % to 40 wt % of a corrosion inhibitor based on the total weight of the sol-gel formulation, the corrosion inhibitor selected from a group consisting of a compound represented by a formula R 1 —S n —X—R 2 wherein R 1 is an organic group, wherein n is an integer greater than or equal to 1, wherein X is a sulfur or a metal atom, wherein R 2 is an organic group, wherein one or both of the organic groups of R 1 and R 2 is a thiol group;
an acid stabilizer; and
an organic solvent,

wherein:
the sol-gel formulation has from 0 wt % to 1 wt % water content based on the total weight of the sol-gel formulation,
the sol-gel formulation has a pH from 2 to 5, and
a ratio of the zirconium alkoxide to organosilane is 2:1 to 3:1.

Assignees

• Boeing Co

Inventors

• Moore James A
• Huff Daniel W
• Kennedy Dennis K

Classifications

• C09J9/00 Primary

  Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks (C09J7/00 takes precedence) · CPC title

• B01J13/003

  Preparation from aqueous sols · CPC title

• B01J13/0065

  containing an organic phase · CPC title

• C09D1/00

  Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances · CPC title

• C09D5/00

  Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced {(electrically insulating plastics, resins or waxes H01B3/30)}; Filling pastes · CPC title