Waterborne epoxy derived adhesive primers

• US 5,266,611 A
• Filed: 07/21/1992
• Issued: 11/30/1993
• Est. Priority Date: 07/21/1992
• Status: Expired due to Fees

• Current Assignee: Loctite Corporation (Henkel AG & Co KGaA)
• Original Assignee: Dexter Corp. (Thermo Fisher Scientific Incorporated)
• Inventors: Teschendorf, Andrew F.
• Primary Examiner(s): Marquis, Melvyn I.
• Assistant Examiner(s): AYLWARD, DAVID E
• Application Number:
  US07/917,582
• Time in Patent Office: 497 Days
• Field of Search: 525/455, 525/530, 525/904, 528/904, 523/416, 523/423, 428/416
• US Class Current: 523/416
• CPC Class Codes: C08L 61/20 Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen with aminophenols C08L61/04
• CPC Class Codes: C08L 63/00 Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• CPC Class Codes: C08L 71/00 Compositions of polyethers obtained by reactions forming an ether link in the main chain of polyacetals C08L59/00; of epoxy resins C08L63/00; of polythioether-ethers C08L81/02; of polyether-sulfones C08L81/06; Compositions of derivatives of such polymers
• CPC Class Codes: C09J 2400/166 in the pretreated surface to be joined
• CPC Class Codes: C09J 5/02 involving pretreatment of the surfaces to be joined
• CPC Class Codes: Y10S 525/904 Activation of preformed polymer in absence or monomer, for subsequent polymerization thereon, e.g. trapped radicals
• CPC Class Codes: Y10T 428/31522 Next to metal

Abstract

An aqueous structural adhesive bonding primer composition containing a water-dispersible, modified phenoxy resin, an amine-aldehyde resin and a catalyst for reaction between the resins. The primer may contain corrosion inhibitors, including a novel chromate-free inhibitor system.

Claims

1. An aqueous structural adhesive bonding primer composition containing a water-dispersible, modified phenoxy resin that has a waterborne polymeric structure and a degree of polymerization of at least 30, an amine aldehyde resin and a catalyst for reacting the epoxy resin and the amine aldehyde resin, which composition when provided as a structural adhesive primer on a solid surface that serves as an adherend for a structural adhesive, protects the adherend surface from being affected by environment, inhibits corrosion of the bonded surface during its service life and provides a compatible surface to which the adhesive can bond for longterm strength.

2. The aqueous structural adhesive bonding primer composition of claim 1 wherein the phenoxy resin contains anionic, cationic or nonionic functional substitution that forms the waterborne polymeric structure.

3. The aqueous structural adhesive bonding primer composition of claim 2 wherein the phenoxy resin contains anionic functional substitution that forms the waterborne polymeric structure.

4. The aqueous structural adhesive bonding primer composition of claim 2 wherein the phenoxy resin contains cationic functional substitution that forms the waterborne polymeric structure.

5. The aqueous structural adhesive bonding primer composition of claim 2 wherein the phenoxy resin contains nonionic functional substitution that forms the waterborne polymeric structure.

6. The aqueous structural adhesive bonding primer composition of claim 2 wherein the phenoxy resin contains grafted acrylyl substitution on the phenoxy resin backbone that provide the anionic, cationic or nonionic substitution thereby forming the waterborne polymeric structure.

7. The aqueous structural adhesive bonding primer composition of claim 2 wherein the grafted acrylyl substitution is derived from the acrylyl compound of the formula:

##STR16## wherein R¹ is hydrogen or a lower C_1-4 alkyl group and X contains an ionically bonded cationic, anionic group or a nonionic group.

8. The aqueous structural adhesive bonding primer composition of claim 7 wherein the grafted acrylyl substitution waterborne phenoxy is derived from acrylyl compounds are the following:

##STR17## wherein [⁺ ]Q is a proton acceptor;

Y is either oxygen, sulfur or amino;

R² is a divalent organic group;

R³ is a carboxy containing group;

R⁴ is an amine, ammonium, phosphonium, or sulfonium;

R⁵ is poly(alkyleneoxy); and

Z is terminal alkyl or hydroxyl.

9. The aqueous structural adhesive bonding primer composition of claim 8 wherein the grafted acrylyl substitution is formed in situ, by grafting the acrylic or methacrylic or other alkyl substituted versions and reacting them with a base or grafting them and then converting the carboxylic group to the acid chloride with a chlorinating reagent followed by reaction with the hydroxyl, mercapto or amino version of the functional group, or an intermediate leading thereto, thereby forming the equivalent waterborne polymeric structure.

10. The aqueous structural adhesive bonding primer composition of claim 2 containing a water-dispersible corrosion inhibitor mixture of components I. and II. in which:

Component I. is at least one of;

(a) a zinc salt of a carboxylic acid of the formula;

##STR18## (b) zinc phosphate, and (c) zinc molybdate,

wherein Y₄ is hydroxyl or a radical of the formula;

##STR19## Y₃ is --CO-- or --SO₂ --, Y₁ is C₁ -C₈ -alkyl, C₁ -C₈ -alkoxy or halogen when Y₄ is other than hydroxyl, carboxyl when Y₄ is hydroxyl, or hydrogen when Y₄ is ##STR20## or Q¹ is nitro, or m is 2, Y₂ is hydrogen, C₁ -C₈ -alkyl, nitro, hydrogen or halogen, Q¹ is hydrogen, nitro or halogen, m and n are each 1 or 2; and

Component II. is at least one other and different corrosion inhibitor from the group consisting of;

i) (2-benzothiazolylthio)succinic acid, and

ii) a corrosion inhibitor containing a metal other than chromium, having an atomic number of at least 3 and not greater than 81, from Groups 1, 2, 3, 4, 5, 6, 7 and 12 of the Periodic Table of the Elements (New Notation), and mixtures thereof.

11. The aqueous structural adhesive bonding primer composition of claim 10 wherein component II. is a member from the group consisting of:

a. (2-benzothiazolylthio)succinic acid;

b. a mixture of (2-benzothiazolylthio)succinic acid and calcium silicate;

c. a mixture of a precipitated calcium silicate, zinc iodide, and lithium borate;

d. a mixture of a precipitated calcium silicate, a calcium strontium zinc phosphosilicate, zinc iodide, and lithium borate;

e. a mixture of zinc iodide and manganese (III) acetate;

f. bismuth nitrate;

g. cerium chloride;

h. cerium molybdate;

i. sodium thioglycolate;

j. calcium strontium zinc phosphosilicate; and

k. a water-dispersible mixture of niobium oxide and cerium molybdate.

12. The aqueous structural adhesive bonding primer composition of claim 11 wherein component I. is a mixture of zinc 5-nitroisophthalate and zinc phosphate, and component II. is the mixture of (2-benzothiazolylthio)succinic acid and calcium silicate.

13. The aqueous structural adhesive bonding primer composition of claim 11 wherein component I. is a mixture of zinc 5-nitroisophthalate and zinc phosphate, and component II. is cerium molybdate.

14. The aqueous structural adhesive bonding primer composition of claim 11 wherein component I. is zinc 5-nitroisophthalate and component II. is sodium thioglycolate.

15. The aqueous structural adhesive bonding primer composition of claim 10 wherein there is provided a small amount of a chromate corrosion inhibitor.

16. The aqueous structural adhesive bonding primer composition of claim 2 wherein there is provided a small amount of a chromate corrosion inhibitor.

17. An aqueous structural adhesive bonding primer composition containing a water-dispersible, modified phenoxy resin and a water-dispersible corrosion inhibitor comprising a mixture of niobium oxide and cerium molybdate.