# US 5,348,635 A · Flexible aryl alkyl epoxy resins, their amine resin derivatives and their use in electrodeposition coatings

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- Number: US 5,348,635 A
- Document ID: US5348635A
- Status: Granted
- Kind: A
- Application number: 08/013,522
- Filed: 1993-02-03
- Granted: 1994-09-20
- Earliest claimed: 1987-07-24
- Assignees: BASF SE
- Inventors: James A. Laugal; Glenn E. Martin; Donald L. St. Aubin; Gerald G. Wold
- Web page: https://patentgrep.com/patent/US5348635A

## CPC

- C08G 59/226: {Mixtures of di-epoxy compounds}
- C08G 59/066: {with chain extension or advancing agents}
- C08G 59/50: Amines
- C09D 5/4434: {characterised by the nature of the epoxy binder}
- C09D 163/00: Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)

## Abstract

A series of oligomeric adducts of diols and diepoxides are disclosed which are precursors of amine resins for use in electrodeposition coatings. The adducts are epoxide-alcohol addition products of a polyaromatic and/or a mono-aromatic diol and a polyaromatic bis-glycidyl ether, and/or a monoaromatic bis-glycidyl ether and/or an alkoxy arylene bis-glycidyl ether, thioether or amine. The coatings which include amine resin, cross linking agent, grind resin and pigment exhibit excellent corrosion resistance.

## Claims

### Claim 1

A 2D3E epoxide compound comprising the addition reaction oligomer of monomers Diol D1, Diol D2, Diepoxide E1, Diepoxide E2 and Diepoxide E3 wherein:
Diol D1 has at least two aryl groups between the hydroxyls,
Diol D2 has only one aryl group between the hydroxyls,
Diepoxide E1 is a bis(glycidyl ether) of Diol D1,
Diepoxide E2 is a bis(glycidyl ether) of a bis (labile hydrogen functionalized alkoxy) arylene, and
Diepoxide E3 is a bis(glycidyl ether) of Diol D2.

### Claim 2 (depends on 1)

A 2D3E epoxide compound according to claim 1 wherein Diol D1 is a bis (aryl alcohol) compound.

### Claim 3 (depends on 1)

A 2D3E epoxide compound according to claim 1 wherein Diol D2 is an aryl diol.

### Claim 4 (depends on 1)

A 2D3E epoxide compound according to claim 1 wherein:
Diol D1 has the formula HO--Ar.sup.1 --OH, Ar.sup.1 being a naphthalene group, or a polyphenylene group having two or three phenylenes linked by carbon-carbon bonds or alkylene groups of 1 to 5 carbons, or a substituted derivative of said naphthalene or polyphenylene group, said substituent being halogen, alkoxy of 1 to 3 carbons, or alkyl of 1 to 3 carbons;
Diol D2 has the formula HO--Ar.sup.3 --OH, Ar.sup.3 being a phenylene or substituted phenylene, the substituent being halogen, alkoxy of 1 to 3 carbons, or alkyl of 1 to 3 carbons;
Diepoxide E1 has the formula ##STR5## Ar.sup.1 being as defined for Diol D1; Diepoxide E2 has the formula ##STR6## R.sup.1 being alkyl of 1 to 8 carbons or alkoxyalkyl of 2 to 8 carbons; X being --O--, --S--, or .dbd.N--R.sup.2, R.sup.2 being H or alkyl of 1 to 3 carbons; and Ar.sup.2 being a naphthalene group, a phenylene group or a polyphenylene group having two or three phenylenes linked by carbon-carbon bonds or alkylene groups of 1 to 5 carbons, or a substituted derivative of said naphthalene, phenylene or polyphenylene group, said substituent being halogen, alkoxy of 1 to 3 carbons, or alkyl of 1 to 3 carbons; and
Diepoxide E3 has the formula ##STR7## Ar.sup.3 being as defined for Diol D2.

### Claim 5 (depends on 1)

A 2D3E epoxide compound compound according to claim 1 wherein the diepoxide monomers and diol monomers alternate in sequence in the oligomer and the distributions of Diepoxide E1, E2 and E3 and Diols D1 and D2 in the oligomer are random.

### Claim 6 (depends on 1)

A 2D3E epoxide compound according to claim 1 wherein the diepoxide monomers and diol monomers alternate in sequence in the oligomer and the distribution of momomers is ordered so as to provide blocks of Diepoxide-Diol: E1-D1, E1-D2, E2-D1, E2-D2, E3-D1, E3-D2.

### Claim 7 (depends on 1)

A 2D3E epoxide compound according to claim 1 wherein the ratio of Diol D1 and D2 equivalents to the sum of Diepoxide E1, E2 and E3 equivalents is calculated to yield an oligomer molecular weight of from about 900 to about 4000, equivalents being the molecular weight of diol or diepoxide divided respectively by the number of hydroxyl groups or epoxide groups present in the diol or diepoxide.

### Claim 8 (depends on 1)

A 2D3E epoxide compound according to claim 1 wherein Diol D1 is p,p'-dihydroxydiphenylalkane of 1 to 3 carbons, p,p'-dihydroxydiphenyl, 1,5-dihydroxynaphthalene or bis(hydroxynaphthalene) methane and Diol D2 is resorcinol, hydroquinone or catechol.

### Claim 9 (depends on 1, 2, 3, 4, 5, 6, 7, 8)

A 2D3E amine resin comprising the reaction product of:
A) the 2D3E epoxide compound of claim 1, 2, 3, 4, 5, 6, 7 or 8; and
B) an amine.

### Claim 10 (depends on 9)

An amine resin according to claim 9 wherein the amine is ammonia, a mono- or poly- organic amine having primary, secondary tertiary groups or combinations thereof, or a heterocyclic amine or a physical blend or chemical mixture of said amine.

### Claim 11 (depends on 9)

An amine resin according to claim 9 wherein the amine contains hydroxy, ether, alkoxy, thio, thioether, carboxyl or amide groups.

### Claim 12 (depends on 9)

An amine resin according to claim 9 wherein the amine is a mono or poly aliphatic, aromatic or alkaromatic amine having from 1 to 6 primary, secondary or tertiary groups or a combination thereof, or a heterocyclic amine.

### Claim 13 (depends on 9)

An 2D3E principal resin emulsion comprising water, an acid solubilized amine resin according to claim 9 and a cross-linking agent.

### Claim 14 (depends on 1)

A principal resin emulsion according to claim 1 wherein the cross-linking agent is a blocked organic polyisocyanate.

### Claim 15 (depends on 13)

An aqueous electrodeposition composition comprising a principal resin emulsion according to claim 13 and a pigment-grind resin formulation wherein the grind resin is a quaternary ammonium salt, or an esterified, alkoxylated aliphatic amine.

### Claim 16 (depends on 15)

An aqueous electrodeposition composition according to claim 15 wherein the solids content is about 10% to about 65% by weight, the ratio of weight of pigment-grind resin formulation to the sum of the weights of amine resin and cross-linking agent is from about 1:10 to about 2:5; the pH is about 2 to 8.5, the ratio by weight of amine resin to cross-linking agent is from 2:3 to 5:1 and the ratio by weight of pigment to grind resin is about 2:1 to about 6:1.

### Claim 17 (depends on 9)

A method of coating a substrate comprising cathodically electrodepositing onto the substrate a 2D3E amine resin according to claim 9.

### Claim 18 (depends on 9)

A 2D3E principal resin emulsion comprising water, an acid solubilized 2D3E amine resin according to claim 9 and a crosslinking agent.