Cationic electrocoating compositions, method of making, and use

• US 5,820,987 A
• Filed: 08/21/1996
• Issued: 10/13/1998
• Est. Priority Date: 08/21/1996
• Status: Expired due to Term

• Current Assignee: PPG Industries Incorporated (Nouryon BV)
• Original Assignee: PPG Industries Incorporated (Nouryon BV)
• Inventors: McCollum, Gregory J., Karabin, Richard F., O'Neill, Patrick, Kaufman, Marvin L.
• Primary Examiner(s): GULAKOWSKI, RANDY P
• Application Number:
  US08/700,977
• Time in Patent Office: 783 Days
• Field of Search: 428/413, 428/423.1, 523/404, 523/415, 523/421, 525/460, 525/504, 525/528
• US Class Current: 428/413
• CPC Class Codes: C08G 18/643 Reaction products of epoxy resins with at least equivalent amounts of amines
• CPC Class Codes: C09D 5/4434 characterised by the nature of the epoxy binder
• CPC Class Codes: Y10T 428/31511 Of epoxy ether
• CPC Class Codes: Y10T 428/31551 Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]

Abstract

An electrodepositable composition that has: (A) an active hydrogen-containing cationic resin, electrodepositable on a cathode, having: (1) a polyepoxide; (2) an oxygen-substituted diamine compound having the following formula: ##STR1## where n is an integer from 2 to 4; and where R¹ or R² are the same or different and either one or both contain at least one oxygen and are alkyl, cycloalkyl, substituted alkyl, or substituted cycloalkyl having from 1 to 6 carbon atoms, or R¹ and R² are alkanol groups having from 2 to 6 carbon atoms, or R¹, R², and the N atom form a cyclic group which is substituted or unsubstituted such as morpholine and 1-(3-aminopropyl) imidazole; and (B) at least partially blocked isocyanate or polyisocyanate curing agent. The diamine compound of Formula I can be used alone or in conjunction with one or more secondary amines, nonhydroxy group containing amines and/or amines with ring structures. Optionally, the polyepoxide can be chain extended with active hydrogen-containing compounds other than polyoxyalkylene polyamines. Also provided is a method of producing an active hydrogen-containing cationic resin composition, electrodepositable on a cathode, comprised of (a) mixing together in a suitable reaction vessel a polyepoxide, or the precursors of the polyepoxide, a polycarboxylic acid, a blocked isocyanate curing agent; (b) adding to the mixture of (a) a base catalyst and the diamine compound of Formula I; (c) polymerizing the mixture of (b) to form a resinous composition; and (d) neutralizing the resinous composition of (c) by adding the resinous composition to a dilute mixture of acid and water to form an aqueous dispersed electrodepositable cationic resin composition.

Claims

1. An electrodepositable composition comprising:

(A) an active hydrogen-containing cationic resin, electrodepositable on a cathode, comprising;

(1) a polyepoxide;

(2) an oxygen-substituted diamine compound having the following formula;

##STR3## where n is an integer from 2 to 4; and

where R¹ or R² are the same or different and are selected from the group consisting of;

     1) R¹, R², and both contain at least one oxygen and are alkyl or cycloalkyl, having from 1 to 6 carbon atoms;

     2) R¹, R² and both are alkanol groups having from 2 to 6 carbon atoms; and

     3) R¹, R², and both contain at least one oxygen and have 1 to 6 carbon atoms and form a cyclic group with the N atom of the tertiary amine group;

wherein the oxygen substituted diamine is an amine reactant for the polyepoxide to form an epoxide amine resinous adduct and is present in an amount of about 30 to 100 percent of the NH equivalents for the active hydrogen-containing cationic resin and on a weight basis is the predominant amine as an amine reactant to form the epoxide amine resinous adduct for the active hydrogen-containing cationic resin; and

(B) at least partially blocked isocyanate curing agent, and wherein the electrodepositable composition is essentially free of polyoxyalkylene polyamine.

2. The electrodepositable composition of claim 1 wherein the oxygen-substituted diamine compound is chosen from the group consisting of aminopropyldiethanolamine, aminopropylmorpholine, and N-(2-amino-ethyl)-morpholine.

3. The electrodepositable composition of claim 1 wherein the at least partially blocked isocyanate is polyisocyanate present in the active hydrogen-containing cationic resin such that there is about 0.1 to about 1.2 capped isocyanate groups for each active hydrogen from hydroxyl, primary and secondary amino groups of the cationic resin.

4. The electrodepositable composition of claim 1 additionally comprising at least one pigment.

5. The electrodepositable composition of claim 1 that is substantially free of lead.

6. The electrodepositable composition of claim 1 additionally comprising cationic microgels.

7. A substrate coated with the electrodepositable composition of claim 1.

8. The electrodepositable composition of claim 1, which includes one or more catalysts are typically used in amounts of 0.05 to 5 percent by weight based on the weight of resin solids.

9. A method of producing an active hydrogen-containing cationic resin composition, electrodepositable on a cathode, comprising:

(a) mixing together in a suitable reaction vessel a polyepoxide, or the precursors of the polyepoxide, and an at least partially blocked isocyanate curing agent;

(b) adding to the mixture of (a) a base catalyst and an oxygen-substituted diamine compound having the following formula;

##STR4## where n is an integer from 2 to 4; and

where R¹ or R² are the same or different and are selected from the group consisting of;

     1) R¹, R², and both contain at least one oxygen and are alkyl or cycloalkyl, having from 1 to 6 carbon atoms;

     2) R¹, R² and both are alkanol groups having from 2 to 6 carbon atoms; and

     3) R¹, R², and both contain at least one oxygen and have 1 to 6 carbon atoms and form a cyclic group with the N atom of the tertiary amine group;

wherein the oxygen substituted diamine is an amine reactant for the polyepoxide to form an epoxide amine resinous adduct and is present in an amount of about 30 to 100 percent of the NH equivalents for the active hydrogen-containing cationic resin and on a weight basis is the predominant amine as an amine reactant to form the epoxide amine resinous adduct for the active hydrogen-containing cationic resin;

(c) polymerizing said mixture of (b) to form a resinous composition; and

(d) neutralizing the resinous composition of (c) by adding the resinous composition to a dilute mixture of acid and water to form an aqueous dispersed cationic resin electrodepositable on a cathode from an electrodepositable composition that is essentially free of polyoxyalkylene polyamine.

10. The method of claim 9 wherein in adding step (b) the addition of the oxygen-substituted diamine compound is of a compound chosen from the group consisting of aminopropyldiethanolamine, aminopropylmorpholine, and N-(2-amino-ethyl)-morpholine.

11. The method of claim 9 wherein the adding step (b) has a base catalyst selected from the group consisting of:

triphenylphosphine, ethyltriphenylphosphonium iodide, benzyldimethylamine, dimethylaminocyclohexane, triethylamine, N-methylimidazole, and tetrabutyl ammonium hydroxide in an effective catalytic amount.

12. The method of claim 9 wherein in mixing step (a), the polyepoxide is the reaction product of a polyglycidyl ether of a polyhydric alcohol and the equivalent ratio of the epoxy to polyhydric alcohol groups is from about 1:

0.75 to 1;

2.

13. The method of claim 9 wherein in mixing step (a), the at least partially blocked isocyanate is polyisocyanate present such that there is about 0.1 to about 1.2 capped isocyanate groups for each active hydrogen from hydroxyl, primary and secondary amino groups of the cationic resin.

14. The method of claim 9 wherein the at least partially blocked isocyanate is added in an amount to have in the active hydrogen-containing cationic resin about 0.1 to about 1.2 capped isocyanate groups for each active hydrogen from hydroxyl, primary and secondary amino groups of the cationic resin to form an electrodepositable composition;

and which includes combining the dispersed cationic resin and at least one pigment to form the electrodepositable composition, which is substantially free of added lead.