Autodeposition process and composition

Claim 2

An acidic aqueous coating composition of the type which is effective in forming on a metallic surface immersed therein a resinous coating which increases in weight or thickness the longer said surface is immersed in said composition in the absence of any electrical charge on said metallic surface other than that which may be imparted thereto by said composition and characterized by the presence therein of resin particles which are: (A) prepared by polymerizing (i) a conjugated diene, (ii) CH 2 ═CH--R wherein R is an aryl or cyano group, (iii) a vinylidene halide, and (iv) a monoethylenically unsaturated monomer having a functional group selected from the class consisting of amide and carboxyl groups; and/or (B) substantially chemically and physically homogeneous, wherein the concentration of surfactant, if any, in the aqueous phase of said composition is below the critical micelle concentration.

Claim 3

A composition according to claim 1 wherein said resin particles are those of (A) and comprise the polymerized constituents of: (A) about 25 to about 70 wt. % of said conjugated diene; (B) about 5 to about 70 wt. % of said CH 2 ═CHR; (C) about 1 to about 50 wt. % of said vinylidene halide; and (D) about 0.5 to about 15 wt. % of said unsaturated monomer.

Claim 4

A composition according to claim 2 wherein said resin particles comprise the polymerized constituents of: (A) about 40 to about 65 wt. % of said conjugated diene; (B) about 30 to about 65 wt. % of said CH 2 ═CHR; (C) about 3 to about 15 wt. % of said vinylidene halide; and (D) about 1 to about 4 wt. % of said unsaturated monomer.

Claim 5

A composition according to claim 2 wherein said conjugated diene is butadiene, said CH 2 ═CHR is styrene, said vinylidene halide is vinylidene chloride and said unsaturated monomer is methacrylic acid.

Claim 6

A composition according to claim 3 wherein said conjugated diene is butadiene, said CH 2 ═CHR is styrene, said vinylidene halide is vinylidene chloride and said unsaturated monomer is methacrylic acid.

Claim 7

A composition according to claim 4 wherein said resin particles are dispersed in said composition by an anionic emulsifier.

Claim 8

A composition according to claim 5 wherein said resin particles are dispersed in said composition by an anionic emulsifier.

Claim 9

A composition according to claim 6 wherein said resin particles are substantially chemically and physically homogeneous.

Claim 10

A composition according to claim 7 wherein said resin particles are substantially chemically and physically homogeneous.

Claim 11

A composition according to claim 1 wherein said resin particles are said (B) resin particles.

Claim 12

A composition according to claim 2 wherein said resin particles are substantially chemically and physically homogeneous.

Claim 13

A composition according to claim 3 wherein said resin particles are substantially chemically and physically homogeneous.

Claim 14

A composition according to claim 10 wherein said resin particles are seed polymerized resin particles.

Claim 15

An acidic aqueous coating composition which is effective in forming on a metallic surface immersed therein a resinous coating which increases in weight or thickness the longer said surface is immersed in said composition in the absence of any electrical charge on said metallic surface other than that which may be imparted thereto by said composition, said composition comprising: (A) about 5 to about 550 g/l of resin solids selected from the class consisting of resin particles prepared by polymerizing (i) a conjugated diene, (II) CH 2 ═CH--R wherein R is an aryl or cyano group, (iii) a vinylidene halide, and (iv) a monoethylenically unsaturated monomer having a functional group selected from the class consisting of amide and carboxyl groups; and resin particles which are substantially chemically and physically homogeneous; (B) a ferric-containing compound which is soluble in the composition in an amount equivalent to about 0.025 to about 3.5 g/l of ferric iron; and (C) acid in an amount sufficient to impart to the composition a pH within the range of about 1.6 to about 5, wherein the concentration of surfactant, if any, in the aqueous phase of said composition is below the critical micelle concentration.

Claim 16

An acidic aqueous coating composition which is effective in forming on a metallic surface immersed therein a resinous coating which increases in weight or thickness the longer said surface is immersed in said composition in the absence of any electrical charge on said metallic surface other than that which may be imparted thereto by said composition, said composition comprising: (A) about 5 to about 550 g/l of resin solids selected from the class consisting of resin particles prepared by polymerizing (i) a conjugated diene, (II) CH 2 ═CH--R wherein R is an aryl or cyano group, (iii) a vinylidene halide, and (iv) a monoethylenically unsaturated monomer having a functional group selected from the class consisting of amide and carboxyl groups; and resin particles which are substantially chemically and physically homogeneous; (B) a ferric-containing compound which is soluble in the composition in an amount equivalent to about 0.025 to about 3.5 g/l of ferric iron; and (C) acid in an amount sufficient to impart to the composition a pH within the range of about 1.6 to about 5, wherein the concentration of surfactant, if any, in the aqueous phase of said composition is below the critical micelle concentration.

Claim 17

A composition according to claim 14 wherein said acid is HF.

Claim 18

A composition according to claim 14 wherein said resin particles are dispersed in said composition by an anionic emulsifier.

Claim 19

A composition according to claim 15 wherein said resin particles are dispersed in said composition by an anionic emulsifier.

Claim 20

A composition according to claim 17 wherein said resin particles are prepared from the monomeric constituents set forth in paragraph (A) of claim 14.

Claim 21

A composition according to claim 17 wherein said resin particles are substantially chemically and physically homogeneous.

Claim 22

An acidic aqueous coating composition which is effective in forming on a metallic surface immersed therein a resinous coating which increases in weight or thickness the longer said surface is immersed in said composition in the absence of any electrical charge on said metallic surface other than that which may be imparted thereto by said composition, said composition comprising: (A) about 50 to about 100 g/l of cross-linked resin solids selected from the class consisting of resin particles prepared by polymerizing (i) a conjugated diene, (ii) CH 2 ═CH--R wherein R is an aryl or cyano group, (iii) a vinylidene halide, and (iv) a monoethylenically unsaturated monomer having a functional group selected from the class consisting of amide and carboxyl groups; and resin particles which are substantially chemically and physically homogeneous; (B) ferric fluoride in an amount such that it contains the equivalent of about 0.5 to about 3.5 g/l of ferric iron; (C) about 0.2 to about 5 g/l of HF; and wherein the pH of said composition is within the range of about 1.6 to about 4, wherein the concentration of surfactant, if any, in the aqueous phase of the composition is below the critical micelle concentration.

Claim 23

An acidic aqueous coating composition which is effective in forming on a metallic surface immersed therein a resinous coating which increases in weight or thickness the longer said surface is immersed in said composition in the absence of any electrical charge on said metallic surface other than that which may be imparted thereto by said composition, said composition comprising: (A) about 50 to about 100 g/l of cross-linked resin solids selected from the class consisting of resin particles prepared by polymerizing (i) a conjugated diene, (ii) CH 2 ═CH--R wherein R is an aryl or cyano group, (iii) a vinylidene halide, and (iv) a monoethylenically unsaturated monomer having a functional group selected from the class consisting of amide and carboxyl groups; and resin particles which are substantially chemically and physically homogeneous; (B) ferric fluoride in an amount such that it contains the equivalent of about 0.5 to about 3.5 g/l of ferric iron; (C) about 0.2 to about 5 g/l of HF; and wherein the pH of said composition is within the range of about 1.6 to about 4, wherein the concentration of surfactant, if any, in the aqueous phase of the composition is below the critical micelle concentration.

Claim 24

A composition according to claim 20 wherein said resin particles comprise the polymerized constituents of: (A) about 25 to about 70 wt. % of said conjugated diene; (B) about 5 to about 70 wt. % of said CH 2 ═CHR; (C) about 1 to about 50 wt. % of said vinylidene halide; and (D) about 0.5 to about 15 wt. % of said unsaturated monomer.

Claim 25

A composition according to claim 21 wherein said resin particles comprise the polymerized constituents of: (A) about 40 to about 65 wt. % of said conjugated diene; (B) about 30 to about 65 wt. % of said CH 2 ═CHR; (C) about 3 to about 15 wt. % of said vinylidene halide; and (D) about 1 to about 4 wt. % of said unsaturated monomer.

Claim 26

A composition according to claim 21 wherein said conjugated diene is butadiene, said CH 2 ═CHR is styrene, said vinylidene halide is vinylidene chloride and said unsaturated monomer is methacrylic acid.

Claim 27

A composition according to claim 22 wherein said conjugated diene is butadiene, said CH 2 ═CHR is styrene, said vinylidene halide is vinylidene chloride and said unsaturated monomer is methacrylic acid.

Claim 28

A composition according to claim 24 wherein the source of said resin particles is a latex containing about 1 to about 4 wt. % of an emulsifier based on the resin solids of the latex and wherein said emulsifier comprises at least about 90 wt. % of an anionic emulsifier.

Claim 29

A composition according to claim 25 wherein said resin particles are substantially chemically and physically homogeneous.

Claim 30

A composition according to claim 25 wherein said emulsifier comprises about 100 wt. % of an anionic emulsifier.

Claim 31

A process for preparing an autodepositing composition from an aqueous resin/pigment concentrate comprising combining an aqueous resin/pigment concentrate consisting essentially of: (A) about 350 to about 550 g/l of resin particles selected from the class consisting of resin particles prepared by polymerizing (i) a conjugated diene, (ii) CH 2 ═CH--R wherein R is an aryl or cyano group, (iii) a vinylidene halide, and (iv) a monoethylenically unsaturated monomer having a functional group selected from the class consisting of amide and carboxyl groups; and resin particles which are substantially chemically and physically homogeneous; and (B) about 10 to about 550 g/l of pigment; with other constituents of said autodepositing composition, including acid, oxidizing agent and additional water; wherein the concentration of surfactant, if any, in the aqueous phase of said composition is below the critical micelle concentration.

Claim 32

A process for preparing an autodepositing composition from an aqueous resin/pigment concentrate comprising combining an aqueous resin/pigment concentrate consisting essentially of: (A) about 350 to about 550 g/l of resin particles selected from the class consisting of resin particles prepared by polymerizing (i) a conjugated diene, (ii) CH 2 ═CH--R wherein R is an aryl or cyano group, (iii) a vinylidene halide, and (iv) a monoethylenically unsaturated monomer having a functional group selected from the class consisting of amide and carboxyl groups; and resin particles which are substantially chemically and physically homogeneous; and (B) about 10 to about 550 g/l of pigment; with other constituents of said autodepositing composition, including acid, oxidizing agent and additional water; wherein the concentration of surfactant, if any, in the aqueous phase of said composition is below the critical micelle concentration.

Claim 33

A process according to claim 28 wherein said resin particles comprise the polymerized constituents of: (A) about 25 to about 70 wt. % of said conjugated diene; (B) about 5 to about 70 wt. % of said CH 2 ═CHR; (C) about 1 to about 50 wt. % of said vinylidene halide; and (D) about 0.5 to about 15 wt. % of said unsaturated monomer.

Claim 34

A process according to claim 29 wherein said resin particles comprise the polymerized constituents of: (A) about 40 to about 65 wt. % of said conjugated diene; (B) about 30 to 65 wt. % of said CH 2 ═CHR; (C) about 3 to about 15 wt. % of said vinylidene halide; and (D) about 1 to about 4 wt. % of said unsaturated monomer.

Claim 35

A process according to claim 30 wherein said conjugated diene is butadiene, said CH 2 ═CHR is styrene, said vinylidene halide is vinylidene chloride and said unsaturated monomer is methacrylic acid.

Claim 36

A process according to claim 31 wherein said resin particles are dispersed in said concentrate by an anionic emulsifier and wherein said pigment is dispersed in said concentrate by a nonionic emulsifier.

Claim 37

A process according to claim 32 wherein said pigment is furnace black.

Claim 38

A composition according to claim 1 including also a pigment.

Claim 39

A composition according to claim 25 including also a pigment.

Claim 40

A composition according to claim 35 wherein said pigment is furnace black.

Claim 41

A composition according to claim 1 including also a dye.

Claim 42

A composition according to claim 20 including also hydrogen peroxide.

Claim 43

A method for coating a metallic surface comprising immersing said surface in the composition of claim 1.

Claim 44

A method for coating an iron surface comprising immersing said surface in the composition of claim 14.

Claim 45

A method for coating an iron surface comprising immersing said surface in the composition of claim 20.

Claim 46

A method for coating an iron surface comprising immersing said surface in the composition of claim 27.

Claim 47

A method for coating a steel surface comprising: (A) cleaning the steel surface with a cleaning agent to the extent that a water break-free film can be formed on the surface; (B) water rinsing the cleaned steel surface to remove therefrom residual cleaning agent; (C) immersing said surface in the coating composition of claim 27 for a period of time of about 45 to about 90 seconds to form on the surface a coating having a thickness of about 0.7 to about 1.3 mils; (D) withdrawing the coated surface from the composition, and either immediately or after a partial air dry of about 30 to about 60 seconds, water rinsing the coated surface to remove therefrom residual coating composition and superficial coating film; (E) contacting the coated surface with an aqueous chromium rinse solution comprising about 1 to about 3 g/l of total chromium, with about 0.75 to about 2.25 g/l being hexavalent chromium and the remainder of the chromium being in the reduced state, for about 10 to about 45 seconds; and (F) baking the coated surface at a temperature within the range of about 120° C. to about 180° C. for a period of time for about 10 to about 30 minutes.

Claim 48

A method according to claim 43 wherein said composition includes about 0.2 to 3g of nonionically dispersed furnace black/100 g of resin solids.

Claim 49

A method according to claim 44 wherein said steel surface is hot rolled steel.

Claim 50

A composition according to claim 1 in which the concentration of surfactant, if any, in the aqueous phase of the composition is below the surfactant concentration which corresponds to the inflection point on a graph of surface tension versus the logarithm of surfactant concentration in the composition.

Claim 52

An acidic aqueous coating composition of the type which is effective in forming on a metallic surface immersed therein a resinous coating which increases in weight or thickness the longer said surface is immersed in said composition in the absence of any electrical charge on said metallic surface other than that which may be imparted thereto by said composition, including as activating ingredients ferric iron and fluoride, and including also dispersed pigment, and characterized by the presence therein of anionically dispersed resin particles which are prepared by polymerizing (i) a conjugated diene, (ii) CH 2 ═CH--R wherein R is an aryl or cyano group, (iii) a vinylidene halide, and (iv) a monoethylenically unsaturated monomer having a functional group selected from the class consisting of amide and carboxyl groups, wherein the concentration of surfactant, if any, in the aqueous phase of said composition is below the critical micelle concentration.

Claim 53

An acidic aqueous coating composition of the type which is effective in forming on a metallic surface immersed therein a resinous coating which increases in weight or thickness the longer said surface is immersed in said composition in the absence of any electrical charge on said metallic surface other than that which may be imparted thereto by said composition, including as activating ingredients ferric iron and fluoride, and including also dispersed pigment, and characterized by the presence therein of anionically dispersed resin particles which are prepared by polymerizing (i) a conjugated diene, (ii) CH 2 ═CH--R wherein R is an aryl or cyano group, (iii) a vinylidene halide, and (iv) a monoethylenically unsaturated monomer having a functional group selected from the class consisting of amide and carboxyl groups, wherein the concentration of surfactant, if any, in the aqueous phase of said composition is below the critical micelle concentration.

Claim 54

An acidic aqueous coating composition of the type which is effective in forming on a metallic surface of immersed therein a resinous coating which increases in weight or thickness the longer said surface is immersed in said composition in the absence of any electrical charge on said metallic surface other than that which may be imparted thereto by said composition, including as activating ingredients ferric iron and fluoride, and including also dispersed pigment, and characterized by the presence therein of anionically dispersed resin particles which are substantially chemically and physically homogeneous, wherein the concentration of surfactant, if any, in the aqueous phase of said composition is below the critical micelle concentration.

Claim 55

An acidic aqueous coating composition of the type which is effective in forming on a metallic surface of immersed therein a resinous coating which increases in weight or thickness the longer said surface is immersed in said composition in the absence of any electrical charge on said metallic surface other than that which may be imparted thereto by said composition, including as activating ingredients ferric iron and fluoride, and including also dispersed pigment, and characterized by the presence therein of anionically dispersed resin particles which are substantially chemically and physically homogeneous, wherein the concentration of surfactant, if any, in the aqueous phase of said composition is below the critical micelle concentration.

Claim 56

A composition according to claim 48 or 49 wherein the concentration of surfactant, if any, in the aqueous phase of said composition is below the surfactant concentration which corresponds to the inflection point on a graph of surface tension versus the logarithm of surfactant concentration in the composition.

Claim 57

A composition according to claim 48 wherein said resin particles are substantially chemically and physically homogeneous.

Claim 58

A composition according to claim 50 which said pigment comprises black pigment particles having adsorbed thereon non-ionic dispersing agent.

Claim 59

A composition according to claim 49 including about 50 to 100 g/l of resin particles, ferric fluoride in an amount such that it contains the equivalent of about 0.5 to about 3.5 g/l of ferric iron and about 0.2 to about 5 g/l of HF, and wherein the pH of the composition is within the range of about 1.6 to about 4.

Claim 60

A composition according to claim 14 in which the concentration of surfactant, if any, in the aqueous phase of the composition is below the surfactant concentration which corresponds to the inflection point on a graph of surface tension versus the logarithm of surfactant concentration in the composition.

Claim 61

A composition according to claim 20 in which the concentration of surfactant, if any, in the aqueous phase of the composition is below the surfactant concentration which corresponds to the inflection point on a graph of surface tension versus the logarithm of surfactant concentration in the composition.