# US 9,040,617 B2 · Aqueous cross-linking compositions and methods

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- Number: US 9,040,617 B2
- Document ID: US9040617B2
- Status: Granted
- Kind: B2
- Application number: 13/762,616
- Filed: 2013-02-08
- Published: 2014-08-14
- Granted: 2015-05-26
- Earliest claimed: 2010-06-04
- Assignees: Columbia Insurance Company
- Applicants: Columbia Insurance Company
- Inventors: Yong Yang; Johanna L. Garcia de Visicaro; Robert Sheerin; Steve Minassian; Glenn Cooper
- Web page: https://patentgrep.com/patent/US9040617B2

## CPC

- C09D 133/26: Homopolymers or copolymers of acrylamide or methacrylamide
- C08F 220/12: of monohydric alcohols or phenols
- C09D 133/068: {containing glycidyl groups}
- C09D 133/08: Homopolymers or copolymers of acrylic acid esters
- C09D 143/02: Homopolymers or copolymers of monomers containing phosphorus
- C08L 2201/54: Aqueous solutions or dispersions
- 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)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)

## Abstract

Water-borne cross-linking polymeric compositions and related embodiments, such as methods of making and using the compositions, as well as products formed with said compositions are described. The water-borne composition may comprise one or more polymers formulated from one or more monomers of which at least one is a monomer that yields acetaldehyde as a hydrolysis product, and incorporating cross-linking functionality such as, but not limited to, carbonyl or epoxy functionality, and a blocked cross-linking agent, for example, a hydrazone. Neither the cross-linking functionality nor the acetaldehyde reacts with the blocked cross-linking agent; however, the blocked cross-linking agent is capable of conversion to an alternative form cross-linking agent such as, but not limited to, a hydrazide, to yield a cross-linked polymer. The alternative form cross-linking agent may be formed in an equilibrium reaction including the blocked cross-linking agent.

## Claims

### Claim 1

A water-borne polymeric composition, which consists essentially of
water;
one or more polymers formulated from one or more monomers of which at least one is a monomer that yields acetaldehyde as a hydrolysis product, said one or more polymers being for coalescence or drying into polymer solids, each polymer comprising one or more carbonyl groups, one or more epoxy groups, or both one or more carbonyl groups and one or more epoxy groups; and
a cross-linking agent, as well as a blocked cross-linking agent having at least one hydrazone group incorporated therein, along with an amount of a ketone or aldehyde, the blocked cross-linking agent being the reaction product of the ketone or aldehyde with the cross-linking agent, the composition being such that in its equilibrium state as formulated the cross-linking agent constitutes 3% or less of the aggregate cross-linking and blocked cross-linking functional groups, and further such that a reduction of the amount of ketone or aldehyde causes the equilibrium to be shifted substantially toward the cross-linking agent's production.

### Claim 2 (depends on 1)

The water-borne polymeric composition of claim 1, wherein each said monomer that yields acetaldehyde is selected from the group consisting of vinyl alkyl esters.

### Claim 3 (depends on 2)

The water-borne polymeric composition of claim 2, wherein said monomer is vinyl acetate.

### Claim 4 (depends on 1)

The water-borne polymeric composition of claim 1, wherein said one or more polymers comprise different chain copolymers each with one or more reactive carbonyl groups, one or more reactive epoxy groups, or both one or more reactive carbonyl groups and one or more reactive epoxy groups, present in the composition in a range of 3% to 60% by weight.

### Claim 5 (depends on 1)

The water-borne polymeric composition of claim 1, wherein the blocked cross-linking agent comprises at least two hydrazone groups.

### Claim 6 (depends on 1)

The water-borne polymeric composition of claim 1, wherein the blocked cross-linking agent further comprises a hydrazine group.

### Claim 7 (depends on 1)

The water-borne polymeric composition of claim 1, wherein the pH of the composition is from 6.5 to 10.3.

### Claim 8 (depends on 7)

The water-borne polymeric composition of claim 7, wherein the pH of the composition is from 8.0 to 9.8.

### Claim 9 (depends on 8)

The water-borne polymeric composition of claim 8, wherein the pH of the composition is from 8.5 to 9.5.

### Claim 10 (depends on 1)

The water-borne polymeric composition of claim 1, wherein there is at least one blocked cross-linking agent of the formula:
and/or at least one blocked cross-linking agent of the formula
wherein R is a divalent organic group or a covalent bond, and each of R1, R2, R3, and R4 is selected to be independently of the others hydrogen or an organic group.

### Claim 11 (depends on 10)

The water-borne polymeric composition of claim 10, wherein each of R1, R2, R3, and R4 is selected to be, independently of the others: C1 to C12 linear alkyl, alkenyl, or alkynyl; or a branched alkyl, alkenyl, or alkynyl having a C1 to C12 primary chain; or R1 and R2 or R3 and R4 are joined together to form a cyclic organic group or said linear or branched alkyl, alkenyl, or alkynyl being substituted with an hydroxyl, amino, phenyl, benzyl, or halogen.

### Claim 12 (depends on 11)

The water-borne polymeric composition of claim 11, wherein each of R1, R2, R3, and R4 is selected to be independently of the others methyl, ethyl, n-propyl, n-butyl, iso-butyl, tert-butyl, n-amyl, iso-amyl, n-hexyl, n-heptyl, n-octyl, iso-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.

### Claim 13 (depends on 11)

The water-borne polymeric composition of claim 11, wherein the cyclic group is cyclopentyl or cyclohexyl.

### Claim 14 (depends on 1)

The water-borne polymeric composition of claim 1, wherein the carbonyl is incorporated within a ketone, aldehyde, or anhydride group.

### Claim 15 (depends on 1)

The water-borne polymeric composition of claim 1, wherein the polymeric composition functions as a paint, primer, other coating, ink, or adhesive.

### Claim 16 (depends on 5)

The water-borne polymeric composition of claim 5, wherein the blocked cross-linking agent has the following formula:
wherein R is a divalent organic group or a covalent bond and each of R1, R2, R3, and R4 is selected to be independently of the others hydrogen or an organic group.

### Claim 17 (depends on 16)

The water-borne polymeric composition of claim 16, wherein R is oxalic, malonic, succinic, glutaric, adipic or sebacic.

### Claim 18

A water-borne polymeric composition, which consists essentially of
water;
one or more polymers formulated from one or more monomers of which at least one is a monomer that yields acetaldehyde as a hydrolysis product, said one or more polymers being for coalescence or drying into polymer solids, each polymer comprising one or more carbonyl groups, one or more epoxy groups, or both one or more carbonyl groups and one or more epoxy groups; and
a cross-linking agent, as well as a blocked cross-linking agent having at least one hydrazone group incorporated therein, along with an amount of a ketone or aldehyde, the blocked cross-linking agent being the reaction product of the ketone or aldehyde with the cross-linking agent, the composition being such that in its equilibrium state as formulated the cross-linking agent constitutes 3% or less of the aggregate cross-linking and blocked cross-linking functional groups, and further such that a reduction of the amount of ketone or aldehyde causes the equilibrium to be shifted substantially toward the cross-linking agent's production,
wherein the blocked cross-linking agent has the following formula:
wherein R is a divalent organic group or a covalent bond and each of R′ and R″ is selected to be independently of the other a cyclic organic group.

### Claim 19 (depends on 1)

The water-borne polymeric composition of claim 1, wherein the blocked cross-linking agent is adipic di(2-butylidene hydrazide).

### Claim 20

A method of preparing a water-borne composition, which consists essentially of combining:
an aqueous dispersion of one or more cross-linkable polymers, wherein at least one polymer in the dispersion is formulated from one or more monomers of which at least one is a monomer that yields acetaldehyde as a hydrolysis product, said one or more polymers being for coalescence or drying into polymer solids, each polymer comprising one or more carbonyl groups, one or more epoxy groups, or both one or more carbonyl groups and one or more epoxy groups; and
a cross-linking agent, as well as a blocked cross-linking agent having at least one hydrazone group incorporated therein, along with an amount of a ketone or aldehyde, the blocked cross-linking agent being the reaction product of the ketone or aldehyde with the cross-linking agent, the composition being such that in its equilibrium state as formulated the cross-linking agent constitutes 3% or less of the aggregate cross-linking and blocked cross-linking functional groups, and further such that a reduction of the amount of ketone or aldehyde causes the equilibrium to be shifted substantially toward the cross-linking agent's production.

### Claim 21

A method of making a cross-linked polymeric material, which consists essentially of combining into a composition
an aqueous dispersion of a first polymer moiety and a second polymer moiety, said moieties being of the same or different polymers, each said moiety having incorporated therein one or more carbonyl groups, one or more epoxy groups, or both one or more carbonyl groups and one or more epoxy groups, at least one of said polymer moieties being formulated from one or more monomers of which at least one is a monomer that yields acetaldehyde as a hydrolysis product; and
a cross-linking agent, as well as a blocked cross-linking agent having at last one hydrazone group incorporated therein, along with an amount of a ketone or aldehyde, the blocked cross-linking agent being the reaction product of the ketone or aldehyde with the cross-linking agent, the composition being such that in its equilibrium state as formulated the cross-linking agent constitutes 3% or less of the aggregate cross-linking and blocked cross-linking functional groups; and
bringing about a reduction of the amount of ketone or aldehyde which causes the equilibrium to be shifted substantially toward the cross-linking agent's production.

### Claim 22

A method of coating a surface, consisting essentially of:
applying a water-borne polymeric dispersion on a surface, wherein the aqueous polymeric dispersion comprises water, one or more polymers, at least one of the polymers being formulated from one or more monomers of which at least one is a monomer that yields acetaldehyde as a hydrolysis product, said one or more polymers each comprising one or more carbonyl groups, one or more epoxy groups or a combination of one or more carbonyl groups and one or more epoxy groups, a cross-linking agent, and a blocked cross-linking agent having at least one hydrazone group incorporated therein, along with an amount of a ketone or aldehyde, the blocked cross-linking agent being the reaction product of the ketone or aldehyde with the cross-linking agent, the polymeric dispersion being such that in its equilibrium state as formulated the cross-linking agent constitutes 3% or less of the aggregate cross-linking and blocked cross-linking functional groups, and further such that a reduction of the amount of ketone or aldehyde causes the equilibrium to be shifted substantially toward the cross-linking agent's production.

### Claim 23

A water-borne primer latex, comprising:
water;
one or more polymers having a number average molecular weight less than 100,000 Daltons, and a glass transition temperature less than 10° C., each of said polymers being formulated from one or more monomers of which at least one is a monomer that yields acetaldehyde as a hydrolysis product, and having one or more carbonyl groups, one or more epoxy groups, or a combination of one or more carbonyl groups and one or more epoxy groups; and
a blocked cross-linking agent having at least one hydrazone group incorporated therein.

### Claim 24 (depends on 23)

The water-borne primer latex of claim 23, wherein said glass transition temperature is less than 6° C.

### Claim 25 (depends on 23)

The water-borne primer latex of claim 23, wherein said glass transition temperature is less than 4° C.

### Claim 26 (depends on 23)

The water-borne primer latex of claim 23, wherein said number average molecular weight is less than 50,000 Daltons.

### Claim 27 (depends on 23)

The water-borne primer latex of claim 23, wherein said number average molecular weight is less than 25,000 Daltons.

### Claim 28 (depends on 23)

The water-borne primer latex of claim 23, wherein each of the polymers is present in the composition in a range of 3% to 60% by weight.

### Claim 29 (depends on 23)

The water-borne primer latex of claim 23, wherein a ratio of the moles of blocked cross-linking agent and the number of reactive carbonyl and epoxy groups on the polymer chains is from 0.1:1 to 2:1.

### Claim 30 (depends on 23)

The water-borne primer latex of claim 23, wherein the blocked cross-linking agent comprises at least two hydrazone groups.

### Claim 31 (depends on 23)

The water-borne primer latex of claim 23, wherein the blocked cross-linking agent further comprises a hydrazine group.

### Claim 32 (depends on 23)

The water-borne primer latex of claim 23, wherein the pH of the composition is from 6.5 to 10.3.

### Claim 33 (depends on 23)

The water-borne primer latex of claim 23, wherein the blocked cross-linking agent is of the formula:
or
a combination thereof;
wherein R is a divalent organic group or a covalent bond, and each of R1, R2, R3, and R4 is selected to be independently of the others hydrogen or an organic group.

### Claim 34 (depends on 33)

The water-borne primer latex of claim 33, wherein each of R1, R2, R3, and R4 is selected to be independently of the others: C1 to C12 linear alkyl, alkenyl, or alkynyl group; a branched alkyl, alkenyl, or alkynyl group having a C1 to C12 primary chain; or R1 and R2 or R3 and R4 joined together to form a cyclic organic group or said linear or branched alkyl, alkenyl, or alkynyl group substituted with an hydroxyl, amino, phenyl, benzyl, or halogen.

### Claim 35 (depends on 34)

The water-borne primer latex of claim 34, wherein each of R1, R2, R3, and R4 is selected to be independently of the others methyl, ethyl, n-propyl, n-butyl, iso-butyl, tert-butyl, n-amyl, iso-amyl, n-hexyl, n-heptyl, n-octyl, iso-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.

### Claim 36 (depends on 34)

The water-borne primer latex of claim 34, wherein the cyclic group is cyclopentyl or cyclohexyl.

### Claim 37 (depends on 23)

The water-borne primer latex of claim 23, wherein the carbonyl is incorporated within ketone, aldehyde, or anhydride group.

### Claim 38 (depends on 31)

The water-borne primer latex of claim 31, wherein the blocked cross-linking agent has the following formula:
wherein R is a divalent organic group or a covalent bond and each of R1, R2, R3, and R4 is selected to be independent of the others hydrogen or an organic group.

### Claim 39 (depends on 38)

The water-borne primer latex of claim 38, wherein R is oxalic, malonic, succinic, glutaric, adipic or sebacic.

### Claim 40 (depends on 23)

The water-borne primer latex of claim 23, wherein the blocked cross-linking agent has the following formula:
wherein R is a divalent organic group or a covalent bond and each of R′ and R″ is selected to be independently of the other a cyclic organic group.

### Claim 41 (depends on 23)

The water-borne primer latex of claim 23, wherein the blocked cross-linking agent is adipic di(2-butylidene hydrazide).

### Claim 42 (depends on 22)

A coating which is formed in accordance with the method defined in claim 22.

### Claim 43 (depends on 1)

The water-borne composition of claim 1, wherein the composition is such that said reduction of the amount of ketone or aldehyde causes the equilibrium to be shifted toward the cross-linking agent's production with nearly all of the blocked cross-linking agent eventually being converted to the cross-linking agent.

### Claim 44 (depends on 1)

The water-borne composition of claim 1, wherein the ketone or aldehyde has a boiling point below 200° C., a vapor pressure at 25° C. above 1.7 mm Hg, and an evaporation rate (versus butyl acetate) above 0.1.

### Claim 45 (depends on 44)

The water-borne composition of claim 44, wherein the ketone or aldehyde has a boiling point below 150° C., a vapor pressure at 25° C. above 15 mm Hg, and an evaporation rate (versus butyl acetate) above 0.2.

### Claim 46 (depends on 45)

The water-borne composition of claim 45, wherein the ketone or aldehyde has a boiling point below 100° C., a vapor pressure at 25° C. above 23 mm Hg, and an evaporation rate (versus butyl acetate) above 0.3.

### Claim 47 (depends on 18)

The water-borne composition of claim 18, wherein the composition is such that said reduction of the amount of ketone or aldehyde causes the equilibrium to be shifted toward the cross-linking agent's production with nearly all of the blocked cross-linking agent eventually being converted to the cross-linking agent.

### Claim 48 (depends on 20)

The method of claim 20, wherein the composition is such that said reduction of the amount of ketone or aldehyde causes the equilibrium to be shifted toward the cross-linking agent's production with nearly all of the blocked cross-linking agent eventually being converted to the cross-linking agent.

### Claim 49 (depends on 21)

The method of claim 21, wherein the equilibrium is caused to be shifted toward the cross-linking agent's production with nearly all of the blocked cross-linking agent eventually being converted to the cross-linking agent.

### Claim 50 (depends on 22)

The method of claim 22, wherein the equilibrium is caused to be shifted toward the cross-linking agent's production with nearly all of the blocked cross-linking agent eventually being converted to the cross-linking agent.