# US 10,767,072 B2 · Polymer, process and use

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 10,767,072 B2
- Document ID: US10767072B2
- Status: Granted
- Kind: B2
- Application number: 15/519,354
- Filed: 2015-10-21
- Published: 2017-08-24
- Granted: 2020-09-08
- Earliest claimed: 2014-10-21
- Assignees: Dsm IP Assets B.V.
- Applicants: DSM IP Assets B.V.
- Inventors: Tijs Nabuurs; Willem-Jan Soer; Gerardus Cornelis Overbeek
- Web page: https://patentgrep.com/patent/US10767072B2

## CPC

- C09D 151/003: {grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds (C09D151/04, C09D151/06 take precedence)}
- B05D 7/02: to macromolecular substances, e.g. rubber (treatment or coating of shaped articles made of macromolecular substances C08J7/00)
- B05D 7/08: using synthetic lacquers or varnishes
- B05D 7/14: to metal, e.g. car bodies (involving a chemical reaction between the metal and the coating C23)
- C03C 17/324: {Polyesters}
- C08F 265/06: Polymerisation of acrylate or methacrylate esters on to polymers thereof
- C09D 4/00: Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond {; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16}
- C23C 26/00: Coating not provided for in groups C23C2/00 - C23C24/00
- C08F 265/04: on to polymers of esters
- 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)
- B05D: PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL (conveying articles or workpieces through baths of liquid B65G, e.g. B65G49/02)
- C03C: CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04)

## Abstract

The current invention relates to a process for preparing an aqueous binder composition free of organic solvent, the process comprising at least the following steps: A) preparing a hydrophilic vinyl polymer (Polymer A) by polymerisation of a monomer composition A that contains: Ai) at least one carboxylic acid functional olefinically unsaturated monomer; and Aii) at least one olefinically unsaturated monomer different than Ai); and Aiii) optionally at least one wet adhesion promoting olefinically unsaturated monomer different than Ai and Aii); where Polymer A has an acid value (AV) from 32 to 98 mg KOH/g of solid Polymer A; B) preparing a hydrophobic vinyl polymer (Polymer B) by emulsion polymerization of a monomer composition B in the presence of Polymer A where the monomer composition B contains: Bi) at least one olefinically unsaturated monomer; Bii) optionally carboxylic acid functional olefinically unsaturated monomer different than Bi); and Biii) optionally wet adhesion promoting olefinically unsaturated monomer different than Bi); where Polymer B has an acid value (AV) of no more than 23.4 mg KOH/g of solid polymer B, wherein at least a part of the carboxylic acid groups that are present in Polymer A and Polymer B are neutralized during or following the steps A and/or B to form a (partially) neutralized polymer emulsion; where the weight average molecular weight (Mw) of Polymer A is lower than the weight average molecular weight (Mw) of polymer B; and wherein the process is further characterized by the presence of a further step C) reacting at least 10 mol % of the carboxylic acid and/or carboxylate salt groups of the (partially) neutralized polymer emulsion with an iminating agent to produce an iminated polymer C; wherein the total amount of surfactant applied in steps A, B and C is at most 0.5 wt. %, based on the total weight of monomers charged for the preparation of polymer A and polymer B.

## Claims

### Claim 1

A process for preparing an aqueous binder composition free of organic solvent, the process comprising at least the following steps:
A) preparing a hydrophilic vinyl polymer (Polymer A) having an acid value (AV) from 32 to 98 mg KOH/g of solid Polymer A by polymerizing a monomer composition A that comprises:
Ai) at least one carboxylic acid functional olefinically unsaturated monomer;
Aii) at least one olefinically unsaturated monomer different than monomer Ai); and
Aiii) optionally at least one wet adhesion promoting olefinically unsaturated monomer different than monomers Ai) and Aii); and
B) preparing a hydrophobic vinyl polymer (Polymer B) having an acid value (AV) of no more than 23.4 mg KOH/g of solid Polymer B by emulsion polymerization of a monomer composition B in the presence of the Polymer A, wherein the monomer composition B comprises:
Bi) at least one olefinically unsaturated monomer;
Bii) optionally a carboxylic acid functional olefinically unsaturated monomer different than monomer Bi); and
Biii) optionally a wet adhesion promoting olefinically unsaturated monomer different than monomer Bi); wherein
at least a part of the carboxylic acid groups that are present in Polymer A and Polymer B are neutralized during or following the step A and/or during the step B to form at least a partially neutralized polymer emulsion; wherein
the Polymer A has a weight average molecular weight (Mw) that is lower than a weight average molecular weight (Mw) of the Polymer B; and
the process further comprises the step of:
C) reacting at least 10 mol % of the carboxylic acid and/or carboxylate salt groups of the at least partially neutralized polymer emulsion with an iminating agent to produce an iminated Polymer C; wherein
surfactant in steps A), B) and C) is present in a total amount of at most 0.5 wt. %, based on total weight of monomers present for preparing the Polymers A and B.

### Claim 2 (depends on 1)

The process according to claim 1, wherein the surfactant in steps A), B) and C) is present in a total amount of at most 0.2 wt. %, based on the total weight of monomers present for the preparing the Polymers A and B.

### Claim 3 (depends on 1)

The process according to claim 1, further comprising adding the total amount of surfactant at the start of step A) and/or during step A).

### Claim 4 (depends on 1)

The process according to claim 1, which comprises reacting from 10 mol % to 90 mol % of the total amount of carboxylic acid and carboxylate salt groups present in the at least partially neutralized polymer emulsion with an iminating agent to produce the iminated Polymer C.

### Claim 5 (depends on 1)

The process according to claim 1, wherein the iminating agent is propyleneimine.

### Claim 6 (depends on 1)

The process according to claim 1, wherein the carboxylic acid and carboxylate salt groups that are reacted with the iminating agent is determined such that the degree of iminization is between DI low and DI high determined by the following formulas:
DILOW(%)=[(AV*0.682)−11.8]*100%,
DIHIGH(%)=[(AV*1.061)−14]*100%,
where AV is the AV of the at least partially neutralized polymer emulsion.

### Claim 7 (depends on 1)

The process according to claim 1, wherein the monomer Ai) is present in an amount from 5 to 15 wt. %, relative to the total weight of monomers present for preparing the polymer A.

### Claim 8 (depends on 1)

The process according to claim 1, wherein polymer A is a reaction product of the monomer composition A which comprises:
Ai) from 5 to 15 wt. %, of the at least one carboxylic acid functional olefinically unsaturated monomer; and
Aii) from 85 to 95 wt. % of the at least one olefinically unsaturated monomer different than monomer Ai), wherein
amounts of monomers Ai) and Aii) are relative to total weight of monomers present for preparing the Polymer A, and wherein the amounts of monomers Ai) and Aii) add up to 100 wt. %.

### Claim 9 (depends on 1)

The process according to claim 1, wherein the Polymer B has an acid value of no more than 6.5 mg KOH/g of solid Polymer B.

### Claim 10 (depends on 1)

The process according to claim 1, which comprises neutralizing from 40 to 100 mol % of the total amount of carboxylic acid groups present in the Polymers A and B during or following the steps A) and/or B).

### Claim 11 (depends on 1)

The process according to claim 1, wherein
a) the Polymer A has a Tg from 40° C. to 125° C.; and
b) the Polymer B has a Tg which is at least 25° C. below the Tg of the Polymer A.

### Claim 12 (depends on 1)

The process according claim 1, wherein
a) the Polymer A has a Tg<50° C.; and
b) the Polymer B has a Tg which is at least 25° C. higher than the Tg of the Polymer A.

### Claim 13 (depends on 1)

The process according to claim 1, wherein step A) comprises preparing the Polymer A by emulsion polymerization.

### Claim 14 (depends on 1)

The process according to claim 1, wherein the carboxylic acid functional olefinically unsaturated monomers Ai) and Bii) are selected from the group consisting of acrylic acid, methacrylic acid, and β-carboxyethyl acrylate and combinations thereof.

### Claim 15 (depends on 1)

The process according claim 1, wherein the monomers Aii) and Bi) are selected from the group consisting of acrylates, methacrylates, arylalkylenes and mixtures thereof.

### Claim 16 (depends on 1)

The process according to claim 1, wherein at least a part of the monomers Aii) and Bi) contain functional groups for imparting crosslinkability when the aqueous binder composition is subsequently dried.

### Claim 17 (depends on 1)

The process according to claim 1, wherein the weight average molecular weight of Polymer A has a weight average molecular weight which is less than 100 kDalton and higher than 2 kDalton.

### Claim 18 (depends on 1)

An aqueous binder composition obtained by the process according to claim 1.

### Claim 19 (depends on 18)

The aqueous binder composition according to claim 18, wherein the binder composition comprises the Polymer C in an amount which is at least 10 wt. % and at most 90 wt. %, relative to the total amount of binders in the aqueous binder composition.

### Claim 20 (depends on 1)

An aqueous coating composition comprising an aqueous binder which is prepared by the process according to claim 1.

### Claim 21 (depends on 20)

A method of protective coating of a substrate comprising the steps of:
(1) applying the aqueous coating composition according to claim 20 to a substrate formed of at least one material selected from the group consisting of lignocellulosic material, aged alkyd resin, plastic, metal and glass-containing composite materials to form a coating thereon, and
(2) drying the coating to form a coated substrate.