# US 9,752,056 B2 · Radiation-curing, water-dispersible polyurethane (meth)acrylates

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- Number: US 9,752,056 B2
- Document ID: US9752056B2
- Status: Granted
- Kind: B2
- Application number: 14/429,456
- Filed: 2013-10-09
- Published: 2015-08-13
- Granted: 2017-09-05
- Earliest claimed: 2012-10-24
- Assignees: BASF SE
- Applicants: BASF SE
- Inventors: Sebastian Berger; Peter Thuery; Susanne Neumann; Tanja Becker; Axel Becker
- Web page: https://patentgrep.com/patent/US9752056B2

## CPC

- C09D 175/16: having terminal carbon-to-carbon unsaturated bonds
- B05D 3/067: {Curing or cross-linking the coating}
- C08G 18/0823: {containing carboxylate salt groups or groups forming them}
- C08G 18/10: Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G 18/227: {of antimony, bismuth or arsenic}
- C08G 18/283: {Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds}
- C08G 18/2865: {Compounds having only one primary or secondary amino group; Ammonia}
- C08G 18/3206: {aliphatic}
- C08G 18/348: {Hydroxycarboxylic acids}
- C08G 18/4216: {from mixtures or combinations of aromatic dicarboxylic acids and aliphatic dicarboxylic acids and dialcohols}
- C08G 18/6659: {with compounds of group C08G18/34}
- C08G 18/672: {Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen}
- C08G 18/675: {Low-molecular-weight compounds}
- C08G 18/722: {Combination of two or more aliphatic and/or cycloaliphatic polyisocyanates}
- C08G 18/755: {and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate}
- C08G 18/792: {formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates}
- Y10T 428/31551: Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T 428/31591: Next to cellulosic
- 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)
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

The present invention describes radiation-curable, water-dispersible polyurethane acrylates which feature good grain highlighting, their use, and the method for producing them.

## Claims

### Claim 1

A urethane (meth)acrylate (A) comprising a reaction product of:
(a) at least one (cyclo)aliphatic di- and/or polyisocyanate,
(b1) at least one (cyclo)aliphatic diol having a molar mass of less than 700 g/mol,
(b2) at least one polyesterdiol having a weight-average molar mass Mw of 700 to 2000 and optionally an acid number to DIN 53240 of not more than 20 mg KOH/g,
(c) at least one compound (c) having at least one isocyanate-reactive group and at least one radically polymerizable unsaturated group,
(d) at least one compound which has at least one isocyanate-reactive group and at least one acid group,
(e) at least one base for at least partial neutralization of at least one acid group of component (d), being different from components (h1) and (h2),
(f) optionally at least one monoalcohol, having precisely one hydroxyl function,
(g) optionally at least one monofunctional polyalkylene oxide polyether alcohol,
(h1) at least one monoamine which is substituted by one or two hydrocarbon radicals, in which the one or two hydrocarbon radicals together have at least 12 carbon atoms, and
(h2) optionally at least one compound having at least two primary and/or secondary amino groups,
wherein the urethane (meth)acrylate (A) is obtained by a process comprising reacting at least a portion of components (b1), (b2), and (c) with component (a).

### Claim 2 (depends on 1)

The urethane (meth)acrylate according to claim 1, wherein component (a) is a mixture of an aliphatic di- and/or polyisocyanate (a1) and a cycloaliphatic di- and/or polyisocyanate (a2).

### Claim 3 (depends on 1)

The urethane (meth)acrylate according to claim 1, wherein component (b1) is at least one selected from the group consisting of ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2,2-dimethyl-1,2-ethanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, and diethylene glycol.

### Claim 4 (depends on 1)

The urethane (meth)acrylate according to claim 1, wherein component (b2) is a polyesterdiol synthesized at least partly from aliphatic diol and/or dicarboxylic acid building blocks.

### Claim 5 (depends on 1)

The urethane (meth)acrylate according to claim 1, wherein component (c) is at least one selected from the group consisting of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2- or 3-hydroxypropyl acrylate, 1,4-butanediol monoacrylate, glyceryl 1,2- or 1,3-diacrylate, trimethylolpropane diacrylate, pentaerythrityl triacrylate, ditrimethylolpropane triacrylate, and dipentaerythrityl pentaacrylate.

### Claim 6 (depends on 1)

The urethane (meth)acrylate according to claim 1,
wherein compound (c) is an epoxy (meth)acrylate of the formula:
where
R1 is hydrogen or methyl.

### Claim 7 (depends on 1)

The urethane (meth)acrylate according to claim 1, wherein component (d) is at least one selected from the group consisting of dimethylolpropionic acid and dimethylolbutyric acid.

### Claim 8 (depends on 1)

The urethane (meth)acrylate according to claim 1,
wherein
the one or two hydrocarbon radicals of the compound (h1) are one or two alkyl radicals, and
both alkyl radicals each independently of one another comprise at least six carbon atoms.

### Claim 9 (depends on 1)

The urethane (meth)acrylate (A) according to claim 1, comprising a reaction product of
(a) at least one (cyclo)aliphatic di- and/or polyisocyanate,
(b1) at least one (cyclo)aliphatic diol having a molar mass of less than 700 g/mol,
(b2) at least one polyesterdiol having a weight-average molar mass Mw of 700 to 2000 and optionally an acid number to DIN 53240 of not more than 20 mg KOH/g,
(c) at least one compound (c) having at least one isocyanate-reactive group and at least one radically polymerizable unsaturated group,
(d) at least one compound which has at least one isocyanate-reactive group and at least one acid group,
(e) at least one base for at least partial neutralization of at least one acid group of component (d), being different from components (h1) and (h2),
(f) at least one monoalcohol, having precisely one hydroxyl function,
(g) at least one monofunctional polyalkylene oxide polyether alcohol,
(h1) at least one monoamine which is substituted by one or two hydrocarbon radicals, in which the one or two hydrocarbon radicals together have at least 12 carbon atoms, and
(h2) at least one compound having at least two primary and/or secondary amino groups.

### Claim 10 (depends on 1)

The urethane (meth)acrylate (A) of claim 1, obtained by a process that comprises reacting at least a portion of components (b1), (b2), and (c) with component (a) to obtain a reaction mixture, and then, after the reacting substantially consumes components of the reaction mixture, adding component (h1).

### Claim 11 (depends on 1)

A coating material, comprising:
the urethane (meth)acrylate according to claim 1.

### Claim 12 (depends on 1)

A coating material comprising:
the urethane (meth)acrylate according to claim 1 and
a (meth)acrylate (B) which has at least two (meth)acrylate functions and an average molecular weight of up to 1000 g/mol.

### Claim 13 (depends on 12)

The coating material according to claim 12,
wherein the (meth)acrylate (B) is a compound of the formula (VIIIa) to (VIIId):
where
R7 and R8 independently of one another are hydrogen or optionally aryl-, alkyl-, aryloxy-, alkyloxy-, heteroatom- and/or heterocycle-substituted C1-C18 alkyl,
k, l, m, q independently of one another are each an integer from 1 to 10, and
each Xi for i=1 to k, 1 to l, 1 to m, and 1 to q is optionally selected independently of one another from the group consisting of —CH2—CH2—O—, —CH2—CH(CH3)—O—, —CH(CH3)—CH2—O—, —CH2—C(CH3)2—O—, —C(CH3)2—CH2—O—, —CH2—CHVin-O—, —CHVin-CH2—O—, —CH2—CHPh-O—, and —CHPh-CH2—O—,
where Ph is phenyl and Vin is vinyl.

### Claim 14 (depends on 12)

A substrate coated with the coating material according to claim 12.

### Claim 15 (depends on 12)

A method for coating a substrate, the method comprising:
applying the coating material of claim 12 to the substrate, thereby producing an applied substrate,
drying the applied substrate, thereby producing a dried substrate and
radiation-curing the dried product.

### Claim 16 (depends on 1)

A substrate coated with the urethane (meth)acrylate according to claim 1.

### Claim 17 (depends on 16)

The substrate according to claim 16, comprising: coated oak, spruce, pine, beech, maple, chestnut, plane, robinia, ash, birch, stone pine, elm, walnut, or macore.

### Claim 18 (depends on 16)

The substrate according to claim 16 coated with the urethane (meth)acrylate, wherein the substrate is wood, paper, textile, leather, nonwoven, plastics surfaces, glass, ceramic, mineral building materials, metals, coated metals, paper, paperboard, or cardboard.

### Claim 19 (depends on 16)

The substrate according to claim 16 coated with the urethane (meth)acrylate, wherein the substrate is oak, spruce, pine, beech, maple, chestnut, plane, robinia, ash, birch, stone pine, elm, walnut, macore, or cork.

### Claim 20 (depends on 1)

A method for coating a substrate, the method comprising:
applying the urethane (meth)acrylate according to claim 1 to the substrate, thereby producing an applied substrate,
drying the applied substrate, thereby producing a dried substrate and
radiation-curing the dried product.

### Claim 21 (depends on 20)

The method according to claim 20, wherein the substrate comprises: coated oak, spruce, pine, beech, maple, chestnut, plane, robinia, ash, birch, stone pine, elm, walnut, or macore.