Solvent-free aqueous polyurethane dispersions and methods of producing solvent-free aqueous polyurethane dispersions

Patent metadata

Field	Value
Publication number	US-10329449-B2
Application number	US-201415038079-A
Country	US
Kind code	B2
Filing date	Nov 21, 2014
Priority date	Nov 22, 2013
Publication date	Jun 25, 2019
Grant date	Jun 25, 2019

Abstract

A solvent-free aqueous curable polyurethane dispersion is derived from at least one isocyanate-terminated ethylenically unsaturated polyurethane pre-polymer in a reactive diluent. The polyurethane pre-polymer comprises at least one (meth)acrylate functional group and at least one isocyanate functional group. Methods for making a solvent-free aqueous polyurethane dispersion, curable compositions comprising the dispersion and resulting cured products are also disclosed.

First claim

The invention claimed is:

1. An aqueous curable polyurethane dispersion, comprising a polyurethane polymer in at least one reactive diluent (F), wherein said polyurethane polymer is formed by chain extending at least one isocyanate-terminated ethylenically unsaturated polyurethane pre-polymer (P), with at least one chain extender (E) bearing at least 2 isocyanate-reactive groups, wherein said pre-polymer is formed by reacting:
(A) one or more isocyanate reactive components comprising (A1) a monoalcohol of formula (1) below bearing 3 (meth)acrylate groups and (A2) a diol of formula (2) below bearing 2 (meth)acrylate groups

(B) one or more polyisocyanates;
(C) one or more isocyanate reactive components containing ionic groups, potentially ionic groups or hydrophilic ether groups with said component (C) bearing two isocyanate reactive groups; and
(D) optionally, one or more isocyanate reactive components other than component (A) or component (C), bearing two isocyanate reactive groups, such that the mole ratios of components (A), (B), (C) and (D) result in a polyurethane pre-polymer comprising terminal isocyanate groups,
when A′ and B′ represent the residues of corresponding polyols (tetrols) partially esterified by acrylic acid and which may be linear, cyclic, or branched, substituted or unsubstituted hydrocarbon chains, the optional substituents including cyclic groups, heteroatoms or both and wherein the polyurethane dispersion is free of non-reactive solvent.

2. The polyurethane dispersion of claim 1 , wherein the polyurethane dispersion is a radiation curable dispersion.

3. The polyurethane dispersion of claim 2 , wherein the polyurethane dispersion is an actinic radiation curable dispersion.

4. The polyurethane dispersion of claim 3 , wherein said actinic radiation is: UV, LED, laser, or visible light radiation.

5. The polyurethane dispersion of claim 1 , wherein the polyurethane polymer is substantially free of terminal isocyanate groups.

6. The polyurethane dispersion of claim 1 , wherein said component (C) is a diol bearing an ionic group resulting from an acidic group chosen from carboxylic, sulfonic, phosphonic or phosphinic groups, with said group being at least partly neutralized with a basic agent.

7. The polyurethane dispersion of claim 1 , wherein the polyurethane pre-polymer is further reacted with a component (E), comprising at least two isocyanate reactive groups.

8. The polyurethane dispersion of claim 7 , wherein said component (E) comprising at least two isocyanate reactive groups is selected from diamines.

9. The polyurethane dispersion of claim 1 , wherein said reactive diluent (F) represents from about 10% to about 90% by weight relative to the solids content of the dispersion.

10. The polyurethane dispersion of claim 9 , wherein said diluent (F) represents from 10 to 50% by weight relative to the solids content of the dispersion.

11. The polyurethane dispersion of claim 1 , wherein said polyurethane polymer bears ethylenic unsaturation end-groups and optionally side-groups.

12. The polyurethane dispersion of claim 1 , wherein said polyisocyanate (B) is a diisocyanate.

13. The polyurethane dispersion of claim 1 , wherein said one or more isocyanate reactive components contain said ionic groups and said ionic groups of component (C) is derived from acidic groups.

14. The polyurethane dispersion of claim 1 , wherein said component (C) bears two OH groups.

15. The polyurethane dispersion of claim 1 , wherein optional component (D) is present and said component (I)) bears two OH groups.

16. A curable aqueous composition comprising as a reactive binder at least one polyurethane dispersion as defined according to claim 1 .

17. The curable aqueous composition of claim 16 , wherein the composition is a radiation curable composition.

18. The curable composition of claim 16 , wherein the composition is a coating composition for substrates selected from the group consisting of wood, plastic, metal, glass, fibers, textiles, leather, stone, concrete, ceramic and a composite.

19. The curable composition of claim 17 , wherein the composition is an actinic radiation curable composition.

20. A method of coating a substrate selected from the group consisting of wood, plastic, metal, glass, fibers, textiles, leather, stone, ceramic, concrete and a composite, with said method comprising:
i) coating the substrate with the polyurethane dispersion as defined according to claim 1 ;
ii) removing the water and
iii) curing the coating with radiation.

21. A cured product, wherein the cured product results from the use of at least one polyurethane dispersion as defined according to claim 1 .

22. The cured product of claim 21 , wherein the cured product is selected from the group consisting of coatings, adhesives, inks, sealants and cosmetics.

23. A method for producing an aqueous polyurethane dispersion, said method comprising:
i) reacting in at least one reactive diluent (F) to form a polyurethane pre-polymer (P):
(A) one or more isocyanate reactive components comprising: (A1) a monoalcohol of formula (1) below bearing 3 (meth)acrylate groups and (A2) a diol of formula (2) below bearing 2 (meth)acrylate groups

(B) one or more di- or polyisocyanates:
(C) one or more isocyanate reactive components containing ionic groups, potentially ionic groups or hydrophilic ether groups, with said component (C) bearing two isocyanate reactive groups; and
(D) optionally, one or more isocyanate reactive components other than component (A) or component (C), bearing two isocyanate reactive groups, such that the mole ratios of components (A), (B), (C) and (D) result in a polyurethane pre-polymer comprising terminal isocyanate groups;

ii) dispersing said polyurethane pre-polymer (P) in water; and
iii) reacting isocyanate groups of the polyurethane pre-polymer (P) with a chain extender (F) bearing at least two isocyanate-reactive groups to form a polyurethane polymer aqueous dispersion
wherein A′ and B′ represent the residues of corresponding polyols (tetrols) partially esterified by acrylic acid and which may be linear, cyclic, or branched, substituted or unsubstituted hydrocarbon chains, the optional substituents including cyclic groups, heteroatoms or both and wherein the polyurethane dispersion is free of non-reactive solvent.

24. The method of claim 23 , wherein the said component (C) is a diol bearing an ionic group resulting from an acidic group chosen from carboxylic, sulfonic, phosphonic or phosphinic groups and wherein said dispersing step ii) comprises neutralizing, at least partly, said acidic group of said pre-polymer, with a basic agent.

25. An aqueous dispersion comprising an isocyanate-terminated ethylenically unsaturated polyurethane pre-polymer formed by reacting:
(A) one or more isocyanate reactive components comprising: (A1) a monoalcohol of formula (1) below bearing 3 (meth)acrylate groups and (A2) a diol of formula (2) below bearing 2 (meth)acrylate groups

(B) one or more polyisocyanates;
(C) o

Assignees

• Arkema France

Inventors

• Klang Jeffrey A
• Lu Jin
• Vappala Indu

Classifications

• C09D175/06 Primary

  from polyesters · CPC title

• C08G18/755

  and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate · CPC title

• C08G18/673

  containing two or more acrylate or alkylacrylate ester groups · CPC title

• C08G18/0838

  Manufacture of polymers in the presence of non-reactive compounds (preparation of compositions C08L75/00) · CPC title

• C09D175/16

  having terminal carbon-to-carbon unsaturated bonds · CPC title