Fluorinate polyacrylate coating composition, the preparation method therefore and use thereof

Patent metadata

Field	Value
Publication number	US-11613667-B2
Application number	US-201816955685-A
Country	US
Kind code	B2
Filing date	Dec 21, 2018
Priority date	Dec 26, 2017
Publication date	Mar 28, 2023
Grant date	Mar 28, 2023

Abstract

The embodiments herein relate to a composition of a fluorinated polyurethane acrylate resin and a polyurethane acrylate resin, which, upon curing, is durable and has anti-stain and anti-scratch properties. The preparation of the composition is conducted with a one-pot multicomponent synthesis process, wherein multiple components are put together to carry out reactions simultaneously. The process is especially suitable for industrial scale production, and open for adding additive components to further adjust the performance of the prepared composition. The embodiments herein also relate to oligomers prepared in the synthesis process, as well as the use of the composition or oligomer to form a coating onto a substrate.

First claim

The invention claimed is:

1. A coating composition comprising:
(a) a polyacrylate oligomer of the following structure (I)

and
(b) a fluorinated polyacrylate oligomer of the following structure (II)

wherein,
U originates from an isocyanate structure that had at least two —N═C═O functional groups;
A originates from a diol or polyol structure selected from the group consisting of ethylene glycol, diethylene glycol, neopentyl glycol, 1,6-hexanediol, cyclohexanedimethanol, polyester diols, polycarbonate diols, polyether diols, polyethylene glycol 200 (PEG200), polyethylene glycol 400 (PEG400), polyethylene glycol 600 (PEG600), polypropylene glycol 1000 (PPG1000), and a mixture thereof; F originates from a fluorinated diol or polyol structure, or a perfluoropolyether structure that contained at least two hydroxyl groups, or a mixture thereof; B originates from a structure that had at least one double bond and at least one hydroxyl group; n 1 , n 2 , n 3 and n 4 are integers, the sum of n 1 and n 2 is ranging from 0 to 20, the sum of n 3 and n 4 is ranging from 1 to 20.

2. The coating composition according to claim 1 , wherein the weight ratio between the oligomers (I) and (II) is from 90:10 to 10:90.

3. The coating composition according to claim 1 , wherein U originates from a diisocyanate structure selected from the group consisting of 1,6-hexane diisocyanate, isophorone diisocyanate, 4,4′-diphenyl-methane-diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, xylylene diisocyanate, tolylene-2,4-diisocyanate, and a mixture thereof.

4. The coating composition according to claim 1 , wherein B originates from a hydroxyl (meth)acrylate structure that contains at least one (meth)acryloyl group and one hydroxyl group, selected from the group consisting of 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, 1-hydroxybutyl(meth)acrylate, neopentylglycolmono(meth)acrylate, 1,6-hexanediolmono(meth)acrylate, polycaprolactone polyol mono(meth)acrylate, pentaerythritolpenta(meth)acrylate, dipentaerythritolpenta(meth)acrylate, and a mixture thereof.

5. The coating composition according to claim 1 , wherein F is selected from structures originating from the group consisting of:
2,2,3,3-tetrafluoro-1,4-butanediol;
2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol;
2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro-1,8-octanediol;
2,2,3,3,4,4,5,5,6,6,7,7,8,8-tetradecafluoro-1,9-nonanediol;
2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1,10-decanediol; and
1H,1H,12H,12H-Perfluoro-1,12-dodecanediol.

6. A method for preparing the coating composition according to claim 1 , comprising steps of:
a) preparing a solution of a fluorinated diol or polyol or a perfluoropolyether that contains at least two hydroxyl groups, or a mixture thereof in a solvent;
b) dropping the solution of step a) into an isocyanate that has at least two isocyanate functional groups, forming a mixture which is heated to 50 to 60° C., and maintaining the temperature at 50 to 60° C. for 1 to 2 hours, to form a structure -U-F-U- to obtain a reaction mixture comprising structure -U-F-U-;
c) adding a diol or polyol selected from the group consisting of ethylene glycol, diethylene glycol, neopentyl glycol, 1,6-hexanediol, cyclohexanedimethanol, polyester diols, polycarbonate diols, polyether diols, polyethylene glycol 200 (PEG200), polyethylene glycol 400 (PEG400), polyethylene glycol 600 (PEG600), polypropylene glycol 1000 (PPG1000), and a mixture thereof into the reaction mixture comprising structure -U-F-U- of step b), together with unreacted isocyanate, with maintaining the temperature at 50 to 60° C. for 1 to 2 hours, to form structures -(U-A) n3 -U-F-U-(A-U) n4 - and -(U-A) n1 -U-(A-U) n2 to obtain a reaction mixture comprising structures -(U-A) n3 -U-F-U-(A-U) n4 - and -(U-A) n1 -U-(A-U) n2;
d) at a temperature of 80 to 90° C. adding a monomer that has at least one double bond and at least one hydroxyl group into the reaction mixture comprising structures -(U-A) n3 -U-F-U-(A-U) n4 - and -(U-A) n1 -U-(A-U) n2 - of step c), with maintaining the temperature at 80 to 90° C. for 1 to 2 hours to form structures B-(U-A) n3 -U-F-U-(A-U) n4 -B (II) and B-(U-A)n 1 -U-(A-U) n2 -B (I).

7. A coating composition comprising:
(a) a polyacrylate oligomer of the following structure (I)

and
(b) a fluorinated polyacrylate oligomer of the following structure (II)

wherein,
U originates from an isocyanate structure that had at least two —N═C═O functional groups;
A originates from a diol or polyol structure;
F is selected from structures originating from the group consisting of:

HO(CH 2 CH 2 O) n CH 2 CF 2 O(CF 2 CF 2 O) p (CF 2 O) q CF 2 CH 2 (OCH 2 CH 2 ) n OH
HOCH 2 CF 2 O(CF 2 CF 2 O) p (CF 2 O) q CF 2 CH 2 OH
HOH 2 C(CF 3 )FC(CF(CF 3 )CF 2 O) n CF(CF 3 )CH 2 OH
HOH 2 C(CF 3 )CF(CF 2 CF 2 O) n CF(CF 3 )CH 2 OH
HOH 2 CCF 2 (CF 2 CF 2 O) n CF 2 CH 2 OH
HOH 2 CF 2 C(CF 2 CF 2 OCF 2 CF 2 CF 2 O) n CF 2 CH 2 OH
HOH 2 CCH 2 CF 2 O(CF 2 CF 2 O) m (CF 2 O) n CF 2 CH 2 CH 2 OH;
B originates from a structure that had at least one double bond and at least one hydroxyl group; n 1 , n 2 , n 3 and n 4 are integers, the sum of n 1 and n 2 is ranging from 0 to 20, the sum of n 3 and n 4 is ranging from 1 to 20;
wherein m is from 1 to 50, n is from 1 to 50, p is from 1 to 5, q is from 1 to 5.

8. The coating composition according to claim 7 , wherein the weight ratio between the oligomers (I) and (II) is from 90:10 to 10:90.

9. The coating composition according to claim 7 , wherein U originates from a diisocyanate structure selected from the group consisting of 1,6-hexane diisocyanate, isophorone diisocyanate, 4,4′-diphenyl-methane-diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, xylylene diisocyanate, tolylene-2,4-diisocyanate, and a mixture thereof.

10. The coating composition according to claim 7 , wherein B originates from a hydroxyl (meth)acrylate structure that contains at least one (meth)acryloyl group and one hydroxyl group, selected from the group consisting of 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, 1-hydroxybutyl(meth)acrylate, neopentylglycolmono(meth)acrylate, 1,6-hexanediolmono(meth)acrylate, polycaprolactone polyol mono(meth)acrylate, pentaerythritolpenta(meth)acrylate, dipentaerythritolpenta(meth)acrylate, and a mixture thereof.

11. A method for preparing the coating composition according to claim 7 , comprising steps of:
a) preparing a solution of a fluorinated diol or polyol, or a perfluoropolyether selected from the group consisting of:
HO(CH 2 CH 2 O) n CH 2 CF 2 O(CF 2 CF 2 O) p (CF 2 O) q CF 2 CH 2 (OCH 2 CH 2 ) n OH
HOCH 2 CF 2 O(CF 2 CF 2 O) p (CF 2 O) q CF 2 CH 2 OH
HOH 2 C(CF 3 )FC(CF(CF 3 )CF 2 O) n CF(CF 3 )CH 2 OH
HOH 2 C(CF 3 )CF(CF 2 CF 2 O) n CF(CF 3 )CH 2 OH
HOH 2 CCF 2 (CF 2 CF 2 O) n CF 2 CH 2 OH
HOH 2 CF 2 C(CF 2 CF 2 OCF 2 CF 2 CF 2 O) n CF 2 CH 2 OH
HOH 2 CCH 2 CF 2 O(CF 2 CF 2 O) m (CF 2 O) n CF 2 CH 2 CH 2 OH, wherein m is from 1 to 50, n is from 1 to 50, p is from 1 to 5, and q is from 1 to 5, or a mixture thereof in a solvent;
b) dropping the solution of step a) into an isocyanate that has at least two isocyanate functional groups, forming a mixture wh

Assignees

• Akzo Nobel Coatings Int Bv

Inventors

• Shi Zheng
• Wang Jianhui
• Lu Junbiao
• Xu Zhenglin
• Xing Shili

Classifications

• C08G18/3212

  containing cycloaliphatic groups · CPC title

• C08G18/5015 Primary

  having fluorine atoms · CPC title

• C08G18/73

  acyclic · CPC title

• C08G18/246

  containing also tin-carbon bonds · CPC title

• C09D4/06 Primary

  {Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond} in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00 · CPC title