Method for producing fluorinated copolymer solution, and coating composition

Patent metadata

Field	Value
Publication number	US-10472535-B2
Application number	US-201514674565-A
Country	US
Kind code	B2
Filing date	Mar 31, 2015
Priority date	Oct 3, 2012
Publication date	Nov 12, 2019
Grant date	Nov 12, 2019

Abstract

A method for producing a fluorinated copolymer solution polymerizing a monomer mixture of a fluoro-olefin (A), a monomer (B) having a crosslinkable group and a monomer (C) having no fluorine atom and no crosslinkable group in the presence of an organic solvent and a compound having two or more piperidyl group represented by the formula (1):

First claim

What is claimed is:

1. A method for producing a fluorinated copolymer solution, the method comprising polymerizing a monomer mixture comprising a fluoro-olefin (A), a monomer (B) having a crosslinkable group and a monomer (C) having no fluorine atom and no crosslinkable group, in the presence of an organic solvent, and a compound having two or more piperidyl groups to form a fluorinated copolymer solution,
wherein the molar ratio of the total molar amount of piperidyl groups contained in the compound to the total molar amount of monomers in the monomer mixture, is from 0.00105 to 0.00380, wherein the compound having two or more piperidyl groups is formula (3):

wherein to the fluorinated copolymer solution obtained is added a polyisocyanate and a curing catalyst to obtain a coating composition and the coating composition is applied as a coating film on a glass substrate, the resulting coating film has a cure degree of at least 70% as determined by the difference of the mass of the coating film before and after being immersed in acetone for 1 hour under reflux.

2. The method for producing a fluorinated copolymer solution according to claim 1 , therein to the total molar amount of monomers in the monomer mixture, the content of the fluoro-olefin (A) is from 25 to70 mol %, the content of the monomer (B) having a crosslinkable group is from 1 to 70 mol %, the content of the monomer (C) having no fluorine atom and no crosslinkable group is from 1 to 70 mol %, and the total content of (A)+(B)+(C) is 100 mol %.

3. The method for producing a fluorinated copolymer solution according to claim 1 , wherein the monomer (B) having a crosslinkable group is at least one member selected from the group consisting of an alkyl vinyl ether having a crosslinkable group, an alkyl allyl ether having a crosslinkable group, an alkanoic acid vinyl ester having a crosslinkable group, an alkanoic acid allyl ester having a crosslinkable group, and a (meth)acrylic acid ester having a crosslinkable group.

4. The method for producing a fluorinated copolymer solution according to claim 1 , wherein the crosslinkable group is at least one member selected from the group consisting of a hydroxy group, a carboxy group, an epoxy group, an oxetanyl group, an amino group and an alkoxysilyl group.

5. The method for producing a fluorinated copolymer solution according to claim 1 , wherein the monomer (C) having no fluorine atom and no crosslinkable group is at least one member selected from the group consisting of an alkyl vinyl ether, an alkyl allyl ether, an alkanoic acid vinyl ester, an alkanoic acid allyl ester and a (meth)acrylic acid alkyl ester.

6. The method for producing a fluorinated copolymer solution according to claim 1 , wherein the polymerization is conducted in the presence of a radical polymerization initiator.

7. The method for producing a fluorinated copolymer solution according to claim 6 , wherein the radical polymerization initiator is a compound represented by the following formula (5):

wherein each of R 5 and R 6 which are independent of each other, is a C 1-12 alkyl group or a C 6-12 aryl group.

8. The method for producing a fluorinated copolymer solution according to claim 7 , wherein R 5 in the formula (5) is a group represented by the following formula (6):

wherein R 7 is a C 1-9 alkyl group.

9. The method for producing a fluorinated copolymer solution according to claim 1 , wherein the organic solvent is at least one member selected from the group consisting of xylene, ethanol, tert-butyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethoxyethyl propionate, cyclohexanone, tert-butyl acetate, chlorobenzene trifluoride, mineral spirits, cyclohexane, ethyl acetate, butyl acetate, HCFC-141b and HCFC-225.

10. The method for producing a fluorinated copolymer solution according to claim 1 , wherein
the fluoro-olefin (A) is chlorotrifluoroethylene or tetrafluoroethylene,
the monomer (B) is a hydroxyalkyl vinyl ether,
the monomer (C) is an alkyl vinyl ether or an alkanoic acid vinyl ester,
the content of the fluoro-olefin (A) is from 25 to70 mol %, the content of the monomer (B) having a crosslinkable group is from 1 to 70 mol %, the content of the monomer (C) having no fluorine atom and no crosslinkable group is from 1 to 70 mol %, and the total content of (A)+(B)+(C) is 100 mol %, and
the molar ratio of the total molar amount of piperidyl groups contained in the compound to the total molar amount of monomers in the monomer mixture, is from 0.00115 to 0.00360.

11. The method for producing a fluorinated copolymer solution according to claim 1 , wherein-the fluorinated copolymer comprises from 45 to 55 mol % of the monomer unit (A), 3 to 30 mol % of the monomer unit (B), and 30 to 50 mol % of monomer unit (C) and wherein the monomer unit (A) is chlorotrifluorethylene, the monomer unit (B) is hydroxybutyl vinyl ether, and the monomer unit (C) is an alkyl vinyl ether.

Assignees

• Agc Inc

Inventors

• Ebata Shiro
• Tomita Toshinori
• Ataku Masakazu
• Saito Shun
• Masuda Sho

Classifications

• C08F214/18

  Monomers containing fluorine · CPC title

• C08F2/38

  Polymerisation using regulators, e.g. chain terminating agents {, e.g. telomerisation} · CPC title

• C08K5/3435

  Piperidines · CPC title

• C09D127/12 Primary

  containing fluorine atoms · CPC title