Granted Patent B2

US 12,428,524 · App. 17/685,498 · Granted Sep 30, 2025

Inventors: Shouta Shibutani (Osaka, JP); Shingo Okuno (Osaka, JP); Masatoshi Nose (Cheonan-si, KR)

Assignee: DAIKIN INDUSTRIES, LTD.

C08G65/007C08L53/00C08G2150/00C08G2650/48

Abstract

Claims (91)

1. A fluorine-containing copolymer represented by the following formula (1) or (2):

wherein

R F1 is Rf 1 —R F —O q —;

R F2 is —Rf 2 p —R F —O q —;

Rf 1 is a C 1-16 alkyl group optionally substituted with one or more fluorine atoms;

Rf 2 is a C 1-6 alkylene group optionally substituted with one or more fluorine atoms;

R F is each independently a divalent fluoropolyether group;

p is 0 or 1;

q is each independently 0 or 1;

R 4 is each independently at each occurrence R 4a or R 4b ;

R 4a is each independently at each occurrence a divalent organic group having a functional group selected from substituent group A;

R 4b is —CH 2 —CR 4d R 4e —,

wherein

R 4d is a hydrogen atom or an alkyl group,

R 4e is —COO—R 4f ,

R 4f is -linker-R 4g or —R 4g ,

the linker is one selected from (b) to (f):

(b) —(CHR 4h ) s2 —O—, wherein s2 represents the number of repetitions, which is an integer of 1 to 40, and R 4h represents hydrogen or a methyl group;

(c) —(CH 2 —CH 2 —O) s1 —CO—NH—CH 2 —CH 2 —O—, wherein s1 represents an integer of 1 to 10;

(d) —CH 2 —CH 2 —O—CH 2 —CH 2 —;

(e) —(CH 2 ) s3 —, wherein s3 represents an integer of 1 to 6; or

(f) —(CH 2 ) s4 —O—CONH—(CH 2 ) s5 —, wherein s4 represents an integer of 1 to 8, and s5 represents an integer of 1 to 6;

R 4g is selected from (i) to (vi):

(i) an alkyl group;

(ii) a chain group comprising an alkyl group substituted with fluorine;

(iii) a group comprising one or more cyclic moieties selected from the group consisting of a monocyclic carbocycle, a bicyclic carbocycle, a tricyclic carbocycle and a tetracyclic carbocycle;

(iv) hydrogen, provided that the hydrogen atom is not bonded to the oxygen atom of the linker;

(v) a group comprising an imidazolium salt;

(vi) a group comprising silicon

wherein, R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 17 are each independently an alkyl group or an aryl group;

n4 is an integer of 1 to 500;

R 18 is a divalent organic group;

the substituent group A is a group containing a carbon-carbon double bond, a carbon-carbon triple bond, a cyclic ether group, a hydroxyl group, a thiol group, an amino group, an azide group, a nitrogen-containing heterocyclic group, an isocyanate group, a halogen atom, a phosphoric acid-containing group, or a silane coupling group, or a precursor group thereof;

n is an integer of 1 to 100;

X a is each independently a divalent organic group;

X b is each independently a divalent organic group;

R a is each independently alkyl, phenyl, —SR a1 , —OR a2 , —NR a3 2 , or

R a1 , R a2 , R a3 , R a4 , R a5 , and R a6 are each independently an alkyl group or a phenyl group; and

R a7 is a hydrogen atom or a halogen atom.

2. The fluorine-containing copolymer according to claim 1 , wherein R F is each independently a group represented by the formula:

—(OC 6 F 12 ) a —(OC 5 F 10 ) b —(OC 4 F 8 ) c —(OC 3 R Fa 6 ) d —(OC 2 F 4 ) e —(OCF 2 ) f —

wherein R Fa is each independently at each occurrence a hydrogen atom, a fluorine atom, or a chlorine atom; and

a, b, c, d, e and f are each independently an integer of 0 to 200, the sum of a, b, c, d, e and f is 1 or more, and the occurrence order of the respective repeating units enclosed in parentheses provided with a, b, c, d, e or f is not limited in the formula.

3. The fluorine-containing copolymer according to claim 1 , wherein R F is each independently a group represented by the following formula (f1), (f2), (f3), (f4), or (f5):

—(OC 3 F 6 ) d —  (f1)

wherein d is an integer of 1 to 200;

—(OC 4 F 8 ) c —(OC 3 F 6 ) d —(OC 2 F 4 ) e —(OCF 2 ) f —  (f2)

wherein c and d are each independently an integer of 0 to 30;

e and f are each independently an integer of 1 to 200;

the sum of c, d, e, and f is an integer of 10 to 200; and

the occurrence order of the respective repeating units enclosed in parentheses provided with a subscript c, d, e, or f is not limited in the formula;

—(R 6 —R 7 ) g —  (f3)

wherein R 6 is OCF 2 or OC 2 F 4 ;

R 7 is a group selected from OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 , and OC 6 F 12 , or is a combination of two or three groups selected from these groups; and

g is an integer of 2 to 100;

—(OC 6 F 12 ) a —(OC 5 F 10 ) b —(OC 4 F 8 ) c —(OC 3 F 6 ) d —(OC 2 F 4 ) e —(OCF 2 ) f —  (f4)

wherein e is an integer of 1 or more and 200 or less, a, b, c, d, and f are each independently an integer of 0 or more and 200 or less, the sum of a, b, c, d, e, and f is at least 1, and the occurrence order of the respective repeating units enclosed in parentheses provided with a, b, c, d, e, or f is not limited in the formula; and

—(OC 6 F 12 ) a —(OC 5 F 10 ) b —(OC 4 F 8 ) c —(OC 3 F 6 ) d —(OC 2 F 4 ) e —(OCF 2 ) f —  (f5)

wherein f is an integer of 1 or more and 200 or less, a, b, c, d, and e are each independently an integer of 0 or more and 200 or less, the sum of a, b, c, d, e, and f is at least 1, and the occurrence order of the respective repeating units enclosed in parentheses provided with a, b, c, d, e, or f is not limited in the formula.

4. The fluorine-containing copolymer according to claim 1 , wherein R 4 is R 4a .

5. The fluorine-containing copolymer according to claim 1 , wherein R 4a is a group represented by the following formula:

wherein

R 31 is each independently at each occurrence a hydrogen atom or an alkyl group;

R 32 is each independently at each occurrence a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group optionally substituted with fluorine;

R 33 is each independently at each occurrence a functional group selected from substituent group A;

Y 1 is a single bond, —C(═O)O—, —C(═O)NH—, —OC(═O)—, —NHC(═O)—, —O—, —N(R c )—, phenylene or carbazolylene;

R c is an organic group; and

Y 2 is a single bond or a linker having 1 to 16 atoms in the main chain.

6. The fluorine-containing copolymer according to claim 1 , wherein the functional group selected from substituent group A of R 4a is a group having an epoxy group, a glycidyl group, an alicyclic epoxy group, an acryloyl group, or a methacryloyl group.

7. The fluorine-containing copolymer according to claim 1 , wherein n is an integer of 2 to 50.

8. A surface-treating agent comprising one or more fluorine-containing copolymers according to claim 1 .

9. A curable composition comprising:

the fluorine-containing copolymer according to claim 1 ; and

a matrix forming composition.

10. A curable composition comprising:

the surface-treating agent according to claim 8 ; and

a matrix forming composition.

11. A film formed from the surface-treating agent according to claim 8 .

12. A film formed from the curable composition according to claim 9 .

13. An article comprising:

a substrate; and

a layer formed on a surface of the substrate from the surface-treating agent according to claim 8 .

14. An article comprising:

a substrate; and

a layer formed on a surface of the substrate from the curable composition according to claim 9 .

15. The article according to claim 13 , wherein the article is an optical member.

16. The article according to claim 13 , which is a LiDAR cover member.

17. The article according to claim 13 , which is a sensor member.

18. The article according to claim 13 , which is an instrument panel cover member.

19. The article according to claim 13 , which is an automobile interior member.

20. The article according to claim 13 , which is an insulator or a dielectric.

Assignments (2)

Priority Claims (1)

Continuity (2)

References Cited (14)