Fluorine-containing polymer having acid-reactive group and chemically amplifying type photoresist composition prepared from same

1. A chemically amplifying type photoresist composition which comprises:

(A) a fluorine-containing polymer having an acid-reactive functional group,

(B) a photoacid generator and

(C) a solvent,

wherein the fluorine-containing polymer (A) having an acid-reactive group is a fluorine-containing polymer represented by the formula (2):

—(M1)—(M2)—(N)—  (2)

in which

{circle around (1)} the structural unit M1 is a structural unit derived from the fluorine-containing alicyclic monomer having an acid-reactive group of the formula (1):

 wherein the fluorine-containing polymer (A) having an acid-labile or acid-degradable group is a fluorine-containing polymer represented by the formula (3):

—(M1)—(M2)—(M3)—(N)—  (3)

in which

{circle around (1)} the structural unit M1 is a structural unit derived from the fluorine-containing alicyclic monomer having an acid-reactive group of the formula (1):

 in which A, B and C are the same or different and each is H, F, an alkyl group having 1 to 10 carbon atoms or a fluorine-containing alkyl group having 1 to 10 carbon atoms; R is a divalent hydrocarbon group having 1 to 20 carbon atoms, a fluorine-containing alkylene group having 1 to 20 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and ether bond; a is 0 or an integer of from 1 to 3; b is 0 or 1; Y 2 is an acid-labile or acid-degradable functional group; provided that when b is 0 or R does not have fluorine atom, at least one of A to C is fluorine atom or a fluorine-containing alkyl group,

{circle around (2)} the structural unit M2 is a structural unit derived from a fluorine-containing ethylenic monomer, in which A, B and C are the same or different and each is H, F, an alkyl group having 1 to 10 carbon atoms or a fluorine-containing alkyl group having 1 to 10 carbon atoms; R is a divalent hydrocarbon group having 1 to 20 carbon atoms, a fluorine-containing alkylene group having 1 to 20 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and ether bond; a is 0 or an integer of from 1 to 3; b is 0 or 1; Y 2 is an acid-reactive functional group; provided that at least one of A to C is fluorine atom or a fluorine-containing alkyl group,

{circle around (2)} the structural unit M2 is a structural unit derived from a fluorine-containing ethylenic monomer and

{circle around (3)} the structural unit N is a structural unit derived from a monomer copolymerizable with M1 and M2,

when M1+M2 is assumed to be equal to 100% by mole, the percent by mole ratio M1/M2 is 1 to 99/1 to 99,

said polymer comprises from 1 to 99% by mole of the structural unit M1, from 1 to 99% by mole of the structural unit M2 and from 0 to 98% by mole of the structural unit N.

2. The chemically amplifying type photoresist composition of claim 1 , wherein the acid-reactive group Y 2 of the flourine-containing alicyclic monomer of the formula (1)constituting the fluorine-containing polymer (A) having an acid-reactive group is an acid-labile or acid-degradable functional group.

3. The chemically amplifying type photoresist composition of claim 2 , wherein the acid-labile or acid-degradable functional group is:

wherein R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 14 , R 18 , R 19 , R 20 , R 21 , R 20 , R 21 , R 22 , R 24 , R 25 , R 26 , R 27 , R 28 and R 29 are the same or different and each is a hydrocarbon group having 1 to 10 carbon atoms; R 13 , R 15 and R 16 are H or hydrocarbon groups having 1 to 10 carbon atoms; and R 17 and R 23 are divalent hydrocarbon groups having 2 to 10 carbon atoms.

4. The chemically amplifying type photoresist composition of claim 3 , wherein the acid-labile or acid-degradable functional group is:

—OC(CH 3 ) 3 , —OCH 2 COOC(CH 3 ) 3 ,

 —COOC(CH 3 ) 3 or —OSi(CH 3 ) 3 ,

wherein R 30 is an alkyl group having 1 to 10 carbon atoms.

5. The chemically amplifying type photoresist composition of claim 2 , wherein the acid-labile or acid-degradable functional group is a functional group which is converted to carboxyl group by a reaction with an acid.

6. The chemically amplifying type photoresist composition of claim 1 , wherein the acid-reactive group Y 2 is a functional group which is capable of undergoing condensation reaction by an acid.

7. The chemically amplifying type photoresist composition of claim 6 , wherein the functional group which is capable of undergoing condensation reaction by an acid is selected from the group consisting of —OH, —COOH, —CN, —SO 3 H and epoxy group.

8. The chemically amplifying type photoresist composition of claim 1 , wherein in the fluorine-containing alicyclic monomer of the formula (1) constituting the fluorine-containing polymer (A) having an acid-reactive group, at least one of A, B and C is fluorine atom.

9. The chemically amplifying type photoresist composition of claim 1 , wherein in the fluorine-containing polymer (A) having an acid-reactive group, the structural unit M2 is a fluorine-containing ethylenic monomer having 2 or 3 carbon atoms.

10. The chemically amplifying type photoresist composition of claim 9 , wherein in the fluorine-containing polymer (A) having an acid-reactive group, the structural unit M2 is a structural unit derived from a monomer selected from tetrafluoroethylene and chlorotrifluoroethylene.

11. The chemically amplifying type photoresist composition of claim 1 , wherein in the fluorine-containing polymer (A) having an acid-reactive group, the proportion of the structural unit M1 is not less than 10% by mole based on the whole structural units constituting the fluorine-containing copolymer.

12. A chemically amplifying type photoresist composition which comprises:

(A) a fluorine-containing polymer having an acid-labile or acid-degradable functional group,

(B) a photoacid generator and

(C) a solvent,

{circle around (3)} the structural unit M3 is a structural unit derived from an alicyclic monomer represented by the formula(4):

 wherein A 1 , B 1 , C 1 and D 1 are the same or different and each is H, F, an alkyl group having 1 to 10 carbon atoms or a fluorine-containing alkyl group having 1 to 10 carbon atoms; a is 0 or an integer of from 1 to 3, and

{circle around (4)} the structural unit N is a structural unit derived from a monomer copolymerizable with M1, M2 and M3,

when M1+M2+M3 is assumed to be equal to 100% by mole, the percent by mole ratio M1+M3/M2 is 30/70 to 70/30,

said polymer comprises from 1 to 98% by mole of the structural unit M1, from 1 to 98% by mole of the structural unit M2, from 1 to 98% by mole of the structural unit M3 and from 0 to 97% by mole of the structural unit N.

13. The chemically amplifying type photoresist composition of claim 12 , wherein the acid-labile or acid-degradable functional group is:

wherein R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 14 , R 18 , R 19 , R 20 , R 21 , R 22 , R 24 , R 25 , R 26 , R 27 , R 28 and R 29 are the same or different and each is a hydrocarbon group having 1 to 10 carbon atoms; R 13 , R 15 and R 16 are H or hydrocarbon groups having 1 to 10 carbon atoms; and R 17 and R 23 are divalent hydrocarbon groups having 2 to 10 carbon atoms.

14. The chemically amplifying type photoresist composition of claim 13 , wherein the acid-labile or acid-degradable functional group is:

—OC(CH 3 ) 3 , —OCH 2 COOC(CH 3 ) 3 ,

 —COOC(CH 3 ) 3 or —OSi(CH 3 ) 3 ,

wherein R 30 is an alkyl group having 1 to 10 carbon atoms.

15. The chemically amplifying type photoresist composition of claim 12 wherein the acid-labile or acid-degradable functional group is a functional group which is converted to carboxyl group by a reaction with an acid.

16. The chemically amplifying type photoresist composition of claim 12 , wherein in the fluorine-containing alicyclic monomer of the formula (1) constituting the fluorine-containing polymer (A) having an acid-labile or acid-degradable group, at least one of A to C is fluorine atom or a fluorine-containing alkyl group.

17. The chemically amplifying type photoresist composition of claim 12 , wherein in the fluorine-containing alicyclic monomer of the formula (1) constituting the fluorine-containing polymer (A) having an acid-labile or acid-degradable group, at least one of A, B and C is fluorine atom.

18. The chemically amplifying type photoresist composition of claim 12 , wherein in the fluorine-containing polymer (A) having an acid-labile or acid-degradable group, the structural unit M2 is a fluorine-containing ethylenic monomer having 2 or 3 carbon atoms.

19. The chemically amplifying type photoresist composition of claim 18 , wherein in the fluorine-containing polymer (A) having an acid-labile or acid-degradable group, the structural unit M2 is a structural unit derived from a monomer selected from tetrafluoroethylene and chlorotrifluoroethylene.

20. The chemically amplifying type photoresist composition of claim 12 , wherein in the fluorine-containing polymer (A) having an acid-labile or acid-degradable group, the proportion of the structural unit M1 is not less than 10% by mole based on the whole structural units constituting the fluorine-containing copolymer.

21. A fluorine-containing polymer having a number average molecular weight of from 1,000 to 1,000,000 and represented by the formula (2):

—(M1)—(M2)—(N)—  (2)

in which

{circle around (1)} the structural unit M1 is a structural unit derived from a fluorine-containing alicyclic monomer having an acid-reactive group of the formula (1):

 in which A, B and C are the same or different and each is H, F, an alkyl group having 1 to 10 carbon atoms or a fluorine-containing alkyl group having 1 to 10 carbon atoms; R is a divalent hydrocarbon group having 1 to 20 carbon atoms, a fluorine-containing alkylene group having 1 to 20 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and ether bond; a is 0 or an integer of from 1 to 3; b is 0 or 1; Y 2 is an acid-reactive functional group; provided that at least one of A to C is fluorine atom or a fluorine-containing alkyl group,

{circle around (2)} the structural unit M2 is a structural unit derived from a fluorine-containing ethylenic monomer, and

{circle around (3)} the structural unit N is a structural unit derived from a monomer copolymerizable with M1 and M2,

when M1+M2 is assumed to be equal to 100% by mole, the percent by mole ratio M1/M2 is 1 to 99/1 to 99,

said polymer comprises from 1 to 99% by mole of the structural unit M1, from 1 to 99% by mole of the structural unit M2 and from 0 to 98% by mole of the structural unit N.

22. The fluorine-containing polymer of claim 21 , wherein the acid-reactive group Y 2 of the fluorine-containing alicyclic monomer of the formula (1) constituting the fluorine-containing polymer (A) having an acid-reactive group is an acid-labile or acid-degradable functional group.

23. The fluorine-containing polymer of claim 22 , wherein the acid-labile or acid-degradable functional group is:

wherein R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 14 , R 18 , R 19 , R 20 , R 21 , R 22 , R 24 , R 25 , R 26 , R 27 , R 28 and R 29 are the same or different and each is a hydrocarbon group having 1 to 10 carbon atoms; R 13 , R 15 and R 16 are H or hydrocarbon groups having 1 to 10 carbon atoms; and R 17 and R 23 are divalent hydrocarbon groups having 2 to 10 carbon atoms.

24. The fluorine-containing polymer of claim 23 , wherein the acid-labile or acid-degradable functional group is:

—OC(CH 3 ) 3 , —OCH 2 COOC(CH 3 ) 3 ,

 —COOC(CH 3 ) 3 or —OSi(CH 3 ) 3,

wherein R 30 is an alkyl group having 1 to 10 carbon atoms.

25. The fluorine-containing polymer of claim 22 , wherein the acid-labile or acid-degradable functional group is a functional group which is converted to carboxyl group by a reaction with an acid.

26. The fluorine-containing polymer of claim 21 , wherein the acid-reactive group Y 2 is a functional group which is capable of undergoing condensation reaction by an acid.

27. The fluorine-containing polymer of claim 26 , wherein the functional group which is capable of undergoing condensation reaction by an acid is selected from group consisting of —OH, —COOH, —CN, —SO 3 H and epoxy group.

28. The fluorine-containing polymer of claim 21 , wherein in the fluorine-containing alicyclic monomer of the formula (1), at least one of A, B and C is fluorine atom.

29. The fluorine-containing polymer of claim 21 , wherein the structural unit M2 is a fluorine-containing ethylenic monomer having 2 or 3 carbon atoms.

30. The fluorine-containing polymer of claim 29 , wherein in the fluorine-containing polymer (A) having an acid-reactive group, the structural unit M2 is a structural unit derived from a monomer selected from tetrafluoroethylene and chlorotrifluoroethylene.

31. A fluorine-containing polymer having a number average molecular weight of from 1,000 to 1,000,000 which is represented by the formula (3):

—(M1)—(M2)—(M3)—(N)—  (3)

in which

{circle around (1)} the structural unit M1 is a structural unit derived from a fluorine-containing alicyclic monomer having an acid-labile or acid-degradable group of the formula (1):

 in which A, B and C are the same or different and each is H, F, an alkyl group having 1 to 10 carbon atoms or a fluorine-containing alkyl group having 1 to 10 carbon atoms; R is a divalent hydrocarbon group having 1 to 20 carbon atoms, a fluorine-containing alkylene group having 1 to 20 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and ether bond; a is 0 or an integer of from 1 to 3; b is 0 or 1; Y 2 is an acid-labile or acid-degradable functional group; provided that when b is 0 or R does not have fluorine atom, at least one of A to C is fluorine atom or a fluorine-containing alkyl group,

{circle around (2)} the structural unit M2 is a structural unit derived from a fluorine-containing ethylenic monomer,

{circle around (3)} the structural unit M3 is a structural unit derived from an alicyclic monomer represented by the formula (4):

 wherein A 1 , B 1 , C 1 and D 1 are the same or different and each is H, F, an alkyl group having 1 to 10 carbon atoms or a fluorine-containing alkyl group having 1 to 10 carbon atoms; a is 0 or an integer of from 1 to 3, and

{circle around (4)} the structural unit N is a structural unit derived from a monomer copolymerizable with M1, M2 and M3,

when M1+M2+M3 is assumed to be equal to 100% by mole, the percent by mole ratio M1+M3/M2 is 30/70 to 70/30,

said polymer comprises from 1 to 98% by mole of the structural unit M1, from 1 to 98% by mole of the structural unit M2, from 1 to 98% by mole of the structural unit M3 and from 0 to 97% by mole of the structural unit N.

32. The fluorine-containing polymer of claim 31 , wherein the acid-labile or acid-degradable functional group is:

wherein R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 14 , R 18 , R 19 , R 20 , R 21 , R 22 , R 24 , R 25 , R 26 , R 27 , R 28 and R 29 are the same or different and each is a hydrocarbon group having 1 to 10 carbon atoms; R 13 , R 15 and R 16 are H or hydrocarbon groups having 1 to 10 carbon atoms; and R 17 and R 23 are divalent hydrocarbon groups having 2 to 10 carbon atoms.

33. The fluorine-containing polymer of claim 32 , wherein the acid-labile or acid-degradable functional group is:

—OC(CH 3 ) 3 , —OCH 2 COOC(CH 3 ) 3 ,

 —COOC(CH 3 ) 3 or —OSi(CH 3 ) 3 ,

wherein R 30 is an alkyl group having 1 to 10 carbon atoms.

34. The fluorine-containing polymer of claim 31 , wherein the acid-labile or acid-degradable functional group is a functional group which is converted to carboxyl group by a reaction with an acid.

35. The chemically amplifying type photoresist composition of claim 31 , wherein in the fluorine-containing alicyclic monomer of the formula (1) constituting the fluorine-containing polymer (A) having an acid-labile or acid-degradable group, at least one of A to C is fluorine atom or a fluorine-containing alkyl group.

36. The fluorine-containing polymer of claim 31 , wherein in the fluorine-containing alicyclic monomer of the formula (1) constituting the fluorine-containing polymer (A) having an acid-labile or acid-degradable group, at least one of A, B and C is fluorine atom.

37. The fluorine-containing polymer of claim 31 , wherein in the fluorine-containing polymer (A) having an acid-labile or acid-degradable group, the structural unit M2 is a fluorine-containing ethylenic monomer having 2 or 3 carbon atoms.

38. The fluorine-containing polymer of claim 37 , wherein in the fluorine-containing polymer (A) having an acid-labile or acid-degradable group, the structural unit M2 is a structural unit derived from a monomer selected from tetrafluoroethylene and chlorotrifluoroethylene.