Resist polymer and resist composition

1. A resist polymer, comprising:

a constitutional unit represented by formula (2),

a constitutional unit having an acid-dissociable group, and

a constitutional unit having a lactone skeleton that is represented by at least one selected from the group consisting of formulas (4-1), (4-2), (4-3), (4-5), (4-6), and (4-10):

wherein, in formula (2), R 01 represents a methyl group,

wherein,

in formula (4-1), R 41 represents a hydrogen atom or a methyl group; each of R 401 and R 402 independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, or a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, or R 401 and R 402 together represent —O—, —S—, —NH—, or a —(CH 2 ) j — chain wherein j represents an integer between 1 and 6; i represents 0 or 1; X 5 represents a linear or branched alkyl group having 1 to 6 carbon atoms optionally, having, as a substituent, at least one selected from the group consisting of a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, a cyano group, and an amino group, a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, or an amino group; and n5 represents an integer between 0 and 4, and m represents 1 or 2, provided that when n5 is 2 or greater, X 5 may be a plurality of different groups independently of one another,

in formula (4-2), R 42 represents a hydrogen atom or a methyl group; each of R 201 and R 202 independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, or a carboxy group esterified with alcohol having 1 to 6 carbon atoms; A 1 and A 2 together represent —O—, —S—, —NH—, or a —(CH 2 ) k — chain wherein k represents an integer between 1 and 6; X 6 represents a linear or branched alkyl group having 1 to 6 carbon atoms that may have, as a substituent, at least one selected from the group consisting of a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, a cyano group, and an amino group, a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, or an amino group; and n6 represents an integer between 0 and 4, provided that when n6 is 2 or greater, X 6 may be a plurality of different groups independently of one another,

in formula (4-3), R 43 represents a hydrogen atom or a methyl group; each of R 203 and R 204 independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, or a carboxy group esterified with alcohol having 1 to 6 carbon atoms; each of A 3 and A 4 independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, or a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, or A 3 and A 4 together represent —O—, —S—, —NH—, or a —(CH 2 ) l — chain wherein l represents an integer between 1 and 6; X 7 represents a linear or branched alkyl group having 1 to 6 carbon atoms that may have, as a substituent, at least one selected from the group consisting of a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, a cyano group, and an amino group, a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, or an amino group; and n7 represents an integer between 0 and 4, provided that when n7 is 2 or greater, X 7 may be a plurality of different groups independently of one another,

in formula (4-5), R 45 represents a hydrogen atom or a methyl group; each of R 8 and R 9 independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms; each of R 52 , R 62 , and R 72 independently represents a hydrogen atom or a methyl group; each of Y 12 , Y 22 , and Y 32 independently represents —CH 2 — or —CO—O—, and at least one of them represents —CO—O—; X 9 represents a linear or branched alkyl group having 1 to 6 carbon atoms that may have, as a substituent, at least one selected from the group consisting of a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, a cyano group, and an amino group, a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, or an amino group; and n9 represents an integer between 0 and 4, provided that when n9 is 2 or greater, X 9 may be a plurality of different groups independently of one another,

in formula (4-6), R 46 represents a hydrogen atom or a methyl group; R 10 represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms; each of R 53 , R 63 , and R 73 independently represents a hydrogen atom or a methyl group; each of Y 13 , Y 23 , and Y 33 independently represents —CH 2 — or —CO—O—, and at least one of them represents —CO—O—; X 10 represents a linear or branched alkyl group having 1 to 6 carbon atoms that may have, as a substituent, at least one selected from the group consisting of a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, a cyano group, and an amino group, a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, or an amino group; and n10 represents an integer between 0 and 4, provided that when n10 is 2 or greater, X 10 may be a plurality of different groups, and

in formula (4-10), each of R 91 , R 92 , R 93 , and R 94 independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, or a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, or R 91 and R 92 together represent —O—, —S—, —NH—, or a —(CH 2 ) t — chain wherein t represents an integer between 1 and 6; and m1 represents 1 or 2, and

wherein said constitutional unit having an acid-dissociable group is a constitutional unit represented by formula (3-5):

wherein, in formula (3-5), R 35 represents a hydrogen atom or a methyl group.

2. The resist polymer according to claim 1 , which has a mass average molecular weight between 1,000 and 100,000.

3. A resist composition, which comprises the resist polymer according to claim 1 .

4. A chemically amplified resist composition, which comprises the resist polymer according to claim 1 and a photoacid generator.

5. The chemically amplified resist composition according to claim 4 , which further comprises a nitrogen-containing compound.

6. The resist polymer according to claim 1 , which has a mass average molecular weight between 5,000 and 8,000.

7. The resist polymer according to claim 6 , which further comprises a constitutional unit derived from a chain transfer agent.

8. A resist composition, which comprises the resist polymer according to claim 7 .

9. A chemically amplified resist composition, which comprises the resist polymer according to claim 7 and a photoacid generator.

10. The chemically amplified resist composition according to claim 9 , which further comprises a nitrogen-containing compound.

11. A resist composition, which comprises the resist polymer according to claim 6 .

12. A chemically amplified resist composition, which comprises the resist polymer according to claim 6 and a photoacid generator.

13. The chemically amplified resist composition according to claim 12 , which further comprises a nitrogen-containing compound.

14. A resist polymer, which comprises:

at least one constitutional unit selected from the group consisting of those represented by said formula (2):

wherein, in formula (2), R 01 represents a methyl group;

at least one constitutional unit having an acid-dissociable group selected from the group consisting of those represented by said formulas (3-1-1), (3-3-1), and (3-5)

wherein, in formula (3-1-1), R 31 represents a hydrogen atom or a methyl group; R 1 represents an alkyl group having 1 to 3 carbon atoms; X 1 represents a linear or branched alkyl group having 1 to 6 carbon atoms that may have, as a substituent, at least one selected from the group consisting of a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, and an amino group, a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, or an amino group; and n1 represents an integer between 0 and 4, and when n1 is 2 or greater, X 1 may be a plurality of different groups,

wherein, in formula (3-3-1), R 33 represents a hydrogen atom or a methyl group; R 4 represents an alkyl group having 1 to 3 carbon atoms; X 3 represents a linear or branched alkyl group having 1 to 6 carbon atoms that may have, as a substituent, at least one selected from the group consisting of a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, and an amino group, a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, or an amino group; and n3 represents an integer between 0 and 4, and q represents 0 or 1, provided that when n3 is 2 or greater, X 3 may be a plurality of different groups, and

wherein, in formula (3-5), R 35 represents a hydrogen atom or a methyl group, and at least one constitutional unit having a lactone skeleton represented by the following formula (4-11):

wherein, in formula (4-11), R 411 represents a hydrogen atom or a methyl group.

15. The resist polymer according to claim 14 , wherein the total ratio of at least one constitutional unit selected from those represented by said formula (2) is between 5% and 30% by mole,

the total ratio of at least one constitutional unit having an acid-dissociable group selected from the group consisting of those represented by said formulas (3-1-1), (3-3-1), and (3-5) is between 30% and 60% by mole, and

the total ratio of the constitutional unit having a lactone skeleton represented by said formula (4-11) is between 30% and 60% by mole.

16. The resist polymer according to claim 14 , which has a mass average molecular weight between 1,000 and 100,000.

17. A resist composition, which comprises the resist polymer according to claim 14 .

18. A chemically amplified resist composition, which comprises the resist polymer according to claim 14 and a photoacid generator.

19. The chemically amplified resist composition according to claim 18 , which further comprises a nitrogen-containing compound.

20. The resist polymer according to claim 14 , which has a mass average molecular weight between 5,000 and 8,000.

21. The resist polymer according to claim 20 , which further comprises a constitutional unit derived from a chain transfer agent.

22. A resist composition, which comprises the resist polymer according to claim 21 .

23. A chemically amplified resist composition, which comprises the resist polymer according to claim 21 and a photoacid generator.

24. The chemically amplified resist composition according to claim 23 , which further comprises a nitrogen-containing compound.

25. A resist composition, which comprises the resist polymer according to claim 20 .

26. A chemically amplified resist composition, which comprises the resist polymer according to claim 20 and a photoacid generator.

27. The chemically amplified resist composition according to claim 26 , which further comprises a nitrogen-containing compound.

28. A resist polymer, which comprises:

at least one constitutional unit selected from the group consisting of those represented by said formulas (2)

wherein, in formula (2), R 01 represents a methyl group,

at least one constitutional unit having an acid-dissociable group selected from the group consisting of those represented by said formulas (3-1-1), (3-3-1), and (3-5):

wherein, in formula (3-1-1), R 31 represents a hydrogen atom or a methyl group; R 1 represents an alkyl group having 1 to 3 carbon atoms; X 1 represents a linear or branched alkyl group having 1 to 6 carbon atoms that may have, as a substituent, at least one selected from the group consisting of a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, and an amino group, a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, or an amino group; and n1 represents an integer between 0 and 4, and when n1 is 2 or greater, X 1 may be a plurality of different groups,

wherein, in formula (3-3-1), R 33 represents a hydrogen atom or a methyl group; R 4 represents an alkyl group having 1 to 3 carbon atoms; X 3 represents a linear or branched alkyl group having 1 to 6 carbon atoms that may have, as a substituent, at least one selected from the group consisting of a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, and an amino group, a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, or an amino group; and n3 represents an integer between 0 and 4, and q represents 0 or 1, provided that when n3 is 2 or greater, X 3 may be a plurality of different groups, and

wherein, in formula (3-5), R 35 represents a hydrogen atom or a methyl group, and

at least one constitutional unit having a lactone skeleton represented by the following formula (4-9):

wherein, in formula (4-9), R 49 represents a hydrogen atom or a methyl group.

29. The resist polymer according to claim 28 , wherein the total ratio of at least one constitutional unit selected from those represented by said formulas (2)-is between 5% and 30% by mole,

the total ratio of at least one constitutional unit having an acid-dissociable group selected from the group consisting of those represented by said formulas (3-1-1), (3-3-1), and (3-5) is between 30% and 60% by mole, and

the total ratio of the constitutional unit having a lactone skeleton represented by said formula (4-9) is between 30% and 60% by mole.

30. The resist polymer according to claim 28 , which has a mass average molecular weight between 1,000 and 100,000.

31. A resist composition, which comprises the resist polymer according to claim 28 .

32. A chemically amplified resist composition, which comprises the resist polymer according to claim 28 and a photoacid generator.

33. The chemically amplified resist composition according to claim 32 , which further comprises a nitrogen-containing compound.

34. The resist polymer according to claim 28 , which has a mass average molecular weight between 5,000 and 8,000.

35. The resist polymer according to claim 34 , which further comprises a constitutional unit derived from a chain transfer agent.

36. A resist composition, which comprises the resist polymer according to claim 35 .

37. A chemically amplified resist composition, which comprises the resist polymer according to claim 35 and a photoacid generator.

38. The chemically amplified resist composition according to claim 37 , which further comprises a nitrogen-containing compound.

39. A resist composition, which comprises the resist polymer according to claim 34 .

40. A chemically amplified resist composition, which comprises the resist polymer according to claim 34 and a photoacid generator.

41. The chemically amplified resist composition according to claim 40 , which further comprises a nitrogen-containing compound.