Onium salt compound and radiation-sensitive resin composition

1. An onium salt compound having a cation moiety of the following formula (1),

wherein A represents an iodine atom or a sulfur atom, when A is an iodine atom, m is 1 or 2 and n is 0 or 1, provided that (m+n)=2, and x is an integer of 1–10, and when A is a sulfur atom, m is 1–3 and n is 0–2, provided that (m+n)=3, and x is an integer of 1–15; Ar 1 represents a substituted or unsubstituted aromatic hydrocarbon group having 6–20 carbon atoms with a valence of 1 to (x+1) or a substituted or unsubstituted heterocyclic group having 3–20 atoms with a valence of 1 to (x+1), Ar 2 represents a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6–20 carbon atoms or a substituted or unsubstituted monovalent heterocyclic group having 3–20 atoms, or Ar 1 and Ar 2 mutually bond together with A + in the formula to form a group possessing a cyclic structure with 3–8 atoms; and the x-number of P groups bonding to one or more of the m-number of Ar 1 groups individually represent —O—SO 2 R 1 , —O—S(O)R 2 , or —SO 2 R 3 , wherein R 1 , R 2 , and R 3 individually represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1–20 carbon atoms, a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3–20 carbon atoms, an alkenyl group having 2–20 carbon atoms, a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6–20 carbon atoms, or a substituted or unsubstituted monovalent heterocyclic group having 3–20 atoms, or a group —N(R′) 2 , wherein R′ individually represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1–20 carbon atoms, a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3–20 carbon atoms, an alkenyl group having 2–20 carbon atoms, a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6–20 carbon atoms, or a substituted or unsubstituted monovalent heterocyclic group having 3–20 atoms, or two R′ groups form, in combination and together with the nitrogen atom in the formula, a group having a cyclic structure with 3–8 atoms and wherein R 3 represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1–20 carbon atoms, a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3–20 carbon atoms, an alkenyl group having 2–20 carbon atoms, or a substituted or unsubstituted monovalent heterocyclic group having 3–20 atoms, or a group —N(R′) 2 , wherein R′ individually represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1–20 carbon atoms, a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3–20 carbon atoms, an alkenyl group having 2–20 carbon atoms, a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6–20 carbon atoms, or a substituted or unsubstituted monovalent heterocyclic group having 3–20 atoms, or two R′ groups form, in combination and together with the nitrogen atom in the formula, a group having a cyclic structure with 3–8 atoms.

2. The onium salt compound according to claim 1 , wherein A in formula (1) is a sulfur atom.

3. An onium salt compound having a cationic moiety of the following formula (2),

wherein A represents an iodine atom or a sulfur atom, when A is an iodine atom, m is 1 or 2 and n is 0 or 1, provided that (m+n)=2, and x is an integer of 1–10, and when A is a sulfur atom, m is 1–3 and n is 0–2, provided that (m+n)=3, and x is an integer of 1–15; Ar 1 represents a substituted or unsubstituted aromatic hydrocarbon group having 6–20 carbon atoms with a valence of 1 to (x+1) or a substituted or unsubstituted heterocyclic group having 3–20 atoms with a valence of 1 to (x+1), Ar 2 represents a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6–20 carbon atoms or a substituted or unsubstituted monovalent heterocyclic group having 3–20 atoms, or Ar 1 and Ar 2 mutually bond together with A + in the formula to form a group possessing a cyclic structure with 3–8 atoms and R 4 represents a hydrogen atom, fluorine atom, nitro group, cyano group, or a monovalent organic group having 1–20 carbon atoms.

4. The onium salt compound according to claim 3 , wherein A in formula (2) is a sulfur atom.

5. The onium salt compound according to claim 3 , wherein R 4 in the formula (2) is a group of the following formula (3),

wherein R 5 represents a substituted or unsubstituted alkyl group having 1–20 carbon atoms, a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3–20 carbon atoms, an alkenyl group having 2–20 carbon atoms, a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6–20 carbon atoms, a substituted or unsubstituted monovalent heterocyclic group having 3–20 atoms, or a group —N(R 2′ ) 2 , wherein R 2′ individually represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1–20 carbon atoms, a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3–20 carbon atoms, an alkenyl group having 2–20 carbon atoms, a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6–20 carbon atoms, or a substituted or unsubstituted, monovalent heterocyclic group having 3–20 atoms, or two R 2′ groups form, in combination and together with the nitrogen atom in the formula, a group having a cyclic structure with 3–8 atoms, p is an integer of 0–16, q is an integer of 0–8, and r is an integer of 1–3.

6. An onium salt compound according to claim 5 , wherein both p and q are 0 and both r's are 1.

7. An onium salt compound having a cationic moiety represented by the following formula (4)

wherein A represents an iodine atom or a sulfur atom, when A is an iodine atom, m is 1 or 2 and n is 0 or 1, provided that (m+n)=2, and x is an integer of 1–10, and when A is a sulfur atom, m is 1–3 and n is 0–2, provided that (m+n)=3, and x is an integer of 1–15; Ar 1 represents a substituted or unsubstituted aromatic hydrocarbon group having 6–20 carbon atoms with a valence of 1 to (x+1) or a substituted or unsubstituted heterocyclic group having 3–20 atoms with a valence of 1 to (x+1), Ar 2 represents a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6–20 carbon atoms or a substituted or unsubstituted monovalent heterocyclic group having 3–20 atoms, or Ar 1 and Ar 2 mutually bond together with A + in the formula to form a group possessing a cyclic structure with 3–8 atoms; p is an integer of 0–16; q is an integer of 0–8; and R 6 represents a substituted or unsubstituted alkyl group having 1–20 carbon atoms, a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3–20 carbon atoms, an alkenyl group having 2–20 carbon atoms, a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6–20 carbon atoms, or a substituted or unsubstituted monovalent heterocyclic group having 3–20 atoms, or a group or a group —N(R 3′ ) 2 , wherein R 3′ individually represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1–20 carbon atoms, a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3–20 carbon atoms, an alkenyl group having 2–20 carbon atoms, a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6–20 carbon atoms, or a substituted or unsubstituted, monovalent heterocyclic group having 3–20 atoms, or two R 3′ groups form, in combination and together with the nitrogen atom in the formula, a group having a cyclic structure with 3–8 atoms.

8. An onium salt compound having a cationic moiety represented by the following formula (5),

wherein A represents an iodine atom or a sulfur atom, when A is an iodine atom, m is 1 or 2 and n is 0 or 1, provided that (m+n)=2, and x is an integer of 1–10, and when A is a sulfur atom, m is 1–3 and n is 0–2, provided that (m+n)=3, and x is an integer of 1–15; Ar 1 represents a substituted or unsubstituted aromatic hydrocarbon group having 6–20 carbon atoms with a valence of 1 to (x+1) or a substituted or unsubstituted heterocyclic group having 3–20 atoms with a valence of 1 to (x+1), Ar 2 represents a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6–20 carbon atoms or a substituted or unsubstituted monovalent heterocyclic group having 3–20 atoms, or Ar 1 and Ar 2 mutually bond together with A + in the formula to form a group possessing a cyclic structure with 3–8 atoms, or Ar 1 and Ar 2 mutually bond together with A + in the formula to form a group possessing a cyclic structure with 3–8 atoms; R 7 represents a substituted or unsubstituted alkyl group having 1–20 carbon atoms, a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3–20 carbon atoms, an alkenyl group having 2–20 carbon atoms, a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6–20 carbon atoms, or a substituted or unsubstituted monovalent heterocyclic group having 3–20 atoms, or a group —N(R 4′ ) 2 , wherein R 4′ individually represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1–20 carbon atoms, a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3–20 carbon atoms, an alkenyl group having 2–20 carbon atoms, a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6–20 carbon atoms, or a substituted or unsubstituted, monovalent heterocyclic group having 3–20 atoms, or two R 4′ groups form, in combination and together with the nitrogen atom in the formula, a group having a cyclic structure with 3–8 atoms, s is an integer of 0–6, t is an integer of 0–5, and u is an integer of 1–3.

9. An onium salt compound having a cationic moiety represented by the following formula (6),

wherein A represents an iodine atom or a sulfur atom, when A is an iodine atom, m is 1 or 2 and n is 0 or 1, provided that (m+n)=2, and x is an integer of 1–10, and when A is a sulfur atom, m is 1–3 and n is 0–2, provided that (m+n)=3, and x is an integer of 1–15; Ar 1 represents a substituted or unsubstituted aromatic hydrocarbon group having 6–20 carbon atoms with a valence of 1 to (x+1) or a substituted or unsubstituted heterocyclic group having 3–20 atoms with a valence of 1 to (x+1), Ar 2 represents a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6–20 carbon atoms or a substituted or unsubstituted monovalent heterocyclic group having 3–20 atoms, or Ar 1 and Ar 2 mutually bond together with A + in the formula to form a group possessing a cyclic structure with 3–8 atoms, or Ar 1 and Ar 2 mutually bond together with A + in the formula to form a group possessing a cyclic structure with 3–8 atoms; R 8 and R 9 individually represent a substituted or unsubstituted alkyl group having 1–20 carbon atoms or a substituted or unsubstituted monovalent alicyclic group having 3–20 carbon atoms, or R 8 and R 9 may form, in combination and together with one carbon atom and two oxygen atoms in the formula, a group having a cyclic structure with 4–10 atoms; and v and w are respectively the integers of 0–5, satisfying the formula (v+w)≧1.

10. A positive tone radiation-sensitive resin composition comprising:

(A) at least one onium salt compound having a cation moiety of the following formula (1),

 wherein A represents an iodine atom or a sulfur atom, when A is an iodine atom, m is 1 or 2 and n is 0 or 1, provided that (m+n)=2, and x is an integer of 1–10, and when A is a sulfur atom, m is 1–3 and n is 0–2, provided that (m+n)=3, and x is an integer of 1–15; Ar 1 represents a substituted or unsubstituted aromatic hydrocarbon group having 6–20 carbon atoms with a valence of 1 to (x+1) or a substituted or unsubstituted heterocyclic group having 3–20 atoms with a valence of 1 to (x+1), Ar 2 represents a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6–20 carbon atoms or a substituted or unsubstituted monovalent heterocyclic group having 3–20 atoms, or Ar 1 and Ar 2 mutually bond together with A + in the formula to form a group possessing a cyclic structure with 3–8 atoms; and the x-number of P groups bonding to one or more of the m-number of Ar 1 groups individually represent —O—SO 2 R 1 , —O—S(O)R 2 , or —SO 2 R 3 , wherein R 1 , R 2 , and R 3 individually represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1–20 carbon atoms, a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3–20 carbon atoms, an alkenyl group having 2–20 carbon atoms, a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6–20 carbon atoms, or a substituted or unsubstituted monovalent heterocyclic group having 3–20 atoms, or a group —N(R′) 2 , wherein R′ individually represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1–20 carbon atoms, a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3–20 carbon atoms, an alkenyl group having 2–20 carbon atoms, a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6–20 carbon atoms, or a substituted or unsubstituted monovalent heterocyclic group having 3–20 atoms, or two R′ groups form, in combination and together with the nitrogen atom in the formula, a group having a cyclic structure with 3–8 atoms; and

(B) a resin having an acid-dissociable group and which is insoluble or scarcely soluble in alkali, but which becomes alkali soluble when the acid-dissociable group dissociates.

11. The positive tone radiation-sensitive resin composition according to claim 10 , wherein the onium salt compound is selected from the onium salt compounds having —SO 2 R 3 for the group P in the formula (1).

12. A positive tone radiation-sensitive resin composition comprising (A) at least one onium salt compound according to claim 3 as a photoacid generator; and (B) a resin having an acid-dissociable group and which is insoluble or scarcely soluble in alkali, but becomes alkali soluble when the acid-dissociable group dissociates.

13. A positive tone radiation-sensitive resin composition comprising: (A) at least one onium salt compound according to claim 5 as a photoacid generator; and (B) a resin having an acid-dissociable group and which is insoluble or scarcely soluble in alkali, but becomes alkali soluble when the acid-dissociable group dissociates.

14. An onium salt compound having a cation moiety of the following formula (1),

wherein A represents an iodine atom or a sulfur atom, when A is an iodine atom, m is 1 or 2 and n is 0 or 1, provided that (m+n)=2, and x is an integer of 1–10, and when A is a sulfur atom, m is 2 or 3 and n is 0 or 1, provided that (m+n)=3, and x is an integer of 1–15; Ar 1 represents a substituted or unsubstituted aromatic hydrocarbon group having 6–20 carbon atoms with a valence of 1 to (x+1) or a substituted or unsubstituted heterocyclic group having 3–20 atoms with a valence of 1 to (x+1), Ar 2 represents a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6–20 carbon atoms or a substituted or unsubstituted monovalent heterocyclic group having 3–20 atoms, or Ar 1 and Ar 2 mutually bond together with A + in the formula to form a group possessing a cyclic structure with 3–8 atoms; and the x-number of P groups bonding to the m-number of Ar 1 groups individually represent —O—SO 2 R 1 , —O—S(O)R 2 , or —SO 2 R 3 , wherein R 1 , R 2 , and R 3 individually represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1–20 carbon atoms, a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3–20 carbon atoms, an alkenyl group having 2–20 carbon atoms, a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6–20 carbon atoms, or a substituted or unsubstituted monovalent heterocyclic group having 3–20 atoms, or a group —N(R′) 2 , wherein R′ individually represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1–20 carbon atoms, a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3–20 carbon atoms, an alkenyl group having 2–20 carbon atoms, a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6–20 carbon atoms, or a substituted or unsubstituted monovalent heterocyclic group having 3–20 atoms, or two R′ groups form, in combination and together with the nitrogen atom in the formula, a group having a cyclic structure with 3–8 atoms.

15. A positive tone radiation-sensitive resin composition comprising:

(A) at least one onium salt compound having a cation moiety selected from the group consisting of:

as a photoacid generator and;

(B) a resin having an acid-dissociable group and which is insoluble or scarcely soluble in alkali, but becomes alkali soluble when the acid-dissociable group dissociates.