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

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

• -(M3)-(M4)-(M5)-(A2)- (2)
• in which
• M3 is represented by:
• 341
• M4 is represented by:
• 342
• M5 is represented by:
• 343
• wherein X7, X8, X9, X10, X11, X12, X13, X14, X16, X17 and X18 are the same or different and each is H or F;
• X15 is H, F or CF3;
• Y1 is an acid-labile or acid-degradable functional group;
• Z1 is a functional group which is not dissociated or degraded by an acid;
• Z2 is H, F or Cl;
• R2, Rf2 and Rf3 are the same or different and each is a fluorine-containing alkylene group having 1 to 20 carbon atoms, a fluorine-containing alkylene group having 2 to 100 carbon atoms and ether bond or a fluorine-containing arylene group having 3 to 20 carbon atoms;
• n3, n4 and n5 are the same or different and each is 0 or an integer of 1 or 2;
• n6, n7, n8 and n10 are the same or different and each is 0 or 1;
• n9 is 1,
• A2 is a structural unit derived from a monomer copolymerizable with the structural units M3 to M5,
• when M3+M4+M5 is assumed to be equal to 100% by mole, the percent by mole ratio M3/M4/M5 is 1 to 100/0 to 99/0 to 99,
• said fluorine-containing polymer comprises from 1 to 100% by mole of the structural unit M3, from 0 to 99% by mole of the structural unit M4, from 0 to 99% by mole of the structural unit M5 and from 0 to 99% by mole of the structural unit A2.

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

• -(M3a)-(M4a)-(M5a)-(A2)- (2a)
• in which
• M3a is represented by:
• 344
• M4a is represented by:
• 345
• M5a is represented by:
• 346
• wherein R2a is a divalent hydrocarbon group having 1 to 20 carbon atoms, a fluorine-containing alkylene group having 1 to 20 carbon atoms, a fluorine-containing alkylene group having 2 to 100 carbon atoms and ether bond or a fluorine-containing arylene group having 3 to 20 carbon atoms;
• n9 is 0 or 1;
• X7, X8, X9, X10, X11, X12, x13, X14, X15, X16, X17, X18, Y1, Z1, Z2, Rf2, Rf3, n3, n4, n5, n6, n7, n8 and n10 are as defined in said formula (2);
• at least one of X13, X14 and Z2 is F or X15 is F or CF3,
• A2 is a structural unit derived from a monomer copolymerizable with the structural units M3a to M5a,
• when M3a+M4a+M5a is assumed to be equal to 100% by mole, the percent by mole ratio M3a/(M4a+M5a) is 1 to 90/10 to 99,
• said fluorine-containing polymer comprises from 1 to 90% by mole of the structural unit M3a, from 0 to 99% by mole of the structural unit M4a, from 0 to 99% by mole of the structural unit M5a and from 0 to 99% by mole of the structural unit A2.

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

• -(M6)-(M7)-(A3)- (3)
• in which
• M6 is represented by:
• 349
• M7 is represented by:
• 350
• wherein X19, X20, X23, X24, X25 and X26 are the same or different and each is H or F;
• X21 and X22 are the same or different and each is H, F, Cl or CF3;
• Rf4 is a fluorine-containing alkylene group having 1 to 10 carbon atoms or a fluorine-containing alkylene group having 2 to 10 carbon atoms and ether bond;
• n12 is 0 or an integer of from 1 to 3;
• n11, n13, n14 and n15 are the same or different and each is 0 or 1;
• X27, X28, X29 and X30 are the same or different and each is H or F;
• Y1 is an acid-labile or acid-degradable functional group;
• R3 is a divalent hydrocarbon group having 1 to 20 carbon atoms, a fluorine-containing alkylene group having 1 to 20 carbon atoms, a fluorine-containing alkylene group having 2 to 100 carbon atoms and ether bond or a fluorine-containing arylene group having 3 to 20 carbon atoms;
• n16 is 0 or an integer of 1 or 2;
• n17 is 0 or 1,
• A3 is a structural unit derived from a monomer copolymerizable with the structural units M6 and M7,
• when M6+M7 is assumed to be equal to 100% by mole, the percent by mole ratio M6/M7 is 1 to 99/1 to 99,
• said polymer comprises from 1 to 99% by mole of the structural unit M6, from 1 to 99% by mole of the structural unit M7 and from 0 to 98% by mole of the structural unit A3.

A material for a fluorine-containing base polymer which is used for a photoresist and contains a polymer having a structural unit derived from a fluorine-containing ethylenic monomer and represented by the formula (4):

• 355
• wherein X31, X32 and X34 are the same or different and each is H or F;
• X33 is H, CH3, Cl, F or CF3;
• Y2 is an acid-reactive functional group;
• R4 is a divalent hydrocarbon group having 1 to 20 carbon atoms, a fluorine-containing alkylene group having 1 to 20 carbon atoms, a fluorine-containing alkylene group having 2 to 100 carbon atoms and ether bond or a fluorine-containing arylene group having 3 to 20 carbon atoms;
• p1 is 0, 1 or 2;
• q1 is 0 or 1;
• r1 is 0 or 1;
• s1 is 0 or 1;
• provided that s1 is 0 or R4 does not have fluorine atom, at least one of X31, X32 and X34 is fluorine atom or X33 is fluorine atom or CF3.

A material for a fluorine-containing base polymer which is used for a photoresist and contains a polymer comprising a structural unit (a) derived from an ethylenic monomer and represented by the formula (5):

• 356
• wherein X35, X36 and X38 are the same or different and each is H or F;
• X37 is H, CH3, Cl, F or CF3;
• Y2 is an acid-reactive functional group;
• R5 is a divalent hydrocarbon group having 1 to 20 carbon atoms, a fluorine-containing alkylene group having 1 to 20 carbon atoms, a fluorine-containing alkylene group having 2 to 100 carbon atoms and ether bond or a fluorine-containing arylene group having 3 to 20 carbon atoms;
• p2 is 0, 1 or 2;
• q2 is 0 or 1;
• r2 is 0 or 1;
• s2 is 0 or 1;
• and
• a structural unit (b) derived from a fluorine-containing ethylenic monomer and represented by the formula (6):
• 357
• wherein X39, X40 and X42 are the same or different and each is H or F;
• X41 is H, CH3, Cl, F or CF3;
• Z3 is H, F or Cl;
• R6 is a divalent hydrocarbon group having 1 to 20 carbon atoms, a fluorine-containing alkylene group having 1 to 20 carbon atoms, a fluorine-containing alkylene group having 2 to 100 carbon atoms and ether bond or a fluorine-containing arylene group having 3 to 20 carbon atoms;
• p3 is 0, 1 or 2;
• q3 is 0 or 1;
• r3 is 0 or 1;
• s3 is 0 or 1;
• provided that s3 is 0 or R6 does not have fluorine atom, at least one of X39, X40, X42 and Z3 is fluorine atom or X41 is F or CF3.

A material for a fluorine-containing base polymer which is used for a photoresist and contains a polymer comprising a structural unit (a) derived from an ethylenic monomer and represented by the formula (5):

• 358
• wherein X35, X36 and X38 are the same or different and each is H or F;
• X37 is H, CH3, Cl, F or CF3;
• Y2 is an acid-reactive functional group;
• R5 is a divalent hydrocarbon group having 1 to 20 carbon atoms, a fluorine-containing alkylene group having 1 to 20 carbon atoms, a fluorine-containing alkylene group having 2 to 100 carbon atoms and ether bond or a fluorine-containing arylene group having 3 to 20 carbon atoms;
• p2 is 0, 1 or 2;
• q2 is 0 or 1;
• r2 is 0 or 1;
• s2 is 0 or 1;
• and
• a fluorine-containing aliphatic ring structural unit (c) represented by the formula (7):
• 359
• wherein X43, X44, X47, X48, X49 and X50 are the same or different and each is H or F;
• X45 and X46 are the same or different and each is H, F, Cl or CF3;
• Rf5 is a fluorine-containing alkylene group having 1 to 10 carbon atoms or a fluorine-containing alkylene group having 1 to 10 carbon atoms and ether bond;
• n19 is 0 or an integer of from 1 to 3;
• n18, n20, n2 1 and n22 are the same or different and each is 0 or 1.

A chemically amplifying type photoresist composition which comprises:

• (A) a fluorine-containing polymer having an acid-reactive 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 (1):
• -(M1)-(M2)-(N)- (1)
• in which
• {circle over (1)} the structural unit M1 is a structural unit derived from an ethylenic monomer having an acid-reactive group,
• {circle over (2)} the structural unit M2 is a structural unit derived from a fluorine-containing ethylenic monomer and
• {circle over (3)} the structural unit N is a structural unit derived from an ethylenic 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 and does not have a polycyclic structure in its side chain.

A chemically amplifying type photoresist composition which comprises:

• (A) a fluorine-containing polymer having an acid-reactive 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 (1):
• -(M1)-(M2)-(N)- (1)
• in which
• {circle over (1)} the structural unit M1 is a structural unit derived from a fluorine-containing ethylenic monomer having an acid-reactive group,
• {circle over (2)} the structural unit M2 is a structural unit derived from a fluorine-containing ethylenic monomer and
• {circle over (3)} the structural unit N is a structural unit derived from an ethylenic 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 100/0 to 99,
• said polymer comprises from 1 to 100% by mole of the structural unit M1, from 0 to 99% by mole of the structural unit M2 and from 0 to 99% by mole of the structural unit N and does not have a polycyclic structure in its side chain.

A chemically amplifying type photoresist composition which comprises:

• (A) a fluorine-containing polymer having an acid-reactive 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 (1):
• -(M1)-(M2)-(N)- (1)
• in which
• {circle over (1)} the structural unit M1 is a structural unit derived from an ethylenic monomer having an acid-reactive group,
• {circle over (2)} the structural unit M2 is a structural unit having a fluorine-containing aliphatic ring structure in the polymer trunk chain, and
• {circle over (3)} the structural unit N is a structural unit derived from a fluorine-containing ethylenic 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 and does not have a polycyclic structure in its trunk chain and side chain.

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,
• wherein the fluorine-containing polymer (A) having an acid-reactive group is a polymer represented by the formula (1):
• -(M1)-(M2)-(M3)-(N)-
• in which
• {circle over (1)} the structural unit M1 is a structural unit derived from a fluorine-containing ethylenic monomer having a functional group which is dissociated or degraded by an acid and is converted to carboxyl group by a reaction with an acid,
• {circle over (2)} the structural unit M2 is a structural unit derived from an alicyclic monomer,
• {circle over (3)} the structural unit M3 is a structural unit derived from a fluorine-containing ethylenic monomer, and
• {circle over (4)} the structural unit N is a structural unit derived from an ethylenic 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/M2/M3 is 1 to 98/1 to 98/1 to 98,
• 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.

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

• -(M1)-(M2)-(M3)-(N)-
• in which
• {circle over (1)} the structural unit M1 is a structural unit derived from a fluorine-containing ethylenic monomer having a functional group which is dissociated or degraded by an acid and is converted to carboxyl group by a reaction with an acid,
• {circle over (2)} the structural unit M2 is a structural unit derived from an alicyclic monomer,
• {circle over (3)} the structural unit M3 is a structural unit derived from a fluorine-containing ethylenic monomer, and
• {circle over (4)} the structural unit N is a structural unit derived from an ethylenic monomer copolymerizable with M1, M2 and M3,
• in which the structural unit M1 is M1-1 represented by:
• 385
• wherein X1 and X2 are the same or different and each is H or F;
• X3 is H, Cl, CH3, F or CF3;
• Y1 is a functional group which is dissociated or degraded by an acid and is converted to carboxyl group by a reaction with an acid;
• R1 is a divalent hydrocarbon group having 1 to 20 carbon atoms, a fluorine-containing alkylene group having 1 to 20 carbon atoms, a fluorine-containing alkylene group having 2 to 100 carbon atoms and ether bond or a fluorine-containing arylene group having 3 to 20 carbon atoms;
• n1 is 0 or 1;
• provided that n1 is 0 or fluorine atom is not contained in R1, at least one of X1 and X2 is fluorine atom or X3 is fluorine atom or CF3,
• when M1+M2+M3 is assumed to be equal to 100% by mole, the percent by mole ratio M1/M2/M3 is 1 to 98/1 to 98/1 to 98,
• 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.

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 having the structural unit M1 derived from a fluorine-containing alicyclic monomer which has an acid-reactive group and is represented by the formula (1):
• 388
• 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;
• Y2 is an acid-reactive functional group;
• provided that b is 0 or R does not have fluorine atom, any one of A to C is fluorine atom or a fluorine-containing alkyl group.

A fluorine-containing polymer having a number average molecular weight of from 1,000 to 1,000,000 and having the structural unit M1 derived from a fluorine-containing alicyclic monomer which has an acid-reactive group and is represented by the formula (1):

• 392
• 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;
• Y2 is an acid-reactive functional group;
• provided that b is 0 or R does not have fluorine atom, any one of A to C is fluorine atom or a fluorine-containing alkyl group.