Fluorinated monomer of cyclic acetal structure, polymer, resist protective coating composition, resist composition, and patterning process
A fluorinated monomer of cyclic acetal structure has formula (1) wherein R is a C 1 -C 20 alkyl group which may be substituted with halogen or separated by oxygen or carbonyl, and Z is a divalent organic group which forms a ring with alkylenoxy and contains a polymerizable unsaturated group. A polymer derived from the fluorinated monomer may be endowed with appropriate water repellency, water sliding property, lipophilicity, acid lability and hydrolyzability and is useful in formulating a protective coating composition and a resist composition.
1. A polymer comprising recurring units of the general formula (6) and having a weight average molecular weight of 1,000 to 500,000,
wherein R 1 is hydrogen, methyl or trifluoromethyl, and Y is a structure having the general formula (Y-1), (Y-2) or (Y-3),
in formula (Y-1), R 2a , R 2b , R 3a , and R 3b are each independently a single bond, hydrogen, hydroxyl, halogen, or a straight, branched or cyclic monovalent C 1 -C 15 organic group, or any two of R 2a , R 2b , R 3a , and R 3b may bond together to form a ring with the carbon atom to which they are attached, the structure (Y-1) is linked to the —(C═O)—O— linkage in recurring unit (6) via any one of R 2a , R 2b , R 3a , and R 3b ,
in formula (Y-2), R 5a , R 5b , R 6a , R 6b , R 7a , and R 7b are each independently a single bond, hydrogen, hydroxyl, halogen, or a straight, branched or cyclic monovalent C 1 -C 15 organic group, or any two of R 5a , R 5b , R 6a , R 6b , R 7a , and R 7b may bond together to form a ring with the carbon atom to which they are attached, the structure (Y-2) is linked to the —(C═O)—O— linkage in recurring unit (6) via any one of R 5a , R 5b , R 6a , R 6b , R 7a , and R 7b ,
in formula (Y-3), R 8a , R 8b , R 9a , and R 9b are each independently a single bond, hydrogen, hydroxyl, halogen, or a straight, branched or cyclic monovalent C 1 -C 15 organic group, or any two of R 8a , R 8b , R 9a , and R 9b may bond together to form a ring with the carbon atom to which they are attached, the structure (Y-3) is linked to the —(C═O)—O— linkage in recurring unit (6) via any one of R 8a , R 8b , R 9a , and R 9b , and
R 10 is a straight, branched or cyclic C 1 -C 19 alkyl group in which at least one hydrogen atom may be substituted by a halogen atom or at least one methylene moiety may be substituted by an oxygen atom or carbonyl group,
with the proviso that when the structure (Y-1), (Y-2) or (Y-3) is linked to the —(C═O)—O—linkage in recurring unit (6) via a linking group which is any one of R 2a , R 2b , R 3a , R 3b , R 5a , R 5b , R 6a , R 6b , R 7a , R 7b , R 8a , R 8b , R 9a , and R 9b , the linking group is an organic group as defined above, but having a valence bond as a result of one hydrogen atom being eliminated therefrom.
2. The polymer of claim 1 , further comprising recurring units of one or more type selected from the general formulae (8a) to (8f):
wherein R 1 is hydrogen, methyl or trifluoromethyl, R 13a and R 13b each are hydrogen or a straight, branched or cyclic C 1 -C 15 alkyl group, or R 13a and R 13b may bond together to form a ring with the carbon atom to which they are attached, R 14 is hydrogen, a straight, branched or cyclic C 1 -C 15 alkyl or fluoroalkyl group, or an acid labile group, R 15 is a straight, branched or cyclic C 1 -C 15 fluoroalkyl group, and R 16 is an acid labile group.
3. A resist protective coating composition comprising a polymer comprising recurring units of the general formula (6):
wherein R 1 is hydrogen, methyl or trifluoromethyl, and Y is a structure having the general formula (Y-1), (Y-2) or (Y-3),
in formula (Y-1), R 2a , R 2b , R 3a , and R 3b are each independently a single bond, hydrogen, hydroxyl, halogen, or a straight, branched or cyclic monovalent C 1 -C 15 organic group, or any two of R 2a , R 2b , R 3a , and R 3b may bond together to form a ring with the carbon atom to which they are attached, the structure (Y-1) is linked to the —(C═O)—O— linkage in recurring unit (6) via any one of R 2a , R 2b , R 3a , and R 3b ,
in formula (Y-2), R 5a , R 5b , R 6a , R 6b , R 7a , and R 7b are each independently a single bond, hydrogen, hydroxyl, halogen, or a straight, branched or cyclic monovalent C 1 -C 15 organic group, or any two of R 5a ,R 5b , R 6a , R 6b , R 7a , and R 7b may bond together to form a ring with the carbon atom to which they are attached, the structure (Y-2) is linked to the —(C═O)—O— linkage in recurring unit (6) via any one of R 5a , R 5b , R 6a , R 6b , R 7a , and R 7b ,
in formula (Y-3), R 8a , R 8b , R 9a , and R 9b are each independently a single bond, hydrogen, hydroxyl, halogen, or a straight, branched or cyclic monovalent C 1 -C 15 organic group, or any two of R 8a , R 8b , R 9a , and R 9b may bond together to form a ring with the carbon atom to which they are attached, the structure (Y-3) is linked to the —(C═O)—O— linkage in recurring unit (6) via any one of R 8a , R 8b , R 9a , and R 9b , and
R 10 is a straight, branched or cyclic C 1 -C 19 alkyl group in which at least one hydrogen atom may be substituted by a halogen atom or at least one methylene moiety may be substituted by an oxygen atom or carbonyl group,
with the proviso that when the structure (Y-1), (Y-2) or (Y-3) is linked to the —(C═O)—O— linkage in recurring unit (6) via a linking group which is any one of R 2a , R 2b , R 3a , R 3b , R 5a , R 5b , R 6a , R 6b , R 7a , R 7b , R 8a , R 8b , R 9a , and R 9b , the linking group is an organic group as defined above, but having a valence bond as a result of one hydrogen atom being eliminated therefrom.
4. The resist protective coating composition of claim 3 wherein said polymer further comprises recurring units of one or more type selected from the general formulae (8a) to (8f):
wherein R 1 is hydrogen, methyl or trifluoromethyl, R 13a and R 13b each are hydrogen or a straight, branched or cyclic C 1 -C 15 alkyl group, or R 13a and R 13b may bond together to form a ring with the carbon atom to which they are attached, R 14 is hydrogen, a straight, branched or cyclic C 1 -C 15 alkyl or fluoroalkyl group, or an acid labile group, R 15 is a straight, branched or cyclic C 1 -C 15 fluoroalkyl group, and R 16 is an acid labile group.
5. The protective coating composition of claim 3 , further comprising a second polymer comprising recurring units of the general formula (9) or (10):
wherein R 31a and R 31b are hydrogen or methyl,
R 32 is a single bond, C 1 -C 4 alkylene, phenylene, —C(═O)—O—, or —C(═O)—NH—,
R 33 is a single bond or a straight, branched or cyclic C 1 -C 8 alkylene group,
R 34a to R 34d and R 36a to R 36c are each independently hydrogen, a straight, branched or cyclic C 1 -C 12 alkyl, alkenyl, oxoalkyl or oxoalkenyl group, C 6 -C 20 aryl group, or C 7 -C 12 aralkyl or aryloxoalkyl group, in which some or all hydrogen atoms may be substituted by alkoxy groups, R 34a to R 34d and R 36a to R 36c may contain a nitrogen atom, ether group, ester group, hydroxyl group or carboxyl group therein, any two of R 34a to R 34d and R 36a to R 36c may bond together to form a ring with the nitrogen atom to which they are attached, and when they form a ring, they are each independently a C 3 -C 15 alkylene or a hetero-aromatic ring having the nitrogen atom therein,
R 35 is a straight, branched or cyclic C 1 -C 8 alkylene group, and
R 37 is a straight, branched or cyclic C 1 -C 20 alkyl group which may contain carbonyl, ester, ether or halogen, or a C 6 -C 15 aryl group which may contain carbonyl, ester, ether, halogen, or C 1 -C 15 alkyl or fluoroalkyl.
6. The protective coating composition of claim 5 , wherein the second polymer further comprises recurring units of the general formula (11):
wherein R 31c is hydrogen or methyl, R 38a and R 38b are hydrogen or a straight, branched or cyclic C 1 -C 15 alkyl group, or R 38a and R 38b may bond together to form a ring with the carbon atom to which they are attached.
7. A resist protective coating composition comprising a polymer comprising recurring units of the general formula (5) and a second polymer comprising recurring units of the general formula (9) or (10):
wherein R 1 is hydrogen, methyl or trifluoromethyl, and X is a structure having the general formula (X-1), (X-2) or (X-3),
in formula (X-1) R 2a , R 2b , R 3a , and R 3b are each independently a single bond, hydrogen, hydroxyl, halogen, or a straight, branched or cyclic monovalent C 1 -C 15 organic group, or any two of R 2a , R 2b , R 3a , and R 3b may bond together to form a ring with the carbon atom to which they are attached, the structure (X-1) is linked to the —(C═O)—O— linkage in recurring unit (5) via any one of R 2a , R 2b , R 3a , and R 3b ,
in formula (X-2), R 5a , R 5b , R 6a , R 6b , R 7a , are R 7b each independently a single bond, hydrogen, hydroxyl, halogen, or a straight, branched or cyclic monovalent C 1 -C 15 organic group, or any two of R 5a ,R 5b , R 6a , R 6b , R 7a , and R 7b may bond together to form a ring with the carbon atom to which they are attached, the structure (X-2) is linked to the —(C═O)—O— linkage in recurring unit (5) via any one of R 5a ,R 5b , R 6a , R 6b ,R 7a , and R 7b ,
in formula (X-3), R 8a , R 8b , R 9a , and R 9b are each independently a single bond, hydrogen, hydroxyl, halogen, or a straight, branched or cyclic monovalent C 1 -C 15 organic group, or any two of R 8a , R 8b , R 9a , and R 9b may bond together to form a ring with the carbon atom to which they are attached, the structure (X-3) is linked to the —(C═O)—O— linkage in recurring unit (5) via any one of R 8a , R 8b , R 9a , and R 9b ,
R 4 is a straight, branched or cyclic C 1 -C 20 alkyl group in which at least one hydrogen atom may be substituted by a halogen atom or at least one methylene moiety may be substituted by an oxygen atom or carbonyl group,
with the proviso that when the structure (X-1), (X-2) or (X-3) is linked to the —(C═O)—O— linkage in recurring unit (5) via a linking group which is any one of R 2a , R 2b , R 3a , R 3b , R 5a , R 5b , R 6a , R 6b , R 7a , R 7b , R 8a , R 8b , R 9a , and R 9b , the linking group is an organic group as defined above, but having a valence bond as a result of one hydrogen atom being eliminated therefrom,
wherein R 31a and R 31b are hydrogen or methyl,
R 32 is a single bond, C 1 -C 4 alkylene, phenylene, —C(═O)—O—, or —C(═O)—NH—,
R 33 is a single bond or a straight, branched or cyclic C 1 -C 8 alkylene group,
R 34a to R 34d and R 36a to R 36c are each independently hydrogen, straight, branched or cyclic C 1 -C 12 alkyl, alkenyl, oxoalkyl or oxoalkenyl group, C 6 -C 20 aryl group, or C 7 -C 12 aralkyl or aryloxoalkyl group, in which some or all hydrogen atoms may be substituted by alkoxy groups, R 34a to R 34d and R 36a to R 36c may contain a nitrogen atom, ether group, ester group, hydroxyl group or carboxyl group therein, any two of R 34a to R 34d and R 36a to R 36c may bond together to form a ring with the nitrogen atom to which they are attached, and when they form a ring, they are each independently a C 3 -C 15 alkylene or a hetero-aromatic ring having the nitrogen atom therein,
R 35 is a straight, branched or cyclic C 1 -C 8 alkylene group, and
R 37 is a straight, branched or cyclic C 1 -C 20 alkyl group which may contain carbonyl, ester, ether or halogen, or a C 6 -C 15 aryl group which may contain carbonyl, ester, ether, halogen, or C 1 -C 15 alkyl or fluoroalkyl.
8. The protective coating composition of claim 7 , wherein the second polymer further comprises recurring units of the general formula (11):
wherein R 31c is hydrogen or methyl, R 38a and R 38b are hydrogen or a straight, branched or cyclic C 1 -C 15 alkyl group, or R 38a and R 38b may bond together to form a ring with the carbon atom to which they are attached.
9. A resist protective coating composition comprising a polymer comprising recurring units of the general formula (5) and an ether compound of 8 to 12 carbon atoms as a solvent:
wherein R 1 is hydrogen, methyl or trifluoromethyl, and X is a structure having the general formula (X-1), (X-2) or (X-3),
in formula (X-1), R 2a , R 2b , R 3a , and R 3b are each independently a single bond, hydrogen, hydroxyl, halogen, or a straight, branched or cyclic monovalent C 1 -C 15 organic group, or any two of R 2a , R 2b , R 3a , and R 3b may bond together to form a ring with the carbon atom to which they are attached, the structure (X-1) is linked to the —(C═O)—O— linkage in recurring unit (5) via any one of R 2a , R 2b , R 3a , and R 3b ,
in formula (X-2), R 5a , R 5b , R 6a , R 6b , R 7a , and R 7b are each independently a single bond, hydrogen, hydroxyl, halogen, or a straight, branched or cyclic monovalent C 1 -C 15 organic group, or any two of R 5a , R 5b , R 6a , R 6b , R 7a , and R 7b may bond together to form a ring with the carbon atom to which they are attached, the structure (X-2) is linked to the —(C═O)—O— linkage in recurring unit (5) via any one of R 5a , R 5b , R 6a , R 6b ,R 7a , and R 7b ,
in formula (X-3), R 8a , R 8b , R 9a , and R 9b are each independently a single bond, hydrogen, hydroxyl, halogen, or a straight, branched or cyclic monovalent C 1 -C 15 organic group, or any two of R 8a , R 8b , R 9a , and R 9b may bond together to form a ring with the carbon atom to which they are attached, the structure (X-3) is linked to the —(C═O)—O— linkage in recurring unit (5) via any one of R 8a , R 8b , R 9a , and R 9b ,
R 4 is a straight, branched or cyclic C 1 -C 20 alkyl group in which at least one hydrogen atom may be substituted by a halogen atom or at least one methylene moiety may be substituted by an oxygen atom or carbonyl group,
with the proviso that when the structure (X-1), (X-2) or (X-3) is linked to the —(C═O)—O— linkage in recurring unit (5) via a linking group which is any one of R 2a , R 2b , R 3a , R 3b , R 5a , R 5b , R 6a , R 6b , R 7a , R 7b , R 8a , R 8b , R 9a , and R 9b , the linking group is an organic group as defined above, but having a valence bond as a result of one hydrogen atom being eliminated therefrom.
10. The protective coating composition of claim 9 wherein the solvent comprises at least one ether compound of 8 to 12 carbon atoms selected from the group consisting of di-n-butyl ether, diisobutyl ether, di-sec-butyl ether, di-n-pentyl ether, diisopentyl ether, di-sec-pentyl ether, di-t-amyl ether, and di-n-hexyl ether.
11. The protective coating composition of claim 9 wherein the solvent comprises a mixture of the ether compound and 0.1 to 90% by weight of an alcohol of 4 to 10 carbon atoms.
12. A pattern forming process comprising the steps of (1) applying a resist material onto a substrate to form a photoresist film, (2) applying a resist protective coating composition onto the photoresist film to form a protective coating thereon, (3) heat treating and exposing the coated substrate to high-energy radiation from a projection lens through a photomask while holding a liquid between the substrate and the projection lens, and (4) developing with a developer,
said resist protective coating composition comprising a polymer comprising recurring units of the general formula (5):
wherein R 1 is hydrogen, methyl or trifluoromethyl, and X is a structure having the general formula (X-1) or (X-3),
in formula (X-1), R 2a , R 2b , R 3a , and R 3b are each independently a single bond, hydrogen, hydroxyl, halogen, or a straight, branched or cyclic monovalent C 1 -C 15 organic group, or any two of R 2a , R 2b , R 3a , and R 3b may bond together to form a ring with the carbon atom to which they are attached, the structure (X-1) is linked to the —(C═O)—O— linkage in recurring unit (5) via any one of R 2a , R 2b , R 3a , and R 3b ,
in formula (X-3), R 8a , R 8b , R 9a , and R 9b are each independently a single bond, hydrogen, hydroxyl, halogen, or a straight, branched or cyclic monovalent C 1 -C 15 organic group, or any two of R 8a , R 8b , R 9a , and R 9b may bond together to form a ring with the carbon atom to which they are attached, the structure (X-3) is linked to the —(C═O)—O— linkage in recurring unit (5) via any one of R 8a , R 8b , R 9a , and R 9b ,
R 4 is a straight, branched or cyclic C 1 -C 20 alkyl group in which at least one hydrogen atom may be substituted by a halogen atom or at least one methylene moiety may be substituted by an oxygen atom or carbonyl group,
with the proviso that when the structure (X-1) or (X-3) is linked to the —(C═O)—O— linkage in recurring unit (5) via a linking group which is any one of R 2a , R 2b , R 3a , R 3b , R 8a , R 8b , R 9a , and R 9b , the linking group is an organic group as defined above, but having a valence bond as a result of one hydrogen atom being eliminated therefrom.
13. The process of claim 12 wherein the liquid is water.
14. The process of claim 12 wherein the high-energy radiation has a wavelength in the range of 180 to 250 nm.
15. The process of claim 12 wherein the developing step uses a liquid alkaline developer for thereby developing the photoresist film to form a resist pattern and stripping the resist protective coating therefrom at the same time.
16. A lithography process for forming a pattern, comprising the steps of forming a protective coating on a photoresist layer disposed on a mask blank, exposing the layer structure in vacuum to electron beam, and developing,
the protective coating being formed of a protective coating composition comprising a polymer comprising recurring units of the general formula (5):
wherein R 1 is hydrogen, methyl or trifluoromethyl, and X is a structure having the general formula (X-1) or (X-3),
in formula (X-1), R 2a , R 2b , R 3a , and R 3b are each independently a single bond, hydrogen, hydroxyl, halogen, or a straight, branched or cyclic monovalent C 1 -C 15 organic group, or any two of R 2a , R 2b , R 3a , and R 3b may bond together to form a ring with the carbon atom to which they are attached, the structure (X-1) is linked to the —(C═O)—O— linkage in recurring unit (5) via any one of R 2a , R 2b , R 3a , and R 3b ,
in formula (X-3), R 8a , R 8b , R 9a , and R 9b are each independently a single bond, hydrogen, hydroxyl, halogen, or a straight, branched or cyclic monovalent C 1 -C 15 organic group, or any two of R 8a , R 8b , R 9a , and R 9b may bond together to form a ring with the carbon atom to which they are attached, the structure (X-3) is linked to the —(C═O)—O— linkage in recurring unit (5) via any one of R 8a , R 8b , R 9a , and R 9b ,
R 4 is a straight, branched or cyclic C 1 -C 20 alkyl group in which at least one hydrogen atom may be substituted by a halogen atom or at least one methylene moiety may be substituted by an oxygen atom or carbonyl group,
with the proviso that when the structure (X-1) or (X-3) is linked to the —(C═O)—O— linkage in recurring unit (5) via a linking group which is any one of R 2a , R 2b , R 3a , R 3b , R 8a , R 8b , R 9a , and R 9b , the linking group is an organic group as defined above, but having a valence bond as a result of one hydrogen atom being eliminated therefrom.
17. A resist composition comprising (A) a polymer comprising recurring units of the general formula (6), (B) a base polymer having a structure derived from lactone ring, hydroxyl group and/or maleic anhydride, said base polymer becoming soluble in alkaline developer under the action of acid, (C) a compound capable of generating an acid upon exposure to high-energy radiation, and (D) an organic solvent,
wherein R 1 is hydrogen, methyl or trifluoromethyl, and Y is a structure having the general formula (Y-1), (Y-2) or (Y-3),
in formula (Y-1), R 2a , R 2b , R 3a , and R 3b are each independently a single bond, hydrogen, hydroxyl, halogen, or a straight, branched or cyclic monovalent C 1 -C 15 organic group, or any two of R 2a , R 2b , R 3a , and R 3b may bond together to form a ring with the carbon atom to which they are attached, the structure (Y-1) is linked to the —(C═O)—O— linkage in recurring unit (6) via any one of R 2a , R 2b , R 3a , and R 3b ,
in formula (Y-2), R 5a , R 5b , R 6a , R 6b , R 7a , and R 7b are each independently a single bond, hydrogen, hydroxyl, halogen, or a straight, branched or cyclic monovalent C 1 -C 15 organic group, or any two of R 5a , R 5b , R 6a , R 6b , R 7a , and R 7b may bond together to form a ring with the carbon atom to which they are attached, the structure (Y-2) is linked to the —(C═O)—O— linkage in recurring unit (6) via any one of R 5a , R 5b , R 6a , R 6b , R 7a , and R 7b ,
in formula (Y-3), R 8a , R 8b , R 9a , and R 9b are each independently a single bond, hydrogen, hydroxyl, halogen, or a straight, branched or cyclic monovalent C 1 -C 15 organic group, or any two of R 8a , R 8b , R 9a , and R 9b may bond together to form a ring with the carbon atom to which they are attached, the structure (Y-3) is linked to the —(C═O)—O— linkage in recurring unit (6) via any one of R 8a , R 8b , R 9a , and R 9b , and
R 10 is a straight, branched or cyclic C 1 -C 19 alkyl group in which at least one hydrogen atom may be substituted by a halogen atom or at least one methylene moiety may be substituted by an oxygen atom or carbonyl group,
with the proviso that when the structure (Y-1), (Y-2) or (Y-3) is linked to the —(C═O)—O— linkage in recurring unit (6) via a linking group which is any one of R 2a , R 2b , R 3a , R 3b , R 5a , R 5b , R 6a , R 6b , R 7a , R 7b , R 8a , R 8b , R 9a, and R 9b , the linking group is an organic group as defined above, but having a valence bond as a result of one hydrogen atom being eliminated therefrom.
18. The resist composition of claim 17
wherein said polymer (A) comprises recurring units as set forth in claim 17 , and further recurring units of one or more type selected from the general formulae (8a) to (8f):
wherein R 1 is hydrogen, methyl or trifluoromethyl, R 13a and R 13b each are hydrogen or a straight, branched or cyclic C 1 -C 15 alkyl group, or R 13a and R 13b may bond together to form a ring with the carbon atom to which they are attached, R 14 is hydrogen, a straight, branched or cyclic C 1 -C 15 alkyl or fluoroalkyl group, or an acid labile group, R 15 is a straight, branched or cyclic C 1 -C 15 fluoroalkyl group, and R 16 is an acid labile group.
19. A pattern forming process comprising the steps of:
(1) applying the resist composition of claim 17 onto a substrate to form a resist film,
(2) heat treating the resist film and exposing it to high-energy radiation through a photomask, and
(3) developing the exposed resist film with a developer.
20. A pattern forming process comprising the steps of:
(1) applying the resist composition of claim 17 onto a substrate to form a resist film,
(2) heat treating the coated substrate, and exposing it to high-energy radiation through a photomask while keeping a liquid between a projection lens and the coated substrate, and
(3) developing the exposed resist film with a developer.
21. A pattern forming process comprising the steps of:
(1) applying the resist composition of claim 17 onto a substrate to form a resist film,
(2) forming a protective coating on the resist film,
(3) heat treating the coated substrate, and exposing it to high-energy radiation through a photomask while keeping a liquid between a projection lens and the coated substrate, and
(4) developing the exposed resist film with a developer.
22. A pattern forming process comprising the steps of:
(1) applying the resist composition of claim 17 onto a mask blank substrate to form a coating,
(2) heat treating the coating and irradiating it in vacuum with an electron beam, and
(3) developing the coating with a developer.
23. A resist protective coating composition comprising a polymer comprising recurring units of the general formula (7) and a second polymer comprising recurring units of the general formula (9) or (10):
wherein R 1 is hydrogen, methyl or trifluoromethyl, and Z is a structure having the general formula (Z-1), (Z-2) or (Z-3),
in formula (Z-1), R 2a , R 2b , R 3a , and R 3b are each independently a single bond, hydrogen, hydroxyl, halogen, or a straight, branched or cyclic monovalent C 1 -C 15 organic group, or any two of R 2a , R 2b , R 3a , and R 3b ) may bond together to form a ring with the carbon atom to which they are attached, the structure (Z-1) is linked to the —(C═O)—O— linkage in recurring unit (7) via any one of R 2a , R 2b , R 3a , and R 3b ,
in formula (Z-2), R 5a , R 5b , R 6a , R 6b , R 7a , and R 7b are each independently a single bond, hydrogen, hydroxyl, halogen, or a straight, branched or cyclic monovalent C 1 -C 15 organic group, or any two of R 5a , R 5b , R 6a , R 6b , R 7a , and R 7b may bond together to form a ring with the carbon atom to which they are attached, the structure (Z-2) is linked to the —(C═O)—O— linkage in recurring unit (7) via any one of R 5a , R 5b , R 6a , R 6b , R 7a , and R 7b ,
in formula (Z-3), R 8a , R 8b , R 9a , and R 9b are each independently a single bond, hydrogen, hydroxyl, halogen, or a straight, branched or cyclic monovalent C 1 -C 15 organic group, or any two of R 8a , R 8b , R 9a , and R 9b may bond together to form a ring with the carbon atom to which they are attached, the structure (Z-3) is linked to the —(C═O)—O— linkage in recurring unit (7) via any one of R 8a , R 8b , R 9a , and R 9b ,
R 11 is hydrogen or a straight, branched or cyclic C 1 -C 18 alkyl group in which at least one hydrogen atom may be substituted by a halogen atom or at least one methylene moiety may be substituted by an oxygen atom or carbonyl group,
R 12 is a straight, branched or cyclic C 1 -C 19 alkyl group in which at least one hydrogen atom may be substituted by a halogen atom or at least one methylene moiety may be substituted by an oxygen atom or carbonyl group, or R 11 and R 12 may bond together to form a cyclic structure with the carbon and oxygen atoms to which they are attached,
with the proviso that when the structure (Z-1), (Z-2) or (Z-3) is linked to the —(C═O)—O— linkage in recurring unit (7) via a linking group which is any one of R 2a , R 2b , R 3a , R 3b , R 5a , R 5b , R 6a , R 6b , R 7a , R 7b , R 8a , R 8b , R 9a , and R 9b the linking group is an organic group as defined above, but having a valence bond as a result of one hydrogen atom being eliminated therefrom,
wherein R 31a and R 31b are hydrogen or methyl,
R 32 is a single bond, C 1 -C 4 alkylene, phenylene, —C(═O)—O—or —C(═O)—NH—,
R 33 is a single bond or a straight, branched or cyclic C 1 -C 8 alkylene group,
R 34a to R 34d and R 36a to R 36c are each independently hydrogen, a straight, branched or cyclic C 1 -C 12 alkyl, alkenyl, oxoalkyl or oxoalkenyl group, C 6 -C 20 aryl group, or C 7 -C 12 aralkyl or aryloxoalkyl group, in which some or all hydrogen atoms may be substituted by alkoxy groups, R 34a to R 34d and R 36a to R 36c may contain a nitrogen atom, ether group, ester group, hydroxyl group or carboxyl group therein, any two of R 34a to R 34d and R 36a to R 36c may bond together to form a ring with the nitrogen atom to which they are attached, and when they form a ring, they are each independently a C 3 -C 15 alkylene or a hetero-aromatic ring having the nitrogen atom therein,
R 35 is a straight, branched or cyclic C 1 -C 8 alkylene group, and
R 37 is a straight, branched or cyclic C 1 -C 20 alkyl group which may contain carbonyl, ester, ether or halogen, or a C 6 -C 15 aryl group which may contain carbonyl, ester, ether, halogen, or C 1 -C 15 alkyl or fluoroalkyl.
24. The protective coating composition of claim 23 , wherein the second polymer further comprises recurring units of the general formula (11):
wherein R 31c is hydrogen or methyl, R 38a and R 38b are hydrogen or a straight, branched or cyclic C 1 -C 15 alkyl group, or R 38a and R 38b may bond together to form a ring with the carbon atom to which they are attached.
25. A resist protective coating composition comprising a polymer comprising recurring units of the general formula (6) and an ether compound of 8 to 12 carbon atoms as a solvent:
wherein R 1 is hydrogen, methyl or trifluoromethyl, and Y is a structure having the general formula (Y-1), (Y-2) or (Y-3),
in formula (Y-1), R 2a , R 2b , R 3a , and R 3b are each independently a single bond, hydrogen, hydroxyl, halogen, or a straight, branched or cyclic monovalent C 1 -C 15 organic group, or any two of R 2a , R 2b , R 3a , and R 3b may bond together to form a ring with the carbon atom to which they are attached, the structure (Y-1) is linked to the —(C═O)—O— linkage in recurring unit (6) via any one of R 2a , R 2b , R 3a , and R 3b , in formula (Y-2), and R 5a , R 5b , R 6a , R 6b , R 7a , and R 7b are each independently a single bond, hydrogen, hydroxyl, halogen, or a straight, branched or cyclic monovalent C 1 -C 15 organic group, or any two of R 5a , R 5b , R 6a , R 6b , R 7a , and R 7b may bond together to form a ring with the carbon atom to which they are attached, the structure (Y-2) is linked to the —(C═O)—O— linkage in recurring unit (6) via any one of R 5a , R 5b , R 6a , R 6b , R 7a , and R 7b ,
in formula (Y-3), R 8a , R 8b , R 9a , and R 9b are each independently a single bond, hydrogen, hydroxyl, halogen, or a straight, branched or cyclic monovalent C 1 -C 15 organic group, or any two of R 8a , R 8b , R 9a , and R 9b may bond together to form a ring with the carbon atom to which they are attached, the structure (Y-3) is linked to the —(C═O)—O— linkage in recurring unit (6) via any one of R 8a , R 8b , R 9a , and R 9b , and
R 10 is a straight, branched or cyclic C 1 -C 19 alkyl group in which at least one hydrogen atom may be substituted by a halogen atom or at least one methylene moiety may be substituted by an oxygen atom or carbonyl group,
with the proviso that when the structure (Y-1), (Y-2) or (Y-3) is linked to the —(C═O)—O— linkage in recurring unit (6) via a linking group which is any one of R 2a , R 2b , R 3a , R 3b , R 5a , R 5b , R 6a , R 6b , R 7a , R 7b , R 8a , R 8b , R 9a , and R 9b , the linking group is an organic group as defined above, but having a valence bond as a result of one hydrogen atom being eliminated therefrom.
26. The protective coating composition of claim 25 wherein the solvent comprises a mixture of the ether compound and 0.1 to 90% by weight of an alcohol of 4 to 10 carbon atoms.
27. A resist protective coating composition comprising a polymer comprising recurring units of the general formula (7) and an ether compound of 8 to 12 carbon atoms as a solvent:
wherein R 1 is hydrogen, methyl or trifluoromethyl, and Z is a structure having the general formula (Z-1), (Z-2) or (Z-3), in formula (Z-1), R 2a , R 2b , R 3a , and R 3b are each independently a single bond, hydrogen, hydroxyl, halogen, or a straight, branched or cyclic monovalent C 1 -C 15 organic group, or any two of R 2a , R 2b , R 3a , and R 3b may bond together to form a ring with the carbon atom to which they are attached, the structure (Z-1) is linked to the —(C═O)—O— linkage in recurring unit (7) via any one of R 2a , R 2b , R 3a , and R 3b ,
in formula (Z-2), R 5a , R 5b , R 6a , R 6b ,R 7a , and R 7b are each independently a single bond, hydrogen, hydroxyl, halogen, or a straight, branched or cyclic monovalent C 1 -C 15 organic group, or any two of R 5a , R 5b , R 6a , R 6b , R 7a , and R 7b may bond together to form a ring with the carbon atom to which they are attached, the structure (Z-2) is linked to the —(C═O)—O— linkage in recurring unit (7) via any one of R 5a , R 5b , R 6a , R 6b , R 7a , and R 7b ,
in formula (Z-3), R 8a , R 8b , R 9a , and R 9b are each independently a single bond, hydrogen, hydroxyl, halogen, or a straight, branched or cyclic monovalent C 1 -C 15 organic group, or any two of R 8a , R 8b , R 9a , and R 9b may bond together to form a ring with the carbon atom to which they are attached, the structure (Z-3) is linked to the —(C═O)—O— linkage in recurring unit (7) via any one of R 8a , R 8b , R 9a , and R 9b ,
R 11 is hydrogen or a straight, branched or cyclic C 1 -C 18 alkyl group in which at least one hydrogen atom may be substituted by a halogen atom or at least one methylene moiety may be substituted by an oxygen atom or carbonyl group,
R 12 is a straight, branched or cyclic C 1 -C 19 alkyl group in which at least one hydrogen atom may be substituted by a halogen atom or at least one methylene moiety may be substituted by an oxygen atom or carbonyl group, or R 11 and R 12 may bond together to form a cyclic structure with the carbon and oxygen atoms to which they are attached,
with the proviso that when the structure (Z-1), (Z-2) or (Z-3) is linked to the —(C═O)—O— linkage in recurring unit (7) via a linking group which is any one of R 2a , R 2b , R 3a , R 3b , R 5a , R 5b , R 6a , R 6b , R 7a , R 7b , R 8a , R 8b , R 9a , and R 9b , the linking group is an organic group as defined above, but having a valence bond as a result of one hydrogen atom being eliminated therefrom.
28. The protective coating composition of claim 27 wherein the solvent comprises a mixture of the ether compound and 0.1 to 90% by weight of an alcohol of 4 to 10 carbon atoms.