Fluoroalcohol preparation method, fluorinated monomer, polymer, resist composition and patterning process

Abstract

Fluoroalcohol compounds of formula (4) are prepared by reacting a fluorine compound of formula (1) with reducing agents or organometallic reagents of formulas (2) and (3) wherein R1 is H or a monovalent C1-C20 hydrocarbon group in which any —CH2— moiety may be replaced by —O— or —C(═O)—, R2 is H or a monovalent C1-C6 hydrocarbon group, R3 and R4 are H or a monovalent C1-C8 hydrocarbon group, and M1 is Li, Na, K, Mg, Zn, Al, B, or Si. From the fluoroalcohol compounds, fluorinated monomers can be produced in a simple and economic way, which are useful in producing polymers for the formulation of radiation-sensitive resist compositions.

Description

Claims

1. A method for preparing a fluoroalcohol compound having the general formula (4), said method comprising the step of reacting a fluorine compound having the general formula (1) with reducing agents or organometallic reagents having the general formulas (2) and (3):

2. A fluorinated monomer having the general formula (5), which is obtained by esterifying the fluoroalcohol compound having formula (4) as set forth in claim 1,

3. A fluorinated monomer having the general formula (6), which is obtained by esterifying the fluoroalcohol compound having formula (4) as set forth in claim 1,

4. A method for preparing a fluoroalcohol compound having the general formula (8), said method comprising the steps of addition reaction of an organometallic reagent having the general formula (7) to a fluorine compound having the general formula (1) as set forth in claim 1, and subsequent reducing reaction,

5. A fluorinated monomer having the general formula (9), which is obtained by esterifying the fluoroalcohol compound having formula (8) as set forth in claim 4,

6. A fluorinated monomer having the general formula (10), which is obtained by esterifying the fluoroalcohol compound having formula (8) as set forth in claim 4,

7. A method for preparing a fluoroalcohol compound having the general formula (12), said method comprising the step of addition reaction of an organometallic reagent having the general formula (11) to a fluorine compound having the general formula (1) as set forth in claim 1,

8. A fluorinated monomer having the general formula (13), which is obtained by esterifying the fluoroalcohol compound having formula (12) as set forth in claim 7,

9. A fluorinated monomer having the general formula (14), which is obtained by esterifying the fluoroalcohol compound having formula (12) as set forth in claim 7,

10. A method for preparing a fluoroalcohol compound having the general formula (16), said method comprising the step of addition reaction of an organometallic reagent having the general formula (15) to a fluorine compound having the general formula (1) as set forth in claim 1,

11. A fluorinated monomer having the general formula (17), which is obtained by esterifying the fluoroalcohol compound having formula (16) as set forth in claim 10,

12. A fluorinated monomer having the general formula (18), which is obtained by esterifying the fluoroalcohol compound having formula (16) as set forth in claim 10,

13. A polymer comprising recurring units derived from the fluorinated monomer of claim 2.

14. A polymer comprising recurring units having any one of the general formulas (1a) to (1c):

15. A polymer comprising recurring units having any one of the general formulas (2a) to (2c):

16. A polymer comprising recurring units having any one of the general formulas (3a) to (3c):

17. A polymer comprising recurring units having any one of the general formulas (4a) to (4c):

18. The polymer of claim 13, comprising recurring units of at least one type selected from the general formulas (19) to (22):

19. A resist composition comprising the polymer of claim 13 as a base resin.

20. A pattern forming process comprising the steps of: applying the resist composition of claim 19 onto a substrate to form a coating,heat treating the coating and exposing it to high-energy radiation or electron beam through a photomask,optionally heat treating the exposed coating, and developing it with a developer.