Fluorine-containing polymerizable monomer and polymer prepared by using same
The present invention relates to a polymerizable monomer represented by the general formula (1), wherein R 1 is a hydrogen atom, a halogen atom, a hydrocarbon group or a fluorine-containing alkyl group; R 2 is a straight-chain or branched alkyl group, a cyclic alkyl group, an aromatic group, or a substituent having at least two of these groups, the R 2 being optionally partially fluorinated; R 3 is a hydrogen atom, a hydrocarbon group that is optionally branched, a fluorine-containing alkyl group, or a cyclic group having an aromatic or alicyclic structure, the R 3 optionally containing a bond of an oxygen atom or carbonyl group; and n is an integer of 1–2.
1. A polymer prepared by polymerizing a polymerizable monomer represented by the formula (19),
wherein
R 1 is a hydrogen atom, a halogen atom, a hydrocarbon group or a fluorine-containing alkyl group;
R 3 is a hydrogen atom, a hydrocarbon group that is optionally branched, a fluorine-containing alkyl group, or a cyclic group having an aromatic or alicyclic structure, said R 3 optionally containing an oxygen atom or carbonyl group; and
R 5 is a methylene group or a direct bond.
2. A polymer according to claim 1 , wherein R 1 is a hydrogen atom, methyl group, trifluoromethyl group, or nonafluoro-n-butyl group.
3. A polymer according to claim 1 , wherein R 1 is a methyl group.
4. A polymer according to claim 1 , wherein R 3 is a hydrogen atom.
5. A polymer according to claim 1 , wherein R 1 is a methyl group, and R 3 is a hydrogen atom.
6. A polymer according to claim 1 , wherein the polymerizable monomer is represented by the formula (20),
wherein R 1 and R 3 are defined as in the formula (19).
7. A polymer according to claim 1 , wherein the polymerizable monomer is represented by the formula (21),
wherein R 1 and R 3 are defined as in the formula (19).
8. A polymer according to claim 1 , wherein the polymerizable monomer is represented by the following formula (7).
9. A polymer according to claim 1 , which is prepared by polymerizing the polymerizable monomer with another comonomer.
10. A polymer according to claim 9 , wherein the another comonomer is at least one selected from the group consisting of olefins, fluorine-containing olefins, acrylic esters, methacrylic esters, fluorine-containing acrylic esters, fluorine-containing methacrylic esters, norbornene compounds, fluorine-containing norbornene compounds, styrene compounds, fluorine-containing styrene compounds, vinyl ethers, and fluorine-containing vinyl ethers.
11. A polymer according to claim 1 , which has a number average molecular weight of from 1,000 to 100,000.
12. A polymer prepared by polymerizing a polymerizable monomer represented by the formula (19),
wherein
R 1 is a halogen atom;
R 3 is a hydrogen atom, a hydrocarbon group that is optionally branched, a fluorine-containing alkyl group, or a cyclic group having an aromatic or alicyclic structure, said R 3 optionally containing an oxygen atom or carbonyl group; and
R 5 is a methylene group or a direct bond.
13. A polymer according to claim 12 , wherein R 3 is a hydrogen atom.
14. A polymer according to claim 12 , wherein the polymerizable monomer is represented by the formula (20),
wherein R 1 and R 3 are defined as in the formula (19).
15. A polymer according to claim 12 , wherein the polymerizable monomer is represented by the formula (21),
wherein R 1 and R 3 are defined as in the formula (19).
16. A polymer according to claim 12 , which is prepared by polymerizing the polymerizable monomer with another comonomer.
17. A polymer according to claim 16 , wherein the another comonomer is at least one selected from the group consisting of olefins, fluorine-containing olefins, acrylic esters, methacrylic esters, fluorine-containing acrylic esters, fluorine-containing methacrylic esters, norbornene compounds, fluorine-containing norbornene compounds, styrene compounds, fluorine-containing styrene compounds, vinyl ethers, and fluorine-containing vinyl ethers.
18. A polymer according to claim 12 , which has a number average molecular weight of from 1,000 to 100,000.
19. A polymer prepared by polymerizing a polymerizable monomer represented by the formula (19),
wherein
R 1 is a hydrogen atom, a halogen atom, a hydrocarbon group or a fluorine-containing alkyl group;
R 3 is a hydrocarbon group that is optionally branched, a fluorine-containing alkyl group, or a cyclic group having an aromatic or alicyclic structure, said R 3 optionally containing an oxygen atom or carbonyl group; and
R 5 is a methylene group or a direct bond.
20. A polymer according to claim 19 , wherein R 1 is a hydrogen atom, methyl group, trifluoromethyl group, or nonafluoro-n-butyl group.
21. A polymer according to claim 19 , wherein R 1 is a methyl group.
22. A polymer according to claim 19 , wherein the polymerizable monomer is represented by the formula (20),
wherein R 1 and R 3 are defined as in the formula (19).
23. A polymer according to claim 19 , wherein the polymerizable monomer is represented by the formula (21),
wherein R 1 and R 3 are defined as in the formula (19).
24. A polymer according to claim 19 , which is prepared by polymerizing the polymerizable monomer with another comonomer.
25. A polymer according to claim 24 , wherein the another comonomer is at least one selected from the group consisting of olefins, fluorine-containing olefins, acrylic esters, methacrylic esters, fluorine-containing acrylic esters, fluorine-containing methacrylic esters, norbornene compounds, fluorine-containing norbornene compounds, styrene compounds, fluorine-containing styrene compounds, vinyl ethers, and fluorine-containing vinyl ethers.
26. A polymer according to claim 19 , which has a number average molecular weight of from 1,000 to 100,000.
27. A reflection preventive material or optical device material comprising a polymer prepared by polymerizing a polymerizable monomer represented by the formula (19),
wherein
R 1 is a hydrogen atom, a halogen atom, a hydrocarbon group or a fluorine-containing alkyl group;
R 3 is a hydrogen atom, a hydrocarbon group that is optionally branched, a fluorine-containing alkyl group, or a cyclic group having an aromatic or alicyclic structure, said R 3 optionally containing an oxygen atom or carbonyl group; and
R 5 is a methylene group or a direct bond.
28. A material according to claim 27 , wherein R 1 is a hydrogen atom, methyl group, trifluoromethyl group, or nonafluoro-n-butyl group.
29. A material according to claim 27 , wherein R 1 is a methyl group.
30. A material according to claim 27 , wherein R 3 is a hydrogen atom.
31. A material according to claim 27 , wherein R 1 is a methyl group, and R 3 is a hydrogen atom.
32. A material according to claim 27 , wherein the polymerizable monomer is represented by the formula (20),
wherein R 1 and R 3 are defined as in the formula (19).
33. A material according to claim 27 , wherein the polymerizable monomer is represented by the formula (21),
wherein R 1 and R 3 are defined as in the formula (19).
34. A material according to claim 27 , wherein the polymer is prepared by polymerizing the polymerizable monomer with another comonomer.
35. A material according to claim 34 , wherein the another comonomer is at least one selected from the group consisting of olefins, fluorine-containing olefins, acrylic esters, methacrylic esters, fluorine-containing acrylic esters, fluorine-containing methacrylic esters, norbornene compounds, fluorine-containing norbornene compounds, styrene compounds, fluorine-containing styrene compounds, vinyl ethers, and fluorine-containing vinyl ethers.
36. A material according to claim 27 , wherein the polymer has a number average molecular weight of from 1,000 to 100,000.
37. A reflection preventive material, optical device material or resist material comprising a polymer prepared by polymerizing a polymerizable monomer represented by the formula (19),
wherein
R 1 is a halogen atom;
R 3 is a hydrogen atom, a hydrocarbon group that is optionally branched, a fluorine-containing alkyl group, or a cyclic group having an aromatic or alicyclic structure, said R 3 optionally containing an oxygen atom or carbonyl group; and
R 5 is a methylene group or a direct bond.
38. A material according to claim 37 , wherein R 3 is a hydrogen atom.
39. A material according to claim 37 , wherein the polymerizable monomer is represented by the formula (20),
wherein R 1 and R 3 are defined as in the formula (19).
40. A material according to claim 37 , wherein the polymerizable monomer is represented by the formula (21),
wherein R 1 and R 3 are defined as in the formula (19).
41. A material according to claim 37 , which is a resist material.
42. A material according to claim 37 , wherein the polymer is prepared by polymerizing the polymerizable monomer with another comonomer.
43. A material according to claim 42 , wherein the another comonomer is at least one selected from the group consisting of olefins, fluorine-containing olefins, acrylic esters, methacrylic esters, fluorine-containing acrylic esters, fluorine-containing methacrylic esters, norbornene compounds, fluorine-containing norbornene compounds, styrene compounds, fluorine-containing styrene compounds, vinyl ethers, and fluorine-containing vinyl ethers.
44. A material according to claim 37 , which has a number average molecular weight of from 1,000 to 100,000.
45. A reflection preventive material, optical device material or resist material comprising a polymer prepared by polymerizing a polymerizable monomer represented by the formula (19),
wherein
R 1 is a hydrogen atom, a halogen atom, a hydrocarbon group or a fluorine-containing alkyl group;
R 3 is a hydrocarbon group that is optionally branched, a fluorine-containing alkyl group, or a cyclic group having an aromatic or alicyclic structure, said R 3 optionally containing an oxygen atom or carbonyl group; and
R 5 is a methylene group or a direct bond.
46. A material according to claim 45 , wherein R 1 is a hydrogen atom, methyl group, trifluoromethyl group, or nonafluoro-n-butyl group.
47. A material according to claim 45 , wherein R 1 is a methyl group.
48. A material according to claim 45 , wherein the polymerizable monomer is represented by the formula (20),
wherein R 1 and R 3 are defined as in the formula (19).
49. A material according to claim 45 , wherein the polymerizable monomer is represented by the formula (21),
wherein R 1 and R 3 are defined as in the formula (19).
50. A material according to claim 45 , which is a resist material.
51. A material according to claim 45 , wherein the polymer is prepared by polymerizing the polymerizable monomer with another comonomer.
52. A material according to claim 51 , wherein the another comonomer is at least one selected from the group consisting of olefins, fluorine-containing olefins, acrylic esters, methacrylic esters, fluorine-containing acrylic esters, fluorine-containing methacrylic esters, norbornene compounds, fluorine-containing norbornene compounds, styrene compounds, fluorine-containing styrene compounds, vinyl ethers, and fluorine-containing vinyl ethers.
53. A material according to claim 45 , which has a number average molecular weight of from 1,000 to 100,000.
54. A polymer prepared by polymerizing a polymerizable monomer represented by the formula (5),
wherein
R 1 is a hydrogen atom, a halogen atom, a hydrocarbon group or a fluorine-containing alkyl group;
R 3 is a hydrogen atom, a hydrocarbon group that is optionally branched, a fluorine-containing alkyl group, or a cyclic group having an aromatic or alicyclic structure, said R 3 optionally containing an oxygen atom or carbonyl group;
R 5 is a straight-chain or branched, divalent, saturated hydrocarbon group having carbon atom number of 1–5; and
n is an integer of 1–2.
55. A polymer according to claim 54 , wherein R 1 is a hydrogen atom, methyl group, trifluoromethyl group, or nonafluoro-n-butyl group.
56. A polymer according to claim 54 , wherein R 1 is a methyl group.
57. A polymer according to claim 54 , wherein R 3 is a hydrogen atom.
58. A polymer according to claim 54 , wherein R 1 is a methyl group, and R 3 is a hydrogen atom.
59. A polymer according to claim 54 , which is prepared by polymerizing the polymerizable monomer with another comonomer.
60. A polymer according to claim 59 , wherein the another comonomer is at least one selected from the group consisting of olefins, fluorine-containing olefins, acrylic esters, methacrylic esters, fluorine-containing acrylic esters, fluorine-containing methacrylic esters, norbornene compounds, fluorine-containing norbornene compounds, styrene compounds, fluorine-containing styrene compounds, vinyl ethers, and fluorine-containing vinyl ethers.
61. A polymer according to claim 54 , which has a number average molecular weight of from 1,000 to 100,000.
62. A polymer prepared by polymerizing a polymerizable monomer represented by the formula (5),
wherein
R 1 is a halogen atom;
R 3 is a hydrogen atom, a hydrocarbon group that is optionally branched, a fluorine-containing alkyl group, or a cyclic group having an aromatic or alicyclic structure, said R 3 optionally containing an oxygen atom or carbonyl group;
R 5 is a straight-chain or branched, divalent, saturated hydrocarbon group having carbon atom number of 1–5; and
n is an integer of 1–2.
63. A polymer according to claim 62 , wherein R 3 is a hydrogen atom.
64. A polymer according to claim 62 , which is prepared by polymerizing the polymerizable monomer with another comonomer.
65. A polymer according to claim 64 , wherein the another comonomer is at least one selected from the group consisting of olefins, fluorine-containing olefins, acrylic esters, methacrylic esters, fluorine-containing acrylic esters, fluorine-containing methacrylic esters, norbornene compounds, fluorine-containing norbornene compounds, styrene compounds, fluorine-containing styrene compounds, vinyl ethers, and fluorine-containing vinyl ethers.
66. A polymer according to claim 62 , which has a number average molecular weight of from 1,000 to 100,000.
67. A polymer prepared by polymerizing a polymerizable monomer represented by the formula (5),
wherein
R 1 is a hydrogen atom, a halogen atom, a hydrocarbon group or a fluorine-containing alkyl group;
R 3 is a hydrocarbon group that is optionally branched, a fluorine-containing alkyl group, or a cyclic group having an aromatic or alicyclic structure, said R 3 optionally containing an oxygen atom or carbonyl group;
R 5 is a straight-chain or branched, divalent, saturated hydrocarbon group having carbon atom number of 1–5; and
n is an integer of 1–2.
68. A polymer according to claim 67 , wherein R 1 is a hydrogen atom, methyl group, trifluoromethyl group, or nonafluoro-n-butyl group.
69. A polymer according to claim 67 , wherein R 1 is a methyl group.
70. A polymer according to claim 67 , which is prepared by polymerizing the polymerizable monomer with another comonomer.
71. A polymer according to claim 70 , wherein the another comonomer is at least one selected from the group consisting of olefins, fluorine-containing olefins, acrylic esters, methacrylic esters, fluorine-containing acrylic esters, fluorine-containing methacrylic esters, norbornene compounds, fluorine-containing norbornene compounds, styrene compounds, fluorine-containing styrene compounds, vinyl ethers, and fluorine-containing vinyl ethers.
72. A polymer according to claim 67 , which has a number average molecular weight of from 1,000 to 100,000.
73. A reflection preventive material, optical device material or resist material comprising a polymer prepared by polymerizing a polymerizable monomer represented by the formula (5),
wherein
R 1 is a hydrogen atom, a halogen atom, a hydrocarbon group or a fluorine-containing alkyl group;
R 3 is a hydrogen atom, a hydrocarbon group that is optionally branched, a fluorine-containing alkyl group, or a cyclic group having an aromatic or alicyclic structure, said R 3 optionally containing an oxygen atom or carbonyl group;
R 5 is a straight-chain or branched, divalent, saturated hydrocarbon group having carbon atom number of 1–5; and
n is an integer of 1–2.
74. A material according to claim 73 , wherein R 1 is a hydrogen atom, methyl group, trifluoromethyl group, or nonafluoro-n-butyl group.
75. A material according to claim 73 , wherein R 1 is a methyl group.
76. A material according to claim 73 , wherein R 3 is a hydrogen atom.
77. A material according to claim 73 , wherein R 1 is a methyl group, and R 3 is a hydrogen atom.
78. A material according to claim 73 , wherein the polymer is prepared by polymerizing the polymerizable monomer with another comonomer.
79. A material according to claim 78 , wherein the another comonomer is at least one selected from the group consisting of olefins, fluorine-containing olefins, acrylic esters, methacrylic esters, fluorine-containing acrylic esters, fluorine-containing methacrylic esters, norbornene compounds, fluorine-containing norbornene compounds, styrene compounds, fluorine-containing styrene compounds, vinyl ethers, and fluorine-containing vinyl ethers.
80. A material according to claim 73 , wherein the polymer has a number average molecular weight of from 1,000 to 100,000.
81. A reflection preventive material, resist material or optical device material comprising a polymer prepared by polymerizing a polymerizable monomer represented by the formula (5),
wherein
R 1 is a halogen atom;
R 3 is a hydrogen atom, a hydrocarbon group that is optionally branched, a fluorine-containing alkyl group, or a cyclic group having an aromatic or alicyclic structure, said R 3 optionally containing an oxygen atom or carbonyl group;
R 5 is a straight-chain or branched, divalent, saturated hydrocarbon group having carbon atom number of 1–5; and
n is an integer of 1–2.
82. A material according to claim 81 , wherein R 3 is a hydrogen atom.
83. A material according to claim 81 , wherein the polymer is prepared by polymerizing the polymerizable monomer with another comonomer.
84. A material according to claim 83 , wherein the another comonomer is at least one selected from the group consisting of olefins, fluorine-containing olefins, acrylic esters, methacrylic esters, fluorine-containing acrylic esters, fluorine-containing methacrylic esters, norbornene compounds, fluorine-containing norbornene compounds, styrene compounds, fluorine-containing styrene compounds, vinyl ethers, and fluorine-containing vinyl ethers.
85. A material according to claim 81 , wherein the polymer has a number average molecular weight of from 1,000 to 100,000.
86. A material according to claim 81 , which is a resist material.
87. A reflection preventive material, resist material or optical device material comprising a polymer prepared by polymerizing a polymerizable monomer represented by the formula (5),
wherein
R 1 is a hydrogen atom, a halogen atom, a hydrocarbon group or a fluorine-containing alkyl group;
R 3 is a hydrocarbon group that is optionally branched, a fluorine-containing alkyl group, or a cyclic group having an aromatic or alicyclic structure, said R 3 optionally containing an oxygen atom or carbonyl group;
R 5 is a straight-chain or branched, divalent, saturated hydrocarbon group having carbon atom number of 1–5; and
n is an integer of 1–2.
88. A material according to claim 87 , wherein R 1 is a hydrogen atom, methyl group, trifluoromethyl group, or nonafluoro-n-butyl group.
89. A material according to claim 87 , wherein R 1 is a methyl group.
90. A material according to claim 87 , wherein the polymer is prepared by polymerizing the polymerizable monomer with another comonomer.
91. A material according to claim 90 , wherein the another comonomer is at least one selected from the group consisting of olefins, fluorine-containing olefins, acrylic esters, methacrylic esters, fluorine-containing acrylic esters, fluorine-containing methacrylic esters, norbornene compounds, fluorine-containing norbornene compounds, styrene compounds, fluorine-containing styrene compounds, vinyl ethers, and fluorine-containing vinyl ethers.
92. A material according to claim 87 , wherein the polymer has a number average molecular weight of from 1,000 to 100,000.
93. A material according to claim 87 , which is a resist material.
94. A resist material comprising a polymer prepared by polymerizing a polymerizable monomer represented by the formula (19),
wherein
R 1 is a hydrogen atom, a halogen atom, a hydrocarbon group or a fluorine-containing alkyl group;
R 3 is a hydrogen atom, a hydrocarbon group that is optionally branched, a fluorine-containing alkyl group, or a cyclic group having an aromatic or alicyclic structure, said R 3 optionally containing an oxygen atom or carbonyl group; and
R 5 is a methylene group or a bond.
95. A material according to claim 94 , wherein R 1 is a hydrogen atom, methyl group, trifluoromethyl group, or nonafluoro-n-butyl group.
96. A material according to claim 94 , wherein R 1 is a methyl group.
97. A material according to claim 94 , wherein R 3 is a hydrogen atom.
98. A material according to claim 94 , wherein R 1 is a methyl group, and R 3 is a hydrogen atom.
99. A material according to claim 94 , wherein the polymerizable monomer is represented by the formula (20),
wherein R 1 and R 3 are defined as in the formula (19).
100. A material according to claim 94 , wherein the polymerizable monomer is represented by the formula (21),
wherein R 1 and R 3 are defined as in the formula (19).
101. A material according to claim 94 , wherein the polymer is prepared by polymerizing the polymerizable monomer with another comonomer.
102. A material according to claim 101 , wherein the another comonomer is at least one selected from the group consisting of olefins, fluorine-containing olefins, acrylic esters, methacrylic esters, fluorine-containing acrylic esters, fluorine-containing methacrylic esters, norbornene compounds, fluorine-containing norbornene compounds, styrene compounds, fluorine-containing styrene compounds, vinyl ethers, and fluorine-containing vinyl ethers.
103. A material according to claim 94 , wherein the polymer has a number average molecular weight of from 1,000 to 100,000.