U.S. patent application number 13/201973 was filed with the patent office on 2011-12-08 for imprint product and method for producing the same.
This patent application is currently assigned to Mitsui Chemicals, Inc.. Invention is credited to Takashi Oda, Hitoshi Onishi, Tadahiro Sunaga.
Application Number | 20110301313 13/201973 |
Document ID | / |
Family ID | 42665317 |
Filed Date | 2011-12-08 |
United States Patent
Application |
20110301313 |
Kind Code |
A1 |
Sunaga; Tadahiro ; et
al. |
December 8, 2011 |
IMPRINT PRODUCT AND METHOD FOR PRODUCING THE SAME
Abstract
Provided is an imprint product, which is for transcribing a fine
pattern of a mold surface and which contains a fluorine-containing
cyclic olefin polymer containing repeating unit represented by
formula (1) and having a fluorine atom content rate of 40% to 75%
by mass. ##STR00001##
Inventors: |
Sunaga; Tadahiro; (Kanagawa,
JP) ; Oda; Takashi; (Chiba, JP) ; Onishi;
Hitoshi; (Chiba, JP) |
Assignee: |
Mitsui Chemicals, Inc.
Minato-ku
JP
|
Family ID: |
42665317 |
Appl. No.: |
13/201973 |
Filed: |
February 25, 2010 |
PCT Filed: |
February 25, 2010 |
PCT NO: |
PCT/JP2010/001271 |
371 Date: |
August 17, 2011 |
Current U.S.
Class: |
526/252 ;
264/225; 264/447; 425/385 |
Current CPC
Class: |
B82Y 40/00 20130101;
C08G 61/08 20130101; B29C 59/005 20130101; G03F 7/0002 20130101;
C08G 2261/3324 20130101; G02B 3/0031 20130101; B82Y 10/00 20130101;
C08G 2261/418 20130101; C08L 65/00 20130101; C08G 2261/146
20130101 |
Class at
Publication: |
526/252 ;
264/225; 264/447; 425/385 |
International
Class: |
C08F 36/20 20060101
C08F036/20; B29C 59/16 20060101 B29C059/16; B29C 59/02 20060101
B29C059/02; B29C 33/42 20060101 B29C033/42 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 27, 2009 |
JP |
2009-046122 |
Claims
1. An imprint product on which a fine pattern of a mold surface is
transcribed, wherein the imprint product is comprised of a
fluorine-containing cyclic olefin polymer containing a repeating
structural unit represented by formula (1) and having a fluorine
atom content rate of 40% to 75% by mass: ##STR00011## wherein in
the formula (1), at least one of R.sup.1 to R.sup.4 represents
fluorine, a fluorine-containing C1-C10 alkyl, a fluorine-containing
C1-C10 alkoxy, or a fluorine-containing C2-C10 alkoxyalkyl; when
R.sup.1 to R.sup.4 represent groups containing no fluorine, R.sup.1
to R.sup.4 are each selected from hydrogen, a C1-C10 alkyl, a
C1-C10 alkoxy, and a C2-C10 alkoxyalkyl; each of R.sup.1 to R.sup.4
may be identical with or different from the others; and R.sup.1 to
R.sup.4 may be joined together to form a cyclic structure.
2. The imprint product as set forth in claim 1, wherein said
fluorine-containing cyclic olefin polymer has the variation in the
storage modulus or loss modulus thereof obtained by dynamic
mechanical analysis by tensile mode at a frequency of 1 Hz and a
rate of temperature increase of 3.degree. C./min, which lies in a
region of -1 MPa/.degree. C. to 0 MPa/.degree. C. to the changes in
temperature in a range of temperature which is not less than the
glass transition temperature.
3. The imprint product as set forth in claim 2, wherein said the
region of variation in the storage modulus or loss modulus of said
fluorine-containing cyclic olefin polymer in the range of
temperature which is not less than the glass transition
temperature, lies in a storage modulus region or loss modulus
region of 0.1 MPa or more.
4. The imprint product as set forth in claim 1, wherein said
fluorine-containing cyclic olefin polymer is composed of a
repeating structural unit [A] represented by said formula (1) and a
repeating structural unit [B] represented by formula (2), with the
molar ratio of the structural units being [A]/[B]=95/5 to 25/75,
and has a fluorine atom content rate of 40% to 75% by mass:
##STR00012## wherein in the formula (2), at least one of R.sup.5 to
R.sup.5 represents fluorine, a fluorine-containing C1-C10 alkyl, a
fluorine-containing C1-C10 alkoxy, or a fluorine-containing C2-C10
alkoxyalkyl; when R.sup.5 to R.sup.8 represent groups containing no
fluorine, R.sup.5 to R.sup.8 are each selected from hydrogen, a
C1-C10 alkyl, a C1-C10 alkoxy, and a C2-C10 alkoxyalkyl; each of
R.sup.5 to R.sup.8 may be identical with or different from the
others; R.sup.5 to R.sup.8 may be joined together to form a cyclic
structure; and n represents an integer of 1 or 2.
5. A method for producing the imprint product using a
fluorine-containing cyclic olefin polymer as set forth in claim 1,
comprising: bringing a solution containing said fluorine-containing
cyclic olefin polymer and an organic solvent into contact with a
mold having a fine pattern on the surface and evaporating the
solvent to transcribe the pattern of the mold.
6. A method for producing the imprint product on which a fine
pattern of a mold surface is transcribed as set forth in claim 1,
comprising: applying a solution containing said fluorine-containing
cyclic olefin polymer and an organic solvent on the surface of a
mold having a fine pattern, and evaporating the solvent from said
solution.
7. A method for producing the imprint product on which a fine
pattern of a mold surface is transcribed as set forth in claim 1,
comprising: pressing the surface of a film containing said
fluorine-containing cyclic olefin polymer with the surface of a
mold having a fine pattern.
8. A method for producing a cured product by using the imprint
product as set forth in claim 1 as a mold, comprising: bringing the
surface of said imprint product having a fine pattern into contact
with a photocurable monomer composition; curing said photocurable
monomer composition by light irradiation to obtain a cured product;
and releasing said cured product from said imprint product.
9. A resin composition for pattern transcription for obtaining an
imprint product on which a fine pattern of a mold surface is
transcribed, comprising a fluorine-containing cyclic olefin polymer
containing a repeating structural unit represented by formula (1)
and having a fluorine atom content rate of 40% to 75% by mass:
##STR00013## wherein in the formula (1), at least one of R.sup.1 to
R.sup.4 represents fluorine, a fluorine-containing C1-C10 alkyl, a
fluorine-containing C1-C10 alkoxy, or a fluorine-containing C2-C10
alkoxyalkyl; when R.sup.1 to R.sup.4 represent groups containing no
fluorine, R.sup.1 to R.sup.4 are each selected from hydrogen, a
C1-C10 alkyl, a C1-C10 alkoxy, and a C2-C10 alkoxyalkyl; each of
R.sup.1 to R.sup.4 may be identical with or different from the
others; and R.sup.1 to R.sup.4 may be joined together to form a
cyclic structure.
10. The resin composition for pattern transcription as set forth in
claim 9, wherein said fluorine-containing cyclic olefin polymer has
the variation in the storage modulus or loss modulus thereof which
lies in a region of -1 MPa/.degree. C. to 0 MPa/.degree. C. to the
changes in temperature in a range of temperature which is not less
than the glass transition temperature.
11. The resin composition for pattern transfer as set forth in
claim 10, wherein said the region of variation in the storage
modulus or loss modulus of said fluorine-containing cyclic olefin
polymer in the region of temperature which is not less than the
glass transition temperature, lies in a storage modulus region or
loss modulus region of 0.1 MPa or more.
12. The resin composition for pattern transcription as set forth in
claim 9, wherein said fluorine-containing cyclic olefin polymer is
composed of a repeating structural unit [A] represented by said
formula (1) and a repeating structural unit [B] represented by
formula (2), with the molar ratio of the structural units being
[A]/[B]=95/5 to 25/75, and has a fluorine atom content rate of 40%
to 75% by mass: ##STR00014## wherein in the formula (2), at least
one of R.sup.5 to R.sup.8 represents fluorine, a
fluorine-containing C1-C10 alkyl, a fluorine-containing C1-C10
alkoxy, or a fluorine-containing C2-C10 alkoxyalkyl; when R.sup.5
to R.sup.8 represent groups containing no fluorine, R.sup.5 to
R.sup.8 are each selected from hydrogen, a C1-C10 alkyl, a C1-C10
alkoxy, and a C2-C10 alkoxyalkyl; each of R.sup.5 to R.sup.8 may be
identical with or different from the others; R.sup.5 to R.sup.8 may
be joined together to form a cyclic structure; and n represents an
integer of 1 or 2.
Description
TECHNICAL FIELD
[0001] The present invention relates to an imprint product in which
a fine pattern is formed, and a method for producing the same.
BACKGROUND ART
[0002] A resin molding product having a fine pattern is useful such
as an optical element (such as a micro lens array, an optical
waveguide, an optical switch, a Fresnel zone plate, a binary
optical element, a blaze optical element, a photonic crystal), an
antireflection filter, a biochip, a microreactor chip, a recording
medium, a display material, a catalyst support, or the like. In
recent years, there has been a demand for further refinement of
such patterns, along with a demand for miniaturization of devices.
As a method for manufacturing a resin molding product having such a
fine structure on the surface, there has been suggested a method
for manufacturing an imprint product having a fine pattern formed
thereon by transcribing the pattern on a mold having a fine pattern
to a resin, that is, a so-called nanoimprint method (for example,
Patent Document 1 and Patent Document 2). Furthermore, as a method
substituting for a photolithographic method in a process of
manufacturing semiconductor, there has been suggested a nanoimprint
method of applying a resist on a silicon substrate, pressing
thereon a mold on which a fine pattern is formed, and thereby
transcribing the fine pattern onto the resist (for example, Patent
Document 3 and Patent Document 4).
[0003] However, all of the above-described nanoimprint methods have
problems that the shape accuracy of the fine pattern in an imprint
product is decreased because the mold can not be smoothly released
in a process of releasing the mold. Thus, in order to smoothly
release the mold, a method of applying a release agent on the mold
surface has been attempted. In this case, there is a problem in
which the pattern accuracy of the mold is decreased due to
unevenness of the thickness of the release agent layer, and there
is also a problem in which the releasing agent layer becomes
thinning when the mold is continuously used, and it is necessary to
reapply the release agent on the mold, which lowers
productivity.
[0004] In order to solve these problems, a method of using a
non-adhesive material having a surface energy of less than about 30
dyn/cm as a mold material (Patent Document 5) has been suggested.
Examples of the non-adhesive material include fluoropolymers such
as a fluorinated ethylene-propylene copolymer and a
tetrafluoroethylene polymer; fluorinated siloxane polymers, and
silicones.
[0005] However, the method described in Patent Document 5 is to
imprint a mold or its negative pattern made of a non-adhesive
material onto a photocurable or thermosetting thin film formed on a
substrate. That is, the method involves use of a mold pattern or
its negative pattern as a lithographic tool. In Patent Document 5,
the non-adhesive material is mainly intended to play the role of a
releasing agent. Furthermore, a mold using silicone has a low
elastic modulus, and it is difficult to imprint a pattern shape
accurately as using such a mold.
[0006] Furthermore, Patent Document 6 discloses a method of forming
a pattern on a transfer layer, which consists of a thermoplastic
resin containing a fluorine-containing polymer which has 35% by
mass or more of a fluorine content, is pressed with a mold having
an inverse pattern of a desired pattern, and thereby forming the
desired pattern on the transfer layer; and a step of releasing the
mold from the transfer layer. It is described in the document that
this method is excellent in the releasability of the transfer layer
from a mold and thus can form a fine pattern. Examples of the
fluorine-containing polymer include polytetrafluoroethylene, a
1,1,1-trifluoro-2-trifluoromethylpenten-2-ol copolymer, a perfluoro
cyclic ether polymer (trade name: Cytop (registered trademark)),
and a copolymer of chlorotrifluoroethylene and vinyl ether (trade
name: Lumiflon (registered trademark)).
[0007] However, when the fluorine content of these polymers is 60%
by mass or less, their dimensional accuracy in terms of the depth,
width and interval of convex structures is low and dimensional
difference is large, because the elastic modulus is rapidly
decreased at a temperature above the glass transition temperature,
and after the polymer is subjected to press molding, when cooling
rapidly, the shrinkage ratio is increased due to the decreased
elastic modulus. In addition, even if fluorine content is 60% by
mass or more, the fluorine resins such as polytetrafluoroethylene
which exhibit a high melting point temperature (Tm), although it is
necessary to set the molding temperature markedly higher, provide
significant differences in the dimensions between the convex
structure mold and the imprint product because of increase in the
differences between the elastic modulus and shrinkage ratio during
the process of heating and cooling. Furthermore, the fluorine
resins must be decomposed when heated at temperature of 300.degree.
C. or higher to generate hydrogen fluoride gas, which associate
with a high possibility of decomposition of the fluorine resins
when heated at the temperature of 260.degree. C. Thus, problems
such as corrosion of the mold and peripheral devices, or
environmental contamination, are caused.
[0008] The imprint methods which comprise molding by heat press as
suggested as described above, are required to uniformly put high
pressure on a large area in order to obtain an imprint produc with
a large area, and thus a large-sized heat press molding machine is
necessitated. Thus, there is a large problem in manufacturing an
imprint product with a large area because of limitations on the
area of the imprint product that can be industrially processed.
RELATED DOCUMENT
Patent Document
[0009] [Patent Document 1] Japanese Laid-open Patent Publication
No. 2004-504718 [0010] [Patent Document 2] Japanese Laid-open
Patent Publication No. 2002-539604 [0011] [Patent Document 3]
Japanese Laid-open Patent Publication No. 2000-323461 [0012]
[Patent Document 4] Japanese Laid-open Patent Publication No.
2003-155365 [0013] [Patent Document 5] Japanese Laid-open Patent
Publication No. 2005-515617 [0014] [Patent Document 6] Japanese
Laid-open Patent Publication No. 2006-54300
DISCLOSURE OF THE INVENTION
[0015] It is an object of the present invention to provide an
imprint product having a fine pattern on the surface, which is
formed by transcribing a fine pattern on a mold surface with high
dimensional accuracy. The object of the present invention is
achieved by using a specific fluorine-containing cyclic olefin
polymer and thereby optimizing the changes in the elastic modulus
and shrinkage ratio of the resin during the heating and cooling
processes in the manufacturing process for a nanoimprint product.
Another object of the present invention is to provide a method for
manufacturing an imprint product which can efficiently produce an
imprint product with high dimensional accuracy, and is capable of
obtaining an imprint product with a large area by simple and
convenient processes; a method for producing a cured product in
which a fine pattern has been transcribed onto the surface of a
photocured resin by using the imprint product as a replica mold;
and a resin composition for pattern transfer, which is capable of
molding the imprint product of the present invention.
[0016] The present invention will be described below.
[0017] [1] An imprint product on which a fine pattern of a mold
surface is transcribed, wherein the imprint product is comprised of
a fluorine-containing cyclic olefin polymer containing a repeating
structural unit represented by formula (1) and having a fluorine
atom content rate of 40% to 75% by mass:
##STR00002##
[0018] wherein in the formula (1), at least one of R.sup.1 to
R.sup.4 represents fluorine, a fluorine-containing C1-C10 alkyl, a
fluorine-containing C1-C10 alkoxy, or a fluorine-containing C2-C10
alkoxyalkyl; when R.sup.1 to R.sup.4 represent groups containing no
fluorine, R.sup.1 to R.sup.4 are each selected from hydrogen, a
C1-C10 alkyl, a C1-C10 alkoxy, and a C2-C10 alkoxyalkyl; each of
R.sup.1 to R.sup.4 may be identical with or different from the
others; and R.sup.1 to R.sup.4 may be joined together to form a
cyclic structure.
[0019] [2] The imprint product as set forth in [1], wherein the
fluorine-containing cyclic olefin polymer has the variation in the
storage modulus or loss modulus thereof obtained by dynamic
mechanical analysis by tensile mode at a frequency of 1 Hz and a
rate of temperature increase of 3.degree. C./min, which lies in a
region of -1 MPa/.degree. C. to 0 MPa/.degree. C. to the changes in
temperature in a range of temperature which is not less than the
glass transition temperature.
[0020] [3] The imprint product as set forth in [2], wherein the
region of variation in the storage modulus or loss modulus of the
fluorine-containing cyclic olefin polymer in a range of temperature
which is not less than the glass transition temperature, lies in a
storage modulus region or loss modulus region of 0.1 MPa or
more.
[0021] [4] The imprint product as set forth in any one of [1] to
[3], wherein the fluorine-containing cyclic olefin polymer is
composed of a repeating structural unit [A] represented by the
formula (1) and a repeating structural unit [B] represented by
formula (2), with the molar ratio of the structural units being
[A]/[B]=95/5 to 25/75, and has a fluorine atom content rate of 40%
to 75% by mass:
##STR00003##
[0022] wherein in the formula (2), at least one of R.sup.5 to
R.sup.8 represents fluorine, a fluorine-containing C1-C10 alkyl, a
fluorine-containing C1-C10 alkoxy, or a fluorine-containing C2-C10
alkoxyalkyl; when R.sup.5 to R.sup.8 represent groups containing no
fluorine, R.sup.5 to R.sup.8 are each selected from hydrogen, a
C1-C10 alkyl, a C1-C10 alkoxy, and a C2-C10 alkoxyalkyl; each of
R.sup.5 to R.sup.8 may be identical with or different from the
others; R.sup.5 to R.sup.8 may be joined together to form a cyclic
structure; and n represents an integer of 1 or 2.
[0023] [5]A method for producing the imprint product using a
fluorine-containing cyclic olefin polymer as set forth in any one
of [1] to [4], comprising:
[0024] bringing a solution containing the fluorine-containing
cyclic olefin polymer and an organic solvent into contact with a
mold having a fine pattern on the surface and evaporating the
solvent to transcribe the pattern of the mold.
[0025] [6]A method for producing the imprint product on which a
fine pattern of a mold surface is transcribed as set forth in any
one of [1] to [4], comprising:
[0026] applying a solution containing the fluorine-containing
cyclic olefin polymer and an organic solvent on the surface of a
mold having a fine pattern, and
[0027] evaporating the solvent from the solution.
[0028] [7]A method for producing the imprint product on which a
fine pattern of a mold surface is transcribed as set forth in any
one of [1] to [4], comprising:
[0029] pressing the surface of a film containing the
fluorine-containing cyclic olefin polymer with the surface of a
mold having a fine pattern.
[0030] [8]A method for producing a cured product by using the
imprint product as set forth in any one of [1] to [4] as a mold,
comprising:
[0031] bringing the surface of the imprint product having a fine
pattern into contact with a photocurable monomer composition;
[0032] curing the photocurable monomer composition by light
irradiation to obtain a cured product; and
[0033] releasing the cured product from the imprint product.
[0034] [9]A resin composition for pattern transcription for
obtaining an imprint product on which a fine pattern of a mold
surface is transcribed, comprising a fluorine-containing cyclic
olefin polymer containing a repeating structural unit represented
by formula (1) and having a fluorine atom content rate of 40% to
75% by mass:
##STR00004##
[0035] wherein in the formula (1), at least one of R.sup.1 to
R.sup.4 represents fluorine, a fluorine-containing C1-C10 alkyl, a
fluorine-containing C1-C10 alkoxy, or a fluorine-containing C2-C10
alkoxyalkyl; when R.sup.1 to R.sup.4 represent groups containing no
fluorine, R.sup.1 to R.sup.4 are each selected from hydrogen, a
C1-C10 alkyl, a C1-C10 alkoxy, and a C2-C10 alkoxyalkyl; each of
R.sup.1 to R.sup.4 may be identical with or different from the
others; and R.sup.1 to R.sup.4 may be joined together to form a
cyclic structure.
[0036] [10] The resin composition for pattern transcription as set
forth in [9], wherein the fluorine-containing cyclic olefin polymer
has the variation in the storage modulus or loss modulus thereof
which lies in a region of -1 MPa/.degree. C. to 0 MPa/.degree. C.
to the changes in temperature in a range of temperature which is
not less than the glass transition temperature.
[0037] [11] The resin composition for pattern transcription as set
forth in [10], wherein the region of variation in the storage
modulus or loss modulus of the fluorine-containing cyclic olefin
polymer in a range of temperature which is not less than the glass
transition temperature, lies in a storage modulus region or loss
modulus region of 0.1 MPa or more.
[0038] [12] The resin composition for pattern transcription as set
forth in any one of [9] to [11], wherein the fluorine-containing
cyclic olefin polymer is composed of a repeating structural unit
[A] represented by the formula (1) and a repeating structural unit
[B] represented by formula (2), with the molar ratio of the
structural units being [A]/[B]=95/5 to 25/75, and has a fluorine
atom content rate of 40% to 75% by mass:
##STR00005##
[0039] wherein in the formula (2), at least one of R.sup.5 to
R.sup.8 represents fluorine, a fluorine-containing C1-C10 alkyl, a
fluorine-containing C1-C10 alkoxy, or a fluorine-containing C2-C10
alkoxyalkyl; when R.sup.5 to R.sup.8 represent groups containing no
fluorine, R.sup.5 to R.sup.8 are each selected from hydrogen, a
C1-C10 alkyl, a C1-C10 alkoxy, and a C2-C10 alkoxyalkyl; each of
R.sup.5 to R.sup.8 may be identical with or different from the
others; R.sup.5 to R.sup.8 may be joined together to form a cyclic
structure; and n represents an integer of 1 or 2.
[0040] According to the present invention, the term "fine pattern"
means a structure having convex portions and concave portions, in
which the width of the convex portions and/or concave portions is
10 nm to 50 .mu.m, the depth of the concave portion is 30 nm to 50
.mu.m, and the aspect ratio which is the ratio of the width of the
convex portions and the depth of the concave portions is 0.1 to
500.
[0041] According to the present invention, the phrase "bringting a
solution containing the fluorine-containing cyclic olefin polymer
and an organic solvent into contact with a mold having a fine
pattern on the surface" includes all of the steps wherein the
solution comprised of a polymer and an organic solvent is applied
on the mold surface on which a fine pattern is formed, and the
steps wherein the solution is applied on a support (substrate), and
then the surface of the coating layer is pressed with the mold
surface on which a fine pattern is formed. Furthermore, the same
also applies to the phrase "bringing the surface of the imprint
product having a fine pattern into contact with a photocurable
monomer composition."
[0042] According to the present invention, since a specific
fluorine-containing cyclic olefin polymer having a hydrocarbon
structure in the main chain and a fluorine-containing aliphatic
cyclic structure in a side chain is used, hydrogen bonding can be
formed between the molecules or within the molecule, and thereby
changes in the elastic modulus and shrinkage ratio of the resin
during the heating and cooling processes in the production process
of a nanoimprint imprint product can be optimized. Thus, an imprint
product having a fine pattern formed on the surface, which is
formed by transcribing a fine pattern of a mold surface with high
dimensional accuracy, can be formed, and an imprint product with a
large area can be obtained by simple and convenient processes. This
imprint product is excellent in releasability and exhibits high
production efficiency, such that the imprint product is
industrially valuable.
BRIEF DESCRIPTION OF THE DRAWINGS
[0043] FIG. 1 is a diagram showing changes in the dynamic
viscoelastic modulus measured in a tensile mode of the
fluorine-containing cyclic olefin polymer obtained in Example 1,
which has a flat region of change of the storage modulus or loss
modulus over a temperature region of 113.degree. C. to 152.degree.
C.
DESCRIPTION OF EMBODIMENTS
[0044] The imprint product of the present invention has a fine
pattern which is formed by transcribing a fine pattern of a mold
surface, and is comprised of a fluorine-containing cyclic olefin
polymer which contains a hydrocarbon structure in the main chain
and a fluorine-containing aliphatic cyclic structure in a side
chain within a repeating structural unit represented by formula
(1), and has a fluorine atom content rate of 40% to 75% by
mass.
##STR00006##
[0045] wherein in the formula (1), at least one of R.sup.1 to
R.sup.4 represents fluorine, a fluorine-containing C1-C10 alkyl, a
fluorine-containing C1-C10 alkoxy, or a fluorine-containing C2-C10
alkoxyalkyl; when R.sup.1 to R.sup.4 represent groups containing no
fluorine, R.sup.1 to R.sup.4 are each selected from hydrogen, a
C1-C10 alkyl, a C1-C10 alkoxy, and a C2-C10 alkoxyalkyl; to R.sup.4
may be identical with or different from each other; and R.sup.1 to
R.sup.4 may be joined together to form a cyclic structure.
[0046] More particularly, examples of R.sup.1 to R.sup.4 in the
formula (1) include fluorine; a fluorine-containing C1-C10 alkyl
such as an alkyl obtained by substituting a part or all of the
hydrogen atoms of an alkyl group with fluorine atoms such as
fluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl,
pentafluoroethyl, heptafluoropropyl, hexafluoroisopropyl,
heptafluoroisopropyl, hexafluoro-2-methylisopropyl,
perfluoro-2-methylisopropyl, n-perfluorobutyl, n-perfluoropentyl,
or perfluorocyclopentyl; a fluorine-containing C1-C10 alkoxy such
as an alkoxy obtained by substituting a part or all of the hydrogen
atoms of an alkoxy group with fluorine atoms such as fluoromethoxy,
difluoromethoxy, trifluoromethoxy, trifluoroethoxy,
pentafluoroethoxy, heptafluoropropoxy, hexafluoroisopropoxy,
heptafluoroisopropoxy, hexafluoro-2-methylisopropoxy,
perfluoro-2-methylisopropoxy, n-perfluorobutoxy,
n-perfluoropentoxy, or perfluorocyclopentoxy; and a
fluorine-containing C2-C10 alkoxyalkyl such as an alkoxyalkyl
obtained by substituting a part or all of the hydrogen atoms of an
alkoxy group with fluorine such as fluoromethoxymethyl,
difluoromethoxymethyl, trifluoromethoxymethyl,
trifluoroethoxymethyl, pentafluoroethoxymethyl,
heptafluoropropoxymethyl, hexafluoroisopropoxymethyl,
heptafluoroisopropoxymethyl, hexafluoro-2-methylisopropoxymethyl,
perfluoro-2-methylisopropoxymethyl, n-perfluorobutoxymethyl,
n-perfluoropentoxymethyl, or perfluorocyclopentoxymethyl.
[0047] Furthermore, R.sup.1 to R.sup.4 may be joined together to
form a cyclic structure, and may form a ring such as
perfluorocycloalkyl or perfluorocycloether interrupted with an
oxygen atom.
[0048] Examples of the other R.sup.1 to R.sup.4 that do not contain
fluorine include hydrogen; a C1-C10 alkyl such as methyl, ethyl,
propyl, isopropyl, 2-methylisopropyl, n-butyl, n-pentyl, or
cyclopentyl; a C1-C10 alkoxy such as methoxy, ethoxy, propoxy,
butoxy, or pentoxy; and a C2-C10 alkoxyalkyl such as methoxymethyl,
ethoxymethyl, propoxymethyl, butoxymethyl, or pentoxymethyl.
[0049] The fluorine-containing cyclic olefin polymer according to
the present invention may be composed only of the repeating
structural unit represented by the formula (1), or may also be
composed of two or more kinds of structural units which differ from
each other in terms of at least one of R.sup.1 to R.sup.4 in the
formula (1).
[0050] Specific examples of the fluorine-containing cyclic olefin
polymer containing the repeating structural unit represented by the
formula (1) according to the present invention include
poly(1-fluoro-2-trifluoromethyl-3,5-cyclopentylene ethylene),
poly(1-fluoro-1-trifluoromethyl-3,5-cyclopentylene ethylene),
poly(1-methyl-1-fluoro-2-trifluoromethyl-3,5-cyclopentylene
ethylene), poly(1,1-difluoro-2-trifluoromethyl-3,5-cyclopentylene
ethylene), poly(1,2-difluoro-2-trifluoromethyl-3,5-cyclopentylene
ethylene), poly(1-perfluoroethyl-3,5-cyclopentylene ethylene),
poly(1,1-bis(trifluoromethyl)-3,5-cyclopentylene ethylene),
poly(1,1,2-trifluoro-2-trifluoromethyl-3,5-cyclopentylene
ethylene), poly(1,2-bis(trifluoromethyl)-3,5-cyclopentylene
ethylene), poly(1-perfluoropropyl-3,5-cyclopentylene ethylene),
poly(1-methyl-2-perfluoropropyl-3,5-cyclopentylene ethylene),
poly(1-butyl-2-perfluoropropyl-3,5-cyclopentylene ethylene),
poly(1-perfluoro-isopropyl-3,5-cyclopentylene ethylene),
poly(1-methyl-2-perfluoro-isopropyl-3,5-cyclopentylene ethylene),
poly(1,2-difluoro-1,2-bis(trifluoromethyl)-3,5-cyclopentylene
ethylene),
poly(1,1,2,2,3,3,3a,6a-octafluorocyclopentyl-4,6-cyclopentylene
ethylene),
poly(1,1,2,2,3,3,4,4,3a,7a-decafluorocyclohexyl-5,7-cyclopentylene
ethylene), poly(1-perfluorobutyl-3,5-cyclopentylene ethylene),
poly(1-perfluoro-isobutyl-3,5-cyclopentylene ethylene),
poly(1-perfluoro-tert-butyl-3,5-cyclopentylene ethylene),
poly(1-methyl-2-perfluoro-isobutyl-3,5-cyclopentylene ethylene),
poly(1-butyl-2-perfluoro-isobutyl-3,5-cyclopentylene ethylene),
poly(1,2-difluoro-1-trifluoromethyl-2-perfluoroethyl-3,5-cyclopentylene
ethylene),
poly(1-(1-trifluoromethyl-2,2,3,3,4,4,5,5-octafluorocyclopentyl)-3,5-cycl-
opentylene ethylene),
poly(1,1,2-trifluoro-2-perfluorobutyl-3,5-cyclopentylene ethylene),
poly(1,2-difluoro-1-trifluoromethyl-2-perfluorobutyl-3,5-cyclopentylene
ethylene),
poly(1-fluoro-1-perfluoroethyl-2,2-bis(trifluoromethyl)-3,5-cyclopentylen-
e ethylene),
poly(1,2-difluoro-1-perfluoropropanyl-2-trifluoromethyl-3,5-cyclopentylen-
e ethylene), poly(1-perfluorohexyl-3,5-cyclopentylene ethylene),
poly(1-methyl-2-perfluorohexyl-3,5-cyclopentylene ethylene),
poly(1-butyl-2-perfluorohexyl-3,5-cyclopentylene ethylene),
poly(1-hexyl-2-perfluorohexyl-3,5-cyclopentylene ethylene),
poly(1-octyl-2-perfluorohexyl-3,5-cyclopentylene ethylene),
poly(1-perfluoroheptyl-3,5-cyclopentylene ethylene),
poly(1-perfluorooctyl-3,5-cyclopentylene ethylene),
poly(1-perfluorodecanyl-3,5-cyclopentylene ethylene),
poly(1,1,2-trifluoro-perfluoropentyl-3,5-cyclopentylene ethylene),
poly(1,2-difluoro-1-trifluoromethyl-2-perfluorobutyl-3,5-cyclopentylene
ethylene), poly(1,1,2-trifluoro-perfluorohexyl-3,5-cyclopentylene
ethylene),
poly(1,2-difluoro-1-trifluoromethyl-2-perfluoropentyl-3,5-cyclopentylene
ethylene), poly(1,2-bis(perfluorobutyl)-3,5-cyclopentylene
ethylene), poly(1,2-bis(perfluorohexyl)-3,5-cyclopentylene
ethylene), poly(1-methoxy-2-trifluoromethyl-3,5-cyclopentylene
ethylene),
poly(1-tert-butoxymethyl-2-trifluoromethyl-3,5-cyclopentylene
ethylene), and
poly(1,1,3,3,3a,6a-hexafluorofuranyl-3,5-cyclopentylene
ethylene).
[0051] Specific examples of the fluorine-containing cyclic olefin
polymer containing the repeating structural unit represented by the
formula (1) according to the present invention include
poly(1-fluoro-2-trifluoromethyl-3,5-cyclopentylene ethylene),
poly(1-fluoro-1-trifluoromethyl-3,5-cyclopentylene ethylene),
poly(1-methyl-1-fluoro-2-trifluoromethyl-3,5-cyclopentylene
ethylene), poly(1,1-difluoro-2-trifluoromethyl-3,5-cyclopentylene
ethylene), poly(1,2-difluoro-2-trifluoromethyl-3,5-cyclopentylene
ethylene), poly(1-perfluoroethyl-3,5-cyclopentylene ethylene),
poly(1,1-bis(trifluoromethyl)-3,5-cyclopentylene ethylene),
poly(1,1,2-trifluoro-2-trifluoromethyl-3,5-cyclopentylene
ethylene), poly(1,2-bis(trifluoromethyl)-3,5-cyclopentylene
ethylene), poly(1-perfluoropropyl-3,5-cyclopentylene ethylene),
poly(1-methyl-2-perfluoropropyl-3,5-cyclopentylene ethylene),
poly(1-butyl-2-perfluoropropyl-3,5-cyclopentylene ethylene),
poly(1-perfluoro-isopropyl-3,5-cyclopentylene ethylene),
poly(1-methyl-2-perfluoroisopropyl-3,5-cyclopentylene ethylene),
poly(1,2-difluoro-1,2-bis(trifluoromethyl)-3,5-cyclopentylene
ethylene),
poly(1,1,2,2,3,3,3a,6a-octafluorocyclopentyl-4,6-cyclopentylene
ethylene),
poly(1,1,2,2,3,3,4,4,3a,7a-decafluorocyclohexyl-5,7-ethylene),
poly(1-perfluorobutyl-3,5-cyclopentylene ethylene),
poly(1-perfluoro-isobutyl-3,5-cyclopentylene ethylene),
poly(1-perfluoro-tert-butyl-3,5-cyclopentylene ethylene),
poly(1-methyl-2-perfluoro-isobutyl-3,5-cyclopentylene ethylene),
poly(1-butyl-2-perfluoro-isobutyl-3,5-cyclopentylene ethylene),
poly(1,2-difluoro-1-trifluoromethyl-2-perfluoroethyl-3,5-cyclopentylene
ethylene),
poly(1-(1-trifluoromethyl-2,2,3,3,4,4,5,5-octafluorocyclopentyl)-3,5-cycl-
opentylene ethylene)),
poly(1,1,2-trifluoro-2-perfluorobutyl-3,5-cyclopentylene ethylene),
poly(1,2-difluoro-1-trifluoromethyl-2-perfluorobutyl-3,5-cyclopentylene
ethylene),
poly(1-fluoro-1-perfluoroethyl-2,2-bis(trifluoromethyl)-3,5-cyclopentylen-
e ethylene),
poly(1,2-difluoro-1-perfluoropropanyl-2-trifluoromethyl-3,5-cyclopentylen-
e ethylene), poly(1-perfluorohexyl-3,5-cyclopentylene ethylene),
poly(1-methyl-2-perfluorohexyl-3,5-cyclopentylene ethylene),
poly(1-butyl-2-perfluorohexyl-3,5-cyclopentylene ethylene),
poly(1-hexyl-2-perfluorohexyl-3,5-cyclopentylene ethylene),
poly(1-octyl-2-perfluorohexyl-3,5-cyclopentylene ethylene),
poly(1-perfluoroheptyl-3,5-cyclopentylene ethylene),
poly(1-perfluorooctyl-3,5-cyclopentylene ethylene),
poly(1-perfluorodecanyl-3,5-cyclopentylene ethylene),
poly(1,1,2-trifluoro-perfluoropentyl-3,5-cyclopentylene ethylene),
poly(1,2-difluoro-1-trifluoromethyl-2-perfluorobutyl-3,5-cyclopentylene
ethylene), poly(1,1,2-trifluoro-perfluorohexyl-3,5-cyclopentylene
ethylene),
poly(1,2-difluoro-1-trifluoromethyl-2-perfluoropentyl-3,5-cyclopentylene
ethylene), poly(1,2-bis(perfluorobutyl)-3,5-cyclopentylene
ethylene), poly(1,2-bis(perfluorohexyl)-3,5-cyclopentylene
ethylene), poly(1-methoxy-2-trifluoromethyl-3,5-cyclopentylene
ethylene),
poly(1-tert-butoxymethyl-2-trifluoromethyl-3,5-cyclopentylene
ethylene), poly(1,1,3,3,3a,6a-hexafluorofuranyl-3,5-cyclopentylene
ethylene), poly(1-fluoro-2-trifluoromethoxy-3,5-cyclopentylene
ethylene), poly(1-fluoro-1-trifluoromethoxy-3,5-cyclopentylene
ethylene),
poly(1-methyl-1-fluoro-2-trifluoromethoxy-3,5-cyclopentylene
ethylene), poly(1,1-difluoro-2-trifluoromethoxy-3,5-cyclopentylene
ethylene), poly(1,2-difluoro-2-trifluoromethoxy-3,5-cyclopentylene
ethylene), poly(1-perfluoroethoxy-3,5-cyclopentylene ethylene),
poly(1,1-bis(trifluoromethoxy)-3,5-cyclopentylene ethylene),
poly(1,1,2-trifluoro-2-trifluoromethoxy-3,5-cyclopentylene
ethylene), poly(1,2-bis(trifluoromethoxy)-3,5-cyclopentylene
ethylene), poly(1-perfluoropropoxy-3,5-cyclopentylene ethylene),
poly(1-methyl-2-perfluoropropoxy-3,5-cyclopentylene ethylene),
poly(1-butyl-2-perfluoropropoxy-3,5-cyclopentylene ethylene),
poly(1-perfluoro-isopropoxy-3,5-cyclopentylene ethylene),
poly(1-methyl-2-perfluoro-isopropoxy-3,5-cyclopentylene ethylene),
poly(1,2-difluoro-1,2-bis(trifluoromethoxy)-3,5-cyclopentylene
ethylene), poly(1-perfluorobutoxy-3,5-cyclopentylene ethylene),
poly(1-perfluoro-isobutoxy-3,5-cyclopentylene ethylene),
poly(1-perfluoro-tert-butoxy-3,5-cyclopentylene ethylene),
poly(1-methyl-2-perfluoro-isobutoxy-3,5-cyclopentylene ethylene),
poly(1-butyl-2-perfluoro-isobutoxy-3,5-cyclopentylene ethylene),
poly(1,2-difluoro-1-trifluoromethoxy-2-perfluoroethoxy-3,5-cyclo
pentylene ethylene),
poly(1,1,2-trifluoro-2-perfluorobutoxy-3,5-cyclopentylene
ethylene),
poly(1,2-difluoro-1-trifluoromethoxy-2-perfluorobutoxy-3,5-cyclo
pentylene ethylene),
poly(1-fluoro-1-perfluoroethoxy-2,2-bis(trifluoromethoxy)-3,5-cyclopentyl-
ene ethylene),
poly(1,2-difluoro-1-perfluoropropoxy-2-trifluoromethoxy-3,5-cyclopentylen-
e ethylene), poly(1-perfluorohethoxy-3,5-cyclopentylene ethylene),
poly(1-methyl-2-perfluorohethoxy-3,5-cyclopentylene ethylene),
poly(1-butyl-2-perfluorohethoxy-3,5-cyclopentylene ethylene),
poly(1-hexyl-2-perfluorohethoxy-3,5-cyclopentylene ethylene),
poly(1-octyl-2-perfluorohethoxy-3,5-cyclopentylene ethylene),
poly(1-perfluoroheptoxy-3,5-cyclopentylene ethylene),
poly(1-perfluorooctoxy-3,5-cyclopentylene ethylene),
poly(1-perfluorodethoxy-3,5-cyclopentylene ethylene),
poly(1,1,2-trifluoroperfluoropentoxy-3,5-cyclopentylene ethylene),
poly(1,2-difluoro-1-trifluoromethoxy-2-perfluorobutoxy-3,5-cyclo
pentylene ethylene),
poly(1,1,2-trifluoro-2-perfluorohethoxy-3,5-cyclopentylene
ethylene),
poly(1,2-difluoro-1-trifluoromethoxy-2-perfluoropentyl-3,5-cyclo
pentylene ethylene),
poly(1,2-bis(perfluorobutoxy)-3,5-cyclopentylene ethylene),
poly(1,2-bis(perfluoroethoxy)-3,5-cyclopentylene ethylene),
poly(1-methoxy-2-trifluoromethoxy-3,5-cyclopentylene ethylene),
poly(1-tert-butoxymethyl-2-trifluoromethoxy-3,5-cyclopentylene
ethylene), poly(1-(2',2',2'-trifluoroethoxy)-3,5-cyclopentylene
ethylene),
poly(1-(2',2',3',3',3'-pentafluoropropoxy)-3,5-cyclopentylene
ethylene),
poly(1-methyl-2-(2',2',3',3',3'-pentafluoropropoxy)-3,5-cyclopentylene
ethylene),
poly(1-butyl-2-(2',2',3',3',3-pentafluoropropoxy)-3,5-cyclopent
ylene ethylene),
poly(1-(1',1',1'-trifluoro-isopropoxy)-3,5-cyclopentylene
ethylene),
poly(1-methyl-(1',1',1'-trifluoro-isopropoxy)-3,5-cyclopentylene
ethylene),
poly(1-(2',2',3',3',4',4',4'-heptafluorobutoxy)-3,5-ethylene),
poly(1-(1',1',1'-trifluoro-isobutoxy)-3,5-cyclopentylene ethylene),
poly(1-(1',1',1'-trifluoro-isobutoxy)-3,5-cyclopentylene ethylene),
poly(1-methyl-2-(1',1',1'-trifluoro-isobutoxy)-3,5-cyclopentylene
ethylene),
poly(1-butyl-2-(1',1',1'-trifluoro-isobutoxy)-3,5-cyclopentylene
ethylene),
poly(1,2-difluoro-1-trifluoromethoxy-2-(2',2',2'-trifluoroethoxy)-3,5-cyc-
lopentylene ethylene),
poly(1,1,2-trifluoro-2-(2',2',3',3',4',4',4'-heptafluorobutoxy)-3,5-cyclo-
pentylene ethylene),
poly(1,2-difluoro-1-trifluoromethoxy-2-(2',2',3',3',4',4',4'-heptafluorob-
utoxy)-3,5-cyclopentylene ethylene),
poly(1-fluoro-1-(2',2',2'-trifluoroethoxy)-2,2-bis(trifluoromethoxy)-3,5--
cyclopentylene ethylene),
poly(1,2-difluoro-1-(2',2',3',3',3'-pentafluoropropoxy)-2-trifluoromethox-
y-3,5-cyclopentylene ethylene),
poly(1-(2',2',3',3',4',4',5',5',6',6',6'-undecafluorohethoxy)-3,5-cyclope-
ntylene ethylene),
poly(1-methyl-2-(2',2',3',3',4',4',5',5',6',6',6'-undecafluorohethoxy)-3,-
5-cyclopentylene ethylene),
poly(1-butyl-2-(2',2',3',3',4',4',5',5',6',6',6'-undecafluorohethoxy)-3,5-
-cyclopentylene ethylene),
poly(1-hexyl-2-(2',2',3',3',4',4',5',5',6',6',6'-undecafluoroheptoxy)-3,5-
-cyclopentylene ethylene),
poly(1-octyl-2-(2',2',3',3',4-undecafluorohethoxy)-3,5-cyclopentylene
ethylene),
poly(1-(2',2',3',3',4',4',5',5',6',6',7',7',7'-tridecafluoroheptoxy)-3,5--
cyclopentylene ethylene),
poly(1-(2',2',3',3',4',4',5',5',6',6',7',7',8',8',8'-pentadecafluorooctox-
y)-3,5-cyclopentylene ethylene),
poly(1-(2',2',3',3',4',4',5',5',6',6',7',7',8',8',9',9',9'-heptadecafluor-
odethoxy)-3,5-cyclopentylene ethylene),
poly(1,1,2-trifluoro-2-(1',1',1'-trifluoro-isopropoxy)-3,5-cyclopentylene
ethylene),
poly(1,2-difluoro-1-trifluoromethoxy-2-(2',2',3',3',4',4',4'-heptafluorob-
utoxy)-3,5-cyclopentylene ethylene),
poly(1,1,2-trifluoro-(2',2',3',3',4',4',5',5',6',6',6'-undecafluorohethox-
y)-3,5-cyclopentylene ethylene),
poly(1,2-bis(2',2',3',3',4',4',4'-heptafluorobutoxy)-3,5-cyclopentylene
ethylene), and
poly(1,2-bis(2',2',3',3',4',4',5',5',6',6',6'-undecafluorohethoxy)-3,5-cy-
clopentylene ethylene).
[0052] Furthermore, in the present invention, the
fluorine-containing cyclic olefin copolymer having the repeating
structural unit [A] represented by the formula (1) and the
repeating structural unit [B] represented by the following formula
(2) has a molar ratio of the structural unit [A] and the structural
unit [B] of [A]/[B]=95/5 to 25/75, and has a fluorine atom content
rate of 40% to 75% by mass. In addition, the structural unit [A]
does not contain the repeating structural unit represented by the
formula (2).
[0053] Thereby, an imprint product which has enhanced heat
resistance of the film while maintaining satisfactory
releasability, and has improved scratch resistance of the film
surface, can be obtained. In regard to the glass transition
temperature as an index representing the heat resistance of the
film, if the rigid aliphatic cyclic structure of the structural
unit [B] represented by the formula (2) is introduced, the mobility
of the polymer under heating is decreased as compared with a
polymer having only the structural unit [A] represented by the
formula (1). As a results, the glass transition temperature
increases without: impairing the characteristics of the
fluorine-containing polymer. Thus, the heat resistance of the film
can be enhanced.
[0054] Unless particularly stated otherwise in the following
descriptions, the fluorine-containing cyclic olefin polymer may
include a fluorine-containing cyclic olefin copolymer.
[0055] Furthermore, the fluorine-containing cyclic olefin copolymer
having the repeating structural unit [A] represented by the formula
(1) and the repeating structural unit [B] represented by the
following formula (2) can have improved surface hardness such as
pencil hardness and can have improved scratch resistance of the
film surface, by introducing the rigid cyclic structure of the
repeating structural unit [B]. When the ratio [A]/[B] is less than
95/5, the effect of enhancing heat resistance and the effect of
improving scratch resistance of the film surface are low. The molar
ratio is preferably such that [A]/[B]-90/10 to 25/75.
##STR00007##
[0056] wherein in the formula (2), at least one of R.sup.5 to
R.sup.8 represents fluorine, a fluorine-containing C1-C10 alkyl, a
fluorine-containing C1-C10 alkoxy, or a fluorine-containing C2-C10
alkoxyalkyl; when R.sup.5 to R.sup.8 represent groups containing no
fluorine, R.sup.5 to R.sup.8 are each selected from hydrogen, a
C1-C10 alkyl, a C1-C10 alkoxy, and a C2-C10 alkoxyalkyl; R.sup.5 to
R.sup.8 may be identical with or different from each other; R.sup.5
to R.sup.8 may be joined together to form a cyclic structure; and n
represents an integer of 1 or 2.
[0057] The fluorine-containing cyclic olefin copolymer according to
the present invention is such that R.sup.1 to R.sup.4 of the
repeating structural unit represented by the formula (1) and
R.sup.5 to R.sup.8 of the repeating structural unit represented by
the formula (2) may be identical or different, and R.sup.1 to
R.sup.4 or R.sup.5 to R.sup.8 may be composed of two or more kinds
of structural units that are different from each other.
[0058] Specific examples of the fluorine-containing cyclic olefin
polymer containing the repeating structural unit represented by the
formula (2) according to the present invention include
poly(3-fluoro-4-trifluoromethyl-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3-fluoro-3-trifluoromethyl-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3-methyl-3-fluoro-4-trifluoromethyl-7,9-tricyclo[4.3.0.1.sup.2,5]
decanylene ethylene),
poly(3,3-difluoro-4-trifluoromethyl-7,9-tricyclo[4.3.0.1.sup.2,5]decanyle-
ne ethylene),
poly(3,4-difluoro-4-trifluoromethyl-7,9-tricyclo[4.3.0.1.sup.2,5]decanyle-
ne ethylene),
poly(3-perfluoroethyl-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3,3-bis(trifluoromethyl)-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3,3,4-trifluoro-4-trifluoromethyl-7,9-tricyclo[4.3.0.1.sup.2,5]decan-
ylene ethylene),
poly(3,4-bistrifluoromethyl-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3-perfluoropropyl)-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3-methyl-4-perfluoropropyl-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3-butyl-4-perfluoropropyl-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3-perfluoro-isopropyl-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3-methyl-9-perfluoro-isopropyl-7,9-tricyclo[4.3.0.1.sup.2,5]decanyle-
ne ethylene),
poly(3,4-difluoro-3,4-bis(trifluoromethyl)-7,9-tricyclo[4.3.0.1.sup.2,5]d-
ecanylene ethylene),
poly(2,3,3,4,4,5,5,6-octafluoro-9,11-tetracyclo[5.5.1.0.sup.2,6.
0.sup.8,12]tridecanylene ethylene),
poly(2,3,3,4,4,5,5,6,6,7-decafluoro-10,12-tetracyclo[6.5.1.0.sup.2,7.0.su-
p.9,13]tetradecanylene ethylene),
poly(3-perfluorobutyl-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3-perfluoro-isobutyl-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3-perfluoro-tert-butyl-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3-methyl-4-perfluoro-tert-butyl-7,9-tricyclo[4.3.0.1.sup.2,5]decanyl-
ene ethylene),
poly(3-butyl-4-perfluoro-tert-butyl-7,9-tricyclo[4.3.0.1.sup.2,5]decanyle-
ne ethylene),
poly(3,4-dimethyl-3-perfluoro-tert-butyl-7,9-tricyclo[4.3.0.1.sup.2,5]
decanylene ethylene),
poly(3,3,4-trifluoro-4-perfluorobutyl-7,9-tricyclo[4.3.0.1.sup.2,5]decany-
lene ethylene),
poly(3,4-difluoro-3-trifluoromethyl-4-perfluorobutyl-7,9-tricyclo[4.3.0.1-
.sup.2,5]decanylene ethylene),
poly(3-fluoro-3-perfluoroethyl-4,4-bis(trifluoromethyl)-7,9-tricyclo[4.3.-
0.1.sup.2,5]decanylene ethylene),
poly(3,4-difluoro-3-perfluoropropanyl-4-trifluoromethyl-7,9-tricyclo[4.3.-
0.1.sup.2,5]decanylene ethylene),
poly(3-perfluorohexyl-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3-methyl-4-perfluorohexyl-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3-butyl-4-perfluorohexyl-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3-hexyl-4-perfluorohexyl-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3-octyl-4-perfluorohexyl-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3-perfluoroheptyl-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3,3,4-trifluoro-4-perfluoropentyl-7,9-tricyclo[4.3.0.1.sup.2,5]decan-
ylene ethylene),
poly(3,4-difluoro-3-trifluoromethyl-4-perfluorobutyl-7,9-tricyclo[4.3.0.1-
.sup.2,5]decanylene ethylene),
poly(3,3,4-trifluoro-3-perfluorohexyl-7,9-tricyclo[4.3.0.1.sup.2,5]decany-
lene ethylene),
poly(3,4-difluoro-3-trifluoromethyl-4-perfluoropentyl-7,9-tricyclo[4.3.0.-
1.sup.2,5]decanylene ethylene),
poly(3,4-bis(perfluorobutyl)-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3,4-bis(perfluorohexyl)-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3-methoxy-4-trifluoromethyl-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3-tert-butoxymethyl-4-trifluoromethyl-7,9-tricyclo[4.3.0.1.sup.2,5]d-
ecanylene ethylene),
poly(4-fluoro-5-trifluoromethyl-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,-
13.1.sup.3,6]pentadecanylene ethylene),
poly(4-methyl-5-fluoro-5-trifluoromethyl-10,12-pentacyclo[6.5.1.0.sup.2,7-
.0.sup.9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4,4-difluoro-5-trifluoromethyl-10,12-pentacyclo[6.5.1.0.sup.2,7.0.su-
p.9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4-perfluoroethyl-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,13.1.sup.3-
,6]pentadecanylene ethylene),
poly(4,4-bis(trifluoromethyl)-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,13-
.1.sup.3,6]pentadecanylene ethylene),
poly(4,4,5-trifluoro-5-trifluoromethyl-10,12-pentacyclo[6.5.1.0.sup.2,7.0-
.sup.9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4,5-bis(trifluoromethyl)-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,13-
.1.sup.3,6]pentadecanylene ethylene),
poly(4-perfluoropropyl-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,13.1.sup.-
3,6]pentadecanylene ethylene),
poly(4-methyl-5-perfluoropropyl-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,-
13.1.sup.3,6]pentadecanylene ethylene),
poly(4-methyl-5-perfluoropropyl-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,-
13.1.sup.3,6]pentadecanylene ethylene),
poly(4-butyl-5-perfluoropropyl-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,1-
3.1.sup.3,6]pentadecanylene ethylene),
poly(4-perfluoro-isopropyl-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,13.1.-
sup.3,6]pentadecanylene ethylene),
poly(4-methyl-5-perfluoro-isopropyl-10,12-pentacyclo[6.5.1.0.sup.2,7.0.su-
p.9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4,5-difluoro-4,5-bis(trifluoromethyl)-10,12-pentacyclo[6.5.1.0.sup.2-
,7.0.sup.9,13.1.sup.3,6]pentadecanylene ethylene),
poly(3,4,4,5,5,6,6,7-octafluoro-12,14-hexacyclo[7.7.0.1.sup.2,8.1.sup.10,-
16.0.sup.3,7. 0.sup.11,15]octadecanylene ethylene),
poly(3,4,4,5,5,6,6,7,7,8-decafluoro-13,15-hexacyclo[8.7.0.1.sup.2,9.1.sup-
.11,17.0.sup.3,8.0.sup.12,16]nonadecanylene ethylene),
poly(4-perfluorobutyl-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,30.1.sup.3-
,6]pentadecanylene ethylene),
poly(4-perfluoro-isobutyl-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,13.1.s-
up.3,6]pentadecanylene ethylene),
poly(4-methyl-5-tert-butyl-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,13.1.-
sup.3,6]pentadecanylene ethylene),
poly(4-butyl-5-tert-butyl-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,13.1.s-
up.3,6]pentadecanylene ethylene),
poly(4,5-methyl-4-tert-butyl-10,12-pentacyclo[6.5.1.0.sup.2,7.
0.sup.9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4,4,5-trifluoro-6-perfluorobutyl-10,12-pentacyclo[6.5.1.0.sup.2,7.0.-
sup.9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4,6-difluoro-4-trifluoromethyl-5-perfluorobutyl-10,12-penta
cyclo[6.5.1.0.sup.2,7.0.sup.9,13.1.sup.3,6]pentadecanylene
ethylene),
poly(4-fluoro-4-perfluoroethyl-5,5-bis(trifluoromethyl)-10,12-pentacyclo[-
6.5.1.0.sup.2,7.0.sup.9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4,5-difluoro-4-perfluoropropanyl-5-trifluoromethyl-10,12-pentacyclo[-
6.5.1.0.sup.2,7.0.sup.9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4-perfluorohexyl-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,13.1.sup.3-
,6]pentadecanylene ethylene),
poly(4-methyl-5-perfluorohexyl-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,1-
3.1.sup.3,6]pentadecanylene ethylene),
poly(4-butyl-5-perfluorohexyl-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,13-
.1.sup.3,6]pentadecanylene ethylene),
poly(4-hexyl-5-perfluorohexyl-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,13-
.1.sup.3,6]pentadecanylene ethylene),
poly(4-octyl-5-perfluorohexyl-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,13-
.1.sup.3,6]pentadecanylene ethylene),
poly(4-perfluoroheptyl-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,13.1.sup.-
3,6]pentadecanylene ethylene),
poly(4-perfluorooctyl-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,13.1.sup.3-
,6]pentadecanylene ethylene),
poly(4-perfluorodecanyl-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,13.1.sup-
.3,6]pentadecanylene ethylene),
poly(4,4,5-trifluoro-6-perfluoropentyl-10,12-pentacyclo[6.5.1.0.sup.2,7.0-
.sup.9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4,5-difluoro-4-trifluoromethyl-6-perfluorobutyl-10,12-penta
cyclo[6.5.1.0.sup.2,7.0.sup.9,13.1.sup.3,6]pentadecanylene
ethylene),
poly(4,4,5-trifluoro-12-perfluorohexyl-10,12-pentacyclo[6.5.1.0.sup.2,7.0-
.sup.9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4,5-difluoro-4-trifluoromethyl-5-perfluoropentyl-10,12-pentacyclo[6.-
5.1.0.sup.2,7.0.sup.9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4,4,5-tris(trifluoromethyl)-5-perfluoro-tert-butyl-10,12-pentacyclo[-
6.5.1.0.sup.2,7.0.sup.9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4,5-bis(perfluorohexyl)-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,13.-
1.sup.3,6] pentadecanylene ethylene),
poly(4-methoxy-5-trifluoromethyl-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9-
,13.1.sup.3,6]pentadecanylene ethylene),
poly(3-fluoro-4-trifluoromethoxy-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3-fluoro-4-trifluoromethoxy-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3-methyl-3-fluoro-4-trifluoromethoxy-7,9-tricyclo[4.3.0.1.sup.2,5]de-
canylene ethylene),
poly(3,3-difluoro-4-trifluoromethoxy-7,9-tricyclo[4.3.0.1.sup.2,5]decanyl-
ene ethylene),
poly(3,4-difluoro-4-trifluoromethoxy-7,9-tricyclo[4.3.0.1.sup.2,5]decanyl-
ene ethylene),
poly(3-perfluoroethoxy-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3,3,4-trifluoro-4-trifluoromethoxy-7,9-tricyclo[4.3.0.1.sup.2,5]deca-
nylene ethylene),
poly(3,4-bis(trifluoromethoxy)-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3-perfluoropropoxy-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3-methyl-4-perfluoropropoxy-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3-butyl-4-perfluoropropoxy-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3-perfluoro-isopropoxy-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3-methyl-4-perfluoro-isopropoxy-7,9-tricyclo[4.3.0.1.sup.2,5]decanyl-
ene ethylene),
poly(3,4-difluoro-3,4-bis(trifluoromethoxy)-7,9-tricyclo[4.3.0.1.sup.2,5]-
decanylene ethylene),
poly(3-perfluorobutoxy-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3-perfluoro-isobutoxy-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3-perfluoro-tert-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3-methyl-4-perfluoro-isobutoxy-7,9-tricyclo[4.3.0.1.sup.2,5]decanyle-
ne ethylene),
poly(3-butyl-4-perfluoro-isobutoxy-7,9-tricyclo[4.3.0.1.sup.2,5]decanylen-
e ethylene),
poly(3,4-difluoro-3-trifluoromethoxy-4-perfluoroethoxy-7,9-tricyolo[4.3.0-
.1.sup.2,5]decanylene ethylene),
poly((3,3,4-trifluoro-4-perfluorobutoxy)-7,9-tricyclo[4.3.0.1.sup.2,5]
decanylene ethylene),
poly(3,4-difluoro-3-trifluoromethoxy-4-perfluorobutoxy-7,9-tricyclo[4.3.0-
.1.sup.2,5]decanylene ethylene),
poly(3-fluoro-3-perfluoroethoxy-2,2-bis(trifluoromethoxy)-7,9-tricyclo[4.-
3.0.1.sup.2,5]decanylene ethylene),
poly(3,4-difluoro-3-perfluoropropoxy-4-trifluoromethoxy)-7,9-tricyclo[4.3-
.0.1.sup.2,5]decanylene ethylene),
poly(3-perfluorohethoxy-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3-methyl-4-perfluorohethoxy-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3-butyl-4-perfluorohethoxy-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3-hexyl-4-perfluorohethoxy-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3-octyl-4-perfluorohethoxy-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3-perfluoroheptoxy-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3-perfluorooctoxy-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3-perfluorodethoxy-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3,3,4-trifluoroperfluoropentoxy-7,9-tricyclo[4.3.0.1.sup.2,5]decanyl-
ene ethylene),
poly(3,4-difluoro-3-trifluoromethoxy-4-perfluorobutoxy-7,9-tricyclo[4.3.0-
.1.sup.2,5]decanylene ethylene),
poly(3,3,4-trifluoro-4-perfluorohethoxy-7,9-tricyclo[4.3.0.1.sup.2,5]deca-
nylene ethylene),
poly(3,4-difluoro-3-trifluoromethoxy-4-perfluoropentyl-7,9-tricyclo[4.3.0-
.1.sup.2,5]decanylene ethylene),
poly(3,4-bis(perfluorobutoxy)-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3,4-bis(perfluorohethoxy)-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3-methoxy-4-trifluoromethoxy-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(3-tert-butoxymethyl-4-trifluoromethoxy-7,9-tricyclo[4.3.0.1.sup.2,5]-
decanylene ethylene),
poly(3-(2',2',2'-trifluoroethoxy)-7,9-tricyclo[4.3.0.1.sup.2,5]decanyl
ene ethylene),
poly(3-(2',2',3',3',3'-pentafluoropropoxy)-7,9-tricyclo[4.3.0.1.sup.2,5]d-
ecanylene ethylene),
poly(3-methyl-4-(2',2',3',3',3'-pentafluoropropoxy)-7,9-tricyclo
[4.3.0.1.sup.2,5]decanylene ethylene),
poly(3-butyl-4-(2',2',3',3',3'-pentafluoropropoxy)-7,9-tricyclo[4.3.0.1.s-
up.2,5]decanylene ethylene),
poly(3-(1',1',1'-trifluoro-isopropoxy)-7,9-tricyclo[4.3.0.1.sup.2,5]decan-
ylene ethylene),
poly(3-methyl-(1',1',1'-trifluoro-isopropoxy)-7,9-tricyclo[4.3.0.1.sup.2,-
5]decanylene ethylene),
poly(3-(2',2',3',3',4',4',4'-heptafluorobutoxy)-7,9-tricyclo[4.3.0.1.sup.-
2,5]decanylene ethylene),
poly(3-(1',1',1'-trifluoro-isobutoxy)-7,9-tricyclo[4.3.0.1.sup.2,5]decany-
lene ethylene),
poly(3-(1',1',1'-trifluoro-isobutoxy)-7,9-tricyclo[4.3.0.1.sup.2,5]decany-
lene ethylene),
poly(3-methyl-4-(1',1',1'-trifluoro-isobutoxy)-7,9-tricyclo[4.3.0.1.sup.2-
,5]decanylene ethylene),
poly(3-butyl-4-(1',1',1'-trifluoro-isobutoxy)-7,9-tricyclo[4.3.0.1.sup.2,-
5]decanylene ethylene),
poly(3,4-difluoro-3-trifluoromethoxy-4-(2',2',2'-trifluoroethoxy)-7,9-tri-
cyclo[4.3.0.1.sup.2,5]decanylene ethylene),
poly(3,3,4-trifluoro-4-(2',2',3',3',4',4',4'-heptafluorobutoxy)-7,9-tricy-
clo[4.3.0.1.sup.2,5]decanylene ethylene),
poly(3,4-difluoro-3-trifluoromethoxy-4-(2',2',3',3',4',4',4'-heptafluorob-
utoxy)-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene ethylene),
poly(3-fluoro-3-(2',2',2'-trifluoroethoxy)-4,4-bis(trifluoromethoxy)-7,9--
tricyclo[4.3.0.1.sup.2,5]decanylene ethylene),
poly(3,4-difluoro-3-(2',2',3',3',3'-pentafluoropropoxy)-4-trifluoromethox-
y)-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene ethylene),
poly(3-(2',2',3',3',4',4',5',5',6',6',6'-undecafluorohethoxy)-7,9-tricycl-
o[4.3.0.1.sup.2,5]decanylene ethylene),
poly(3-methyl-4-(2',2-undecafluorohethoxy)-7,9-tricyclo[4.3.0.1.sup.2,5]d-
ecanylene ethylene),
poly(3-butyl-4-(2',2',3',3',4',4',5',5',6',6',6'-undecafluorohethoxy)-7,9-
-tricyclo[4.3.0.1.sup.2,5]decanylene ethylene),
poly(3-hexyl-4-(2',2',3',3',4',4',5',5',6',6',6'-undecafluorohethoxy)-7,9-
-tricyclo[4.3.0.1.sup.2,5]decanylene ethylene),
poly(3-octyl-4-(2',2',3',3',4',4',5',5',6',6',6'-undecafluorohethoxy)-7,9-
-tricyclo[4.3.0.1.sup.2,5]decanylene ethylene),
poly(3-(2',2',3',3',4',4',5',5',6',6',7',7',7'-tridecafluoroheptoxy)-7,9--
tricyclo[4.3.0.1.sup.2,5]decanylene ethylene),
poly(3-(2',2',3',3',4',4',5',5',6',6',7',7',8',8',8'-pentadecafluorooetox-
y)-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene ethylene),
poly(3-(2',2',3',3',4',4',5',5',6',6',7',7',8',8',9',9',9'-heptadecafluor-
odethoxy 7,9-tricyclo[4.3.0.1.sup.2,5]decanylene ethylene),
poly(3,3,4-trifluoro-4-(1',1',1'-trifluoro-isopropoxy)-7,9-tricyelo[4.3.0-
.1.sup.2,5]decanylene ethylene),
poly(3,4-difluoro-3-trifluoromethoxy-4-(2',2',3',3',4',4',4'-heptafluorob-
utoxy)-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene ethylene),
poly(3,3,4-trifluoro-(2',2',3',3',4',4',5',5',6',6',6'-undecafluorohethox-
y)-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene ethylene),
poly(3,4-bis(2',2',3',3',4',4',4'-heptafluorobutoxy)-7,9-tricyclo[4.3.0.1-
.sup.2,5]decanylene ethylene),
poly(3,4-bis(2',2',3',3',4',4',5',5',6',6',6'-undecafluorohethoxy)-7,9-tr-
icyclo[4.3.0.1
.sup.2,5]decanylene ethylene),
poly(4-fluoro-5-trifluoromethoxy-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9-
,13. 1.sup.3,6]pentadecanylene ethylene),
poly(4-fluoro-5-trifluoromethoxy-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9-
,13. 1.sup.3,6]pentadecanylene ethylene),
poly(4-methyl-4-fluoro-5-trifluoromethoxy-10,12-pentacyclo[6.5.1.0.sup.2,-
7.0.sup.9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4,4-difluoro-5-trifluoromethoxy-10,12-pentacyclo[6.5.1.0.sup.2,7.
0.sup.9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4,5-difluoro-5-trifluoromethoxy-10,12-pentacyclo[6.5.1.0.sup.2,7.
0.sup.9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4-perfluoroethoxy-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene),
poly(4,4,5-trifluoro-5-trifluoromethoxy-10,12-pentacyclo[6.5.1.0.sup.2,7.-
0.sup.9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4,5-bis(trifluoromethoxy)-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,1-
3.1.sup.3,6]pentadecanylene ethylene),
poly(4-perfluoropropoxy-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,13.1.sup-
.3,6]penta decanylene ethylene),
poly(4-methyl-5-perfluoropropoxy-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9-
,13.1.sup.3,6]pentadecanylene ethylene),
poly(4-butyl-5-perfluoropropoxy-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,-
13.1.sup.3,6]pentadecanylene ethylene),
poly(4-perfluoro-isopropoxy-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,13.1-
.sup.3,6]pentadecanylene ethylene),
poly(4-methyl-5-perfluoro-isopropoxy-10,12-pentacyclo[6.5.1.0.sup.2,7.0.s-
up.9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4,5-difluoro-4,5-bis(trifluoromethoxy)-10,12-pentacyclo[6.5.1.0.sup.-
2,7.0.sup.9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4-perfluorobutoxy-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,13.1.sup.-
3,6]pentadecanylene ethylene),
poly(4-perfluoro-isobutoxy-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,13.1.-
sup.3,6]pentadecanylene ethylene),
poly(4-perfluoro-tert-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,13.1.sup.3-
,6]pentadecanylene ethylene),
poly(4-methyl-5-perfluoro-isobutoxy-10,12-pentacyclo[6.5.1.0.sup.2,7.0.su-
p.9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4-butyl-5-perfluoro-isobutoxy-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup-
.9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4,5-difluoro-4-trifluoromethoxy-5-perfluoroethoxy-10,12-pentacyclo[6-
.5.1.0.sup.2,7.0.sup.9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4,4,5-trifluoro-5-perfluorobutoxy-10,12-pentacyolo[6.5.1.0.sup.2,7.0-
.sup.9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4,5-difluoro-4-trifluoromethoxy-5-perfluorobutoxy-10,12-pentacyclo[6-
.5.1.0.sup.2,7.0.sup.9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4-fluoro-4-perfluoroethoxy-5,5-bis(trifluoromethoxy)-10,12-pentacycl-
o[6.5.1.0.sup.2,7.0.sup.9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4,5-difluoro-4-perfluoropropoxy-5-trifluoromethoxy)-10,12-pentacyclo-
[6.5.1.0.sup.2,7.0.sup.9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4-perfluorohethoxy-10,12-pentacyolo[6.5.1.0.sup.2,7.0.sup.9,13.1.sup-
.3,6]pentadecanylene ethylene),
poly(4-methyl-5-perfluorohethoxy-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9-
,13.1.sup.3,6]pentadecanylene ethylene),
poly(4-butyl-5-perfluorohethoxy-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,-
13.1.sup.3,6]pentadecanylene ethylene),
poly(4-hexyl-5-perfluorohethoxy-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,-
13.1.sup.3,6]pentadecanylene ethylene),
poly(4-octyl-5-perfluorohethoxy-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,-
13.1.sup.3,6]pentadecanylene ethylene),
poly(4-perfluoroheptoxy-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,13.1.sup-
.3,6]pentadecanylene ethylene),
poly(4-perfluorooctoxy-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,13.1.sup.-
3,6]pentadecanylene ethylene),
poly(4-perfluorodethoxy-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,13.1.sup-
.3,6]pentadecanylene ethylene),
poly(4,4,5-trifluoroperfluoropentoxy-10,12-pentacyclo[6.5.1.0.sup.2,7.0.s-
up.9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4,5-difluoro-4-trifluoromethoxy-5-perfluorobutoxy-10,12-pentacyclo[6-
.5.1.0.sup.2,7.0.sup.9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4,4,5-trifluoro-5-perfluorohethoxy-10,12-pentacyclo[6.5.1.0.sup.2,7.-
0.sup.9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4,5-difluoro-4-trifluoromethoxy-5-perfluoropentyl-10,12-pentacyclo[6-
.5.1.0.sup.2,7.0.sup.9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4,5-bis(perfluorobutoxy)-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,13-
.1.sup.3,6]pentadecanylene ethylene),
poly(4,5-bis(perfluorohethoxy)-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,1-
3.1.sup.3,6]pentadecanylene ethylene),
poly(4-methoxy-5-trifluoromethoxy-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.-
9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4-tert-butoxymethyl-5-trifluoromethoxy-10,12-pentacyclo[6.5.1.0.sup.-
2,7.0.sup.9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4-(2',2',2'-trifluoroethoxy)-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.-
9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4-(2',2',3',3',3'-pentafluoropropoxy)-10,12-pentacyclo[6.5.1.0.sup.2-
,7.0.sup.9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4-methyl-5-(2',2',3',3',3'-pentafluoropropoxy)-10,12-pentacyolo[6.5.-
1.0.sup.2,7.0.sup.9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4-butyl-5-(2',2',3',3',3'-pentafluoropropoxy)-10,12-pentacyclo[6.5.1-
.0.sup.2,7.0.sup.9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4-(1',1',1'-trifluoro-isopropoxy)-10,12-pentacyclo[6.5.1.0.sup.2,7.0-
.sup.9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4-methyl-(1',1',1'-trifluoro-isopropoxy)-10,12-pentacyclo[6.5.1.0.su-
p.2,7.0.sup.9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4-(2',2',3',3',4',4',4'-heptafluorobutoxy)-10,12-pentacyclo
[6.5.1.0.sup.2,7.0.sup.9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4-(1',1',1'-trifluoro-isobutoxy)-10,12-pentacyclo[6.5.1.0.sup.2,7.0.-
sup.9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4-(1',1',1'-trifluoro-isobutoxy)-10,12-pentacyclo[6.5.1.0.sup.2,7.0.-
sup.9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4-methyl-5-(1',1',1'-trifluoro-isobutoxy)-10,12-pentacyclo[6.5.1.0.s-
up.2,7.0.sup.9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4-butyl-5-(1',1',1'-trifluoro-isobutoxy)-10,12-pentacyclo[6.5.1.0.su-
p.2,7.0.sup.9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4,5-difluoro-4-trifluoromethoxy-5-(2',2',2'-trifluoroethoxy)-10,12-p-
entacyclo[6.5.1.0.sup.2,7.0.sup.9,13.1.sup.3,6]pentadecanylene
ethylene),
poly(4,4,5-trifluoro-5-(2',2',3',3',4',4',4'-heptafluorobutoxy)-10,12-pen-
tacyclo[6.5.1.0.sup.2,7.0.sup.9,13.1.sup.3,6]pentadecanylene
ethylene),
poly(4,5-difluoro-4-trifluoromethoxy-4-(2',2',3',3',4',4',4'-heptafluorob-
utoxy)-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,13.1.sup.3,6]pentadecanyle-
ne ethylene),
poly(4-fluoro-4-(2',2',2'-trifluoroethoxy)-5,5-bis(trifluoromethoxy)-10,1-
2-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,13.1.sup.3,6]pentadecanylene
ethylene),
poly(4,5-difluoro-4-(2',2',3',3',3'-pentafluoropropoxy)-5-trifluoromethox-
y)-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,13.1.sup.3,6]pentadecanylene
ethylene),
poly(4-(2',2',3',3',4',4',5',5',6',6',6'-undecafluorohethoxy)-10,12-penta-
cyclo[6.5.1.0.sup.2,7.0.sup.9,13.1.sup.3,6]pentadecanylene
ethylene),
poly(4-methyl-5-(2',2',3',3',4',4',5',5',6',6',6'-undecafluorohethoxy)-10-
,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,13.1.sup.3,6]pentadecanylene
ethylene),
poly(4-butyl-5-(2',2',3',3',4',4',5',5',6',6',6'-undecafluorohethoxy)-10,-
12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,13.1.sup.3,6]pentadecanylene
ethylene),
poly(4-hexyl-5-(2',2',3',3',4',4',5',5',6',6',6'-undecafluorohethoxy)-10,-
12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,13.1.sup.3,6]pentadecanylene
ethylene),
poly(4-octyl-5-(2',2',3',3',4',4',5',5',6',6',6'-undecafluorohethoxy)-10,-
12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,13.1.sup.3,6]pentadecanylene
ethylene),
poly(4-(2',2',3',3',4',4',5',5',6',6',7',7',7'-tridecafluoroheptoxy)-10,1-
2-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,13.1.sup.3,6]pentadecanylene
ethylene),
poly(4-(2',2',3',3',4',4',5',5',6',6',7',7',8',8',8'-pentadecafluorooctox-
y)-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,13.1.sup.3,6]pentadecanylene
ethylene),
poly(4-(2',2',3',3',4',4',5',5',6',6',7',7',8',8',9',9',9'-heptadecafluor-
odethoxy-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,13.1.sup.3,6]pentadecany-
lene ethylene),
poly(4,4,5-trifluoro-5-(1',1',1'-trifluoro-isopropoxy)-10,12-pentacyclo[6-
.5.1.0.sup.2,7.0.sup.9,13.1.sup.3,6]pentadecanylene ethylene),
poly(4,5-difluoro-4-trifluoromethoxy-5-(2',2',3',3',4',4',4'-heptafluorob-
utoxy)-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,13.1.sup.3,6]pentadecanyle-
ne ethylene),
poly(4,4,5-trifluoro-(2',2',3',3',4',4',5',5',6',6',6'-undecafluorohethox-
y)-10,12-pentacyclo[6.5.1.0.sup.2,7.0.sup.9,13.1.sup.3,6]pentadecanylene
ethylene),
poly(4,5-bis(2',2',3',3',4',4',4'-heptafluorobutoxy)-10,12-pentacyclo[6.5-
.1.0.sup.2,7.0.sup.9,13.1.sup.3,6]pentadecanylene ethylene), and
poly(4,5-bis(2',2',3',3',4',4',5',5',6',6',6'-undecafluorohethoxy)-10,12--
pentacyclo[6.5.1.0.sup.2,7.0.sup.9,13.1.sup.3,6]pentadecanylene
ethylene).
[0059] The polymer may also include other repeating structural
units in addition to the repeating structural units represented by
the formula (1) and the formula (2), in an amount that gives a
fluorine atom content rate in the range of 40% to 75% by mass, to
the extent that the effect of the present invention is not
impaired, but the content of the repeating structural unit of the
formula (1) or the content of the repeating structural units of the
formula (1) and the formula (2) is usually 30% to 100% by mass,
preferably 70% to 100% by mass, and more preferably 90% to 100% by
mass.
[0060] Furthermore, in the present invention, the
fluorine-containing cyclic olefin polymer containing the repeating
structural unit represented by the formula (1) preferably has a
region in which the storage modulus or loss modulus obtainable by
dynamic mechanical analysis by tensile mode (frequency 1 Hz, rate
of temperature increase 3.degree. C./min) varies in the range of -1
MPa/.degree. C. to 0 MPa/.degree. C. with respect to the changes in
temperature in a range of temperature which is not less than the
glass transition temperature. The characteristics are based on the
hydrogen bonding formed between the molecules or within the
molecule of the polymer having a hydrocarbon structure in the main
chain of the repeating structural unit, and having a substituent
selected from fluorine, an alkyl containing fluorine, a
fluorine-containing C1-C10 alkoxy, and a fluorine-containing C2-C10
alkoxyalkyl, for the at least one of R.sup.1 to R.sup.4 in a side
chain, but are not based on the crosslinking caused by
crystallinity or chemical bonding. The hydrogen bonding exhibited
by this specific structure causes the polymer to have a flat region
in which the variation in the storage modulus or loss modulus with
respect to the changes in temperature in a range of temperature
which is not less than the glass transition temperature, is -1
MPa/.degree. C. to 0 MPa/.degree. C. More preferably, such
variation is -0.5 MPa/.degree. C. to 0 MPa/.degree. C., and more
preferably -0.2 MPa/.degree. C. to 0 MPa/.degree. C.
[0061] Furthermore, in the present invention, the
fluorine-containing cyclic olefin copolymer containing the
repeating structural unit [A] represented by the formula (1) and
the repeating structural unit [B] represented by the formula (2)
has a molar ratio of the structural unit [A] and the structural
unit [B] of [A]/[B]=95/5 to 25/75. The structural unit [A] does not
include the repeating structural unit represented by the formula
(2).
[0062] As described above, the variation in the storage modulus or
loss modulus has a flat region, and this is because when the
polymer has a hydrocarbon structure in the main chain within the
repeating structural units and has a substituent selected from
fluorine, an alkyl containing fluorine, a fluorine-containing
C1-C10 alkoxy, and a fluorine-containing C2-C10 alkoxyalkyl, for at
least one of R.sup.1 to R.sup.4 and at least one of R.sup.5 to
R.sup.8 in a side chain, hydrogen bonding is formed between the
molecules or within the molecule of the polymer. By the hydrogen
bonding exhibited by this specific structure, the polymer has a
flat region in which the variation in the storage modulus or loss
modulus with respect to the changes in temperature in a region of
temperature which is not less than the glass transition temperature
is -1 MPa/.degree. C. to 0 MPa/.degree. C. When this molar ratio
exceeds 25/75, the flat regi on in the variation of the storage
modulus or loss modulus is lost, and the effect caused by hydrogen
bonding is not obtained.
[0063] The fluorine-containing cyclic olefin polymer and the
fluorine-containing cyclic olefin copolymer of the present
invention are amorphous transparent polymers.
[0064] In general, amorphous thermoplastic polymers have a rapidly
decreased elastic modulus in the region of temperature which is not
less than the glass transition temperature when such hydrogen
bonding or chemical crosslinking is not present. Thus, the
variation in the storage modulus or loss modulus with respect to
the changes in temperature exhibits at least -10 MPa/.degree. C. or
less. On the other hand, the excellent characteristics described
above of the fluorine-containing cyclic olefin polymer of the
present invention derived from the interaction of the physical
hydrogen bonding that is reversible with respect to changes in
temperature.
[0065] Furthermore, the fluorine-containing cyclic olefin polymer
containing the repeating structural unit represented by the formula
(1) or the fluorine-containing cyclic olefin copolymer containing
the repeating structural units represented by the formula (1) and
the formula (2) according to the present invention preferably has
the flat variation region of storage modulus or loss modulus
described above with respect to the region of temperature which is
not less than the glass transition temperature in dynamic
mechanical analysis by tensile mode (frequency 1 Hz, rate of
temperature increase 3.degree. C./min), in the region of storage
modulus or loss modulus of 0.1 MPa or more, more preferably of 0.1
MPa to 10000 MPa, and even more preferably 0.1 MPa to 1000 MPa.
When the value is 0.1 MPa or more, the shape can be maintained
during the heating and cooling processes of the production process
for an imprint product, the change in shrinkage during cooling is
small, and the dimensional accuracy of transcription is
increased.
[0066] Thereby, when the variation in the elastic modulus and
shrinkage ratio during the heating and cooling processes during the
production of nanoimprint films through solution application,
heating and drying or heat press, is suppressed to a minimal level
and optimized, production of a film which is capable of forming an
imprint product having a fine pattern transcribed from the surface
with high dimensional accuracy, and which attains small surface
tension and excellent releasability from the mold by containing
fluorine, can be realized. Particularly, a nanoimprint method based
on solution application, heating and drying gives a high degree of
freedom in the film thickness, and is suitable for the production
of a film for imprint products with large areas.
[0067] The glass transition temperature according to the present
invention is the maximum value of the loss modulus/storage modulus
(=tan .delta.) obtainable by measuring the dynamic changes while
the temperature of a sample is constantly increased or decreased,
and a changing point obtainable by measuring the endothermic or
exothermic process in a differential scanning calorimetric
analysis.
[0068] The glass transition temperature is usually in the range of
30.degree. C. to 250.degree. C., preferably 50.degree. C. to
200.degree. C., and more preferably 60.degree. C. to 160.degree. C.
When the glass transition temperature is 30.degree. C. or higher,
it is easy to maintain the shape of the imprint product in which
the pattern shape formed after the release from a mold is highly
accurate. Furthermore, when the glass transition temperature is
250.degree. C. or lower, the heating treatment temperature for melt
fluidization can be lowered, and therefore, yellowing or
deterioration of the support hardly occurs.
[0069] According to the present invention, the fluorine atom
content rate in the fluorine-containing cyclic olefin polymer
containing a repeated structural unit represented by the formula
(1) and the fluorine-containing cyclic olefin copolymer containing
the repeating structural units represented by the formula (1) and
formula (2) can be determined by the following expression (1):
Content of fluorine atoms (mass %)=(Fn.times.19).times.100/Fw
(1)
[0070] Here, in the expression (1), Fn represents the number of
fluorine atoms determined in consideration of the molar proportion
in the structural unit represented by the formula (1) and the
repeating structural unit represented by the formula (2), and Fw
represents the formula weight determined in consideration of the
molar proportion in the repeating structural unit represented by
the formula (1) and the repeating structural unit represented by
the formula (2). Thus, this fluorine atom content rate is 40% to
75% by mass, and preferably 42% to 68% by mass. If this fluorine
atom content rate is less than 40% by mass, the flat region of
variation of the storage modulus or loss modulus is either small or
absent, and the effect of hydrogen bonding is not exhibited.
Furthermore, if the fluorine atom content rate exceeds 75% by mass,
the number of hydrogen atoms within the structural units is small,
and similarly, the effect of hydrogen bonding is not exhibited.
[0071] The fluorine-containing cyclic olefin polymer or
fluorine-containing cyclic olefin copolymer according to the
present invention is such that the weight average molecular weight
(Mw) measured by gel permeation chromatography (GPC) relative to
polystyrene standards at a sample concentration of 3.0 mg/ml to 9.0
mg/ml is usually 5,000 to 1,000,000, and preferably 10,000 to
300,000. When this weight average molecular weight (Mw) is 5,000 or
more, physical properties having a region in which the variation in
the storage modulus or loss modulus with respect to the temperature
change is -1 MPa/.degree. C. to 0 MPa/.degree. C., can be
expressed.
[0072] Furthermore, when the weight average molecular weight is
1,000,000 or less, solvent solubility or fluidity at the time of
heat press molding is satisfactory. The molecular weight
distribution (Mw/Mn) which is the ratio of weight average molecular
weight (Mw) and number average molecular weight (Mn), is usually in
the range of 1.0 to 5.0.
[0073] For example, in order to form a coating film having a
uniform thickness or to obtain satisfactory heating moldability,
the molecular weight distribution is preferably broad, and is
preferably 1.4 to 5.0, and more preferably 1.5 to 3.0.
[0074] The fluorine-containing cyclic olefin polymer according to
the present invention can have a very low refractive index for the
D line, by having the specific structures represented by the
formula (1) and the formula (2).
[0075] The refractive index for light having the D-line wavelength
is usually 1.48 or less, and preferably 1.30 to 1.48, and within
this refractive index range, light exhibits excellent straightness.
Therefore, the light transmittance in the visible light region is
preferably 80% or higher, and more preferably 85% to 100%.
[0076] The fluorine-containing cyclic olefin polymer or
fluorine-containing cyclic olefin copolymer of the present
invention is such that the mass reduction when heated at
300.degree. C. for 5 minutes is usually less than 0.1%, and
preferably less than 0.07%, and since the polymer or copolymer is
thermoplastic and is excellent in thermal stability, the polymer or
copolymer can be treated by heat press molding.
[0077] The fluorine-containing cyclic olefin polymer according to
the present invention can be synthesized by polymerizing a
fluorine-containing cyclic olefin monomer represented by formula
(3) by using a ring-opening metathesis polymerization catalyst, and
hydrogenating the olefin moiety of the main chain of the resulting
polymer.
##STR00008##
[0078] wherein in the formula (3), at least one of R.sup.1 to
R.sup.4 represents fluorine, a fluorine-containing C1-C10 alkyl, a
fluorine-containing C1-C10 alkoxy, or a fluorine-containing C2-C10
alkoxyalkyl; when R.sup.1 to R.sup.4 represent groups containing no
fluorine, R.sup.1 to R.sup.4 are each selected from hydrogen, a
C1-C10 alkyl, a C1-C10 alkoxy, and a C2-C10 alkoxyalkyl; R.sup.1 to
R.sup.4 may be identical with or different from each other; and
R.sup.1 to R.sup.4 may be joined together to form a cyclic
structure.
[0079] More particularly, examples of R.sup.1 to R.sup.4 in the
formula (3) include fluorine; a fluorine-containing C1-C10 alkyl
such as an alkyl obtained by substituting a part or all of the
hydrogen atoms of an alkyl group with fluorine such as
fluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl,
pentafluoroethyl, heptafluoropropyl, hexafluoroisopropyl,
heptafluoroisopropyl, hexafluoro-2-methylisopropyl,
perfluoro-2-methylisopropyl, n-perfluorobutyl, n-perfluoropentyl,
and perfluorocyclopentyl; a fluorine-containing C1-C10 alkoxy such
as an alkoxy obtained by substituting a part or all of the hydrogen
atoms of an alkoxy group with fluorine atoms such as fluoromethoxy,
difluoromethoxy, trifluoromethoxy, trifluoroethoxy,
pentafluoroethoxy, heptafluoropropoxy, hexafluoroisopropoxy,
heptafluoroisopropoxy, hexafluoro-2-methylisopropoxy,
perfluoro-2-methylisopropoxy, n-perfluorobutoxy,
n-perfluoropentoxy, or perfluorocyclopentoxy; and a
fluorine-containing C2-C10 alkoxyalkyl such as an alkoxyalkyl
obtained by substituting a part or all of the hydrogen atoms of an
alkoxy group with fluorine such as fluoromethoxymethyl,
difluoromethoxymethyl, trifluoromethoxymethyl,
trifluoroethoxymethyl, pentafluoroethoxymethyl,
heptafluoropropoxymethyl, hexafluoroisopropoxymethyl,
heptafluoroisopropoxymethyl, hexafluoro-2-methylisopropoxymethyl,
perfluoro-2-methylisopropoxymethyl, n-perfluorobutoxymethyl,
n-perfluoropentoxymethyl, or perfluorocyclopentoxymethyl.
[0080] Furthermore, R.sup.1 to R.sup.4 may be joined together to
form a cyclic structure, and may form a ring such as
perfluorocycloalkyl, or perfluorocycloether interrupted with
oxygen.
[0081] Examples of the other R.sup.1 to R.sup.4 that do not contain
fluorine include hydrogen; a C1-C10 alkyl such as methyl, ethyl,
propyl, isopropyl, 2-methylisopropyl, n-butyl, n-pentyl, or
cyclopentyl; a C1-C10 alkoxy such as methoxy, ethoxy, propoxy,
butoxy, or pentoxy; and a C2-C10 alkoxyalkyl such as methoxymethyl,
ethoxymethyl, propoxymethyl, butoxymethyl, or pentoxymethyl.
[0082] Furthermore, the monomer used in the production of the
fluorine-containing cyclic olefin polymer according to the present
invention may be the only fluorine-containing cyclic olefin monomer
represented by the formula (3), or may be composed of two or more
kinds of structural units which differ from each other in terms of
at least one of R.sup.1 to R.sup.4.
[0083] The monomer used in the production of the
fluorine-containing cyclic olefin copolymer according to the
present invention may be copolymerized with a fluorine-containing
cyclic olefin comonomer represented by formula (4):
##STR00009##
[0084] wherein in the formula (4), at least one of R.sup.5 to
R.sup.8 represents fluorine, a fluorine-containing C1-C10 alkyl, a
fluorine-containing C1-C10 alkoxy, or a fluorine-containing C2-C10
alkoxyalkyl; when R.sup.5 to R.sup.8 represent groups containing no
fluorine, R.sup.5 to R.sup.8 are each selected from hydrogen, a
C1-C10 alkyl, a C1-C10 alkoxy, and a C2-C10 alkoxyalkyl; R.sup.5 to
R.sup.8 may be identical with or different from each other; R.sup.5
to R.sup.8 may be joined together to form a cyclic structure; and n
represents an integer of 1 or 2.
[0085] More particularly, examples of R.sup.5 to R.sup.8 in the
formula (4) include fluorine; a fluorine-containing C1-C10 alkyl
such as an alkyl obtained by substituting a part or all of the
hydrogen atoms of an alkyl group with fluorine such as
fluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl,
pentafluoroethyl, heptafluoropropyl, hexafluoroisopropyl,
heptafluoroisopropyl, hexafluoro-2-methylisopropyl,
perfluoro-2-methylisopropyl, n-perfluorobutyl, n-perfluoropentyl,
and perfluorocyclopentyl; a fluorine-containing C1-C10 alkoxy such
as an alkoxy obtained by substituting a part or all of the hydrogen
atoms of an alkoxy group with fluorine atoms such as fluoromethoxy,
difluoromethoxy, trifluoromethoxy, trifluoroethoxy,
pentafluoroethoxy, heptafluoropropoxy, hexafluoroisopropoxy,
heptafluoroisopropoxy, hexafluoro-2-methylisopropoxy,
perfluoro-2-methylisopropoxy, n-perfluorobutoxy,
n-perfluoropentoxy, or perfluorocyclopentoxy; and a
fluorine-containing C2-C10 alkoxyalkyl such as an alkoxyalkyl
obtained by substituting a part or all of the hydrogen atoms of an
alkoxy group with fluorine such as fluoromethoxymethyl,
difluoromethoxymethyl, trifluoromethoxymethyl,
trifluoroethoxymethyl, pentafluoroethoxymethyl,
heptafluoropropoxymethyl, hexafluoroisopropoxymethyl,
heptafluoroisopropoxymethyl, hexafluoro-2-methylisopropoxymethyl,
perfluoro-2-methylisopropoxymethyl, n-perfluorobutoxymethyl,
n-perfluoropentoxymethyl, or perfluorocyclopentoxymethyl.
[0086] Furthermore, R.sup.5 to R.sup.8 may be joined together to
form a cyclic structure, and may form a ring such as
perfluorocycloalkyl, or perfluorocycloether interrupted with
oxygen.
[0087] Examples of the other R.sup.5 to R.sup.8 that do not contain
fluorine include hydrogen; a C1-C10 alkyl such as methyl, ethyl,
propyl, isopropyl, 2-methyl isopropyl, n-butyl, n-pentyl, or
cyclopentyl; a C1-C10 alkoxy such as methoxy, ethoxy, propoxy,
butoxy, or pentoxy; and a C2-C10 alkoxyalkyl such as methoxymethyl,
ethoxymethyl, propoxymethyl, butoxymethyl, or pentoxymethyl.
[0088] The monomer used in the production of the
fluorine-containing cyclic olefin copolymer according to the
present invention may be the fluorine-containing cyclic olefin
monomer represented by the formula (4) only, or may be composed of
two or more kinds of structural units which differ from each other
in terms of at least one of R.sup.5 to R.sup.8.
[0089] The ring-opening metathesis polymerization catalyst that is
used in the polymerization of the fluorine-containing cyclic olefin
monomer, is not limited as long as it is a catalyst capable of
performing ring-opening metathesis polymerization, but examples
include tungsten-based alkylidene catalysts such as
W(N-2,6-Pr.sup.i.sub.2C.sub.6H.sub.3) (CHBu.sup.t)
(OBu.sup.t).sub.2,
W(N-2,6-Pr.sup.i.sub.2C.sub.6H.sub.3)(CHBu.sup.t)(OCMe.sub.2CF.sub.3).sub-
.2, W(N-2,6-Pr.sup.i.sub.2C.sub.6H.sub.3) (CHBu.sup.t)
(OCMe(CF.sub.3).sub.2).sub.2,
W(N-2,6-Pr.sup.i.sub.2C.sub.6H.sub.3)(CHBu.sup.t)(OC(CFA.sub.3).sub.2,
W(N-2,6-(Me).sub.2C.sub.6H.sub.3)(CHBu.sup.t)(OC(CFA.sub.3).sub.2,
W(N-2,6-Pr.sup.i.sub.2C.sub.6H.sub.3)(CHCMe.sub.2Ph)(OBu.sup.t).sub.2,
W(N-2,6-Pr.sup.i.sub.2C.sub.6H.sub.3) (CHCMe.sub.2Ph)
(OCMe.sub.2CF.sub.3).sub.2, W(N-2,6-Pr.sup.i.sub.2C.sub.6H.sub.3)
(CHCMe.sub.2Ph) (OCMe(CF.sub.3).sub.2).sub.2,
W(N-2,6-Pr.sup.i.sub.2C.sub.6H.sub.3) (CHCMe.sub.2Ph)
(OC(CF.sub.3).sub.3), W(N-2,6-Me.sub.2C.sub.6H.sub.3)
(CHCMe.sub.2Ph) (OC(CF.sub.3).sub.3).sub.2, or
W(N-2,6-Me.sub.2C.sub.6H.sub.3) (CHCHCMePh)
(OBu.sup.t).sub.2(PR.sub.3), W(N-2,6-Me.sub.2C.sub.6H.sub.3)
(CHCHCMe.sub.2) (OBu.sup.t).sub.2(PR.sub.3),
W(N-2,6-Me.sub.2C.sub.6H.sub.3) (CHCHCPh.sub.2)
(OBu.sup.t).sub.2(PR.sub.3), W(N-2,6-Me.sub.2C.sub.6H.sub.3)
(CHCHCMePh) (OCMe.sub.2(CF.sub.3)).sub.2(PR.sub.3),
W(N-2,6-Me.sub.2C.sub.6H.sub.3) (CHCHCMe.sub.2)
(OCMe.sub.2(CF.sub.3)).sub.2(PR.sub.3),
W(N-2,6-Me.sub.2C.sub.6H.sub.3) (CHCHCPh.sub.2)
(OCMe.sub.2(CF.sub.3)).sub.2(PR.sub.3),
W(N-2,6-Me.sub.2C.sub.6H.sub.3) (CHCHCMePh)
(OCMe(CF.sub.3).sub.2).sub.2(PR.sub.3),
W(N-2,6-Me.sub.2C.sub.6H.sub.3) (CHCHCMe.sub.2)
(OCMe(CF.sub.3).sub.2).sub.2(PR.sub.3),
W(N-2,6-Me.sub.2C.sub.6H.sub.3) (CHCHCPh.sub.2)
(OCMe(CF.sub.3).sub.2).sub.2(PR.sub.3),
W(N-2,6-Me.sub.2C.sub.6H.sub.3) (CHCHCMePh)
(OC(CF.sub.3).sub.3).sub.2(PR.sub.3),
W(N-2,6-Me.sub.2C.sub.6H.sub.3) (CHCHCMe.sub.2)
(OC(CF.sub.3).sub.3).sub.2(PR.sub.3),
W(N-2,6-Me.sub.2C.sub.6H.sub.3) (CHCHCPh.sub.2)
(OC(CF.sub.3).sub.3).sub.2(PR.sub.3),
W(N-2,6-Pr.sup.i.sub.2C.sub.6H.sub.3) (CHCHCMePh)
(OCMe.sub.2(CF.sub.3)).sub.2(PR.sub.3),
W(N-2,6-Pr.sup.i.sub.2C.sub.6H.sub.3) (CHCHCMePh)
(OCMe(CF.sub.3).sub.2).sub.2(PR.sub.3),
W(N-2,6-Pr.sup.i.sub.2C.sub.6H.sub.3) (CHCHCMePh)
(OC(CF.sub.3).sub.3).sub.2(PR.sub.3),
W(N-2,6-Pr.sup.i.sub.2C.sub.6H.sub.3) (CHCHCMePh)
(0Ph).sub.2(PH.sub.3) or W(N-2,6-Me.sub.2C.sub.6H.sub.3)
(CHCHCMePh) (OBu.sup.t).sub.2(Py), W(N-2,6-Me.sub.2C.sub.6H.sub.3)
(CHCHCMe.sub.2) (OBu.sup.t).sub.2(Py),
W(N-2,6-Me.sub.2C.sub.6H.sub.3) (CHCHCPh.sub.2)
(OBu.sup.t).sub.2(Py), W(N-2,6-Me.sub.2C.sub.6H.sub.3) (CHCHCMePh)
(OCMe.sub.2(CF.sub.3)).sub.2(Py), W(N-2,6-Me.sub.2C.sub.6H.sub.3)
(CHCHCMe.sub.2) (OCMe.sub.2 (CF.sub.3)).sub.2(Py),
W(N-2,6-Me.sub.2C.sub.6H.sub.3) (CHCHCPh.sub.2)
(OCMe.sub.2(CF.sub.3)).sub.2(Py), W(N-2,6-Me.sub.2C.sub.6H.sub.3)
(CHCHCMePh) (OCMe(CFA.sub.2).sub.2(Py),
W(N-2,6-Me.sub.2C.sub.6H.sub.3) (CHCHCMe.sub.2)
(OCMe(CF.sub.3).sub.2).sub.2(Py), W(N-2,6-Me.sub.2C.sub.6H.sub.3)
(CHCHCPh.sub.2) (OCMe(CF.sub.3).sub.2).sub.2(Py)
W(N-2,6-Me.sub.2C.sub.6H.sub.3) (CHCHCMePh)
(OC(CF.sub.3).sub.3).sub.2(Py) W(N-2,6-Me.sub.2C.sub.6H.sub.3)
(CHCHCMe.sub.2) (OC(CF.sub.3).sub.3).sub.2(Py)
W(N-2,6-Me.sub.2C.sub.6H.sub.3) (CHCHCPh.sub.2)
(OC(CF.sub.3).sub.3).sub.2(Py) W(N-2,6-Pr'.sub.2C.sub.6H.sub.3)
(CHCHCMePh) (OCMe.sub.2 (CF.sub.3)).sub.2(Py)
W(N-2,6-Pr.sup.i.sub.2C.sub.6H.sub.3) (CHCHCMePh)
(OCMe(CF.sub.3).sub.2).sub.2(Py)
W(N-2,6-Pr.sup.i.sub.2C.sub.6H.sub.3) (CHCHCMePh)
(OC(CF.sub.3).sub.3).sub.2(Py) and
W(N-2,6-Pr.sup.i.sub.2C.sub.6H.sub.3) (CHCHCMePh) (OPh).sub.2(Py);
molybdenum-based alkylidene catalysts such as Mo
(N-2,6-Pr.sup.i.sub.2C.sub.6H.sub.3) (CHBu.sup.t)
(OBu.sup.t).sub.2, Mo (N-2,6-Pr.sup.i.sub.2C.sub.6H.sub.3)
(CHBu.sup.t) (OCMe.sub.2CF.sub.3).sub.2, Mo
(N-2,6-Pr.sup.i.sub.2C.sub.6H.sub.3) (CHBu.sup.t)
(OCMe(CF.sub.3).sub.2).sub.2, Mo
(N-2,6-Pr.sup.i.sub.2C.sub.6H.sub.3) (CHBu.sup.t)
(OC(CF.sub.3).sub.3).sub.2, Mo (N-2,6-Me.sub.2C.sub.6H.sub.3)
(CHBu.sup.t) (OC(CF.sub.3).sub.3).sub.2, Mo
(N-2,6-Pr.sup.i.sub.2C.sub.6H.sub.3) (CHCMe.sub.2Ph)
(OCMe.sub.3).sub.2, Mo (N-2,6-Pr.sup.i.sub.2C.sub.6H.sub.3)
(CHCMe.sub.2Ph) (OCMe.sub.2 (CF.sub.3)).sub.2, Mo
(N-2,6-Pr.sup.i.sub.2C.sub.6H.sub.3) (CHCMe.sub.2Ph)
(OCMe(CF.sub.3).sub.2).sub.2, Mo
(N-2,6-Pr.sup.i.sub.2C.sub.6H.sub.3) (CHCMe.sub.2Ph)
(OC(CF.sub.3).sub.3).sub.2, Mo (N-2,6-Me.sub.2C.sub.6H.sub.3)
(CHCMe.sub.2Ph) (OC(CF.sub.3).sub.3).sub.2, Mo
(N-2,6-Pr.sup.i.sub.2C.sub.6H.sub.3) (CHCMe.sub.2Ph)
(OBu.sup.t).sub.2(PR.sub.3), Mo
(N-2,6-Pr.sup.i.sub.2C.sub.6H.sub.3) (CHCMe.sub.2Ph)
(OCMe.sub.2CF.sub.3).sub.2(PR.sub.3), Mo
(N-2,6-Pr.sup.i.sub.2C.sub.6H.sub.3) (CHCMe.sub.2Ph)
(OCMe(CF.sub.3).sub.2).sub.2(PR.sub.3), Mo
(N-2,6-Pr.sup.i.sub.2C.sub.6H.sub.3) (CHCMe.sub.2Ph)
(OC(CF.sub.3).sub.3).sub.2(PR.sub.3), Mo
(N-2,6-Me.sub.2C.sub.6H.sub.3) (CHCMe.sub.2Ph)
(OC(CF.sub.3).sub.3).sub.2(PR.sub.3) Mo
(N-2,6-Pr.sup.i.sub.2C.sub.6H.sub.3) (CHCMe.sub.2Ph)
(OBu.sup.t).sub.2(Py), Mo (N-2,6-Pr.sup.i.sub.2C.sub.6H.sub.3)
(CHCMe.sub.2Ph) (OCMe.sub.2CF.sub.3).sub.2(Py), Mo
(N-2,6-Pr.sup.i.sub.2C.sub.6H.sub.3) (CHCMe.sub.2Ph)
(OCMe(CF.sub.3).sub.2).sub.2(Py), Mo
(N-2,6-Pr.sup.i.sub.2C.sub.6H.sub.3) (CHCMe.sub.2Ph)
(OC(CF.sub.3).sub.3).sub.2(Py), and Mo
(N-2,6-Me.sub.2C.sub.6H.sub.3) (CHCMe.sub.2Ph)
(OC(CF.sub.3).sub.3).sub.2(Py)
[0090] (provided that Pr.sup.i in the formulas represents an
isopropyl group; R represents an alkyl group such as a methyl group
or an ethyl group, or an alkoxy group such as a methoxy group or an
ethoxy group; Bu.sup.t represents a tert-butyl group; Me represents
a methyl group; Ph represents a phenyl group; and Py represents a
pyridine group); and ruthenium-based alkylidene catalysts such as
Ru(CHCHCPh.sub.2)(PPh.sub.3).sub.2Cl.sub.2 (provided that Ph in the
formula represents a phenyl group), which can be all preferably
used. Furthermore, these ring-opening metathesis polymerization
catalysts may be used individually or in combination of two or more
kinds.
[0091] On the other hand, in addition to the ring-opening
metathesis polymerization catalysts described above, a ring-opening
metathesis polymerization catalyst formed from a combination of an
organic transition metal complex, a transition metal halide or a
transition metal oxide, and a Lewis acid as a co-catalyst can also
be used, but this catalyst has low catalytic activity and is not
preferable from an industrial viewpoint.
[0092] In regard to the ring-opening metathesis polymerization of
the fluorine-containing cyclic olefin monomer, the molar ratio of
the fluorine-containing cyclic olefin monomer and the ring-opening
metathesis polymerization catalyst is such that in the case of a
transition metal alkylidene catalyst of tungsten, molybdenum or
ruthenium, the monomer is used in an amount of usually 100 moles to
30,000 moles, and preferably 1,000 moles to 20,000 moles, relative
to 1 mole of the transition metal alkylidene catalyst.
[0093] Furthermore, an olefin can be used as a chain transfer agent
in order to control the molecular weight and the molecular weight
distribution. Examples of the olefin include .alpha.-olefins such
as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and
1-octene; and fluorine-containing olefins derived from those
olefins. Further examples include silicon-containing olefins such
as vinyltrimethylsilane, allyltrimethylsilane, allyltriethylsilane,
and allyltriisopropylsilane; and fluorine- and silicon-containing
olefins derived from those olefins, and still other examples of the
dienes include non-conjugated dienes such as 1,4-pentadiene,
1,5-hexadiene, and 1,6-heptadiene; and fluorine-containing
non-conjugated dienes derived from those dienes. These olefins,
fluorine-containing olefins, dienes and fluorine-containing dienes
may be used individually, or two or more kinds may be used
together.
[0094] The amount of the olefins, fluorine-containing olefins,
dienes or fluorine-containing dienes used is such that an olefin or
a diene is usually used in an amount in the range of 0.001 moles to
1,000 moles, and preferably 0.01 moles to 100 moles, based on 1
mole of the fluorine-containing cyclic olefin monomer. Furthermore,
an olefin or a diene is used in an amount in the range of usually
0.1 moles to 1,000 moles, and preferably 1 mole to 500 moles, based
on 1 mole of the transition metal alkylidene catalyst.
[0095] The ring-opening metathesis polymerization of the
fluorine-containing cyclic olefin monomer may be carried out
without solvent or in a solvent, but particularly preferable
examples of the solvent that is used include ethers such as
tetrahydrofuran, diethyl ether, dibutyl ether, dimethoxyethane, and
dioxane; esters such as ethyl acetate, propyl acetate and butyl
acetate; aromatic hydrocarbons such as benzene, toluene, xylene and
ethylbenzene; aliphatic hydrocarbons such as pentane, hexane and
heptane; aliphatic cyclic hydrocarbons such as cyclopentane,
cyclohexane, methylcyclohexane, dimethylcyclohexane, and decalin;
halogenated hydrocarbons such as methylene dichloride,
dichloroethane, dichloroethylene, tetrachloroethane, chlorobenzene,
and trichlorobenzene; fluorine-containing aromatic hydrocarbons
such as fluorobenzene, difluorobenzene, hexafluorobenzene,
trifluoromethylbenzene, and meta-xylene hexafluoride;
fluorine-containing aliphatic hydrocarbons such as perfluorohexane;
fluorine-containing aliphatic cyclic hydrocarbons such as
perfluorocyclodecalin; and fluorine-containing ethers such as
perfluoro-2-butyltetrahydrofuran. These may be used in combination
of two or more kinds.
[0096] In the ring-opening metathesis polymerization of the
fluorine-containing cyclic olefin monomer, the concentration of the
fluorine-containing cyclic olefin monomer in the monomer solution
may vary depending on the reactivity of the monomer and the
solubility of the monomer in the polymerization solvent, but the
concentration is usually preferably in the range of 5% to 100% by
mass, and more preferably 10% to 60% by mass. The reaction
temperature is usually in the range of -30.degree. C. to
150.degree. C., and preferably 30.degree. C. to 100.degree. C. The
reaction time is usually in the range of 10 minutes to 120 hours,
and preferably 30 minutes to 48 hours. Furthermore, a solution of
the polymer can be obtained by terminating the reaction with a
deactivator such as water, an aldehyde such as butyl aldehyde; a
ketone such as acetone; or an alcohol such as methanol.
[0097] The fluorine-containing cyclic olefin polymer or
fluorine-containing cyclic olefin copolymer of the present
invention is obtained by subjecting a fluorine-containing cyclic
olefin monomer to ring-opening metathesis polymerization, and
subjecting the olefin moiety of the main chain of the resulting
polymer to a hydrogenation reaction using a catalyst. The
hydrogenation catalyst may be any of a homogeneous metal complex
catalyst or a heterogeneous metal-supported catalyst, as long as it
is a catalyst capable of hydrogenating the olefin moiety of the
main chain of the polymer without causing a hydrogenation reaction
of the solvent used. Examples of the homogeneous metal complex
catalyst include chlorotris(triphenylphosphine)rhodium,
dichlorotris(triphenylphosphine)osmium,
dichlorohydridobis(triphenylphosphine)iridium,
dichlorotris(triphenylphosphine)ruthenium,
dichlorotetrakis(triphenylphosphine)ruthenium,
chlorohydridocarbonyltris(triphenylphosphine)ruthenium, and
dichlorotris(trimethylphosphine)ruthenium. Examples of the
heterogeneous metal-supported catalyst include activated
carbon-supported palladium, alumina-supported palladium, activated
carbon-supported rhodium, and alumina-supported rhodium. These
hydrogenation catalysts can be used individually or in combination
of two or more kinds.
[0098] When the hydrogenation treatment of the olefin moiety of the
main chain is carried out, in the case of using a known
heterogeneous or homogeneous hydrogenation catalyst, the amount of
the hydrogenation catalyst used is such that the metal component in
the hydrogenation catalyst is usually 5.times.10.sup.-4 parts by
mass to 100 parts by mass, and preferably 1.times.10.sup.-2 parts
by mass to 30 parts by mass, relative to 100 parts by mass of the
polymer prior to the hydrogenation treatment.
[0099] The solvent used in the hydrogenation is not particularly
limited as long as the solvent dissolves the fluorine-containing
cyclic olefin polymer or fluorine-containing cyclic olefin
copolymer, and the solvent itself is not hydrogenated. Examples of
the solvent include ethers such as tetrahydrofuran, diethyl ether,
dibutyl ether, and dimethoxyethane; esters such as ethyl acetate,
propyl acetate and butyl acetate; aromatic hydrocarbons such as
benzene, toluene, xylene, and ethylbenzene; aliphatic hydrocarbons
such as pentane, hexane, and heptane; aliphatic cyclic hydrocarbons
such as cyclopentane, cyclohexane, methylcyclohexane,
dimethylcyclohexane, and decalin; halogenated hydrocarbons such as
methylene dichloride, chloroform, dichloroethane, dichloroethylene,
tetrachloroethane, chlorobenzene, and trichlorobenzene;
fluorine-containing aromatic hydrocarbons such as fluorobenzene,
difluorobenzene, hexafluorobenzene, trifluoromethylbenzene, and
meta-xylene hexafluoride; fluorine-containing aliphatic
hydrocarbons such as perfluorohexane; fluorine-containing aliphatic
cyclic hydrocarbons such as perfluorocyclodecalin; and
fluorine-containing ethers such as
perfluoro-2-butyltetrahydrofuran. Combinations of two or more kinds
of these solvents may also be used.
[0100] The hydrogenation reaction of the olefin moiety of the main
chain is carried out at a hydrogen pressure in the range of normal
pressure to 30 MPa, preferably 0.5 MPa to 20 MPa, and particularly
preferably 2 MPa to 15 MPa, and the reaction temperature is in the
temperature range of usually 0.degree. C. to 300.degree. C.,
preferably room temperature to 250.degree. C., and particularly
preferably 50.degree. C. to 200.degree. C. There are no particular
limitations on the mode of carrying out the hydrogenation reaction,
but examples include a method of performing the reaction with the
catalyst dispersed or dissolved in a solvent, and a method of
filling the catalyst in a column or the like, and performing the
reaction by passing a polymer solution through the column as a
static phase.
[0101] There are no particular limitations on the hydrogenation
treatment of the olefin moiety of the main chain, and the
hydrogenation treatment may be carried out after precipitating a
polymerization solution of the fluorine-containing cyclic olefin
polymer prior to the hydrogenation treatment in a poor solvent,
isolating the polymer, and then dissolving the polymer again in a
solvent, or the hydrogenation treatment may be carried out using
the hydrogenation catalyst described above, without isolating the
polymer from the polymerization solution.
[0102] Furthermore, the hydrogenation rate of the olefin moiety of
the fluorine-containing cyclic olefin polymer is 50% or more,
preferably 70% to 100%, and more preferably 90% to 100%. When this
hydrogenation rate is less than 50%, the olefin moiety may be
deteriorated due to oxidation or light absorption, thereby causing
deterioration of heat resistance or weather resistance.
[0103] When the polymer solution (resin composition for pattern
transfer) according to the present invention is brought into
contact with a mold, the fluorine-containing cyclic olefin polymer
may be recovered from the polymer solution after hydrogenation, and
then the polymer may be dissolved again in a solvent and brought
into contact with a mold. Alternatively, the polymer solution
obtained after hydrogenation may be directly brought into contact
with the mold without recovering the fluorine-containing cyclic
olefin polymer, or two or more kinds of solvents may be mixed with
the polymer solution after hydrogenation and then, the mixture may
be brought into contact with the mold. The method for recovering
the fluorine-containing cyclic olefin polymer from the polymer
solution after hydrogenation is not particularly limited, but
examples include a method of discharging the reaction solution into
a poor solvent under stirring; a method of precipitating the
polymer by a steam stripping method in which steam is blown into
the reaction solution, or the like, and recovering the polymer by
filtration, centrifugation, decantation or the like; and a method
of evaporating and removing the solvent from the reaction solution
through heating or the like. Furthermore, various known additives
such as an ultraviolet absorbent, an antioxidant, a flame
retardant, and an antistatic agent can also be incorporated into
the recovered polymer, to the extent that the purpose of the
present invention is not impaired.
[0104] As a method of bringing the fluorine-containing cyclic
olefin polymer or fluorine-containing cyclic olefin copolymer of
the present invention obtained as described, into contact with a
mold having a fine pattern formed on the surface, and thereby
transcribing the pattern of the mold, there may be mentioned a
method of bringing a solution containing the fluorine-containing
cyclic olefin polymer and an organic solvent, into contact with a
mold, and evaporating the solvent to thereby transcribe the pattern
of the mold; or a method of using a film formed of this polymer,
and pressing the surface of a mold where a fine pattern is present
to thereby transcribe the pattern of the mold.
[0105] According to the present invention, since the polymer
solution (resin composition for pattern transcription) contains a
fluorine-containing cyclic olefin polymer such as described above,
an imprint product can be efficiently produced with high
dimensional accuracy, and an imprint product with a large area can
be produced by simple and convenient processes. Therefore, the
resin composition for pattern transcription of the present
invention can enhance the production efficiency for the imprint
product.
[0106] There are no particular limitations on the shape of the
convex portions and concave portions of the mold having a fine
pattern formed on the surface, which is used in the present
invention, but examples of the shape include a tetragonal shape, a
cylindrical shape, a prism shape, a pyramidal shape, a polyhedral
shape, and a hemispherical shape. Furthermore, examples of the
cross-sectional shape of the convex portions and the concave
portions include a cross-sectional tetragonal shape, a
cross-sectional triangular shape, and a cross-sectional
semicircular shape. As specific examples of the fine pattern of the
imprint product of the mold, a pattern in which the shape
satisfying the conditions described above has a concavo-convex
structure, and the like are preferable, but the disposition may be
continuous at an equal interval, or may be non-continuous at a
non-equal interval, without particular limitations.
[0107] The width of the convex portions and/or concave portions of
the fine pattern is usually 10 nm to 50 .mu.m, and preferably 20 nm
to 1 .mu.m. The depth of the concave portions is usually 30 nm to
50 .mu.m, and preferably 50 nm to 1 .mu.m. The aspect ratio, which
is the ratio of the width of the convex portions and the depth of
the concave portions, is usually 0.1 to 500, and preferably 0.5 to
20.
[0108] Examples of the base material of the mold having a fine
pattern formed on the surface, which is used to produce the imprint
product of the present invention, include metallic materials such
as nickel, iron, stainless steel, germanium, titanium, and silicon;
inorganic materials such as glass, quartz, and alumina; resin
materials such as polyimide, polyamide, polyester, polycarbonate,
polyphenylene ether, polyphenylene sulfide, polyacrylate,
polymethacrylate, polyallylate, an epoxy resin, and a silicone
resin; and carbonaceous materials such as diamond and graphite.
[0109] The imprint product of the present invention can be obtained
by bringing a solution containing the fluorine-containing cyclic
olefin polymer or fluorine-containing cyclic olefin copolymer and
an organic solvent (resin composition for pattern transcription),
into contact with a mold, evaporating the solvent, and thereby
transcribing the pattern of the mold. The mixing ratio of the
polymer and the organic solvent is such that the concentration of
the fluorine-containing cyclic olefin polymer in the solution is in
the range of usually 5% to 90% by mass, and preferably 10% to 60%
by mass, and a concentration which is efficient and suitable for
the optimal polymer thickness on the mold after evaporation of the
solvent or for coatability and the like, can be selected.
[0110] There are no particular limitations on the organic solvent
used, but the organic solvent can be selected from, for example,
fluorine-containing aromatic hydrocarbons such as meta-xylene
hexafluoride, benzotrifluoride, fluorobenzene, difluorobenzene,
hexafluorobenzene, trifluoromethylbenzene,
bis(trifluoromethyl)benzene, and meta-xylene hexafluoride;
fluorine-containing aliphatic hydrocarbons such as perfluorohexane,
and perfluorooctane; fluorine-containing aliphatic cyclic
hydrocarbons such as perfluorocyclodecalin; fluorine-containing
ethers such as perfluoro-2-butyltetrahydrofuran; halogenated
hydrocarbons such as chloroform, chlorobenzene, and
trichlorobenzene; ethers such as tetrahydrofuran, dibutyl ether,
1,2-dimethoxyethane, and dioxane; esters such as ethyl acetate,
propyl acetate, and butyl acetate; and ketones such as methyl
isobutyl ketone, and cyclohexanone, while considering solubility
and film formability. Among these, the organic solvents may be used
individually, or combinations of two or more kinds may be used.
Particularly, from the viewpoint of film formability, a solvent
having a boiling point of 70.degree. C. or higher at atmospheric
pressure is preferable. If the boiling point of the solvent is low,
the rate of evaporation is high, and the solvent begins to
partially dry during application. Thus, a low boiling point of the
solvent causes deterioration of the film thickness accuracy, or
fisheyes on the film surface.
[0111] The method of bringing a solution of the polymer of the
present invention into contact with a mold is not particularly
limited, but examples include a method of applying the polymer
solution on the finely patterned surface of the mold by a method
such as table coating, spin coating, dip coating, die coating,
spray coating, bar coating, roll coating, or curtain flow coating;
and a method of applying the polymer solution on a substrate made
of a metallic material such as stainless steel or silicon; an
inorganic material such as glass or quartz; a rein material such as
polyimide, polyamide, polyester, polycarbonate, polyphenylene
ether, polyphenylene sulfide, polyacrylate, polymethacrylate,
polyallylate, an epoxy resin, or a silicone resin, by a method such
as table coating, spin coating, dip coating, die coating, spray
coating, bar coating, roll coating, or curtain flow coating, and
placing the finely patterned surface of the mold on the applied
solution to bring them into contact.
[0112] Specific examples include:
[0113] (1) a method including a step of applying a solution
containing the fluorine-containing cyclic olefin polymer or
fluorine-containing cyclic olefin copolymer and an organic solvent
on the surface of a mold having a fine pattern, and a step of
evaporating the organic solvent from the solution; and
[0114] (2) a method including a step of applying a solution
containing the fluorine-containing cyclic olefin polymer or
fluorine-containing cyclic olefin copolymer and an organic solvent
on a support (substrate), a step of pressing the surface of the
coating layer with the surface of a mold where a fine pattern is
formed, and a step of evaporating the solvent from the coating
layer. In regard to the method of (2), the solvent may be
evaporated from the coating layer, and then pressing with the mold
can be performed.
[0115] The film thickness on the mold from which the solvent has
been evaporated after the contact is not particularly limited, but
is preferably 1 .mu.m to 10 mm, more preferably 5 .mu.m to 1 mm,
and most preferably 10 .mu.m to 0.5 mm. When the thickness is in
this range, a self-sustaining imprint product can be obtained.
[0116] The temperature at which the solvent is dried by evaporating
from the imprint product is usually in the range of 10.degree. C.
to 300.degree. C., and preferably 50.degree. C. to 200.degree. C.,
and the pressure is usually in the range of 133 Pa to atmospheric
pressure. The drying time is usually in the range of 10 minutes to
120 hours, and preferably 30 minutes to 48 hours. Furthermore, the
drying temperature, pressure and time may be respectively altered
to set values in a stepwise manner.
[0117] In the present invention, the method includes a step of
releasing the imprint product from the mold after forming the
imprint product on a mold by evaporating the solvent. Release of
the imprint product is preferably carried out at a temperature of
the glass transition temperature or lower, and it is more
preferable to release the imprint product at a temperature of
"glass transition temperature -20.degree. C." or higher. Thereby,
the pattern shape formed on the imprint product can be maintained
highly accurately, and release can be easily achieved. In regard to
the method of release, the imprint product may be released from the
mold by peeling, or the imprint product and the mold may be brought
into contact by, for example, a method such as immersion with a
medium such as water or spraying, and then the imprint product can
be peeled off by utilizing the surface tension. Alternatively, a
resin material or an inorganic material such as glass may be pasted
on the back surface of the imprint product, and the substrate may
be released as a support.
[0118] Furthermore, the imprint product of the present invention
can also be obtained by transcribing the pattern of a mold by
pressing the finely patterned surface of the mold on a film
containing the fluorine-containing cyclic olefin polymer or
fluorine-containing olefin copolymer. For example, a method of
pressing the film to the mold which has been heated to a
temperature which is not less than the glass transition
temperature; a method of heating the film to a temperature which is
not less than the glass transition temperature and pressing the
mold to the film; or a method of heating the film and the mold to a
temperature which is not less than the glass transition
temperature, and pressing the mold to the film, is preferable. The
heating temperature is in the range of "the glass transition
temperature" to "glass transition temperature +100.degree. C.", and
preferably "glass transition temperature +5.degree. C." to "glass
transition temperature +50.degree. C.". The pressing pressure is
usually in the range of 1 MPa to 100 MPa, and preferably 1 MPa to
60 MPa. Thus, the pattern shape formed on the imprint product can
be accurately formed.
[0119] The release of the imprint product formed on the mold by
pressing is preferably carried out at a temperature of the glass
transition temperature or lower, and it is more preferable to
release the imprint product at a temperature of "glass transition
temperature -20.degree." or lower. Thereby, the pattern shape
formed on the imprint product can be maintained highly accurately,
and release can be easily achieved. In regard to the method of
release, the imprint product may be released from the mold by
peeling, or the imprint product and the mold may be brought into
contact by, for example, a method such as immersion with a medium
such as water or spraying, and then the imprint product can be
peeled off by utilizing the surface tension. Alternatively, a resin
material or an inorganic material such as glass may be pasted on
the back surface of the imprint product, and the substrate may be
released as a support.
[0120] Furthermore, a cured product having a fine pattern which has
been transcribed to the surface of a photocured resin can be
produced by bringing the surface having the fine pattern of the
imprint product which is comprised of the fluorine-containing
cyclic olefin polymer or fluorine-containing cyclic olefin
copolymer, into contact with a photocurable monomer composition,
irradiating the photocurable monomer composition with light to cure
the composition, and then peeling the imprint product.
[0121] More particularly, the method may be either a method of
using, as a replica mold, an imprint product formed of a
fluorine-containing cyclic olefin polymer or a fluorine-containing
cyclic olefin copolymer, applying a composition of a curable
monomer and a photocuring initiator on the finely patterned surface
of this imprint product, irradiating the composition with light,
and thereby transcribing the fine pattern to the photocured resin;
or a method of applying a composition of a curable monomer and a
photocuring initiator on a substrate made of a metallic material
such as stainless steel or silicon; an inorganic material such as
glass or quartz; a resin material such as polyimide, polyamide,
polyester, polycarbonate, polyphenylene ether, polyphenylene
sulfide, polyacrylate, polymethacrylate, polyallylate, an epoxy
resin or a silicone resin; or the like, placing the finely
patterned surface of this imprint product on the composition,
irradiating the composition with light from the opposite surface of
the patterned surface of the imprint product, and thereby
transcribing the pattern to the photocured resin. Since the imprint
product of the present invention is formed from a
fluorine-containing cyclic olefin polymer and thus has excellent
transparency, even if light is irradiated from the opposite surface
of the patterned surface of the imprint product, the irradiated
light permeates through the imprint product so that the photocured
resin can be efficiently irradiated.
[0122] There are no particular limitations on the method of
bringing the finely patterned surface of the imprint product of a
fluorine-containing cyclic olefin polymer as a replica mold, into
contact with a curable monomer composition, but for example, the
imprint product can be brought into contact with the photocurable
monomer composition by applying the photocurable monomer
composition on the finely patterned surface of the imprint product
by a method such as table coating, spin coating, dip coating, die
coating, spray coating, bar coating, roll coating or curtain flow
coating, or by applying the curable monomer composition on a
substrate made of the metallic material described above, an
inorganic material such as glass or quartz, a resin material or the
like, by a method such as table coating, spin coating, dip coating,
die coating, spray coating, bar coating, roll coating or curtain
flow coating, and then placing the finely patterned surface of the
imprint product on the curable monomer composition.
[0123] The irradiated light is not particularly limited as long as
it can provide energy that induces a radical reaction or an ion
reaction by irradiating a photocuring initiator with the light. As
a light source for this, light rays having a wavelength of 400 nm
or less, for example, a low pressure mercury lamp, a middle
pressure mercury lamp, a high pressure mercury lamp, an ultrahigh
pressure mercury lamp, a chemical lamp, a black light lamp, a
microwave-excited mercury lamp, and a metal halide lamp, i-line,
G-line, KrF excimer laser light, and ArF excimer laser light can be
used.
[0124] The irradiation intensity for the photocurable monomer
composition is controlled in accordance with the target product,
and is not particularly limited. For example, the photoirradiation
intensity of light in a wavelength region effective for the
activation of the photopolymerization initiator that will be
described later (the effective light wavelength region may vary
depending on the photopolymerization initiator, but light having a
wavelength of 300 nm to 420 nm is usually used) is preferably 0.1
mW/cm.sup.2 to 100 mW/cm.sup.2. When the irradiation intensity to
the composition is less than 0.1 mW/cm.sup.2, the reaction time is
excessively lengthened. When the irradiation intensity is more than
100 mW/cm.sup.2, there is a risk that a decrease in the cohesive
force of the resulting cured product, yellowing, or deterioration
of the support may occur due to the heat radiated from the lamp and
the heat generation occurring during the polymerization of the
composition.
[0125] The time for irradiation of light is controlled in
accordance with the target product and is not particularly limited;
however, the integrated amount of light represented by the product
of light irradiation intensity and light irradiation time in the
light wavelength region can be set to 3 mJ/cm.sup.2 to 1000
mJ/cm.sup.2. The integrated amount of light is more preferably 5
mJ/cm.sup.2 to 500 mJ/cm.sup.2, and particularly preferably 10
mJ/cm.sup.2 to 300 mJ/cm.sup.2. When the integrated amount of light
irradiated to the composition is less than 3 mJ/cm.sup.2,
generation of an active species from the photopolymerization
initiator does not occur sufficiently, and there is a risk that a
decrease in the characteristics of the resulting cured product may
occur. When the integrated amount of light is greater than 1000
mJ/cm.sup.2, it is disadvantageous in terms of productivity
enhancement. Furthermore, in some occasions, it is also preferable
to use heating in combination to accelerate the polymerization
reaction. Furthermore, the temperature in the case of curing the
curable resin by irradiating light is preferably 0.degree. C. to
150.degree. C., and more preferably 0.degree. C. to 60.degree.
C.
[0126] The film thickness of the cured resin, which is obtained by
curing the curable resin by irradiating light, is not particularly
limited, but the thickness is preferably 1 .mu.m to 10 mm, more
preferably 5 .mu.m to 1 mm, and most preferably 10 .mu.m to 0.5 mm.
When the thickness is in this range, a self-sustaining cured
product can be obtained.
[0127] Release of the imprint product of the fluorine-containing
cyclic olefin polymer or fluorine-containing cyclic olefin
copolymer from the cured product may be carried out by peeling from
the cured product, or by dissolving the imprint product in an
organic solvent. Furthermore, a resin material or an inorganic
material such as glass may be pasted on the back surface of the
imprint product, and the substrate may be released as a
support.
[0128] Release by peeling is not particularly limited, but for
example, the cured product and the imprint product may be brought
into contact with a medium such as water by a method such as
immersion or spraying, and then peeling can be carried out by using
the surface tension. Release may also be carried out by dissolving
the imprint product using an organic solvent. In the case of
performing release by dissolving the imprint product, there are no
particular limitations on the organic solvent used, but the organic
solvent can be selected from fluorine-containing aromatic
hydrocarbons such as meta-xylene hexafluoride, benzotrifluoride,
fluorobenzene, difluorobenzene, hexafluorobenzene,
trifluoromethylbenzene, bis(trifluoromethyl)benzene, and
meta-xylene hexafluoride; fluorine-containing aliphatic
hydrocarbons such as perfluorohexane, and perfluorooctane;
fluorine-containing aliphatic cyclic hydrocarbons such as
perfluorocyclodecalin; fluorine-containing ethers such as
perfluoro-2-butyltetrahydrofuran; halogenated hydrocarbons such as
chloroform, chlorobenzene, and trichlorobenzene; ethers such as
tetrahydrofuran, dibutyl ether, 1,2-dimethoxyethane, and dioxane;
esters such as ethyl acetate, propyl acetate, and butyl acetate;
and ketones such as methyl isobutyl ketone, and cyclohexanone, in
consideration of solubility.
[0129] Examples of the photocurable monomer of the present
invention include a compound having a reactive double bond group,
and a resin containing a ring-opening polymerizable compound
capable of cation polymerization. These compounds may be may have
one reactive group in one molecule, or may have plural reactive
groups in one molecule. Examples of the photopolymerization
initiator include a photoradical initiator that produces a radical
by irradiation of light, and a photocation initiator that produces
a cation by irradiation of light.
[0130] When a composition is obtained by mixing a photocurable
monomer and a photocuring initiator, the amount of the photocuring
initiator used is preferably 0.05 parts by mass or more, and more
preferably 0.1 parts to 10 parts by mass, relative to 100 parts by
mass of the curable monomer.
[0131] Specific examples of the curable monomer of a compound
having a reactive double bond group include, for example, cyclic
olefins such as norbornene and norbornadiene; alkyl vinyl ethers
such as cyclohexyl methylvinyl ether, isobutyl vinyl ether,
cyclohexyl vinyl ether, and ethyl vinyl ether; vinyl esters such as
vinyl acetate; (meth) acrylic acid and derivatives thereof such as
(meth) acrylic acid, phenoxyethyl acrylate, benzyl acrylate,
stearyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, allyl
acrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate,
1,6-hexanediol diacrylate, trimethylolpropane triacrylate,
pentaerythritol triacrylate, dipentaerythritol hexaacrylate,
ethoxyethyl acrylate, methoxyethyl acrylate, glycidyl acrylate,
tetrahydrofurfuryl acrylate, diethylene glycol diacrylate,
neopentyl glycol diacrylate, polyoxyethylene glycol diacrylate,
tripropylene glycol diacrylate, 2-hydroxyethyl acrylate,
2-hydroxypropyl acrylate, 4-hydroxybutyl vinyl ether,
N,N-diethylaminoethyl acrylate, N,N-dimethylaminoethyl acrylate,
N-vinylpyrrolidone, and dimethylaminoethyl methacrylate, or
fluorine-containing acrylates thereof; and fluorodienes
(CF.sub.2.dbd.CFOCF.sub.2CF.sub.2CF.dbd.CF.sub.2,
CF.sub.2.dbd.CFOCF.sub.2CF (CF.sub.3) CF.dbd.CF.sub.2,
CF.sub.2.dbd.CFCF.sub.2C(OH) (CF.sub.3) CH.sub.2CH.dbd.CH.sub.2,
CF.sub.2.dbd.CFCF.sub.2C(OH) (CF.sub.3) CH.dbd.CH.sub.2,
CF.sub.2.dbd.CFCF.sub.2C(CF.sub.3) (OCH.sub.2OCH.sub.3)
CH.sub.2CH.dbd.CH.sub.2,
CF.sub.2.dbd.CFCH.sub.2C(C(CF.sub.3).sub.2OH)
(CF.sub.3)CH.sub.2CH.dbd.CH.sub.2, and the like). Among these, the
monomers may be used individually, or two or more kinds may be used
in combination.
[0132] Specific examples of the curable monomer of a ring-opening
polymerizable compound capable of cation polymerization include,
for example, epoxy compounds such as alicyclic epoxy resins or
glycidyl ether of hydrogenated bisphenol A, cyclohexene epoxide,
dicyclopentadiene oxide, limonene dioxide, 4-vinylcyclohexene
dioxide, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane
carboxylate, di(3,4-epoxycyclohexyl) adipate,
(3,4-epoxycyclohexyl)methyl alcohol,
(3,4-epoxy-6-methylcyclohexyl)methyl-3,4-epoxy-6-methylcyclohexane
carboxylate, ethylene 1,2-di(3,4-epoxycyclohexanecarboxylic acid)
ester, (3,4-epoxycyclohexyl)ethyltrimethoxysilane, phenyl glycidyl
ether, dicyclohexyl-3,3'-diepoxide, bisphenol A type epoxy resins,
halogenated bisphenol A type epoxy resins, bisphenol F type epoxy
resins, o-, m-, p-cresol novolac type epoxy resins, phenol novolac
type epoxy resins, polyglycidyl ethers of polyhydric alcohols, and
3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate; and
oxetane compounds such as 3-methyl-3-(butoxymethyl)oxetane,
3-methyl-3-(pentyloxymethyl)oxetane,
3-methyl-3-(hexyloxymethyl)oxetane,
3-methyl-3-(2-ethylhexyloxymethyl)oxetane,
3-methyl-3-(octyloxymethyl)oxetane,
3-methyl-3-(decanoloxymethyl)oxetane,
3-methyl-3-(dodecanoloxymethyl)oxetane,
3-methyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(butoxymethyl)oxetane,
3-ethyl-3-(pentyloxymethyl)oxetane,
3-ethyl-3-(hexyloxymethyl)oxetane,
3-ethyl-3-(2-ethylhexyloxymethyl)oxetane,
3-ethyl-3-(octyloxymethyl)oxetane,
3-ethyl-3-(decanoloxymethyl)oxetane,
3-ethyl-3-(dodecanoloxymethyl)oxetane,
3-(cyclohexyloxymethyl)oxetane,
3-methyl-3-(cyclohexyloxymethyl)oxetane,
3-ethyl-3-(cyclohexyloxymethyl)oxetane,
3-ethyl-3-(phenoxymethyl)oxetane, 3,3-dimethyloxetane,
3-hydroxymethyloxetane, 3-methyl-3-hydroxymethyloxetane,
3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-phenoxymethyloxetane,
3-n-propyl-3-hydroxymethyloxetane,
3-isopropyl-3-hydroxymethyloxetane,
3-n-butyl-3-hydroxymethyloxetane,
3-isobutyl-3-hydroxymethyloxetane,
3-sec-butyl-3-hydroxymethyloxetane,
3-tert-butyl-3-hydroxymethyloxetane, and
3-ethyl-3-(2-ethylhexyl)oxetane; and as compounds having two or
more oxetanyl groups, bis(3-ethyl-3-oxetanylmethyl)ether,
1,2-bis[(3-ethyl-3-oxetanylmethoxy)]ethane,
1,3-bis[(3-ethyl-3-oxetanylmethoxy)]propane,
1,3-bis[(3-ethyl-3-oxetanylmethoxy)]-2,2-dimethylpropane,
1,4-bis(3-ethyl-3-oxetanylmethoxy)butane,
1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane,
1,4-bis[(3-methyl-3-oxetanyl)methoxy]benzene,
1,3-bis[(3-methyl-3-oxetanyl)methoxy]benzene,
1,4-bis{[(3-methyl-3-oxetanyl)methoxy]methyl}benzene,
1,4-bis{[(3-methyl-3-oxetanyl)methoxy]methyl}cyclohexane,
4,4'-bis{[(3-methyl-3-oxetanyl)methoxy]methyl}biphenyl,
4,4'-bis{[(3-methyl-3-oxetanyl)methoxy]methyl}bicyclohexane,
2,3-bis[(3-methyl-3-oxetanyl)methoxy]bicyclo[2.2.1]heptane,
2,5-bis[(3-methyl-3-oxetanyl)methoxy]bicyclo[2.2.1]heptane,
2,6-bis[(3-methyl-3-oxetanyl)methoxy]bicyclo[2.2.1]heptane,
1,4-bis[(3-ethyl-3-oxetanyl)methoxy]benzene,
1,3-bis[(3-ethyl-3-oxetanyl)methoxy]benzene,
1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene,
1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}cyclohexane,
4,4'-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}biphenyl,
4,4'-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}bicyclohexane,
2,3-bis[(3-ethyl-3-oxetanyl)methoxy]bicyclo[2.2.1]heptane,
2,5-bis[(3-ethyl-3-oxetanyl)methoxy]bicyclo[2.2.1]heptane, and
2,6-bis[(3-ethyl-3-oxetanyl)methoxy]bicyclo[2.2.1]heptane. Among
these, the compounds may be used individually, or two or more kinds
may be used in combination.
[0133] Furthermore, examples of the photoradical initiator that
produces a radical by irradiation of light include acetophenones
such as acetophenone, p-tert-butyltrichloroacetophenone,
chloroacetophenone, 2,2-diethoxyacetophenone, hydroxyacetophenone,
2,2-dimethoxy-2'-phenylacetophenone, 2-aminoacetophenone, and
dialkylaminoacetophenone; benzoins such as benzoin, benzoin methyl
ether, benzoin ethyl ether, benzoin isopropyl ether,
benzoinisobutyl ether, 1-hydroxycyclohexyl phenyl ketone,
2-hydroxy-2-methyl-1-phenyl-2-methylpropan-1-one, and
1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one; benzophenones
such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate,
methyl-o-benzoylbenzoate, 4-phenylbenzophenone,
hydroxybenzophenone, hydroxypropylbenzophenone, acrylbenzophenone,
and 4,4'-bis(dimethylamino)benzophenone; thioxanthones such as
thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone,
diethylthioxanthone, and dimethylthioxanthone; fluorine-based
peroxides such as perfluoro(tert-butyl peroxide), and
perfluorobenzoyl peroxide; a-acyloxime ester,
benzyl-(o-ethoxycarbonyl)-a-monoxime, acylphosphine oxide,
glyoxyester, 3-ketocoumarin, 2-ethylanthraquinone, camphor-quinone,
tetramethylthiuram sulfide, azobisisobutyronitrile, benzoyl
peroxide, dialkyl peroxide, and tert-butyl peroxypivalate. These
photoradical initiators may be used individually, two or more kinds
may be used in combination.
[0134] The photocation initiator that produces a cation by
irradiation of light is not particularly limited as long as it is a
compound that initiates cation polymerization of a ring-opening
polymerizable compounds capable of cation polymerization, by
irradiation of light. However, the photocation initiator is
preferably, for example, a compound which undergoes a photoreaction
and releases a Lewis acid, such as an onium salt of an onium cation
and a pairing anion.
[0135] Specific examples of the onium cation include
diphenyliodonium, 4-methoxydiphenyliodonium,
bis(4-methylphenyl)iodonium, bis(4-tert-butylphenyl)iodonium,
bis(dodecylphenyl)iodonium, triphenylsulfonium,
diphenyl-4-thiophenoxyphenylsulfonium,
bis[4-(diphenylsulfonio)-phenyl]sulfide,
bis[4-(di(4-(2-hydroxyethyl)phenyl)sulfonio)-phenyl]sulfide, and
.eta.5-2,4-(cyclopentadienyl)[1,2,3,4,5,6-n-(methylethyl)benzene]-iron(1+-
). In addition to the onium cations, perchlorate ions,
trifluoromethanesulfonate ions, toluenesulfonate ions,
trinitrotoluene sulfonate ions, and the like may be used.
[0136] On the other hand, specific examples of the anion include
tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate,
hexafluoroarsenate, hexachloroantimonate,
tetra(fluorophenyl)borate, tetra(difluorophenyl)borate,
tetra(trifluorophenyl)borate, tetra(tetrafluorophenyl)borate,
tetra(pentafluorophenyl)borate, tetra(perfluorophenyl)borate,
tetra(trifluoromethylphenyl)borate, and
tetra(di(trifluoromethyl)phenyl)borate. These photocation
initiators may be used individually, or two or more kinds may be
used in combination.
[0137] Furthermore, in the present invention, other known
components may also be added as necessary, in addition to the
monomer having a photocurable group and the photopolymerization
initiator. Examples of the other components include modifiers such
as an aging preventing agent, a leveling agent, a wettability
improving agent, a surfactant, and a plasticizer; stabilizers such
as an ultraviolet absorbent, an antiseptic agent, and an
antibacterial agent; a photosensitizer, a silane coupling agent,
and a solvent.
[0138] In the present invention, a thermosetting monomer
composition can be used instead of the photocurable monomer
composition. In the case of using a thermosetting monomer, it is
preferable to cure the thermosetting monomer at a temperature of
not more than the glass transition temperature of the
fluorine-containing cyclic olefin polymer or fluorine-containing
cyclic olefin polymer. If the monomer composition is cured at over
the glass transition temperature, the fine pattern may be
deformed.
EXAMPLES
[0139] Hereinafter, the present invention will be described based
on the Examples, but the present invention is not intended to be
limited to these Examples.
[0140] The methods for measuring the property values of the
polymers synthesized in the Examples, the nanoimprint molding
method, and the methods for observation thereof will be described
below.
[0141] [Weight average molecular weight (Mw), molecular weight
distribution (Mw/Mn)]
[0142] The weight average molecular weight (Mw) and number average
molecular weight (Mn) of a polymer dissolved in tetrahydrofuran
(THF) or trifluoromethyltoluene (TFT) were measured by using gel
permeation chromatography (GPC) under the following conditions,
under the correction of the molecular weight relative to
polystyrene standards.
[0143] Detector: RI-2031 and 875-UV manufactured by JASCO Corp., or
Model 270 manufactured by Viscotec Corp.; columns connected in
series: Shodex K-806M, 804, 803, 802.5; column temperature:
40.degree. C.; flow rate: 1.0 ml/min; sample concentration: 3.0
mg/ml to 9.0 mg/ml
[0144] [Hydrogenation rate of fluorine-containing cyclic olefin
polymer]
[0145] A powder of a ring-opening metathesis polymer which had been
subjected to a hydrogenation reaction, was dissolved in deuterated
chloroform, deuterated tetrahydrofuran, or a mixed solvent of
hexafluorobenzene and deuterated chloroform, and the hydrogenation
rate was calculated, using a 270 MHz-.sup.1H-NMR spectrum, from the
integrated values of the absorption spectrum derived from the
hydrogen bonded to the double bond carbons in the main chain at
.delta.=4.5 to 7.0 ppm.
[0146] [Composition Ratio of Fluorine-Containing Cyclic Olefin
Copolymer]
[0147] A powder of a ring-opening metathesis polymer which had been
subjected to a hydrogenation reaction, was dissolved in deuterated
tetrahydrofuran, or a mixed solvent of hexafluorobenzene and
deuterated chloroform, and orthodifluorobenzene was added thereto
as a reference substance. The composition ratio was calculated
using a 373 MHz-.sup.19F-NMR spectrum, from the integrated values
of the signals originating from --CF at .delta.=-150 to -200 ppm,
--CF.sub.2 at .delta.=-100 to -150 ppm, or --CF.sub.3 at
.delta.=-60 to -100 ppm in the respective unit structures of
formula (1) and formula (2), with the orthodifluorobenzene at
6=-139 ppm set as the reference signal.
[0148] [Fluorine Atom Content Rate]
[0149] The fluorine atom content rate was calculated by the
following expression (1):
Fluorine atom content rate (% by mass)=(Fn.times.19).times.100/Fw
(1)
[0150] Here, in the expression (1),
Fn=Fn.sup.1.times.(1-m)+Fn.sup.2.times.m, wherein m represents the
molar proportion of the formula (2), and Fn.sup.l and Fn.sup.2
represent the numbers of fluorine atoms in the structural units
represented by the formula (1) and the formula (2), respectively;
Fw=Fw.sup.1.times.(1-m)+Fw.sup.2.times.m, wherein Fw.sup.1 and
Fw.sup.2 represent the formula weights of the structural units
represented by the formula (1) and the formula (2),
respectively.
[0151] [Glass Transition Temperature]
[0152] A measurement sample was analyzed using DSC-50 manufactured
by Shimadzu Corp., at 10.degree. C./rain as the heating rate of
increase in temperature under a nitrogen atmosphere.
[0153] [Dynamic Mechanical Analysis]
[0154] A measurement sample was analyzed using RSA-III manufactured
by TA Instruments in a tensile mode and under a nitrogen
atmosphere, under the conditions of a rate of temperature increase
of 3.degree. C./rain, an analysis frequency of 1 Hz, and a
measureable distance of a sample deformation between chucks in
dynamic mechanical analyzer was set in the range of 0 to 4.2
mm.
[0155] [Measurement of Scratch Hardness of Film According to Pencil
Method]
[0156] A film obtained by spin coating on a glass substrate was
used to measure the scratch hardness under a load of 100 g
according to JIS K5600-5-4 (Pencil scratch test method).
[0157] [Observation of SEM Pattern]
[0158] The observation of the line-and-space and the cross-section
of a imprint film product to which a fine pattern had been
transcribed, and the measurement of film thickness were carried out
by using a scanning electron microscope JSM-6701F manufactured by
JASCO Corp. (hereinafter, indicated as SEM). The width of the lines
and spaces was obtained by selecting arbitrary the pattern of three
points from a cross-sectional photograph of SEM, measuring the
lines and spaces with the measurement position set at one-half of
the height, and calculating the average value.
[0159] [Mold Used in Imprint]
[0160] A silicon mold manufactured by Kyodo International, Inc. was
used, and the mold dimensions were such that the width of a convex
portion was designated as L1, the equal interval distance between
two convexes as L2, and the height of the convex portion as L3. An
area having a pattern in which the dimensions of a mold A were such
that L1=420 nm, L2=570 nm, and L3=1600 nm, and the dimensions of a
mold B were such that L1=200 nm, L2=100 nm, and L3=160 nm, was used
in the evaluation of transferability.
[0161] [Thermal Imprint Apparatus]
[0162] An imprint by heat pressing method was carried out by using
a nanoimprinter (NM-0501) manufactured by Meisyo Kiko Co., Ltd., by
placing a film between a mold and a silicon wafer, with the
patterned surface of the mold facing downward, and pressing the
mold at predetermined temperature and pressure. Peeling of the film
was carried out after cooling, and after removing the silicon wafer
from the back surface of the film, by peeling from an edge of the
film in a fixed direction.
[0163] [Solution Coating Imprint]
[0164] The coating of a polymer solution on the mold was carried
out by a bar coater made of glass with a size of 8 mm
(diameter).times.100 mm (length). The mold was dried at room
temperature for 30 minutes under a nitrogen gas stream, and then
the mold was put in an inert oven set at a predetermined
temperature, and was dried for a predetermined time period under a
nitrogen gas stream. Peeling of the film to which a pattern had
been transcribed, was carried out by pasting a Kapton tape at a
film edge, and peeling the film in a fixed direction while using
the tape as a support.
[0165] [UV Curing]
[0166] The curing of a UV-curable resin was carried out by
irradiating blue light at 450 nm, using a LUXSPOT-II manufactured
by JASCO Corp. as a light source.
Example 1
Synthesis of
poly(1,1,2-trifluoro-2-trifluoromethyl-3,5-cyclopentylene
ethylene)
[0167] A tetrahydrofuran solution of
5,5,6-trifluoro-6-(trifluoromethyl)bicyclo[2.2.1]hept-2-ene (100 g)
and 1-hexene (268 mg) was mixed with a tetrahydrofuran solution of
Mo (N-2,6-Pr.sup.i.sub.2C.sub.6H.sub.3) (CHCMe.sub.2Ph)
(OCMe(CFA.sub.2).sub.2 (70 mg), and ring-opening metathesis
polymerization was carried out at 70.degree. C. The olefin moiety
of the polymer thus obtained was subjected to a hydrogenation
reaction using palladium alumina (5 g) at 160.degree. C., and thus
a tetrahydrofuran solution of
poly(1,1,2-trifluoro-2-trifluoromethyl-3,5-cyclopentylene ethylene)
was obtained.
[0168] The solution was added to methanol, and a white polymer was
separated by filtration and was dried. Thus, 99 g of a polymer was
obtained. The hydrogenation rate was 100%, the weight average
molecular weight (Mw) was 127,000, the molecular weight
distribution (Mw/Mn) was 1.70, and the glass transition temperature
was 109.degree. C. The fluorine atom content rate was 52.3% by
mass.
[0169] Subsequently, a powder of the hydrogenated polymer thus
obtained was treated by heat pressing, and thus a heat pressed
sheet having a thickness of 0.37 mm was produced. From the results
of the dynamic mechanical analysis by tensile mode carried out, it
was found that a flat region of variation in storage modulus or
loss modulus in the range of temperature which is not less than the
glass transition temperature lies in the range of 113.degree. C. to
152.degree. C. or 117.degree. C. to 152.degree. C., the storage
modulus was 5.81 MPa to 0.57 MPa or the loss modulus was 3.05 MPa
to 0.27 MPa, the variation of the storage modulus with respect to
temperature was -0.13 MPa/.degree. C., and the variation of the
loss modulus was -0.08 MPa/.degree. C. The results of the dynamic
mechanical analysis are shown in FIG. 1.
Example 2
Synthesis of
poly(1,1,2-trifluoro-2-trifluoromethyl-3,5-cyclopentylene
ethylene)
[0170] The synthesis was carried out in the same manner as in
Example 1, except that the catalyst was changed to
Mo(N-2,6-Pr.sup.i.sub.2C.sub.6H.sub.3)(CHCMe.sub.2Ph)(OBu.sup.t).sub.2
(50 mg), and thus
poly(1,1,2-trifluoro-2-trifluoromethyl-3,5-cyclopentylene ethylene)
was obtained (98 g). The hydrogenation rate was 100%, the weight
average molecular weight (Mw) was 83,000, the molecular weight
distribution (Mw/Mn) was 1.73, and the glass transition temperature
was 108.degree. C. The fluorine atom content rate was 52.3% by
mass.
[0171] Subsequently, a powder of the hydrogenated polymer thus
obtained was treated by heat pressing, and thus a heat pressed
sheet having a thickness of 0.37 mm was produced. From the results
of the dynamic mechanical analysis by tensile mode carried out, it
was found that a flat region of variation in storage modulus or
loss modulus in the range of temperature which is not less than the
glass transition temperature lies in the range of 109.degree. C. to
150.degree. C. or 113.degree. C. to 150.degree. C., the storage
modulus was 4.98 MPa to 0.58 MPa or the loss modulus was 2.96 MPa
to 0.31 MPa, the variation of the storage modulus with respect to
temperature was -0.11 MPa/.degree. C., and the variation of the
loss modulus was -0.07 MPa/.degree. C.
Example 3
Synthesis of
poly(1,2-difluoro-1-trifluoromethyl-2-perfluoroethyl-3,5-cyclopentylene
ethylene)
[0172] The synthesis was carried out in the same manner as in
Example 1, except that the monomer was changed to
5,6-difluoro-5-trifluoromethyl-6-perfluoroethylbicyclo[2.2.1]hep
t-2-ene (50 g), and the catalyst was changed to Mo
(N-2,6-Pr.sup.i.sub.2C.sub.6H.sub.3) (CHCMe.sub.2Ph)
(OBu.sup.t).sub.2 (17 mg), and thus
poly(1,2-difluoro-1-trifluoromethyl-2-perfluoroethyl-3,5-cyclopentylene
ethylene) was obtained (49 g). The hydrogenation rate was 100%, the
weight average molecular weight (Mw) was 95,000, the molecular
weight distribution (Mw/Mn) was 1.52, and the glass transition
temperature was 110.degree. C. The fluorine atom content rate was
59.7% by mass.
[0173] Subsequently, a powder of the hydrogenated polymer thus
obtained was treated by heat pressing, and thus a heat pressed
sheet having a thickness of 0.37 mm was produced. From the results
of the dynamic mechanical analysis by tensile mode carried out, it
was found that a flat region of variation in storage modulus or
loss modulus in the range of temperature which is not less than the
glass transition temperature lies in the range of 115.degree. C. to
160.degree. C. or 119.degree. C. to 160.degree. C., the storage
modulus was 5.01 MPa to 0.55 MPa or the loss modulus was 3.10 MPa
to 0.24 MPa, the variation of the storage modulus with respect to
temperature was -0.10 MPa/.degree. C., and the variation of the
loss modulus was -0.07 MPa/.degree. C.
Example 4
Synthesis of
poly(1,2-difluoro-1-heptafluoro-iso-propyl-2-trifluoromethyl-3,5-cyclopen-
tylene ethylene)
[0174] A trifluoromethyltoluene solution of
5,6-difluoro-5-heptafluoro-iso-propyl-6-trifluoromethylbicyclo[2.2.1]hept-
-2-ene (50 g) and 1-hexene (0.034 g) was mixed with a
trifluoromethyltoluene solution of Mo
(N-2,6-Pr.sup.i.sub.2C.sub.6H.sub.3) (CHCMe.sub.2Ph)
(OBu.sup.t).sub.2 (14 mg), and ring-opening metathesis
polymerization was carried out at 70.degree. C. The solvent of the
polymer solution thus obtained was replaced with THF, and the
olefin moiety was subjected to a hydrogenation reaction using
palladium alumina (2.5 g) at 160.degree. C. Thus, a THF solution of
poly(1,2-difluoro-1-heptafluoroisopropyl-2-trifluoromethyl-3,5-cyclopenty-
lene ethylene) was obtained. The solution was added to methanol,
and a white polymer was separated by filtration and was dried.
Thus, 49 g of a polymer was obtained. The hydrogenation rate was
100%, the weight average molecular weight (Mw) was 284,000, the
molecular weight distribution (Mw/Mn) was 1.40, and the glass
transition temperature was 137.degree. C. The fluorine atom content
rate was 61.9% by mass.
[0175] Subsequently, a powder of the hydrogenated polymer thus
obtained was treated by heat pressing, and thus a heat pressed
sheet having a thickness of 0.37 mm was produced. From the results
of the dynamic mechanical analysis by tensile mode carried out, it
was found that a flat region of variation in storage modulus or
loss modulus in the range of temperature which is not less than the
glass transition temperature lies in the range of 157.degree. C. to
183.degree. C. or 162.degree. C. to 183.degree. C., the storage
modulus was 4.88 MPa to 0.49 MPa or the loss modulus was 4.30 MPa
to 0.26 MPa, the variation of the storage modulus with respect to
temperature was -0.17 MPa/.degree. C., and the variation of the
loss modulus was -0.19 MPa/.degree. C.
Example 5
Production of Imprint Product According to Coating Method
[0176] Poly(1,1,2-trifluoro-2-trifluoromethyl-3,5-cyclopentylene
ethylene) having a Mw of 127,000, synthesized in Example 1, was
dissolved in cyclohexanone at a concentration of 20% by mass, and
20 mg of the solution thus prepared was dropped on the pattern of
the mold A and was uniformly applied by bar coating.
[0177] Subsequently, the coated solution was dried at room
temperature for 30 minutes under a nitrogen gas stream, and then
was dried at 150.degree. C. for 30 minutes. The mold was cooled to
room temperature in a nitrogen atmosphere, and the film was peeled
off from the mold. Thus, An imprint film product having a thickness
of 7 .mu.m and having a fine pattern transcribed thereon was
obtained.
[0178] The pattern was observed with SEM, and as a result, the
dimensions were such that L1=568 nm, L2=422 nm, and L3=1594 nm.
Example 6
[0179] An imprint film product having a thickness of 6 .mu.m and
having a fine pattern transcribed thereon was obtained by the same
method as that described in Example 5, except that the drying
temperature was changed to 180.degree. C.
[0180] The pattern was observed with SEM, and as a result, the
dimensions were such that L1=571 nm, L2=419 nm, and L3=1595 nm.
Example 7
[0181] An imprint film product was produced in the same manner as
in Example 5, except that the mold A of Example 5 was changed to
the mold B. The film thickness was 7 .mu.m, and from the results of
SEM observation of the pattern, the dimensions were such that
L1=101 nm, L2=199 nm, and L3-161 nm.
Example 8
[0182] Poly(1,1,2-trifluoro-2-trifluoromethyl-3,5-cyclopentylene
ethylene) having a Mw of 83,000, synthesized in Example 2, was
dissolved in cyclohexanone at a concentration of 30% by mass, and
250 mg of the solution thus prepared was dropped on the pattern of
the mold A and was uniformly applied by bar coating.
[0183] Subsequently, the coated solution was dried at room
temperature for 30 minutes under a nitrogen gas stream, and then
was dried at 180.degree. C. for 90 minutes. The mold was cooled to
room temperature in a nitrogen atmosphere, and the film was peeled
off from the mold. Thus, an imprint film product having a thickness
of 110 .mu.m and having a fine pattern transcribed thereon was
obtained.
[0184] The pattern was observed with SEM, and as a result, the
dimensions were such that L1=569 nm, L2=421 nm, and L3=1592 nm.
Example 9
[0185]
Poly(1,2-difluoro-1-trifluoromethyl-2-perfluoroethyl-3,5-cyclopenty-
lene ethylene) synthesized in Example 3 was dissolved in butyl
acetate at a concentration of 30% by mass, and 120 mg of the
solution thus prepared was dropped on the pattern of the mold A and
was uniformly applied by bar coating.
[0186] Subsequently, the coated solution was dried at room
temperature for 30 minutes under a nitrogen gas stream, and then
was dried at 180.degree. C. for 60 minutes. The mold was cooled to
room temperature in a nitrogen atmosphere, and the film was peeled
off from the mold. Thus, an imprint film product having a thickness
of 93 .mu.m and having a fine pattern transcribed thereon was
obtained.
[0187] The pattern was observed with SEM, and as a result, the
dimensions were such that L1=569 nm, L2=421 nm, and L3=1595 nm.
Example 10
[0188]
Poly(1,2-difluoro-1-heptafluoroisopropyl-2-trifluoromethyl-3,5-cycl-
opentylene ethylene) synthesized in Example 4 was dissolved in
1,3-bis(trifluoromethyl)benzene at a concentration of 20% by mass,
and 150 mg of the solution thus prepared was dropped on the pattern
of the mold A and was uniformly applied by bar coating.
[0189] Subsequently, the coated solution was dried at room
temperature for 30 minutes under a nitrogen gas stream, and then
was dried at 180.degree. C. for 60 minutes. The mold was cooled to
room temperature in a nitrogen atmosphere, and the film was peeled
off from the mold. Thus, an imprint film product having a thickness
of 87 .mu.m and having a fine pattern transcribed thereon was
obtained.
[0190] The pattern was observed with SEM, and as a result, the
dimensions were such that L1=570 nm, L2=420 nm, and L3=1594 nm.
Example 11
Synthesis of
poly(1,2-difluoro-1,2-bis(trifluoromethyl)-3,5-cyclopentylene
ethylene) and production of imprint product according to coating
method
[0191] Poly(1,2-difluoro-1,2-bis(trifluoromethyl)-3,5-ethylene) was
obtained in the same manner as in Example 1 (49 g), except that the
monomer was changed to
5,6-difluoro-5,6-bis(trifluoromethyl)bicyclo[2.2.1]hept-2-ene (50
g). The hydrogenation rate was 100%, the weight average molecular
weight (Mw) was 188,000, the molecular weight distribution (Mw/Mn)
was 1.50, and the glass transition temperature was 126.degree. C.
The fluorine atom content rate was 56.7% by mass.
[0192] Subsequently, a powder of the hydrogenated polymer thus
obtained was treated by heat pressing, and thus a heat pressed
sheet having a thickness of 0.37 mm was measured. From the results
of the dynamic mechanical analysis by tensile mode carried out, it
was found that a flat region of variation in storage modulus or
loss modulus in the range of temperature which is not less than the
glass transition temperature lies in the range of 131.degree. C. to
172.degree. C. or 135.degree. C. to 172.degree. C., the storage
modulus was 4.99 MPa to 0.55 MPa or the loss modulus was 3.70 MPa
to 0.33 MPa, the variation of the storage modulus with respect to
temperature was -0.11 MPa/.degree. C., and the variation of the
loss modulus was -0.09 MPa/.degree. C.
[0193] Subsequently, an imprint film product having a thickness of
10 .mu.m and having a fine pattern transcribed thereon was obtained
by the same method as that described in Example 5, except that the
drying temperature was changed to 170.degree. C.
[0194] The pattern was observed with SEM, and as a result, the
dimensions were such that L1 =572 nm, L2=418 nm, and L3=1594
nm.
Example 12
Synthesis of
poly(1,1,2,2,3,3,3a,6a-octafluorocyclopentyl-3,5-cyclopentylene
ethylene) and production of imprint product according to coating
method
[0195]
Poly(1,1,2,2,3,3,3a,6a-octafluorocyclopentyl-3,5-cyclopentylene
ethylene) was obtained in the same manner as in Example 1 (48 g),
except that the monomer was changed to
2,3,3,4,4,5,5,6-octafluorotricyclo[5.2.1.0.sup.2,6]dec-8-ene (50
g). The hydrogenation rate was 100%, the weight average molecular
weight (Mw) was 126,000, the molecular weight distribution (Mw/Mn)
was 1.49, and the glass transition temperature was 150.degree. C.
The fluorine atom content rate was 54.3% by mass.
[0196] Subsequently, a powder of the hydrogenated polymer thus
obtained was treated by heat pressing, and thus a heat pressed
sheet having a thickness of 0.37 mm was measured. From the results
of the dynamic mechanical analysis by tensile mode carried out, it
was found that flat region of variation in storage modulus or loss
modulus in the range of temperature which is not less than the
glass transition temperature lies in the range of 172.degree. C. to
192.degree. C. or 176.degree. C. to 192.degree. C., the storage
modulus was 5.03 MPa to 0.48 MPa or the loss modulus was 3.90 MPa
to 0.37 MPa, the variation of the storage modulus with respect to
temperature was -0.23 MPa/.degree. C., and the variation of the
loss modulus was -0.22 MPa/.degree. C.
[0197] Subsequently, an imprint film product having a thickness of
9 .mu.m and having a fine pattern transcribed thereon was obtained
by the same method as that described in Example 5, except that the
drying temperature was changed to 190.degree. C.
[0198] The pattern was observed with SEM, and as a result, the
dimensions were such that L1=573 nm, L2=417 nm, and L3=1596 nm.
Example 13
Synthesis of
poly(1-fluoro-1-perfluoroethyl-2,2-bis(trifluoromethyl)-3,5-cyclopentylen-
e ethylene) and production of imprint product according to coating
method
[0199]
Poly(1-fluoro-1-perfluoroethyl-2,2-bis(trifluoromethyl)-3,5-cyclope-
ntylene ethylene) was obtained in the same manner as in Example 1
(48 g), except that the monomer was changed to
5-fluoro-5-perfluoroethyl-6,6-bis(trifluoromethyl) bicyclo[2.2.1]
hept-2-ene (50 g). The hydrogenation rate was 100%, the weight
average molecular weight (Mw) was 126,000, the molecular weight
distribution (Mw/Mn) was 1.51, and the glass transition temperature
was 142.degree. C. The fluorine atom content rate was 61.9% by
mass.
[0200] Subsequently, a powder of the hydrogenated polymer thus
obtained was treated by heat pressing, and thus a heat pressed
sheet having a thickness of 0.37 mm was measured. From the results
of the dynamic mechanical analysis by tensile mode carried out, it
was found that a flat region of variation in storage modulus or
loss modulus in the range of temperature which is not less than the
glass transition temperature lies in the range of 165.degree. C. to
187.degree. C. or 169.degree. C. to 187.degree. C., the storage
modulus was 4.89 MPa to 0.58 MPa or the loss modulus was 4.50 MPa
to 0.40 MPa, the variation of the storage modulus with respect to
temperature was -0.20 MPa/.degree. C., and the variation of the
loss modulus was -0.23 MPa/.degree. C.
[0201] Subsequently, an imprint film product having a thickness of
10 .mu.m and having a fine pattern transcribed thereon was obtained
by the same method as that described in Example 5, except that the
drying temperature was changed to 180.degree. C.
[0202] The pattern was observed with SEM, and as a result, the
dimensions were such that L1 =572 nm, L2=418 nm, and L3=1591
nm.
Example 14
Production of Imprint Product According to Heat Pressing Method
[0203] A cyclohexanone solution of
poly(1,1,2-trifluoro-2-trifluoromethyl-3,5-cyclopentylene ethylene)
produced in Example 1 was coated on a quartz glass substrate using
an applicator. Subsequently, the coated substrate was heated for 30
minutes on a hot plate heated to 80.degree. C. in air, and then was
dried for 30 minutes at 230.degree. C. under a nitrogen gas stream.
The substrate was left to cool, and then the quartz glass was
detached. Thus, a film having a size of 450 mm.times.550 mm
(thickness =30 .mu.m) was obtained.
[0204] Subsequently, the film thus obtained was heated to
160.degree. C. and was brought into contact with the mold A. The
film was pressed as heating at a pressure of 10 MPa and was
maintained as such for 5 seconds. The film was cooled to 70.degree.
C., and then the mold was detached. Thus, an imprint film product
having a thickness of 31 .mu.m and having a fine pattern
transcribed thereon was obtained.
[0205] The pattern was observed with SEM, and as a result, the
dimensions were such that L1=581 nm, L2=409 nm, and L3=1601 nm.
Example 15
[0206]
Poly(1,2-difluoro-1-heptafluoroisopropyl-2-trifluoromethyl-3,5-cycl-
opentylene ethylene) synthesized in Example 4 was pressed as
heating, and thus a film having a size of 50 mm.times.50 mm
(thickness=80 .mu.m) was obtained.
[0207] Subsequently, the film thus obtained was heated to
180.degree. C. and was brought into contact with the mold A. The
film was pressed as heating at a pressure of 10 MPa and was
maintained as such for 5 seconds. The film was cooled to 70.degree.
C., and then the mold was detached. Thus, an imprint film product
having a thickness of 77 .mu.m and having a fine pattern
transcribed thereon was obtained.
[0208] The pattern was observed with SEM, and as a result, the
dimensions were such that L1=583 nm, L2=407 nm, and L3=1604 nm.
Example 16
Production of Acrylic Curable Resin Imprint Product Using Replica
Mold
[0209] 50 mg of an acrylic UV-curable resin (Aronix (trade name),
Toagosei Co., Ltd.) was uniformly applied on a quartz glass plate
using a bar coater.
[0210] Subsequently, the film-like imprint product of
poly(1,1,2-trifluoro-2-trifluoromethyl-3,5-cyclopentylene ethylene)
produced in Example 5 as a replica mold was pressed on the coating
liquid film to cover the patterned surface, and the system was
irradiated with UV at room temperature for 15 minutes from the back
surface of the replica mold (amount of irradiated radiation: 34
mJ/cm.sup.2). After the irradiation, the film was peeled off from
the mold, and an imprint film product having a thickness of 100
.mu.m and having a fine pattern transcribed thereon was
obtained.
[0211] The pattern was observed with SEM, and as a result, the
dimensions were such that L1=421 nm, L2=569 nm, and L3=1595 nm.
Example 17
Production of Epoxy-Based Curable Resin Imprint Product Using
Replica Mold
[0212] 53 mg of an epoxy-based curable resin (a mixture of 40% by
mass of 4,4'-bis(7-oxabicyclo[4.1.0]heptan-3-yl), 50% by mass of
3-ethyl-3-(phenoxymethyl)oxetane, and 10% by mass of
1,4-bis[((3-ethyloxetan-3-yl)methoxy)methyl]benzene), with a
sulfonium salt as an initiator, was applied uniformly on a quartz
glass plate using a bar coater.
[0213] Subsequently, the film-like imprint product of
poly(1,1,2-trifluoro-2-trifluoromethyl-3,5-cyclopentylene ethylene)
produced in Example 6 as a replica mold was pressed on the coating
liquid film to cover the patterned surface of that mold, and the
system was irradiated with UV at room temperature for 15 minutes
from the back surface of the replica mold (amount of irradiated
radiation: 34 mJ/cm.sup.2). After the irradiation, the film was
peeled off from the mold, and an imprint film product having a
thickness of 95 .mu.m and having a fine pattern transcribed thereon
was obtained.
[0214] The pattern was observed with SEM, and as a result, the
dimensions were such that L1=420 nm, L2=570 nm, and L3=1596 nm.
Comparative Example 1
Synthesis of poly(1-trifluoromethyl-3,5-cyclopentylene ethylene)
and production of imprint product according to coating method
[0215] Poly(1-trifluoromethyl-3,5-cyclopentylene ethylene) was
obtained in the same manner as in Example 1 (9 g), except that the
monomer was changed to 5-(trifluoromethyl)bicyclo[2.2.1]hept-2-ene
(10 g). The hydrogenation rate was 100%, the weight average
molecular weight (Mw) was 98,000, the molecular weight distribution
(Mw/Mn) was 1.17, and the glass transition temperature was
47.degree. C. The fluorine atom content rate was 34.7% by mass.
[0216] From the results of the dynamic mechanical analysis by
tensile mode, which was carried out using a heat pressed sheet
having a thickness of 0.37 mm, a flat variation region of storage
modulus or loss modulus in the region of temperature which is not
less than the glass transition temperature was not observed. The
storage modulus in the range 48.degree. C. to 57.degree. C. was
92.3 MPa to 0.11 MPa, the loss modulus in the same temperature
range was 97.1 MPa to 0.13 MPa, the variation of the storage
modulus with respect to temperature was -10.2 MPa/.degree. C., and
the variation of the loss modulus was -10.8 MPa/.degree. C.
[0217] Subsequently, poly(1-trifluoromethyl-3,5-cyclopentylene
ethylene) thus obtained was dissolved in cyclohexanone at a
concentration of 20% by mass, and 23 mg of the solution thus
prepared was dropped on the pattern of the mold A and was uniformly
applied by bar coating. The coated solution was dried at room
temperature for 30 minutes under a nitrogen gas stream, and then
was dried at 150.degree. C. for 30 minutes. The mold was cooled to
5.degree. C. in a nitrogen atmosphere, and the film was peeled off
from the mold. Thus, an imprint film product having a thickness of
7 .mu.m and having a fine pattern transcribed thereon was
obtained.
[0218] The pattern was observed with SEM, and as a result, the
pattern had a shape of disarrayed lines, with L1 =569 nm to 598
nm.
Comparative Example 2
Synthesis of
poly(3,4-bis(trifluoromethyl)-2,5-(1-oxacyclopentylene)ethylene)
and production of imprint product according to coating method
[0219] Poly(3,4-bis(trifluoromethyl)-2,5-(1-oxacyclopentylene)
ethylene) was obtained in the same manner as in Example 1 (9 g),
except that the monomer was changed to
2,3-bis(trifluoromethyl)-7-oxabicyclo[2.2.1]hept-2-ene (10 g). The
hydrogenation rate was 100%, the weight average molecular weight
(Mw) was 90,000, the molecular weight distribution (Mw/Mn) was
1.41, and the glass transition temperature was 44.degree. C.
[0220] From the results of the dynamic mechanical analysis by
tensile mode, which was carried out using a heat pressed sheet
having a thickness of 0.37 mm, a flat variation region of storage
modulus or loss modulus in the region of temperature which is not
less than the glass transition temperature was not observed. The
storage modulus in the range 45.degree. C. to 55.degree. C. was
99.3 MPa to 0.12 MPa, the loss modulus in the same temperature
range was 103.2 MPa to 0.11 MPa, the variation of The storage
modulus with respect to temperature was -9.9 MPa/.degree. C., and
the variation of the loss modulus was -10.3 MPa/.degree. C.
[0221] Subsequently,
poly(3,4-bis(trifluoromethyl)-2,5-(1-oxacyclopentylene)ethylene)
thus obtained was dissolved in cyclohexanone at a concentration of
20% by mass, and 24 mg of the solution thus prepared was dropped on
the pattern of the mold A and was uniformly applied by bar coating.
The coated solution was dried at room temperature for 30 minutes
under a nitrogen gas stream, and then was dried at 150.degree. C.
for 30 minutes. The mold was cooled to 5.degree. C. in a nitrogen
atmosphere, and the film was peeled off from the mold. Thus, an
imprint film product having a thickness of 8 .mu.m and having a
fine pattern transcribed thereon was obtained.
[0222] The pattern was observed with SEM, and as a result, the
pattern had a shape of disarrayed lines, with L1=571 nm to 601
nm.
Comparative Example 3
Synthesis of poly(1-methyl-3,5-cyclopentylene ethylene) and
production of imprint product according to coating method
[0223] Poly(1-methyl-3,5-cyclopentylene ethylene) was obtained in
the same manner as in Example 1 (9 g), except that the monomer was
changed to 5-methylbicyclo[2.2.1]hept-2-ene (10 g). The
hydrogenation rate was 100%, the weight average molecular weight
(Mw) was 182,000, the molecular weight distribution (Mw/Mn) was
1.11, and the glass transition temperature was 34.degree. C.
[0224] From the results of the dynamic mechanical analysis by
tensile mode, which was carried out using a heat pressed sheet
having a thickness of 0.37 mm, a flat variation region of storage
modulus or loss modulus in the region of temperature which is not
less than the glass transition temperature was not observed. The
storage modulus in the range 38.degree. C. to 49.degree. C. was
101.1 MPa to 0.11 MPa, the loss modulus in the above region range
38.degree. C. to 49.degree. C. was 94.8 MPa to 0.12 MPa, the
variation of the storage modulus with respect to temperature was
-9.2 MPa/.degree. C., and the variation of the loss modulus was
-8.6 MPa/.degree. C.
[0225] Subsequently, poly(1-methyl-3,5-cyclopentylene ethylene)
thus obtained was dissolved in cyclohexanone at a concentration of
20% by mass, and 27 mg of the solution thus prepared was dropped on
the pattern of the mold A and was uniformly applied by bar coating.
The coated solution was dried at room temperature for 30 minutes
under a nitrogen gas stream, and then was dried at 150.degree. C.
for 30 minutes. The mold was cooled to 5.degree. C. in a nitrogen
atmosphere. Attempts were made to peel off the film from the mold,
but no film was obtained.
Comparative Example 4
Production of Imprint Product by Teflon (Registered Trademark)
AF1600 According to Coating Method
[0226] 25 mg of a perfluoro-2-n-butyl-tetrahydrofuran (Fluorinert
(registered trademark) FC75) solution containing 20% by mass of
Teflon (registered trademark) AF1600 (Aldrich product, glass
transition temperature=162.degree. C.), which is a copolymer of
tetrafluoroethylene and
4,5-difluoro-2,2-bis(trifluoromethyl)-1,3-dioxazole, was applied on
the pattern-formed surfaces of the mold A and the mold B using a
bar coater. However, coating films could not be formed because the
applied liquid repelled on the mold surface.
Comparative Example 5
Production of Imprint Product by Teflon (Registered Trademark)
AF1600 According to Heat Pressing Method
[0227] A powder of Teflon (registered trademark) AF1600 of
Comparative Example 4 was pressed as heating at 260.degree. C., and
thus a film having a size of 50 mm.times.50 mm (thickness =90
.mu.m) was obtained.
[0228] Subsequently, the film thus obtained was heated to
200.degree. C. and was brought into contact with the mold A. The
film was pressed as heating at a pressure of 10 MPa and was
maintained as such for 5 seconds. The film was cooled to 70.degree.
C., and then the mold was detached. Thus, a film having a thickness
of 85 .mu.m and having a fine pattern transcribed thereon was
obtained.
[0229] The pattern was observed with SEM, and areas in which the
convex was smashed and transfer was not achieved, and areas having
a shape of disarrayed lines with L1 =510 nm to 650 nm, were
observed. Thus, it was not possible to obtain an imprint
product.
Example 18
Synthesis of copolymer of
poly(1,1,2-trifluoro-2-trifluoromethyl-3,5-cyclopentylene ethylene)
and
poly(3,3,4-trifluoro-4-trifluoromethyl-7,9-tricyclo[4.3.0.1.sup.2,5]decan-
ylene ethylene)
[0230] A tetrahydrofuran solution of
5,5,6-trifluoro-6-(trifluoromethyl) bicyclo[2.2.1]hept-2-ene (50
g),
8,8,9-trifluoro-9-(trifluoromethyl)-tetracyclo[4.4.0.1.sup.2,5.1.sup.7,10-
]-3-dodecene (22 g), and 1-hexene (0.462 g) was mixed with a
tetrahydrofuran solution of Mo (N-2,6-Pr.sup.i.sub.2C.sub.6H.sub.3)
(CHCMe.sub.2Ph) (OBu.sup.t).sub.2 (33.9 mg), and ring-opening
metathesis polymerization was carried out at 70.degree. C. The
olefin moiety of the polymer thus obtained was subjected to a
hydrogenation reaction using palladium alumina (3.6 g) at
160.degree. C., and thus a tetrahydrofuran solution of a copolymer
of poly(1,1,2-trifluoro-2-trifluoromethyl-3,5-cyclopentylene
ethylene) and
poly(3,3,4-trifluoro-4-trifluoromethyl-7,9-tricyclo[4.3.0.1.sup.2,5]decan-
ylene ethylene) was obtained. The solution was added to methanol,
and a white polymer was separated by filtration and was dried.
Thus, 71 g of a polymer was obtained. The hydrogenation rate was
100%, the weight average molecular weight (Mw) was 98,000, the
molecular weight distribution (Mw/Mn) was 2.51, and the glass
transition temperature was 129.degree. C. The composition ratio
[A]/[B] was 75/25, and the fluorine atom content rate was 49.2% by
mass.
[0231] Subsequently, a powder of the hydrogenated polymer thus
obtained was treated by heat pressing, and thus a heat pressed
sheet having a thickness of 0.37 mm was produced. From the results
of the dynamic mechanical analysis by tensile mode carried out, it
was found that a flat region of variation in storage modulus or
loss modulus in the range of temperature which is not less than the
glass transition temperature lies in the range of 149.degree. C. to
163.degree. C. or 153.degree. C. to 163.degree. C., the storage
modulus was 1.21 MPa to 0.26 MPa or the loss modulus was 0.62 MPa
to 0.18 MPa, the variation of the storage modulus with respect to
temperature was -0.07 MPa/.degree. C., and the variation of the
loss modulus was -0.04 MPa/.degree. C.
Example 19
Synthesis of copolymer of
poly(1,1,2-trifluoro-2-trifluoromethyl-3,5-cyclopentylene ethylene)
and
poly(3,3,4-trifluoro-4-trifluoromethyl-7,9-tricyclo[4.3.0.1.sup.2,5]decan-
ylene ethylene)
[0232] A copolymer of
poly(1,1,2-trifluoro-2-trifluoromethyl-3,5-cyclopentylene ethylene)
and
poly(3,3,4-trifluoro-4-trifluoromethyl-7,9-tricyclo[4.3.0.1.sup.2,5]decan-
ylene ethylene) (62 g) was obtained in the same manner as in
Example 18, except that the injection molar ratio of
5,5,6-trifluoro-6-(trifluoromethyl)bicyclo[2.2.1]hept-2-ene and
8,8,9-trifluoro-9-(trifluoromethyl)-tetracyclo[4.4.0.1.sup.2,5.1.sup.7,10-
]-3-dodecene monomers was changed to 25/75. The hydrogenation rate
was 100%, the weight average molecular weight (Mw) was 112,000, the
molecular weight distribution (Mw/Mn) was 2.51, and the glass
transition temperature was 175.degree. C. The composition ratio
[A]/[B] was 25/75, and the fluorine atom content rate was 42.9% by
mass.
[0233] Subsequently, a powder of the hydrogenated polymer thus
obtained was treated by heat pressing, and thus a heat pressed
sheet having a thickness of 0.37 mm was produced. From the results
of the dynamic mechanical analysis by tensile mode carried out, it
was found that a flat region of variation in storage modulus or
loss modulus in the range of temperature which is not less than the
glass transition temperature lies in the range of 195.degree. C. to
209.degree. C. or 199.degree. C. to 209.degree. C., the storage
modulus was 1.19 MPa to 0.24 MPa or the loss modulus was 0.60 MPa
to 0.16 MPa, the variation of the storage modulus with respect to
temperature was -0.07 MPa/.degree. C., and the variation of the
loss modulus was -0.044 MPa/.degree. C.
Example 20
Synthesis of copolymer of
poly(1,2-difluoro-1,2-bis(trifluoromethyl)-3,5-cyclopentylene
ethylene) and
poly(3,3,4-trifluoro-4-trifluoromethyl-7,9-tricyclo[4.3.0.1.sup.2,5]d-
ecanylene ethylene)
[0234] A tetrahydrofuran solution of
5,6-difluoro-5,6-bis(trifluoromethyl) bicyclo[2.2.1]hept-2-ene (50
g),
8,8,9-trifluoro-9-(trifluoromethyl)-tetracyclo[4.4.0.1.sup.2,50.1.sup.7,1-
0]-3-dodecene (54 g), and 1-hexene (0.462 g) was mixed with a
tetrahydrofuran solution of Mo (N-2,6-Pr.sup.i.sub.2C.sub.6H.sub.3)
(CHCMe.sub.2Ph) (OBu.sup.t).sub.2 (41.3 mg), and ring-opening
metathesis polymerization was carried out at 70.degree. C. The
olefin moiety of the polymer thus obtained was subjected to a
hydrogenation reaction using palladium alumina (5.0 g) at
160.degree. C., and thus a tetrahydrofuran solution of a copolymer
of poly(1,2-difluoro-1,2-bis(trifluoromethyl)-3,5-cyclopentylene
ethylene) and
poly(3,3,4-trifluoro-4-trifluoromethyl-7,9-tricyclo[4.3.0.1.sup.2,5]d-
ecanylene ethylene) was obtained. The solution was added to
methanol, and a white polymer was separated by filtration and was
dried. Thus, 101 g of a polymer was obtained. The hydrogenation
rate was 100%, the weight average molecular weight (Mw) was
106,000, the molecular weight distribution (Mw/Mn) was 2.54, and
the glass transition temperature was 158.degree. C. The composition
ratio [A]/[B] was 50/50, and the fluorine atom content rate was
48.4% by mass.
[0235] Subsequently, a powder of the hydrogenated polymer thus
obtained was treated by heat pressing, and thus a heat pressed
sheet having a thickness of 0.36 mm was produced. From the results
of the dynamic mechanical analysis by tensile mode carried out, it
was found that a flat region of variation in storage modulus or
loss modulus in the range of temperature which is not less than the
glass transition temperature lies in the range of 178.degree. C. to
192.degree. C. or 182.degree. C. to 192.degree. C., the storage
modulus was 1.20 MPa to 0.24 MPa or the loss modulus was 0.63 MPa
to 0.19 MPa, the variation of the storage modulus with respect to
temperature was -0.07 MPa/.degree. C., and the variation of the
loss modulus was -0.04 MPa/.degree. C.
Example 21
Synthesis of
poly(1,1,2-trifluoro-2-trifluoromethoxy-3,5-cyclopentylene
ethylene)
[0236] A tetrahydrofuran solution of
5,5,6-trifluoro-6-(trifluoromethoxy) bicyclo[2.2.1]hept-2-ene (50
g) and 1-hexene (134 mg) was mixed with a tetrahydrofuran solution
of Mo (N-2,6-Pr.sup.i.sub.2C.sub.6H.sub.3) (CHCMe.sub.2Ph)
(OCMe(CF.sub.3).sub.2).sub.2 (35 mg), and ring-opening metathesis
polymerization was carried out at 70.degree. C. The olefin moiety
of the polymer thus obtained was subjected to a hydrogenation
reaction using palladium alumina (2.5 g) at 160.degree. C., and
thus a tetrahydrofuran solution of
poly(1,1,2-trifluoro-2-trifluoromethoxy-3,5-cyclopentylene
ethylene) was obtained. The solution was added to methanol, and a
white polymer was separated by filtration and was dried. Thus, 48 g
of a polymer was obtained. The hydrogenation rate was 100%, the
weight average molecular weight (Mw) was 131,000, the molecular
weight distribution (Mw/Mn) was 1.73, and the glass transition
temperature was 101.degree. C. The fluorine atom content rate was
48.7% by mass.
[0237] Subsequently, a powder of the hydrogenated polymer thus
obtained was treated by heat pressing, and thus a heat pressed
sheet having a thickness of 0.37 mm was produced. From the results
of the dynamic mechanical analysis by tensile mode carried out, it
was found that a flat region of variation in storage modulus or
loss modulus in the range of temperature which is not less than the
glass transition temperature lies in the range of 104.degree. C. to
143.degree. C. or 108.degree. C. to 141.degree. C., the storage
modulus was 5.79 MPa to 0.52 MPa or the loss modulus was 3.01 MPa
to 0.24 MPa, the variation of the storage modulus with respect to
temperature was -0.14 MPa/.degree. C., and the variation of the
loss modulus was -0.08 MPa/.degree. C.
Example 22
[0238] 30 mg of a solution prepared by dissolving the copolymer of
poly(1,1,2-trifluoro-2-trifluoromethyl-3,5-cyclopentylene ethylene)
and
poly(3,3,4-trifluoro-4-trifluoromethyl-7,9-tricyclo[4.3.0.1.sup.2,5]decan-
ylene ethylene) (composition ratio [A]/[B]=75/25) having a Mw of
98,000, synthesized in Example 18, in cyclohexanone at a
concentration of 20% by mass, was dropped on the pattern of the
mold A, and was uniformly applied by bar coating. Subsequently, the
coated solution was dried at room temperature for 30 minutes under
a nitrogen gas stream, and then was dried at 180.degree. C. for 60
minutes. The mold was cooled to room temperature in a nitrogen
atmosphere, and the film was peeled off from the mold. Thus, an
imprint film product having a thickness of 8 .mu.m and having a
fine pattern transcribed thereon was obtained.
[0239] The pattern was observed with SEM, and as a result, the
dimensions were such that L1=570 nm, L2=420 nm, and L3=1595 nm.
Example 23
[0240] 30 mg of a solution prepared by dissolving the copolymer of
poly(1,1,2-trifluoro-2-trifluoromethyl-3,5-cyclopentylene ethylene)
and
poly(3,3,4-trifluoro-4-trifluoromethyl-7,9-tricyclo[4.3.0.1.sup.2,5]decan-
ylene ethylene) (composition ratio [A]/[B]=25/75) having a Mw of
112,000, synthesized in Example 19, in cyclohexanone at a
concentration of 20% by mass, was dropped on the pattern of the
mold A, and was uniformly applied by bar coating. Subsequently, the
coated solution was dried at room temperature for 30 minutes under
a nitrogen gas stream, and then was dried at 200.degree. C. for 60
minutes. The mold was cooled to room temperature in a nitrogen
atmosphere, and the film was peeled off from the mold. Thus, an
imprint film product having a thickness of 8 .mu.m and having a
fine pattern transcribed thereon was obtained.
[0241] The pattern was observed with SEM, and as a result, the
dimensions were such that L1=571 nm, L2=419 nm, and L3=1594 nm.
Example 24
[0242] 30 mg of a solution prepared by dissolving the copolymer of
poly(1,2-difluoro-1,2-bis(trifluoromethyl)-3,5-cyclopentylene
ethylene) and
poly(3,3,4-trifluoro-4-trifluoromethyl-7,9-tricyclo[4.3.0.1.sup.2,5]d-
ecanylene ethylene) (composition ratio [A]/[B]=50/50) having a Mw
of 106,000, synthesized in Example 20, in cyclohexanone at a
concentration of 20% by mass, was dropped on the pattern of the
mold A, and was uniformly applied by bar coating. Subsequently, the
coated solution was dried at room temperature for 30 minutes under
a nitrogen gas stream, and then was dried at 190.degree. C. for 60
minutes. The mold was cooled to room temperature in a nitrogen
atmosphere, and the film was peeled off from the mold. Thus, an
imprint film product having a thickness of 9 .mu.m and having a
fine pattern transcribed thereon was obtained.
[0243] The pattern was observed with SEM, and as a result, the
dimensions were such that L1=571 nm, L2=419 nm, and L3=1595 nm.
Example 25
[0244] 30 mg of a solution prepared by dissolving
poly(1,1,2-trifluoro-2-trifluoromethoxy-3,5-cyclopentylene
ethylene) having a Mw of 131,000, synthesized in Example 21, in
cyclohexanone at a concentration of 20% by mass, was dropped on the
pattern of the mold A, and was uniformly applied by bar coating.
Subsequently, the coated solution was dried at room temperature for
30 minutes under a nitrogen gas stream, and then was dried at
200.degree. C. for 60 minutes. The mold was cooled to room
temperature in a nitrogen atmosphere, and the film was peeled off
from the mold. Thus, an imprint film product having a thickness of
8 .mu.m and having a fine pattern transcribed thereon was
obtained.
[0245] The pattern was observed with SEM, and as a result, the
dimensions were such that L1=571 nm, L2=419 nm, and L3=1594 nm.
Example 26
Measurement of Scratch Hardness of Film According to Pencil
Method
[0246] A solution prepared by dissolving
poly(1,1,2-trifluoro-2-trifluoromethyl-3,5-cyclopentylene ethylene)
(composition ratio [A]/[B]=100/0) having a Mw of 127,000,
synthesized in Example 1, in cyclohexanone at a concentration of
20% by mass, was dropped on a glass substrate, and was uniformly
applied by spin coating. Subsequently, the coated solution was
dried at 180.degree. C. for 60 minutes under a nitrogen gas stream,
and was left to cool at room temperature in air. Thus, a film
having a thickness of 15 .mu.m and coated on the glass substrate
was obtained. The scratch hardness under a load of 100 g was
4B.
[0247] A film having a thickness of 15 .mu.m and coated on the
glass substrate was obtained by the same method as described above,
except that the polymer was changed to the copolymers synthesized
in Example 18 (Mw 98,000, composition ratio [A]/[B]=75/25) and in
Example 19 (Mw 112,000, composition ratio [A]/[B]=25/75). The
results obtained by measuring the scratch hardness were 3B for the
polymer of Example 18, and 2B for the polymer of Example 19. Thus,
the scratch hardness was enhanced in both of the polymers, as
compared with the polymer of Example 1.
Comparative Example 6
Synthesis of copolymer of
poly(1,2-difluoro-1,2-bis(trifluoromethyl)-3,5-cyclopentylene
ethylene) and
poly(3-trifluoromethyl-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene) having composition ratio of [A]/[B]=10/90, and production
of imprint product according to coating method
[0248] A tetrahydrofuran solution of
5,6-difluoro-5,6-bis(trifluoromethyl)bicyclo[2.2.1]hept-2-ene (5 g)
and
8-trifluoromethyl-tetracyclo[4.4.0.1.sup.2,5.1.sup.7,10]-3-dodecene
(39 g) and 1-hexene (0.418 g) was mixed with a tetrahydrofuran
solution of Mo(N-2,6-Pr.sup.i.sub.2C.sub.6H.sub.3) (CHCMe.sub.2Ph)
(OBu.sup.t).sub.2 (20 mg), and ring-opening metathesis
polymerization was carried out at 70.degree. C. The olefin moiety
of the obtained polymer was subjected to a hydrogenation reaction
using palladium alumina (2.2 g) at 160.degree. C., and a
tetrahydrofuran solution of the copolymer of
poly(1,2-difluoro-1,2-bis(trifluoromethyl)-3,5-cyclopentylene
ethylene) and
poly(3-trifluoromethyl-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene) was obtained. The solution was added to methanol, and a
white polymer was separated by filtration and was dried. Thus, 42 g
of a polymer was obtained. The hydrogenation rate was 100%, the
weight average molecular weight (Mw) was 94,000, the molecular
weight distribution (Mw/Mn) was 2.57, and the glass transition
temperature was 176.degree. C. The composition ratio [A]/[B] was
10/90, and the fluorine atom content rate was 27.9% by mass.
[0249] Subsequently, a powder of the hydrogenated polymer thus
obtained was treated by heat pressing, and thus a heat pressed
sheet having a thickness of 0.36 mm was produced. From the results
of the dynamic mechanical analysis by tensile mode carried out, a
flat variation region of storage modulus or loss modulus in the
region of temperature which is not less than the glass transition
temperature was not observed.
[0250] 30 mg of a solution prepared by dissolving the copolymer of
poly(1,2-difluoro-1,2-bis(trifluoromethyl)-3,5-cyclopentylene
ethylene) and
poly(3-trifluoromethyl-7,9-tricyclo[4.3.0.1.sup.2,5]decanylene
ethylene) (composition ratio [A]/[B]=10/90) thus obtained, in
cyclohexanone at a concentration of 20% by mass, was dropped on the
pattern of the mold A, and was uniformly applied by bar coating.
The coated solution was dried at room temperature for 30 minutes
under a nitrogen gas stream, and then was dried at 200.degree. C.
for 60 minutes. The mold was cooled to room temperature in a
nitrogen atmosphere, and the film was peeled off from the mold.
When the transfer surface of the film was observed by SEM, the
pattern was disarrayed, and it was not possible to obtain a
satisfactory imprint product.
[0251] The present invention may adopt the following
embodiments.
[0252] (a) An imprint product having a fine pattern on the surface,
which is obtained by transcribing a fine pattern on the surface of
a mold to a fluorine-containing cyclic olefin polymer containing a
repeating structural unit represented by formula (1) and having a
fluorine atom content rate of 40% to 75% by mass:
##STR00010##
[0253] wherein in the formula (1), at least one of R.sup.1 to
R.sup.4 represents fluorine, or a fluorine-containing C1-C10 alkyl;
the others of R.sup.1 to R.sup.4 that do not contain fluorine are
each selected from hydrogen and a C1-C10 alkyl; and R.sup.1 to
R.sup.4 may be joined together to form a cyclic structure.
[0254] (b) The imprint product as set forth in (a), wherein the
fluorine-containing cyclic olefin polymer has a region in which the
storage modulus or loss modulus varies in the range of -1
MPa/.degree. C. to 0 MPa/.degree. C. with respect to the
temperature change over a region of temperature which is not less
than the glass transition temperature.
[0255] (c) The imprint product as set forth in the (b), wherein the
flat region of variation of the storage modulus or loss modulus of
the fluorine-containing cyclic olefin polymer over the region of
temperature which is not less than the glass transition
temperature, lies in a storage modulus region or loss modulus
region of 0.1 MPa or more.
[0256] (d) A method for producing the imprint product as set forth
in any one of (a) to (c), the method including bringing a solution
formed from the fluorine-containing cyclic olefin polymer and an
organic solvent into contact with a mold having a fine pattern
formed on the surface, evaporating the solvent, and thereby
transcribing the pattern of the mold.
[0257] (e) A method for producing the imprint product as set forth
in any one of (a) to (c), the method including pressing a mold
having a fine pattern on the surface of a film containing the
fluorine-containing cyclic olefin polymer, and thereby transcribing
the pattern of the mold.
[0258] (f) A method for producing a cured product, the method
including bringing the surface having a fine pattern of the imprint
product as set forth in any one of (a) to (e), into contact with a
photocurable monomer composition; curing the photocurable monomer
composition by light irradiation, detaching the imprint product,
and thereby obtaining a fine pattern transcribed to the surface of
a photocured resin.
INDUSTRIAL APPLICABILITY
[0259] The fluorine-containing cyclic olefin polymer of the present
invention having a specific structure is useful as an imprint
product itself used in a nanoimprint method, or as a replica mold,
and is industrially highly valuable. The imprint product or cured
product having a fine pattern, which is obtained by using the
production method of the present invention, is useful as an optical
element (such as a micro lens array, an optical waveguide, an
optical switch, a Fresnel zone plate, a binary optical element, a
blaze optical element, a photonic crystal), an antireflection
filter, a biochip, a micro reactor chip, a recording medium, a
display material, a catalyst support, or the like.
* * * * *