U.S. patent application number 12/086165 was filed with the patent office on 2010-01-28 for resin for thermal imprinting.
This patent application is currently assigned to SCIVAX CORPORATION. Invention is credited to Mitsuru Fujii, Yuji Hashima, Takahisa Kusuura, Tetsuya Lizuka, Takahito Mita, Anupam Mitra, Takuji Taguchi, Yoshiaki Takaya, Takemori Toshifumi.
Application Number | 20100019410 12/086165 |
Document ID | / |
Family ID | 38122857 |
Filed Date | 2010-01-28 |
United States Patent
Application |
20100019410 |
Kind Code |
A1 |
Toshifumi; Takemori ; et
al. |
January 28, 2010 |
Resin for Thermal Imprinting
Abstract
A cyclic-olefin-based thermoplastic resin for thermal imprint to
be used in the production of a sheet or a film which contains at
least one of skeletons represented by the following chemical
equation 1 or the following chemical equation 2 in a main chain.
The glass transition temperature Tg (.degree. C.) and the value
([M]) of MFR at 260.degree. C. satisfy the following equation 1,
and [M]<30. The thermal imprint characteristics
(transferability, mold release characteristic, and the like) are
superior and the productivity (throughput) is improved.
##STR00001## Tg(.degree. C.)>219.times.log[M]-160 [Equation
1]
Inventors: |
Toshifumi; Takemori; (Chiba,
JP) ; Takaya; Yoshiaki; (Chiba, JP) ; Mita;
Takahito; (Chiba, JP) ; Lizuka; Tetsuya;
(Chiba, JP) ; Hashima; Yuji; (Chiba, JP) ;
Kusuura; Takahisa; (Kanagawa, JP) ; Fujii;
Mitsuru; (Kanagawa, JP) ; Taguchi; Takuji;
(Kanagawa, JP) ; Mitra; Anupam; (Kanagawa,
JP) |
Correspondence
Address: |
FACTOR & LAKE, LTD
1327 W. WASHINGTON BLVD., SUITE 5G/H
CHICAGO
IL
60607
US
|
Assignee: |
SCIVAX CORPORATION
Kanagawa
JP
MARUZEN PETROCHEMICAL CO., LTD.
Tokyo
JP
|
Family ID: |
38122857 |
Appl. No.: |
12/086165 |
Filed: |
July 12, 2006 |
PCT Filed: |
July 12, 2006 |
PCT NO: |
PCT/JP2006/324423 |
371 Date: |
September 15, 2009 |
Current U.S.
Class: |
264/293 ;
524/554; 526/308 |
Current CPC
Class: |
H05K 2201/0158 20130101;
H05K 2203/0108 20130101; B29K 2045/00 20130101; H05K 1/032
20130101; H05K 3/107 20130101; C08F 232/08 20130101; H05K 3/0014
20130101; B29C 59/026 20130101; B29C 59/005 20130101 |
Class at
Publication: |
264/293 ;
526/308; 524/554 |
International
Class: |
B29C 59/02 20060101
B29C059/02; C08F 32/08 20060101 C08F032/08; C08L 55/00 20060101
C08L055/00 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 9, 2005 |
JP |
2005-357014 |
Claims
1. A resin for thermal imprint and for producing a sheet or a film,
the resin comprising a cyclic-olefin-based thermoplastic resin that
contains at least one of skeletons represented by a following
chemical equation 1 or a following chemical equation 2 in a main
chain, and wherein: a glass transition temperature Tg (.degree. C.)
of the resin and a value ([M]) of MFR at 260.degree. C. satisfy a
following equation 1; and [M] <30; wherein ##STR00010##
Tg(.degree. C.)>219.times.log[M]-160 and further, wherein
[Equation 1] R.sup.1 to R.sup.29 in chemical equations 1, 2 may
differ or may be same, each of which is a substituent containing a
hydrogen atom, a deuterium atom, a hydrocarbon radical having a
carbon number of 1 to 15, a halogen atom, and a hetero atom of
oxygen, sulfur, or the like, and may form a monocyclic or
polycyclic structure with one another; m and n are integers greater
than or equal to 0; and, [M] in equation 1 represents a value of
MFR at 260.degree. C.
2. A resin for thermal imprint and for producing a sheet or a film,
the resin comprising a cyclic-olefin-based thermoplastic resin that
contains at least one of skeletons represented by a following
chemical equation 3 or a following chemical equation 4 in a main
chain, and wherein: a glass transition temperature Tg (.degree. C.)
of the resin and a value ([M]) of MFR at 260.degree. C. satisfy a
following equation 1; and [M]<20 and Tg>90.degree. C.;
wherein ##STR00011## Tg(.degree. C.)>219.times.log[M]-160 and
further, wherein [Equation 1] R.sup.1 to R.sup.29 in chemical
equations 3, 4 may differ or may be same, each of which is a
substituent containing a hydrogen atom, a deuterium atom, a
hydrocarbon radical having a carbon number of 1 to 15, a halogen
atom, and a hetero atom of oxygen, sulfur, or the like, and may
form a monocyclic or polycyclic structure with one another; m and n
are integers greater than or equal to 0; and [M] in equation 1
represents a value of MFR at 260.degree. C.
3. The resin for thermal imprinting of claim 2, wherein the
cyclic-olefin-based thermoplastic resin comprises a copolymer of
cyclic-olefin represented by a following chemical equation 5 and
.alpha.-olefin, or a polymer produced by hydrogenation after
ring-opening polymerization of the cyclic-olefin, wherein
##STR00012## and further wherein R.sup.30 to R.sup.48 in chemical
equation 5 may differ or may be same, each of which is a
substituent containing a hydrogen atom, a deuterium atom, a
hydrocarbon radical having a carbon number of 1 to 15, a halogen
atom, and a hetero atom of oxygen, sulfur, or the like, and may
form a monocyclic or polycyclic structure with one another; and, m
and n are integers greater than or equal to 0.
4. The resin for thermal imprint of claim 2, containing greater
than or equal to one additive.
5. The resin for thermal imprint of claim 4, wherein the additive
contains at least either one of an anti-oxidizing agent or a
lubricant.
6. The resin for thermal imprint of claim 2, wherein a resin
containing a skeleton represented by chemical equation 3 is a
copolymer of cyclic-olefin represented by a following chemical
equation 6 and ethylene; and wherein ##STR00013## and further
wherein R.sup.30 to R.sup.48 in chemical equation 6 may differ or
may be same, each of which is a substituent containing a hydrogen
atom, a deuterium atom, a hydrocarbon radical having a carbon
number of 1 to 15, a halogen atom, and a hetero atom of oxygen,
sulfur, or the like, and may form a monocyclic or polycyclic
structure with one another; and, m and n are integers greater than
or equal to 0.
7. A thermal imprint method comprising: pressing a mold, which is
heated to less than or equal to a glass transition temperature Tg
(.degree. C.) of a resin for thermal imprint+65.degree. C., against
a sheet or a film comprising the resin for thermal imprint of claim
1, thereby transferring a pattern of the mold.
8. A thermal imprint method comprising steps of: pressing a mold
against a sheet or a film comprising the resin for thermal imprint
of claim 1; and releasing the mold from the resin for thermal
imprint at a temperature greater than or equal to a glass
transition temperature (Tg) of the resin for thermal
imprint-25.degree. C.
9. A thermal imprint method comprising: pressing a mold against a
sheet or a film comprising the resin for thermal imprint of claim 1
at less than or equal to 2.5 MPa, thereby transferring a pattern of
the mold.
10. A method of using a cyclic-olefin-based thermoplastic resin for
an imprint process, the resin being used for producing a sheet or a
film, and containing at least one of skeletons represented by a
following chemical equation 7 or a following chemical equation 8 in
a main chain, and wherein: a glass transition temperature Tg
(.degree. C.) of the resin and a value ([M]) of MFR at 260.degree.
C. satisfy a following equation 1; and [M]<30 wherein,
##STR00014## Tg(.degree. C.)>219.times.log[M]-160 [Equation 1]
and further wherein R.sup.1 to R.sup.29 in chemical equations 7, 8
may differ or may be same, each of which is a substituent
containing a hydrogen atom, a deuterium atom, a hydrocarbon radical
having a carbon number of 1 to 15, a halogen atom, and a hetero
atom of oxygen, sulfur, or the like, and may form a monocyclic or
polycyclic structure with one another; m and n are integers greater
than or equal to 0; and [M] in equation 1 represents a value of MFR
at 260.degree. C.
11. A method of using a cyclic-olefin-based thermoplastic resin for
an imprint process, the resin being used for producing a sheet or a
film, and containing at least one of skeletons represented by a
following chemical equation 9 or a following chemical equation 10
in a main chain, and wherein: a glass transition temperature Tg
(.degree. C.) of the resin and a value ([M]) of MFR at 260.degree.
C. satisfy a following equation 1; and [M]<20 and
Tg>90.degree. C. wherein ##STR00015## Tg(.degree.
C.)>219.times.log[M]-160 [Equation 1] and further wherein
R.sup.1 to R.sup.29 in chemical equations 9, 10 may differ or may
be same, each of which is a substituent containing a hydrogen atom,
a deuterium atom, a hydrocarbon radical having a carbon number of 1
to 15, a halogen atom, and a hetero atom of oxygen, sulfur, or the
like, and may form a monocyclic or polycyclic structure with one
another; m and n are integers greater than or equal to 0; and, [M]
in equation 1 represents a value of MFR at 260.degree. C.
12. A thermal imprint method comprising: pressing a mold, which is
heated to,less than or equal to a glass transition temperature Tg
(.degree. C.) of a resin for thermal imprint+65.degree. C., against
a sheet or a film comprising the resin for thermal imprint of claim
2 thereby transferring a pattern of the mold.
13. A thermal imprint method comprising steps of: pressing a mold
against a sheet or a film comprising the resin for thermal imprint
of claim 2; and releasing the mold from the resin for thermal
imprint at a temperature greater than or equal to a glass
transition temperature (Tg) of the resin for thermal
imprint-25.degree. C.
14. A thermal imprint method comprising: pressing a mold against a
sheet or a film comprising the resin for thermal imprint of claim 2
at less than or equal to 2.5 MPa, thereby transferring a pattern of
the mold.
15. A thermal imprint method comprising: pressing a mold, which is
heated to less than or equal to a glass transition temperature Tg
(.degree. C.) of a resin for thermal imprint+65.degree. C., against
a sheet or a film comprising the resin for thermal imprint of claim
3 thereby transferring a pattern of the mold.
16. A thermal imprint method comprising steps of: pressing a mold
against a sheet or a film comprising the resin for thermal imprint
of claim 3; and releasing the mold from the resin for thermal
imprint at a temperature greater than or equal to a glass
transition temperature (Tg) of the resin for thermal
imprint-25.degree. C.
17. A thermal imprint method comprising: pressing a mold against a
sheet or a4 film comprising the resin for thermal imprint of claim
3 at less than or equal to 2.5 MPa, thereby transferring a pattern
of the mold.
18. A thermal imprint method comprising: pressing a mold, which is
heated to less than or equal to a glass transition temperature Tg
(.degree. C.) of a resin for thermal imprint+65.degree. C., against
a sheet or a film comprising the resin for thermal imprint of claim
4 thereby transferring a pattern of the mold.
19. A thermal imprint method comprising steps of: pressing a mold
against a sheet or a film comprising the resin for thermal imprint
of claim 4; and releasing the mold from the resin for thermal
imprint at a temperature greater than or equal to a glass
transition temperature (Tg) of the resin for thermal
imprint-25.degree. C.
20. A thermal imprint method comprising: pressing a mold against a
sheet or a film comprising the resin for thermal imprint of claim 4
at less than or equal to 2.5 MPa, thereby transferring a pattern of
the mold.
Description
TECHNICAL FIELD
[0001] The present invention relates to a resin for thermal
imprint. More specifically, the present invention relates to a
cyclic-olefin-based thermoplastic resin which has a specific
correlation between a glass transition temperature Tg (.degree. C.)
and MFR at 260.degree. C., and can be used for producing a sheet or
a film.
BACKGROUND ART
[0002] As the optical fields for optical communications, optical
disks, displays, optical sensors, and the like dramatically
develop, achieving both performance and cost becomes important for
optical resin materials. Expectations for transparent resin
materials which are easy to process become large in fields of
biochips, micro reactors, and the like, in lieu of glasses. In all
fields, processing of a base material surface, in particular,
microprocessing becomes requisite, and the microprocessing becomes
an important technology in a recent semiconductor field where
integration becomes remarkable. Conventionally, to form a minute
pattern on the surface of a transparent material, schemes of
cutting the surface mechanically or of printing a pattern using a
resist, a thermo, ultraviolet, or electron radiation curing resin,
or the like are used. In particular, to cope up with the present
trend and future need for miniaturization of various devices,
several different patterning methods are under continuing
development. Injection molding has its limitation below 500 .mu.m
of film thickness. However, various advanced devices including anti
reflecting film or coating requires patterning on a sheet or a film
with thickness much below the limit of injection molding.
[0003] According to the mechanical cutting, however, there is a
problem such that an advanced and complex processing technique is
required. According to the pattern printing using a resist or the
like, steps thereof are complicated, and there is a problem in the
durability, such as peeling of a printed pattern. Further, as
patterns become minuter, a mechanism which controls a whole process
highly precisely becomes requisite, so that the cost issue becomes
not negligible.
[0004] To cope with such problems, there is proposed a thermal
imprint method for forming a minute pattern at low cost. That is,
this is a method of pressing a mold, having a minute pattern heated
more than or equal to a glass transition temperature of a resin,
against a resin substrate, and of transferring the minute pattern
of the mold on the melted resin surface.
[0005] Disclosed so far to improve the thermal imprint
characteristics (transferability, mold release characteristic, and
the like) and the productivity (throughput) are a scheme of
providing an insulator to shorten a cycle of temperature rising and
cooling (see, for example, patent literature 1), and a scheme of
providing an ultrasonic generation mechanism to reduce the melt
viscosity by ultrasonic (see, for example, patent literature 2).
However, there are few literatures which mentioned materials used
for thermal imprint, and development of the materials for thermal
imprint is desired.
[0006] In general, examples of materials used for thermal imprint
are resin materials, glasses, metals, and the like. The resin
materials can be molded at a lower temperature in comparison with
imprinting to metals or glasses, thus advantageous for the
manufacturing cost.
[0007] An example of resins is a (meta) acrylic resin represented
by polymethacrylic acid (PMMA) or a polycarbonate resin, but have a
problem such that the heat resistance is low and size distortion
occurs due to water absorption. Further, controlling a balance
between the fluidity and the solidification is difficult, so that
it is difficult to maintain and use a minutely-transferred pattern
(see, for example, patent literature 3).
[0008] On the other hand, as a resin having both heat resistance
and dimension stability originating from the low water absorption
coefficient, there are cyclic-olefin-based thermoplastic resins. In
general, the cyclic-olefin-based thermoplastic resins are superior
in the transparency, the chemical resistance property, and the low
moisture absorption characteristic, and its heat resistance can be
easily controlled by the structure of the cyclic-olefin or the
contained amount of the cyclic-olefin in the resin. The resin has a
low viscosity, and a short relaxation time (time necessary for
filling the resin in the pattern of a mold), and is less adhered to
the mold, and is superior in the transfer accuracy of a minute
pattern, so that application as a thermal imprint material is
expected as having a good productivity (see, for example,
non-patent literature 1).
[0009] Patent Literature 1: Japanese Unexamined Patent Application
Laid-open Publication No.2002-361500
[0010] Patent Literature 2: Japanese Unexamined Patent Application
Laid-open Publication No.2004-288811
[0011] Patent Literature 3: Japanese Unexamined Patent Application
Laid-open Publication No. 2000-158532
[0012] Non-patent Literature 1: J. Mater. Chem., 2000, volume 10,
page 2634
[0013] Non-patent Literature 2: Nanoimprint Lithography in Topas, a
highly UV-transparent and chemically resistant thrmoplast, T.
Nielsen, D. Nilsson, et al.
DISCLOSURE OF INVENTION
Problems to be Solved by the Invention
[0014] However, conventional cyclic-olefin-based thermoplastic
resins are not ones that the resin properties, such as a glass
transition temperature Tg (.degree. C.) and the fluidity are
developed for the process of thermal nano-imprint, but require a
high molding temperature and a large molding pressure, thus having
insufficient thermal imprint characteristics (transferability, mold
release characteristic, and the like). Moreover, a long molding
time is required, so that the productivity (throughput) is low. For
example, one disclosed in the foregoing non-patent literature 1 has
a high molding temperature of 240.degree. C., so that it takes a
time to cool it down after the pattern of a mold is transferred,
and the productivity (throughput) for manufacturing imprint
products becomes low. In a non patent literature, as cited in 2, a
polymer with a low Glass Transition temperature of 80.degree. C.
have been used however, the imprinting is performed at 90.degree.
C. above the glass transition temperature of the polymer for 5 min
with a pressure of 2000N, making it a process with prolonged
cooling time having a low practical or commercial impact, similar
to that in citation 1. It is our experience that an optimized
polymer for injection molding does not yield well in thermal
nanoimprinting or, in other words, an ideal polymer film for
thermal nanoimprinting would have to have a different
characteristics that that of an ideal polymer for injection
molding.
[0015] This is primarily because that a correlation between the
resin properties, in particular, a glass transition temperature and
MFR which becomes the barometer of the fluidity of the resin, and a
correlation between an imprint conditions (molding temperature,
molding pressure, mold release temperature, and the like) to the
resin and the imprint characteristics (transferability, mold
release characteristic, and the like) are not figured out.
[0016] Therefore, it is an object of the invention to provide a
cyclic-olefin-based thermoplastic resin which can be used for
manufacturing a sheet or a film like a substrate used for thermal
imprint, is superior in thermal imprint characteristics
(transferability, mold release characteristic, and the like), and
improves a productivity (throughput), and a thermal imprint method
using the same.
Means for Solving the Problems
[0017] To overcome the above mentioned problem, the present
invention enables the development of an ideal polymer for
nanoimprinting co-relating the glass transition temperature and MFR
of the polymer.
[0018] That is, a cyclic-olefin-based thermoplastic resin of the
invention is used for producing a sheet or a film, contains at
least one of skeletons represented by the following chemical
equation 1 or the following chemical equation 2 in a main chain,
and wherein a glass transition temperature Tg (.degree. C.) of the
resin and a value ([M]) of MFR at 260.degree. C. satisfy the
following equation 1, and [M]<30.
##STR00002## Tg(.degree. C.)>219.times.log[M]-160 [Equation
1]
[0019] (R.sup.1 to R.sup.29 in the chemical equations 1, 2 may
differ or may be same, each of which is a substituent containing a
hydrogen atom, a deuterium atom, a hydrocarbon radical having a
carbon number of 1 to 15, a halogen atom, and a hetero atom of
oxygen, sulfur, or the like, and may form a monocyclic or
polycyclic structure with one another. m and n are integers greater
than or equal to 0. [M] in equation 1 represents a value of MFR at
260.degree. C.)
[0020] Another resin for thermal imprint of the invention is used
for producing a sheet or a film, comprises a cyclic-olefin-based
thermoplastic resin that contains at least one of skeletons
represented by the following chemical equation 3 or the following
chemical equation 4 in a main chain, and wherein a glass transition
temperature Tg (.degree. C.) of the resin and a value ([M]) of MFR
at 260.degree. C. satisfy a following equation 1, and [M] <20
and Tg>90.degree. C.
##STR00003## Tg(.degree. C.)>219.times.log[M]-160 [Equation
1]
[0021] (R.sup.1 to R.sup.29 in the chemical equations 3, 4 may
differ or may be same, each of which is a substituent containing a
hydrogen atom, a deuterium atom, a hydrocarbon radical having a
carbon number of 1 to 15, a halogen atom, and a hetero atom of
oxygen, sulfur, or the like, and may form a monocyclic or
polycyclic structure with one another. m and n are integers greater
than or equal to 0. [M] in equation 1 represents a value of MFR at
260.degree. C.)
[0022] In this case, it is preferable that the cyclic-olefin-based
thermoplastic resin should comprise a copolymer of cyclic-olefin
represented by the following chemical equation 5 and x-olefin, or a
polymer produced by hydrogenation after ring-opening polymerization
of the cyclic-olefin.
##STR00004##
[0023] (R.sup.30 to R.sup.48 in chemical equation 5 may differ or
may be same, each of which is a substituent containing a hydrogen
atom, a deuterium atom, a hydrocarbon radical having a carbon
number of 1 to 15, a halogen atom, and a hetero atom of oxygen,
sulfur, or the like, and may form a monocyclic or polycyclic
structure with one another. m and n are integers greater than or
equal to 0)
[0024] The resin for thermal imprint may contain greater than or
equal to one additive. In this case, it is preferable that the
additive should contain at least either one of an anti-oxidizing
agent or a lubricant.
[0025] Further, it is preferable that a resin containing a skeleton
represented by the chemical equation 3 is a copolymer of
cyclic-olefin represented by the following chemical equation 6 and
ethylene.
##STR00005##
[0026] (R.sup.30 to R.sup.48 in the chemical equation 6 may differ
or may be same, each of which is a substituent containing a
hydrogen atom, a deuterium atom, a hydrocarbon radical having a
carbon number of 1 to 15, a halogen atom, and a hetero atom of
oxygen, sulfur, or the like, and may form a monocyclic or
polycyclic structure with one another. m and n are integers greater
than or equal to 0)
[0027] A thermal imprint method of the invention comprises:
pressing a mold, which is heated to less than or equal to a glass
transition temperature Tg (.degree. C.) of a resin for thermal
imprint+65.degree. C., against a sheet or a film comprising the
foregoing resin for thermal imprint, thereby transferring a pattern
of the mold.
[0028] Another thermal imprint method of the invention comprises
steps of: pressing a mold against an injection molded body
comprising the foregoing resin for thermal imprint; and releasing
the mold from the resin for thermal imprint at a temperature
greater than or equal to a glass transition temperature (Tg) of the
resin for thermal imprint-25.degree. C.
[0029] Other thermal imprint method of the invention comprises:
pressing a mold against a sheet or a film comprising the foregoing
resin for thermal imprint at less than or equal to 2.5 MPa, thereby
transferring a pattern of the mold.
[0030] The invention relates to a method of using a
cyclic-olefin-based thermoplastic resin for an imprint process, the
resin is used for producing a sheet or a film, and contains at
least one of skeletons represented by the following chemical
equation 7 or the following chemical equation 8 in a main chain,
and wherein a glass transition temperature Tg (.degree. C.) of the
resin and a value ([M]) of MFR at 260.degree. C. satisfy a
following equation 1, and [M]<30.
##STR00006## Tg(.degree. C.)>219.times.log[M]-160 [Equation
1]
[0031] (R.sup.1 to R.sup.29 in the chemical equations 7, 8 may
differ or may be same, each of which is a substituent containing a
hydrogen atom, a deuterium atom, a hydrocarbon radical having a
carbon number of 1 to 15, a halogen atom, and a hetero atom of
oxygen, sulfur, or the like, and may form a monocyclic or
polycyclic structure with one another. m and n are integers greater
than or equal to 0. [M] in equation 1 represents a value of MFR at
260.degree. C.)
[0032] The invention also relates to a method of using a
cyclic-olefin-based thermoplastic resin for an imprint process, the
resin is used for producing a sheet or a film, and contains at
least one of skeletons represented by the following chemical
equation 9 or the following chemical equation 10 in a main chain,
and wherein a glass transition temperature Tg (.degree. C.) of the
resin and a value ([M]) of MFR at 260.degree. C. satisfy a
following equation 1, and [M]<20 and Tg>90.degree. C.
##STR00007## Tg(.degree. C.)>219.times.log[M]-160 [Equation
1]
[0033] (R.sup.1 to R.sup.29 in the chemical equations 9, 10 may
differ or may be same, each of which is a substituent containing a
hydrogen atom, a deuterium atom, a hydrocarbon radical having a
carbon number of 1 to 15, a halogen atom, and a hetero atom of
oxygen, sulfur, or the like, and may form a monocyclic or
polycyclic structure with one another. m and n are integers greater
than or equal to 0. [M] in equation 1 represents a value of MFR at
260.degree. C.)
EFFECT OF THE INVENTION
[0034] Using a cyclic-olefin-based thermoplastic resin, which has a
specific correlation between a glass transition temperature Tg
(.degree. C.) and MFR at 260.degree. C., enables a thermal imprint
at a low temperature and a low pressure, thereby improving the
imprint characteristics (transferability, mold release
characteristic, and the like) and the productivity
(throughput).
[0035] Further, by applying imprint conditions (molding
temperature, molding pressure, mold release temperature, and the
like) to a cyclic-olefin-based thermoplastic resin having a
specific correlation between a glass transition temperature Tg
(.degree. C.) and MFR at 260.degree. C., the thermal imprint
characteristics (transferability, mold release characteristic, and
the like) and the productivity (throughput) can be further
improved.
BEST MODE FOR CARRYING OUT THE INVENTION
[0036] An embodiment of the invention will be explained in detail
with reference to the drawings.
[0037] A cyclic-olefin-based thermoplastic resin to which the
invention is applied is a copolymer of cyclic-olefin and a-olefin,
i.e., a copolymer with a-olefin containing a repeating unit
indicated by a following chemical equation 11 and derived from
cyclic-olefin, or a polymer that hydrogen is added to cyclic-olefin
indicated by a chemical equation 12 undergone ring-opening
polymerization.
##STR00008##
[0038] R.sup.1 to R.sup.29 in the chemical equation 11 and the
chemical equation 12 may differ, or may be same, and each of which
is a substituent containing hydrogen atoms, deuterium atoms,
hydrocarbon radical having carbon number of 1 to 15, halogen atoms,
or hetero atoms, such as oxygen, or sulfur, and forms a monocyclic
or polycyclic structure with one another. Note that m and n are
integers greater than or equal to zero.
[0039] Cyclic-olefin monomer which constitutes the foregoing resin
has a structure indicated by a chemical equation 13, and examples
of preferable monomer are, for example,
bicyclo[2,2,1]hept-2-ene(norbornene), 5-methylbicyclo[2,2,
1]hept-2-ene, 7-methybicyclo[2,2,1]hept-2-ene,
5-ethylbicyclo[2,2,1]hept-2-ene, 5-propylbicyclo[2,2,1]hept-2-ene,
5-n-butylbicyclo[2,2,1]hept-2-ene,
5-isobutylbicyclo[2,2,1]hept-2-ene
1,4-dimnethylbicyclo[2,2,1]hept-2-ene,
5-bromobicyclo[2,2,1]hept-2-ene, 5-chlorobicyclo[2,2,1]hept-2-ene,
5-fluorobicyclo[2,2,1]hept-2-ene,
5,6-dimethylbicyclo[2,2,1]hept-2-ene, dicyclopentadiene,
tricyclopentadiene,
tetracyclo[4,4,0,1.sup.2.5,1.sup.7.10]-3-dodecene,
5,10-dimethyltetracyclo[4,4,0,1.sup.2.5,1.sup.7.10]-3-dodecene,
2,10-dimethyltetracyclo[4,4,0,1.sup.2.5,1.sup.7.10]-3-dodecene,
11,12-dimethyltetracyclo[4,4,0,1.sup.2.5,1.sup.7.10]-3-dodecene,
2,7,9-trimethyltetracyclo[4,4,0,1.sup.2.5,1.sup.7.10]-3-dodecene,
9-ethyl-2,7-dimethyltetracyclo[4,4,0,1.sup.2.5,1.sup.7.10]-3-dodecene,
9-isobutyl-2,7-dimetyltetracyclo[4,4,0,1.sup.2.5,1.sup.7.10]-3-dodecene,
9-isobutyl-2,7-dimethyltetracyclo[4,4,0,1.sup.2.5,1.sup.7.10]-3-dodecene,
9,11,12-triethyltetmcyclo[4,4,0,1.sup.2.5,1.sup.7.10]-3-dodecene,
9-ethyl-11,12-dimethyltetracyclo[4,4,0,1.sup.2.5,1.sup.7.10]-3-dodecene,
9-isobutyl-11,12-dimethyltetmcyclo[4,4,0,1.sup.2.5,
1.sup.7.10]-3-dodecene,
5,8,9,10-tetramethyltetracyclo[4,4,0,1.sup.2.5,
1.sup.7.10]-3-dodecene,
8-hexyltetracyclo[4,4,0,1.sup.2.5,1.sup.7.10]-3-dodecene,
8-stearyltetracyclo[4,4,0,1.sup.2.5,1.sup.7.10]-3-dodecene,
8-methyl-9-ethyltetracyclo[4,4,0,1.sup.2.5,1.sup.7.10]-3-dodecene,
8-cyclohexyltetracyclo[4,4,0,1.sup.2.5,1.sup.7.10]-3-dodecene,
8-ethylidenetetracyclo[4,4,0,1.sup.2.5,1.sup.7.10]-3-dodecene,
8-chlorotetracyclo[4,4,0,1.sup.2.5,1.sup.7.10]-3-dodecene,
8-bromotetracyclo[4,4,0,1.sup.2.5,1.sup.7.10]-3-dodecene,
8-fluorotetracyclo[4,4,0,1.sup.2.5,1.sup.7.10]-3-dodecene,
8,9-dichlorotetmcyclo[4,4,0,1.sup.2.5,1.sup.7.10]-3-dodecene,
hexacyclo[6,6,1,1.sup.3.6,1.sup.10.13,0.sup.2.7,
0.sup.9.14]-4-deptadecene,
12-methylhexacyclo[6,6,1,1.sup.3.6,1.sup.10.13,0.sup.2.7,
0.sup.9.14])-4-deptadecene,
12-ethylhexacyclo[6,6,1,1.sup.3.6,1.sup.10.13,0.sup.2.7,
0.sup.9.14]-4-deptadecene, 12-isobutylhexacyclo[6,6,1,1.sup.3.6,
1.sup.10.13,0.sup.2.7,0.sup.9.14]-4-deptadecene,
1,6,10-trimethyl-12-isobutylhexacyclo[6,6,1,1.sup.3.6,1.sup.10.13,0.sup.2-
.7,0.sup.9.4]-4-deptadecene,
5-methyl-5-phenyl-bicyclo[2,2,1]hept-2-ene,
5-ethyl-5-phenyl-bicyclo[2,2,1]hept-2-ene,
5-n-propyl-5-phenyl-bicyclo[2,2,1]hept-2-ene,
5-n-butyl-5-phenyl-bicyclo[2,2,1]hept-2-ene,
5,6-dimethyl-5-phenyl-bicyclo[2,2,1]hept-2-ene,
5-methyl-6-ethyl-5-phenylbicyclo[2,2,1]hept-2-ene,
5,6,6-trimethyl-5-phenyl-bicyclo[2,2,1]hept-2-ene,
1,4,5-trimethylbicyclo[2,2,1]hept-2-ene,
5,6-diethyl-5-phenylbicyclo[2,2,1]hept-2-ene,
5-bromo-5-phenyl-bicyclo[2,2,1]hept-2-ene,
5-chloro-5-phenyl-bicyclo[2,2,1]hept-2-ene,
5-fluoro-5-phenyl-bicyclo[2,2,1]hept-2-ene,
5-methyl-5-(tert-butylphenyl)-bicyclo[2,2,1]hept-2-ene,
5-methyl-5-(bromophenyl)-bicyclo[2,2,1]hept-2-ene,
5-methyl-5-(chlorophenyl)-bicyclo[2,2,1]hept-2-ene,
5-methyl-5-(fluorophenyl)-bicyclo[2,2,1]hept-2-ene,
5-methyl-5-(a-naphthyl)-bicyclo[2,2,1]hept-2-ene,
5-methyl-5-antracenyl-bicyclo[2,2,1]hept-2-ene,
8-methyl-8-phenyl-tetracyclo[4,4,0,1.sup.2.5,1.sup.7.10]-3-dodecene,
8-ethyl-8-phenyl-tetracyclo[4,4,0,1.sup.2.5,1.sup.7.10]-3-dodecene,
8-n-propyl-8-phenyl-tetracyclo[4,4,0,1.sup.2.5,1.sup.7.10]-3-dodecene,
8-n-butyl-8-phenyl-tetracyclo[4,4,0,1.sup.2.5,1.sup.7.10]-3-dodecene,
8-chloro-8-phenyl-tetracyclo[4,4,0,1.sup.2.5,1.sup.7.10]-3-dodecene,
11-methyl-11-phenyl-hexacyclo[6,6,1,
1.sup.3.6,1.sup.10.13,0.sup.2.7,0.sup.9.14]-4-heptadecene,
1,4-methano-4a,9,9-trimethyl-1,4,9a-trihydrofluorene. Such various
monomers can be basically made by a thermal Diels-Alder reaction of
corresponding dienes and olefins, and adding hydrogen or the like
appropriately makes it possible to produce a desired monomer.
##STR00009##
[0040] R.sup.30 to R.sup.48 in the chemical equation 13 may differ
or may be same, and each of which is a substituent including
hydrogen atoms, deuterium atoms, hydrocarbon radical having carbon
number of 1 to 15, halogen atoms, or hetero atoms, such as oxygen
and sulfur, and forms a monocyclic or polycyclic structure with
each other. Note that m and n are integers greater than or equal to
zero.
[0041] An example of .alpha.-olefin suitably used for the copolymer
indicated by the chemical equation 11 is .alpha.-olefin having a
carbon number of 2 to 20, preferably, a carbon number of 2 to 10,
and includes, for example, ethylene, propylene, 1-butene,
1-pentene, 3-methyl-1-butene, 3-methyl-1-pentene, 1-hexene,
1-octene, 1-decene, and those can be used individually or combined.
Ethylene and propylene are preferable in those, and ethylene is
particularly preferable from the standpoint of practical aspects,
such as copolymer characteristic, and economic efficiency.
[0042] In the copolymer indicated by the chemical equation 11, the
preferable mole ratio (.alpha.-olefin/cyclic-olefn) between the
.alpha.-olefin and the cyclic-olefin is within a range from 10/90
to 90/10, and further preferably, with in a range from 30/70 to
70/30. The mole ratio in copolymer is decided based on .sup.13C-NMR
(400 MHz, temperature: 120.degree. C./solvent:
1,2,4-trichlorobenzene/1,1,2,2-deuterated tetrachloroethane mixing
system).
[0043] The thermal imprint resin of the invention is adjusted in
such a way that the glass transition temperature Tg (.degree. C.)
thereof and a value ([M]) of MFR at 260.degree. C. satisfy the
following equation 1.
Tg(.degree. C.)>219.times.log[M]-160 [Equation 1]
[0044] The weight average molecular weight Mw of the
cyclic-olefin-based thermoplastic resin indicated by the chemical
equation 11 or the chemical equation 12 is within 10,000 to
1,000,000, preferably, 20,000 to 500,000, and further preferably,
50,000 to 300,000, and the value [M] of MFR at 260.degree. C. is
less than or equal to 30, preferably, less than or equal to 20, and
further preferably, less than or equal to 10. Accordingly, the
strength of the resin becomes high, so that the imprint
characteristics (transferability, mold release characteristic, and
the like) can be improved without deteriorating the fluidity of the
resin.
[0045] In considering the application of the resin on which a
minute pattern is transferred by thermal imprint, it is preferable
that the heat resistance of the resin should be high, and the glass
transition temperature should be greater than or equal to
80.degree. C., preferably, greater than or equal to 90.degree. C.,
and further preferably, higher than the boiling temperature of
water, i.e., beyond 100.degree. C. in view of the practicality.
[0046] A polymerization method for producing the resin is not
limited to any particular ones, and well-known methods, such as a
method of coordination polymerization using Ziegler-Natta catalyst
or single-site catalyst, and further, causing a copolymer to be
subjected to hydrogen addition in accordance with necessity, and a
method of adding hydrogen after ring-opening polymerization using
metathesis polymerization catalyst. As a method of adding hydrogen,
well-known methods can be employed, and this can be carried out
using a catalyst containing metal components, such as nickel, and
palladium. Examples of the single-site catalyst used for producing
the copolymer indicated by, for example, the chemical equation 11
are various kinds of metallocene compounds, and
methylene(cyclopentadienyl)(tetracyclopentadienyl)zirconiumdichloride
or the like disclosed in, for example, Japanese Unexamined Patent
Application Laid-open Publication No. 2003-82017 can be preferably
used. A promoter used for a polymerization reaction is not limited
to any particular one, but methyl aluminoxanes can be used
preferably, and other organic aluminum compounds may coexist and
polymerize in accordance with a reaction. Such a polymerization
reaction can be preferably carried out within a range from a room
temperature (25.degree. C. or so) to 200.degree. C., but it is
desirable to carry out such a reaction within a range from 40 to
150.degree. C. in view of the reactivity and the stability of a
catalyst. An organic solvent used for a polymerization reaction is
not limited to any particular one, and for example, aromatic
solvents, such as benzene, toluene, xylene, and ethyl benzene,
saturated hydrocarbon solvents, such as hexane, cyclohexane,
heptane, methyl cyclohexane, and octane, or a mixed solvent thereof
can be preferably used. After the resin is produced, hetero atoms,
such as oxygen atoms and sulfur atoms can be arbitrarily introduced
by a radical reaction.
[0047] In accordance with necessity, greater than or equal to one
of additives, such as an anti-oxidizing agent, a heat resistance
stabilizer, a weathering stabilizer, a light stabilizer, an
antistatic agent, a slipping agent, anti-blocking agent, an
anti-fog additive, a lubricant, a color, a pigment, a natural oil,
a synthetic oil, and a wax, can be added and mixed, and the mix
ratio thereof can be set arbitrarily. Additives (anti-oxidizing
agent, lubricant, and the like) are not limited to any particular
ones, and well-known compounds can be used preferably.
[0048] Additionally, additives like fluorine containing non-ionic
surfactant or silocone containing leveling material could be used
to reduce surface roughness of a sheet or a film.
[0049] According to the invention, addition of an oxidizing agent
prevents an oxidization of the resin when heated, a creation of a
gel originating from the staining of the resin and a bridge
formation of the resin molecular chain, and a deterioration of
physical property due to a disconnection of the resin molecular
chain.
[0050] According to the invention, addition of a lubricant improves
the mold release characteristic, after imprint, and the
productivity (throughput) of imprint products. Furthermore, there
is an effectiveness such that the resin can be easily put into a
pattern on a mold when fabricating the resin.
[0051] Further, without deteriorating the physical properties
required in the application fields of an imprint product, a rubber
component can be added to improve the durability of the resin
plate, and a well-known compound can be used.
[0052] Examples of the applications of the imprint product are
optical devices, such as an optical waveguide, a light guiding
plate, and a diffraction grating, biochips, fluidic devices, such
as a micro flow channel, and a micro reactor, media for saving
data, and circuit substrates.
[0053] The method of manufacturing a sheet or a film is not limited
to any particular one, and a well-known method of the extrusion
molding, dipping method, solution casting, spin coating method, or
the like can be applied. The thickness can be arbitrarily selected
in accordance with an application of an imprint product, and
molding is possible if the thickness is less than or equal to 500
.mu.m. The sheet or the film using the thermal imprint resin of the
invention can be formed in any shapes, it is preferable that the
thickness is less than or equal to 300 .mu.m, and more preferably
less than or equal to 150 .mu.m.
[0054] Various products can be used as a device for imprinting, and
can be selected arbitrarily. Various sizes, such as less than or
equal to 100 .mu.m, less than or equal to 50 .mu.m, less than or
equal to 10 .mu.m, less than or equal to 1 .mu.m, and less than or
equal to 500 nm can be selected as the size of a transferred
pattern for the thermal imprint resin of the invention.
[0055] Next, an explanation will be given of a method of performing
imprinting on a sheet or a film comprising the resin of the
invention.
[0056] To realize a process having the improved imprint
characteristics (transferability, mold release characteristic, and
the like), it is preferable to reduce a molding pressure and to
shorten the retention time at molding. This is because that if the
molding pressure when performing imprinting is too high and the
retention time of a pressure is too long, the resin adheres to the
mold, so that the pattern is elongated or damaged in mold
releasing, and the transfer precision of the pattern is reduced.
Specifically, in using a sheet or a film of the resin of the
invention, the molding pressure in performing imprinting should be
less than or equal to 3.0 MPa, and more preferably, less than or
equal to 2.5 MPa. Further, the retention time in performing molding
should be less than or equal to 1000 seconds, more preferably, less
than or equal to 600 seconds.
[0057] The polymer film or sheet could be supported by a substrate
of a polymer like poly carbonates, poly acryls, poly imides or
graphite or metal like aluminum, stainless steel, etc, during the
imprinting process. In case a polymer substrate is used as a
support, the glass transition temperature of the said polymer
should be higher than the temperature at which the imprinting is
performed. In case a film is cast on a substrate of aluminum or
silicon, etc, the film on substrate could be used directly.
[0058] Further, to realize a process having the improved
productivity (throughput), it is preferable to reduce the
temperature of the mold, and to shorten the retention time in
performing molding. This is because that if the mold temperature is
low, the cooling time can be shortened, and if the retention time
at which the mold and the sheet or the film are pressed is short,
then the molding time can be shortened.
[0059] Specifically, it is preferable to use a sheet or a film
comprised of the resin of the invention, and to set the temperature
in performing molding to less than or equal to the glass transition
temperature Tg+80.degree. C., and more preferably, less than or
equal to Tg+65.degree. C. It is preferable that the temperatures of
the mold in mold releasing and the sheet or the film should be
greater than or equal to Tg-40.degree. C., and more preferably,
greater than or equal to Tg-25.degree. C.
Examples
[0060] Examples of the invention will be explained below, but the
invention should not be limited to the following examples.
[0061] Regarding the weight average molecular weight (Mw), the
number average molecular weight (Mn), and the molecular weight
fractionation (Mw/Mn) of the resin to be used, an GPC device
manufactured by Wasters was used by the gel permeation
chromatography method (GPC), and those were measured under a
condition such that column: K-805L/K-806L manufactured by Shodex,
column temperature: 40.degree. C., solvent: chloroform, flow rate:
0.8 ml/minute. The glass transition temperature Tg (.degree. C.) of
the resin used was acquired from the heat absorption peak in heat
up using a differential scanning calorimeter (model: EXSTAR 6000,
DSC 6200) manufactured by SEIKO. Further, regarding the value [M]
of MFR at 260.degree. C., the MELT INDEXER (model: L248-2531)
manufactured by TECHNOL SEVEN Co., Ltd. was used, and a value
measured at a loading of 2.16 kgf.
[0062] Film or sheet could be fabricated either by the usage of
Labo Plastomill D-2025 from Toyoseiki or by spin coating in a
SC-300 spin coater from E.H.C Corporation or by casting using an
applicator on a glass plate followed by baking, drying and
annealing.
[0063] For imprint evaluations, an imprint device (VX-2000N-US)
manufactured by SCIVAX was used, and the evaluations were carried
out under condition described in the examples, respectively, using
a mold of 30 mm by 30 mm. Table 1 shows imprint characteristics
inherent to presence/absence of correlations (represented by
equation 1) between a structure of a resin or a glass transition
temperature Tg (.degree. C.) and MFR at 260.degree. C. For
evaluation of imprint characteristics, acquired minute bumpy
patterns were observed through an electronic microscope, and if a
pattern similar to a mold was well transferred, a circular mark is
filled, if a resin adhered to a mold, and a deficit of a pattern
was formed, then a triangle mark is filled, and if a pattern
failure (insufficient filling, elongation, deficit) was confirmed,
then a cross mark is filled. if a resin adhered to a mold and there
is a deficit or film peeling or overstretch, then a cross mark is
filled.
[0064] First, an explanation will be given of the production method
of a sheet or a film used in the examples and comparative examples.
Samples 1 to 8 were sheets or films made of resins which satisfied
the foregoing equation 1, and samples 9 and 10 were sheets or films
made of resins which did not satisfy the equation 1. Note that
polymers used for sheets or films contained an anti-oxidizing agent
and a lubricant, as long as any particular explanations will be
given for product examples.
Product Example 1
Production of a Sheet or a Film
[0065] Ethylene/norbornene copolymer (Tg=134.degree. C., MFR=11 @
260.degree. C.) was molded by the film molding machine, and a
transparent molded body (sample 1) having a thickness of 100 .mu.m
was produced.
Product Example 2
Production of a Sheet or a Film
[0066] Ethylene/norbornene copolymer (Tg=135.degree. C., MFR=10 @
260.degree. C.) was molded by the film molding machine, and a
transparent molded body (sample 2) having a thickness of 90 .mu.m
was produced.
Product Example 3
Production of a Sheet or a Film
[0067] Ethylene/norbornene copolymer (Tg=109.degree. C., MFR=16 @
260.degree. C.) was molded by the film molding machine, and a
transparent molded body (sample 3) having a thickness of 100 .mu.m
was produced.
Product Example 4
Production of a Sheet or a Film
[0068] Hydrogeneration of cyclic-olefin based ring-opening polymer
(Tg=138.degree. C., MFR=8 @ 260.degree. C.) was molded by the film
molding machine, and a transparent molded body (sample 4) having a
thickness of 110 .mu.m was produced.
Product Example 5
Production of a Sheet or a Film
[0069] Hydrogeneration of cyclic-olefin based ring-opening polymer
(Tg=136.degree. C., MFR=7 @ 260.degree. C.) was molded by the film
molding machine, and a transparent molded body (sample 5) having a
thickness of 110 .mu.m was produced.
Product Example 6
Production of a Sheet or a Film
[0070] Hydrogeneration of cyclic-olefin based ring-opening polymer
(Tg=105.degree. C., MFR=9 @ 260.degree. C.) was molded by the film
molding machine, and a transparent molded body (sample 6) having a
thickness of 100 .mu.m was produced.
Product Example 7
Production of a Sheet or a Film
[0071] A solution containing 15wt % of ethylene/norbornane type
copolymer (Tg=135.degree. C., MFR=10@260.degree. C.) in diethyl
benzene solvent is spin coated on a silicon wafer (400 rpm.times.5
s 2000 rpm.times.20 s) followed by baking (100.degree. C..times.15
min, 150.degree. C..times.30 min) and annealing (110.degree.
C..times.30 min) to produce 1.3 .mu.m thick coating (sample 7)
Product Example 8
Production of a Sheet or a Film
[0072] Ethylene/norbornene copolymer (Tg=135.degree. C., MFR=59 @
260.degree. C.) was molded by the film molding machine, and a
transparent molded body (sample 8) having a thickness of 100 .mu.m
was produced.
Product Example 9
Production of a Sheet or a Film
[0073] Ethylene/norbornene copolymer (Tg=132.degree. C., MFR=51 @
260.degree. C.) was molded by the film molding machine, and a
transparent molded body (sample 9) having a thickness of 90 Jim was
produced.
Example 1
Evaluation for Imprinting on a Film
[0074] Sample 1 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 111.degree. C.), a
mold (pattern: pillar, diameter 0.5 .mu.m/depth 1 .mu.m) which was
preheated to a molding set temperature Tg+30.degree. C. (i.e.,
164.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 2000 N, it was held for 10 seconds
by that load. Thereafter, it was cooled to Tg-23.degree. C.
(111.degree. C.) while maintaining the displacement of the mold,
and after the completion of cooling, the mold was released from the
film at a speed of 10 .mu.m/second. It was observed through an
electronic microscope that a good pattern without the elongation
and flaking off was transferred.
Example 2
Evaluation for Imprinting on a Film
[0075] Sample 1 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 111.degree. C.), a
mold (pattern: pillar, diameter 0.75 .mu.m/depth 1 .mu.m) which was
preheated to a molding set temperature Tg+30.degree. C. (i.e.,
164.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 2000 N, it was held for 10 seconds
by that load. Thereafter, it was cooled to Tg-23.degree. C.
(111.degree. C.) while maintaining the displacement of the mold,
and after the completion of cooling, the mold was released from the
film at a speed of 10 .mu.m/second. It was observed through an
electronic microscope that a good pattern without the elongation
and flaking off was transferred.
Example 3
Evaluation for Imprinting on a Film
[0076] Sample 1 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 111.degree. C.), a
mold (pattern: pillar, diameter 1 .mu.m/depth 1 .mu.m) which was
preheated to a molding set temperature Tg+30.degree. C. (i.e.,
164.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 2000 N, it was held for 10 seconds
by that load. Thereafter, it was cooled to Tg-23.degree. C.
(111.degree. C.) while maintaining the displacement of the mold,
and after the completion of cooling, the mold was released from the
film at a speed of 10 .mu.m/second. It was observed through an
electronic microscope that a good pattern without the elongation
and flaking off was transferred.
Example 4
Evaluation for Imprinting on a Film
[0077] Sample 1 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 111.degree. C.), a
mold (pattern: line/space (L/S)=1 .mu.m/1 .mu.m) which was
preheated to a molding set temperature Tg+30.degree. C. (i.e.,
164.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 2000 N, it was held for 10 seconds
by that load. Thereafter, it was cooled to Tg-23.degree. C.
(111.degree. C.) while maintaining the displacement of the mold,
and after the completion of cooling, the mold was released from the
film at a speed of 10 .mu.m/second. It was observed through an
electronic microscope that a good pattern without the elongation
and flaking off was transferred.
Example 5
Evaluation for Imprinting on a Film
[0078] Sample 1 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 111.degree. C.), a
mold (pattern: L/S=1 .mu.m/1 .mu.m) which was preheated to a
molding set temperature Tg+35.degree. C. (i.e., 169.degree. C.) was
pressed against the surface of the film at a speed of 100
.mu.m/second, and when the load sensor attached to the upper part
of the mold reached 500 N, it was held for 10 seconds by that load.
Thereafter, it was cooled to Tg-23.degree. C. (111.degree. C.)
while maintaining the displacement of the mold, and after the
completion of cooling, the mold was released from the film at a
speed of 10 .mu.m/second. It was observed through an electronic
microscope that a good pattern without the elongation and flaking
off was transferred.
Example 6
Evaluation for Imprinting on a Film)
[0079] Sample 1 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 111.degree. C.), a
mold (pattern: L/S=1 .mu.m/1 .mu.m) which was preheated to a
molding set temperature Tg+35.degree. C. (i.e., 169.degree. C.) was
pressed against the surface of the film at a speed of 100
.mu.m/second, and when the load sensor attached to the upper part
of the mold reached 500 N, it was held for 300 seconds by that
load. Thereafter, it was cooled to Tg-23.degree. C. (111.degree.
C.) while maintaining the displacement of the mold, and after the
completion of cooling, the mold was released from the film at a
speed of 10 .mu.m/second. It was observed through an electronic
microscope that a good pattern without the elongation and flaking
off was transferred.
Example 7
Evaluation for Imprinting on a Film
[0080] Sample 1 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 111.degree. C.), a
mold (pattern: hole, diameter 1 .mu.m/depth 1 .mu.m) which was
preheated to a molding set temperature Tg+30.degree. C. (i.e.,
164.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 2000 N, it was held for 10 seconds
by that load. Thereafter, it was cooled to Tg-23.degree. C.
(111.degree. C.) while maintaining the displacement of the mold,
and after the completion of cooling, the mold was released from the
film at a speed of 10 .mu.m/second. It was observed through an
electronic microscope that a good pattern without the elongation
and flaking off was transferred.
Example 8
Evaluation for Imprinting on a Film
[0081] Sample 1 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 111.degree. C.), a
mold (pattern: hole, diameter 1 .mu.m/depth 1 .mu.m) which was
preheated to a molding set temperature Tg+35.degree. C. (i.e.,
169.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 500 N, it was held for 10 seconds by
that load. Thereafter, it was cooled to Tg-23.degree. C.
(111.degree. C.) while maintaining the displacement of the mold,
and after the completion of cooling, the mold was released from the
film at a speed of 10 .mu.m/second. It was observed through an
electronic microscope that a good pattern without the elongation
and flaking off was transferred.
Example 9
Evaluation for Imprinting on a Film
[0082] Sample 2 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 112.degree. C.), a
mold (pattern: pillar, diameter 0.5 .mu.m/depth 1 .mu.m) which was
preheated to a molding set temperature Tg+35.degree. C. (i.e.,
170.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 2000 N, it was held for 10 seconds
by that load. Thereafter, it was cooled to Tg-23.degree. C.
(112.degree. C.) while maintaining the displacement of the mold,
and after the completion of cooling, the mold was released from the
film at a speed of 10 ml/second. It was observed through an
electronic microscope that a good pattern without the elongation
and flaking off was transferred.
Example 10
Evaluation for Imprinting on a Film
[0083] Sample 2 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 112.degree. C.), a
mold (pattern: pillar, diameter 0.75 .mu.m/depth 1 .mu.m) which was
preheated to a molding set temperature Tg+35.degree. C. (i.e.,
170.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 2000 N, it was held for 10 seconds
by that load. Thereafter, it was cooled to Tg-23.degree. C.
(112.degree. C.) while maintaining the displacement of the mold,
and after the completion of cooling, the mold was released from the
film at a speed of 10 .mu.m/second. It was observed through an
electronic microscope that a good pattern without the elongation
and flaking off was transferred.
Example 11
Evaluation for Imprinting on a Film
[0084] Sample 2 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 112.degree. C.), a
mold (pattern: pillar, diameter 1 .mu.m/depth 1 .mu.m) which was
preheated to a molding set temperature Tg+35.degree. C. (i.e.,
170.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 2000 N, it was held for 10 seconds
by that load. Thereafter, it was cooled to Tg-23.degree.
C.(112.degree. C.) while maintaining the displacement of the mold,
and after the completion of cooling, the mold was released from the
film at a speed of 10 .mu.m/second. It was observed through an
electronic microscope that a good pattern without the elongation
and flaking off was transferred.
Example 12
Evaluation for Imprinting on a Film
[0085] Sample 2 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 112.degree. C.), a
mold (pattern: pillar, diameter 0.5 .mu.m/depth 1 .mu.m) which was
preheated to a molding set temperature Tg+35.degree. C. (i.e.,
170.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 500 N, it was held for 10 seconds by
that load. Thereafter, it was cooled to Tg-23.degree. C.
(112.degree. C.) while maintaining the displacement of the mold,
and after the completion of cooling, the mold was released from the
film at a speed of 10 .mu.m/second. It was observed through an
electronic microscope that a good pattern without the elongation
and flaking off was transferred.
Example 13
Evaluation for Imprinting on a Film
[0086] Sample 2 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 112.degree. C.), a
mold (pattern: pillar, diameter 0.75 .mu.m/depth 1 .mu.m) which was
preheated to a molding set temperature Tg+35.degree. C. (i.e.,
170.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 500 N, it was held for 10 seconds by
that load. Thereafter, it was cooled to Tg-23.degree. C.
(112.degree. C.) while maintaining the displacement of the mold,
and after the completion of cooling, the mold was released from the
film at a speed of 10 .mu.m/second. It was observed through an
electronic microscope that a good pattern without the elongation
and flaking off was transferred.
Example 14
Evaluation for Imprinting on a Film
[0087] Sample 2 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 112.degree. C.), a
mold (pattern: L/S=1 .mu.m/1 .mu.m) which was preheated to a
molding set temperature Tg+35.degree. C. (i.e., 170.degree. C.) was
pressed against the surface of the film at a speed of 100
.mu.m/second, and when the load sensor attached to the upper part
of the mold reached 2000 N, it was held for 10 seconds by that
load. Thereafter, it was cooled to Tg-23.degree. C. (112.degree.
C.) while maintaining the displacement of the mold, and after the
completion of cooling, the mold was released from the film at a
speed of 10 .mu.m/second. It was observed through an electronic
microscope that a good pattern without the elongation and flaking
off was transferred.
Example 15
Evaluation for Imprinting on a Film
[0088] Sample 2 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 112.degree. C.), a
mold (pattern: L/S=1 .mu.m/1 .mu.m) which was preheated to a
molding set temperature Tg+35.degree. C. (i.e., 170.degree. C.) was
pressed against the surface of the film at a speed of 100
.mu.m/second, and when the load sensor attached to the upper part
of the mold reached 500 N, it was held for 10 seconds by that load.
Thereafter, it was cooled to Tg-23.degree. C. (112.degree. C.)
while maintaining the displacement of the mold, and after the
completion of cooling, the mold was released from the film at a
speed of 10 .mu.m/second. It was observed through an electronic
microscope that a good pattern without the elongation and flaking
off was transferred.
Example 16
Evaluation for Imprinting on a Film
[0089] Sample 2 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 112.degree. C.), a
mold (pattern: L/S=1 .mu.m/1 .mu.m) which was preheated to a
molding set temperature Tg+35.degree. C. (i.e., 170.degree. C.) was
pressed against the surface of the film at a speed of 100
.mu.m/second, and when the load sensor attached to the upper part
of the mold reached 500 N, it was held for 300 seconds by that
load. Thereafter, it was cooled to Tg-23.degree. C. (112.degree.
C.) while maintaining the displacement of the mold, and after the
completion of cooling, the mold was released from the film at a
speed of 10 .mu.m/second. It was observed through an electronic
microscope that a good pattern without the elongation and flaking
off was transferred.
Example 17
Evaluation for Imprinting on a Film
[0090] Sample 2 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 112.degree. C.), a
mold (pattern: hole, diameter 1 .mu.m/depth 1 .mu.m) which was
preheated to a molding set temperature Tg+35.degree. C. (i.e.,
170.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 2000 N, it was held for 10 seconds
by that load. Thereafter, it was cooled to Tg-23.degree. C.
(112.degree. C.) while maintaining the displacement of the mold,
and after the completion of cooling, the mold was released from the
film at a speed of 10 .mu.m/second. It was observed through an
electronic microscope that a good pattern without the elongation
and flaking off was transferred.
Example 18
Evaluation for Imprinting on a Film
[0091] Sample 2 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 112.degree. C.), a
mold (pattern: hole, diameter 1 .mu.m/depth 1 .mu.m) which was
preheated to a molding set temperature Tg+35.degree. C. (i.e.,
170.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 500 N, it was held for 10 seconds by
that load. Thereafter, it was cooled to Tg-23.degree. C.
(112.degree. C.) while maintaining the displacement of the mold,
and after the completion of cooling, the mold was released from the
film at a speed of 10 .mu.m/second. It was observed through an
electronic microscope that a good pattern without the elongation
and flaking off was transferred.
Example 19
Evaluation for Imprinting on a Film
[0092] Sample 3 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 86.degree. C.), a
mold (pattern: pillar, diameter 1 .mu.m/depth 1 .mu.m) which was
preheated to a molding set temperature Tg+35.degree. C. (i.e.,
144.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 2000 N, it was held for 10 seconds
by that load. Thereafter, it was cooled to Tg-23.degree. C.
(86.degree. C.) while maintaining the displacement of the mold, and
after the completion of cooling, the mold was released from the
film at a speed of 10 .mu.m/second. It was observed through an
electronic microscope that a good pattern without the elongation
and flaking off was transferred.
Example 20
Evaluation for Imprinting on a Film
[0093] Sample 3 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 86.degree. C.), a
mold (pattern: pillar, diameter 1 .mu.m/depth 1 .mu.m) which was
preheated to a molding set temperature Tg+35.degree. C. (i.e.,
144.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 500 N, it was held for 10 seconds by
that load. Thereafter, it was cooled to Tg-23.degree. C.
(86.degree. C.) while maintaining the displacement of the mold, and
after the completion of cooling, the mold was released from the
film at a speed of 10 .mu.m/second. It was observed through an
electronic microscope that a good pattern without the elongation
and flaking off was transferred.
Example 21
Evaluation for Imprinting on a Film
[0094] Sample 3 was fixed on a stainless plate which was heated to
a glass transition temperature Tg-5.degree. C. (i.e., 104.degree.
C.), a mold (pattern: pillar, diameter 1 .mu.m/depth 1 .mu.m) which
was preheated to a molding set temperature Tg+65.degree. C. (i.e.,
174.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 1500 N, it was held for 300 seconds
by that load. Thereafter, it was cooled to Tg-5.degree. C.
(104.degree. C.) while maintaining the load, and after the
completion of cooling, the mold was released from the film at a
speed of 10 .mu.m/second. It was observed through an electronic
microscope that a good pattern without the elongation and flaking
off was transferred.
Example 22
Evaluation for Imprinting on a Film
[0095] Sample 3 was fixed on a stainless plate which was heated to
a glass transition temperature Tg-5.degree. C. (i.e., 104.degree.
C.), a mold (pattern: L/S=1 .mu.m/1 .mu.m) which was preheated to a
molding set temperature Tg+65.degree. C. (i.e., 174.degree. C.) was
pressed against the surface of the film at a speed of 100
.mu.m/second, and when the load sensor attached to the upper part
of the mold reached 1500 N, it was held for 300 seconds by that
load. Thereafter, it was cooled to Tg-5.degree. C. (104.degree. C.)
while maintaining the load, and after the completion of cooling,
the mold was released from the film at a speed of 10 .mu.m/second.
It was observed through an electronic microscope that a good
pattern without the elongation and flaking off was transferred.
Example 23
Evaluation for Imprinting on a Film
[0096] Sample 3 was fixed on a stainless plate which was heated to
a glass transition temperature Tg-5.degree. C. (i.e., 104.degree.
C.), a mold (pattern: hole, diameter 1 .mu.m/depth 1 .mu.m) which
was preheated to a molding set temperature Tg+65.degree. C. (i.e.,
174.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 1500 N, it was held for 300 seconds
by that load. Thereafter, it was cooled to Tg-5.degree. C.
(104.degree. C.) while maintaining the load, and after the
completion of cooling, the mold was released from the film at a
speed of 10 .mu.m/second. It was observed through an electronic
microscope that a good pattern without the elongation and flaking
off was transferred.
Example 24
Evaluation for Imprinting on a Film
[0097] Sample 4 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 115.degree. C.), a
mold (pattern: pillar, diameter 0.5 .mu.m/depth 1 .mu.m) which was
preheated to a molding set temperature Tg+30.degree. C. (i.e.,
168.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 2000 N, it was held for 10 seconds
by that load. Thereafter, it was cooled to Tg-23.degree. C.
(115.degree. C.) while maintaining the load, and after the
completion of cooling, the mold was released from the film at a
speed of 10 .mu.ml/second. It was observed through an electronic
microscope that a good pattern without the elongation and flaking
off was transferred.
Example 25
Evaluation for Imprinting on a Film
[0098] Sample 4 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 115.degree. C.), a
mold (pattern: pillar, diameter 0.75 .mu.m/depth 1 .mu.m) which was
preheated to a molding set temperature Tg+30.degree. C. (i.e.,
168.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 2000 N, it was held for 10 seconds
by that load. Thereafter, it was cooled to Tg-23.degree. C.
(115.degree. C.) while maintaining the displacement of the mold,
and after the completion of cooling, the mold was released from the
film at a speed of 10 .mu.m/second. It was observed through an
electronic microscope that a good pattern without the elongation
and flaking off was transferred.
Example 26
Evaluation for Imprinting on a Film
[0099] Sample 4 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 115.degree. C.), a
mold (pattern: pillar, diameter 1 .mu.m/depth 1 .mu.m) which was
preheated to a molding set temperature Tg+30.degree. C. (i.e.,
168.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 2000 N, it was held for 10 seconds
by that load. Thereafter, it was cooled to Tg-23.degree. C.
(115.degree. C.) while maintaining the displacement of the mold,
and after the completion of cooling, the mold was released from the
film at a speed of 10 .mu.m/second. It was observed through an
electronic microscope that a good pattern without the elongation
and flaking off was transferred.
Example 27
Evaluation for Imprinting on a Film
[0100] Sample 4 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 115.degree. C.), a
mold (pattern: pillar, diameter 0.5 .mu.m/depth 1 .mu.m) which was
preheated to a molding set temperature Tg+35.degree. C. (i.e.,
173.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 2000 N, it was held for 10 seconds
by that load. Thereafter, it was cooled to Tg-23.degree. C.
(115.degree. C.) while maintaining the displacement of the mold,
and after the completion of cooling, the mold was released from the
film at a speed of 10 .mu.m/second. It was observed through an
electronic microscope that a good pattern without the elongation
and flaking off was transferred.
Example 28
Evaluation for Imprinting on a Film
[0101] Sample 4 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 115.degree. C.), a
mold (pattern: pillar, diameter 0.75 .mu.m/depth 1 .mu.m) which was
preheated to a molding set temperature Tg+35.degree. C. (i.e.,
173.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 2000 N, it was held for 10 seconds
by that load. Thereafter, it was cooled to Tg-23.degree. C.
(115.degree. C.) while maintaining the displacement of the mold,
and after the completion of cooling, the mold was released from the
film at a speed of 10 .mu.m/second. It was observed through an
electronic microscope that a good pattern without the elongation
and flaking off was transferred.
Example 29
Evaluation for Imprinting on a Film
[0102] Sample 4 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 115.degree. C.), a
mold (pattern: pillar, diameter 1 .mu.m/depth 1 .mu.m) which was
preheated to a molding set temperature Tg+35.degree. C. (i.e.,
173.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 2000 N, it was held for 10 seconds
by that load. Thereafter, it was cooled to Tg-23.degree. C.
(115.degree. C.) while maintaining the displacement of the mold,
and after the completion of cooling, the mold was released from the
film at a speed of 10 .mu.m/second. It was observed through an
electronic microscope that a good pattern without the elongation
and flaking off was transferred.
Example 30
Evaluation for Imprinting on a Film
[0103] Sample 4 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 115.degree. C.), a
mold (pattern: pillar, diameter 0.5 .mu.m/depth 1 .mu.m) which was
preheated to a molding set temperature Tg+35.degree. C. (i.e.,
173.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 500 N, it was held for 10 seconds by
that load. Thereafter, it was cooled to Tg-23.degree. C.
(115.degree. C.) while maintaining the displacement of the mold,
and after the completion of cooling, the mold was released from the
film at a speed of 10 .mu.m/second. It was observed through an
electronic microscope that a good pattern without the elongation
and flaking off was transferred.
Example 31
Evaluation for Imprinting on a Film
[0104] Sample 4 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 115.degree. C.), a
mold (pattern: pillar, diameter 0.75 .mu.m/depth 1 .mu.m) which was
preheated to a molding set temperature Tg+35.degree. C. (i.e.,
173.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 500 N, it was held for 10 seconds by
that load. Thereafter, it was cooled to Tg-23.degree. C.
(115.degree. C.) while maintaining the displacement of the mold,
and after the completion of cooling, the mold was released from the
film at a speed of 10 .mu.m/second. It was observed through an
electronic microscope that a good pattern without the elongation
and flaking off was transferred.
Example 32
Evaluation for Imprinting on a Film
[0105] Sample 4 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 115.degree. C.), a
mold (pattern: pillar, diameter 0.5 .mu.m/depth 1 .mu.m) which was
preheated to a molding set temperature Tg+15.degree. C. (i.e.,
153.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 2000 N, it was held for 600 seconds
by that load. Thereafter, it was cooled to Tg-23.degree. C.
(115.degree. C.) while maintaining the displacement of the mold,
and after the completion of cooling, the mold was released from the
film at a speed of 10 .mu.m/second. It was observed through an
electronic microscope that a good pattern without the elongation
and flaking off was transferred.
Example 33
Evaluation for Imprinting on a Film
[0106] Sample 4 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 115.degree. C.), a
mold (pattern: pillar, diameter 0.75 .mu.m/depth 1 .mu.m) which was
preheated to a molding set temperature Tg+15.degree. C. (i.e.,
153.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 2000 N, it was held for 600 seconds
by that load. Thereafter, it was cooled to Tg-23.degree. C.
(115.degree. C.) while maintaining the displacement of the mold,
and after the completion of cooling, the mold was released from the
film at a speed of 10 .mu.m/second. It was observed through an
electronic microscope that a good pattern without the elongation
and flaking off was transferred.
Example 34
Evaluation for Imprinting on a Film
[0107] Sample 4 was fixed on a stainless plate which was heated to
a glass transition temperature Tg-5.degree. C. (i.e., 133.degree.
C.), a mold (pattern: pillar, diameter 0.5 .mu.m/depth 1 .mu.m)
which was preheated to a molding set temperature Tg+65.degree. C.
(i.e., 203.degree. C.) was pressed against the surface of the film
at a speed of 100 .mu.m/second, and when the load sensor attached
to the upper part of the mold reached 2000 N, it was held for 300
seconds by that load. Thereafter, it was cooled to Tg-5.degree. C.
(133.degree. C.) while maintaining the load, and after the
completion of cooling, the mold was released from the film at a
speed of 10 .mu.m/second. It was observed through an electronic
microscope that a good pattern without the elongation and flaking
off was transferred.
Example 35
Evaluation for Imprinting on a Film
[0108] Sample 4 was fixed on a stainless plate which was heated to
a glass transition temperature Tg-5.degree. C. (i.e., 133.degree.
C.), a mold (pattern: pillar, diameter 0.5 .mu.m/depth 1 .mu.m)
which was preheated to a molding set temperature Tg+65.degree. C.
(i.e., 203.degree. C.) was pressed against the surface of the film
at a speed of 100 .mu.m/second, and when the load sensor attached
to the upper part of the mold reached 1500 N, it was held for 300
seconds by that load. Thereafter, it was cooled to Tg-5.degree. C.
(133.degree. C.) while maintaining the load, and after the
completion of cooling, the mold was released from the film at a
speed of 10 .mu.m/second. It was observed through an electronic
microscope that a good pattern without the elongation and flaking
off was transferred.
Example 36
Evaluation for Imprinting on a Film
[0109] Sample 4 was fixed on a stainless plate which was heated to
a glass transition temperature Tg-5.degree. C. (i.e., 133.degree.
C.), a mold (pattern: pillar, diameter 0.5 .mu.m/depth 1 .mu.m)
which was preheated to a molding set temperature Tg+55.degree. C.
(i.e., 193.degree. C.) was pressed against the surface of the film
at a speed of 100 .mu.m/second, and when the load sensor attached
to the upper part of the mold reached 1750 N, it was held for 300
seconds by that load. Thereafter, it was cooled to Tg-5.degree. C.
(133.degree. C.) while maintaining the load, and after the
completion of cooling, the mold was released from the film at a
speed of 10 .mu.m/second. It was observed through an electronic
microscope that a good pattern without the elongation and flaking
off was transferred.
Example 37
Evaluation for Imprinting on a Film
[0110] Sample 4 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 115.degree. C.), a
mold (pattern: L/S=1 .mu.m/1 .mu.m) which was preheated to a
molding set temperature Tg+30.degree. C. (i.e., 168.degree. C.) was
pressed against the surface of the film at a speed of 100
.mu.m/second, and when the load sensor attached to the upper part
of the mold reached 2000 N, it was held for 10 seconds by that
load. Thereafter, it was cooled to Tg-23.degree. C. (I 15.degree.
C.) while maintaining the displacement of the mold, and after the
completion of cooling, the mold was released from the film at a
speed of 10 .mu.m/second. It was observed through an electronic
microscope that a good pattern without the elongation and flaking
off was transferred.
Example 38
Evaluation for Imprinting on a Film
[0111] Sample 4 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 115.degree. C.), a
mold (pattern: L/S=1 .mu.m/1 .mu.m) which was preheated to a
molding set temperature Tg+35.degree. C. (i.e., 173.degree. C.) was
pressed against the surface of the film at a speed of 100
.mu.m/second, and when the load sensor attached to the upper part
of the mold reached 500 N, it was held for 300 seconds by that
load. Thereafter, it was cooled to Tg-23.degree. C. (115.degree.
C.) while maintaining the displacement of the mold, and after the
completion of cooling, the mold was released from the film at a
speed of 10 .mu.m/second. It was observed through an electronic
microscope that a good pattern without the elongation and flaking
off was transferred.
Example 39
Evaluation for Imprinting on a Film
[0112] Sample 4 was fixed on a stainless plate which was heated to
a glass transition temperature Tg-5.degree. C. (i.e., 133.degree.
C.), a mold (pattern: L/S=1 .mu.m/1 .mu.m) which was preheated to a
molding set temperature Tg+65.degree. C. (i.e., 203.degree. C.) was
pressed against the surface of the film at a speed of 100
.mu.m/second, and when the load sensor attached to the upper part
of the mold reached 2000 N, it was held for 300 seconds by that
load. Thereafter, it was cooled to Tg-5.degree. C. (133.degree. C.)
while maintaining the load, and after the completion of cooling,
the mold was released from the film at a speed of 10 .mu.m/second.
It was observed through an electronic microscope that a good
pattern without the elongation and flaking off was transferred.
Example 40
Evaluation for Imprinting on a Film
[0113] Sample 4 was fixed on a stainless plate which was heated to
a glass transition temperature Tg-5.degree. C. (i.e., 133.degree.
C.), a mold (pattern: L/S=1 .mu.m/1 .mu.m) which was preheated to a
molding set temperature Tg+65.degree. C. (i.e., 203.degree. C.) was
pressed against the surface of the film at a speed of 100
.mu.m/second, and when the load sensor attached to the upper part
of the mold reached 1750 N, it was held for 300 seconds by that
load. Thereafter, it was cooled to Tg-5.degree. C. (133.degree. C.)
while maintaining the load, and after the completion of cooling,
the mold was released from the film at a speed of 10 .mu.m/second.
It was observed through an electronic microscope that a good
pattern without the elongation and flaking off was transferred.
Example 41
Evaluation for Imprinting on a Film
[0114] Sample 4 was fixed on a stainless plate which was heated to
a glass transition temperature Tg-5.degree. C. (i.e., 133.degree.
C.), a mold (pattern: L/S=1 .mu.m/1 .mu.m) which was preheated to a
molding set temperature Tg+55.degree. C. (i.e., 193.degree. C.) was
pressed against the surface of the film at a speed of 100
.mu.m/second, and when the load sensor attached to the upper part
of the mold reached 1500 N, it was held for 300 seconds by that
load. Thereafter, it was cooled to Tg-5.degree. C. (133.degree. C.)
while maintaining the load, and after the completion of cooling,
the mold was released from the film at a speed of 10 .mu.m/second.
It was observed through an electronic microscope that a good
pattern without the elongation and flaking off was transferred.
Example 42
Evaluation for Imprinting on a Film
[0115] Sample 4 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 115.degree. C.), a
mold (pattern: hole, diameter 1 .mu.m/depth 1 .mu.m) which was
preheated to a molding set temperature Tg+30.degree. C. (i.e.,
168.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 2000 N, it was held for 10 seconds
by that load. Thereafter, it was cooled to Tg-23.degree. C.
(115.degree. C.) while maintaining the displacement of the mold,
and after the completion of cooling, the mold was released from the
film at a speed of 10 .mu.m/second. It was observed through an
electronic microscope that a good pattern without the elongation
and flaking off was transferred.
Example 43
Evaluation for Imprinting on a Film
[0116] Sample 4 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 115.degree. C.), a
mold (pattern: hole, diameter 1 .mu.m/depth 1 .mu.m) which was
preheated to a molding set temperature Tg+35.degree. C. (i.e.,
173.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 750 N, it was held for 10 seconds by
that load. Thereafter, it was cooled to Tg-23.degree. C.
(115.degree. C.) while maintaining the displacement of the mold,
and after the completion of cooling, the mold was released from the
film at a speed of 10 .mu.m/second. It was observed through an
electronic microscope that a good pattern without the elongation
and flaking off was transferred.
Example 44
Evaluation for Imprinting on a Film
[0117] Sample 4 was fixed on a stainless plate which was heated to
a glass transition temperature Tg-5.degree. C. (i.e., 133.degree.
C.), a mold (pattern: hole, diameter 1 .mu.m/depth 1 .mu.m) which
was preheated to a molding set temperature Tg+65.degree. C. (i.e.,
203.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 2000 N, it was held for 300 seconds
by that load. Thereafter, it was cooled to Tg-5.degree. C.
(133.degree. C.) while maintaining the load, and after the
completion of cooling, the mold was released from the film at a
speed of 10 .mu.m/second. It was observed through an electronic
microscope that a good pattern without the elongation and flaking
off was transferred.
Example 45
Evaluation for Imprinting on a Film
[0118] Sample 4 was fixed on a stainless plate which was heated to
a glass transition temperature Tg-5.degree. C. (i.e., 133.degree.
C.), a mold (pattern: hole, diameter 1 .mu.m/depth 1 .mu.m) which
was preheated to a molding set temperature Tg+65.degree. C. (i.e.,
203.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 1500 N, it was held for 300 seconds
by that load. Thereafter, it was cooled to Tg-5.degree. C.
(133.degree. C.) while maintaining the load, and after the
completion of cooling, the mold was released from the film at a
speed of 10 .mu.m/second. It was observed through an electronic
microscope that a good pattern without the elongation and flaking
off was transferred.
Example 46
Evaluation for Imprinting on a Film
[0119] Sample 4 was fixed on a stainless plate which was heated to
a glass transition temperature Tg-5.degree. C. (i.e., 133.degree.
C.), a mold (pattern: hole, diameter 1 .mu.m/depth 1 .mu.m) which
was preheated to a molding set temperature Tg+55.degree. C. (i.e.,
193.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 1750 N, it was held for 300 seconds
by that load. Thereafter, it was cooled to Tg-5.degree. C.
(133.degree. C.) while maintaining the load, and after the
completion of cooling, the mold was released from the film at a
speed of 10 .mu.m/second. It was observed through an electronic
microscope that a good pattern without the elongation and flaking
off was transferred.
Example 47
Evaluation for Imprinting on a Film
[0120] Sample 5 was fixed on a stainless plate which was heated to
a glass transition temperature Tg-5.degree. C. (i.e., 131.degree.
C.), a mold (pattern: pillar, diameter 0.5 .mu.m/depth 1 .mu.m)
which was preheated to a molding set temperature Tg+65.degree. C.
(i.e., 201.degree. C.) was pressed against the surface of the film
at a speed of 100 .mu.m/second, and when the load sensor attached
to the upper part of the mold reached 2000 N, it was held for 300
seconds by that load. Thereafter, it was cooled to Tg-5.degree. C.
(131.degree. C.) while maintaining the load, and after the
completion of cooling, the mold was released from the film at a
speed of 10 .mu.m/second. It was observed through an electronic
microscope that a good pattern without the elongation and flaking
off was transferred.
Example 48
Evaluation for Imprinting on a Film
[0121] Sample 6 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 82.degree. C.), a
mold (pattern: pillar, diameter 1 .mu.m/depth 1 .mu.m) which was
preheated to a molding set temperature Tg+35.degree. C. (i.e.,
140.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 2000 N, it was held for 10 seconds
by that load. Thereafter, it was cooled to Tg-23.degree. C.
(82.degree. C.) while maintaining the displacement of the mold, and
after the completion of cooling, the mold was released from the
film at a speed of 10 .mu.m/second. It was observed through an
electronic microscope that a good pattern without the elongation
and flaking off was transferred.
Example 49
Evaluation for Imprinting on a Film
[0122] Sample 6 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 82.degree. C.), a
mold (pattern: pillar, diameter 1 .mu.m/depth 1 .mu.m) which was
preheated to a molding set temperature Tg+35.degree. C. (i.e.,
140.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 500 N, it was held for 10 seconds by
that load. Thereafter, it was cooled to Tg-23.degree. C.
(82.degree. C.) while maintaining the displacement of the mold, and
after the completion of cooling, the mold was released from the
film at a speed of 10 .mu.m/second. It was observed through an
electronic microscope that a good pattern without the elongation
and flaking off was transferred.
Example 50
Evaluation for Imprinting on a Film
[0123] Sample 6 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 82.degree. C.), a
mold (pattern: pillar, diameter 1 .mu.m/depth 1 .mu.m) which was
preheated to a molding set temperature Tg+15.degree. C. (i.e.,
120.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 2000 N, it was held for 600 seconds
by that load. Thereafter, it was cooled to Tg-23.degree. C.
(82.degree. C.) while maintaining the displacement of the mold, and
after the completion of cooling, the mold was released from the
film at a speed of 10 .mu.m/second. It was observed through an
electronic microscope that a good pattern without the elongation
and flaking off was transferred.
Example 51
Evaluation for Imprinting on a Film
[0124] Sample 6 was fixed on a stainless plate which was heated to
a glass transition temperature Tg-5.degree. C. (i.e., 100.degree.
C.), a mold (pattern: pillar, diameter 1 .mu.m/depth 1 .mu.m) which
was preheated to a molding set temperature Tg+55.degree. C. (i.e.,
160.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 1750 N, it was held for 300 seconds
by that load. Thereafter, it was cooled to Tg-5.degree. C.
(100.degree. C.) while maintaining the load, and after the
completion of cooling, the mold was released from the film at a
speed of 10 .mu.m/second. It was observed through an electronic
microscope that a good pattern without the elongation and flaking
off was transferred.
Example 52
Evaluation for Imprinting on a Film
[0125] Sample 6 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 82.degree. C.), a
mold (pattern: L/S=1 .mu.m/1 .mu.m) which was preheated to a
molding set temperature Tg+35.degree. C. (i.e., 140.degree. C.) was
pressed against the surface of the film at a speed of 100
.mu.m/second, and when the load sensor attached to the upper part
of the mold reached 2000 N, it was held for 10 seconds by that
load. Thereafter, it was cooled to Tg-23.degree. C. (82.degree. C.)
while maintaining the displacement of the mold, and after the
completion of cooling, the mold was released from the film at a
speed of 10 .mu.m/second. It was observed through an electronic
microscope that a good pattern without the elongation and flaking
off was transferred.
Example 53
Evaluation for Imprinting on a Film
[0126] Sample 6 was fixed on a plate which was heated to a glass
transition temperature Tg-5.degree. C. (i.e., 100.degree. C.), a
mold (pattern: US=1 .mu.m/1 .mu.m) which was preheated to a molding
set temperature Tg+55.degree. C. (i.e., 160.degree. C.) was pressed
against the surface of the film at a speed of 100 .mu.m/second, and
when the load sensor attached to the upper part of the mold reached
1750 N, it was held for 300 seconds by that load. Thereafter, it
was cooled to Tg-5.degree. C. (100.degree. C.) while maintaining
the displacement of the mold, and after the completion of cooling,
the mold was released from the film at a speed of 10 .mu.m/second.
It was observed through an electronic microscope that a good
pattern without the elongation and flaking off was transferred.
Example 54
Evaluation for Imprinting on a Film
[0127] Sample 6 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 82.degree. C.), a
mold (pattern: hole, diameter 1 .mu.m/depth 1 .mu.m) which was
preheated to a molding set temperature Tg+35.degree. C. (i.e.,
140.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 2000 N, it was held for 10 seconds
by that load. Thereafter, it was cooled to Tg-23.degree. C.
(82.degree. C.) while maintaining the displacement of the mold, and
after the completion of cooling, the mold was released from the
film at a speed of 10 .mu.m/second. It was observed through an
electronic microscope that a good pattern without the elongation
and flaking off was transferred.
Example 55
Evaluation for Imprinting on a Film
[0128] Sample 6 was fixed on a stainless plate which was heated to
a glass transition temperature Tg-5.degree. C. (i.e., 100.degree.
C.), a mold (pattern: hole, diameter 1 .mu.m/depth 1 .mu.m) which
was preheated to a molding set temperature Tg+55.degree. C. (i.e.,
160.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 1750 N, it was held for 300 seconds
by that load. Thereafter, it was cooled to Tg-5.degree. C.
(100.degree. C.) while maintaining the load, and after the
completion of cooling, the mold was released from the film at a
speed of 10 .mu.m/second. It was observed through an electronic
microscope that a good pattern without the elongation and flaking
off was transferred.
Example 56
Evaluation for Imprinting on a Film
[0129] Sample 7 was fixed on a plate which was heated to a glass
transition temperature Tg-15.degree. C. (i.e., 120.degree. C.), a
mold (pattern: pillar, diameter 1 .mu.m/depth 1 .mu.m) which was
preheated to a molding set temperature Tg+35.degree. C. (i.e.,
170.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 2000 N, it was held for 10 seconds
by that load. Thereafter, it was cooled to Tg-15.degree. C.
(120.degree. C.) while maintaining the displacement of the mold,
and after the completion of cooling, the mold was released from the
film at a speed of 10 .mu.m/second. It was observed through an
electronic microscope that a good pattern without the elongation
and flaking off was transferred.
Comparative Example 1
Evaluation for Imprinting on a Film
[0130] Sample 8 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 112.degree. C.), a
mold (pattern: pillar, diameter 0.5 .mu.m/depth 1 .mu.m) which was
preheated to a molding set temperature Tg+30.degree. C. (i.e.,
165.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 2000 N, it was held for 10 seconds
by that load. Thereafter, it was cooled to Tg-23.degree. C.
(112.degree. C.) while maintaining the displacement of the mold,
and after the completion of cooling, the mold was released from the
film at a speed of 10 .mu.m/second. It was observed through an
electronic microscope that the resin was elongated, so that the
pattern was no good.
Comparative Example 2
Evaluation for Imprinting on a Film
[0131] Sample 8 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 112.degree. C.), a
mold (pattern: pillar, diameter 0.75 .mu.m/depth 1 .mu.m) which was
preheated to a molding set temperature Tg+30.degree. C. (i.e.,
165.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 2000 N, it was held for 10 seconds
by that load. Thereafter, it was cooled to Tg-23.degree. C.
(112.degree. C.) while maintaining the displacement of the mold,
and after the completion of cooling, the mold was released from the
film at a speed of 10 .mu.m/second. It was observed through an
electronic microscope that the resin was elongated, so that the
pattern was no good.
Comparative Example 3
Evaluation for Imprinting on a Film
[0132] Sample 8 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 112.degree. C.), a
mold (pattern: pillar, diameter 1 .mu.m/depth 1 .mu.m) which was
preheated to a molding set temperature Tg+30.degree. C. (i.e.,
165.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 2000 N, it was held for 10 seconds
by that load. Thereafter, it was cooled to Tg-23.degree. C.
(112.degree. C.) while maintaining the displacement of the mold,
and after the completion of cooling, the mold was released from the
film at a speed of 10 .mu.m/second. It was observed through an
electronic microscope that the resin was elongated, so that the
pattern was no good.
Comparative Example 4
Evaluation for Imprinting on a Film
[0133] Sample 8 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 112.degree. C.), a
mold (pattern: pillar, diameter 0.5 .mu.m/depth 1 .mu.m) which was
preheated to a molding set temperature Tg+35.degree. C. (i.e.,
170.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 2000 N, it was held for 10 seconds
by that load. Thereafter, it was cooled to Tg-23.degree. C.
(112.degree. C.) while maintaining the displacement of the mold,
and after the completion of cooling, the mold was released from the
film at a speed of 10 .mu.m/second. It was observed through an
electronic microscope that the resin was elongated and flaked off,
so that the pattern was no good.
Comparative Example 5
Evaluation for Imprinting on a Film
[0134] Sample 8 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 112.degree. C.), a
mold (pattern: pillar, diameter 0.75 .mu.m/depth 1 .mu.m) which was
preheated to a molding set temperature Tg+35.degree. C. (i.e.,
170.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 2000 N, it was held for 10 seconds
by that load. Thereafter, it was cooled to Tg-23.degree. C.
(112.degree. C.) while maintaining the displacement of the mold,
and after the completion of cooling, the mold was released from the
film at a speed of 10 .mu.m/second. It was observed through an
electronic microscope that the resin was elongated, so that the
pattern was no good.
Comparative Example 6
Evaluation for Imprinting on a Film
[0135] Sample 8 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 112.degree. C.), a
mold (pattern: pillar, diameter 1 .mu.m/depth 1 .mu.m) which was
preheated to a molding set temperature Tg+35.degree. C. (i.e.,
170.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 2000 N, it was held for 10 seconds
by that load. Thereafter, it was cooled to Tg-23.degree. C.
(112.degree. C.) while maintaining the displacement of the mold,
and after the completion of cooling, the mold was released from the
film at a speed of 10 .mu.m/second. It was observed through an
electronic microscope that the resin was elongated, so that the
pattern was no good.
Comparative Example 7
Evaluation for Imprinting on a Film
[0136] Sample 8 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 112.degree. C.), a
mold (pattern: pillar, diameter 0.5 .mu.m/depth 1 .mu.m) which was
preheated to a molding set temperature Tg+35.degree. C. (i.e.,
170.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 500 N, it was held for 10 seconds by
that load. Thereafter, it was cooled to Tg-23.degree. C.
(112.degree. C.) while maintaining the displacement of the mold,
and after the completion of cooling, the mold was released from the
film at a speed of 10 .mu.m/second. It was observed through an
electronic microscope that the resin was elongated and flaked off,
so that the pattern was no good.
Comparative Example 8
Evaluation for Imprinting on a Film
[0137] Sample 8 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 112.degree. C.), a
mold (pattern: pillar, diameter 0.75 .mu.m/depth 1 .mu.m) which was
preheated to a molding set temperature Tg+35.degree. C. (i.e.,
170.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 500 N, it was held for 10 seconds by
that load. Thereafter, it was cooled to Tg-23.degree. C.
(112.degree. C.) while maintaining the displacement of the mold,
and after the completion of cooling, the mold was released from the
film at a speed of 10 .mu.m/second. It was observed through an
electronic microscope that the resin was elongated, so that the
pattern was no good.
Comparative Example 9
Evaluation for Imprinting on a Film
[0138] Sample 8 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 112.degree. C.), a
mold (pattern: pillar, diameter 0.5 .mu.m/depth 1 .mu.m) which was
preheated to a molding set temperature Tg+15.degree. C. (i.e.,
150.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 2000 N, it was held for 600 seconds
by that load. Thereafter, it was cooled to Tg-23.degree. C.
(112.degree. C.) while maintaining the displacement of the mold,
and after the completion of cooling, the mold was released from the
film at a speed of 10 .mu.m/second. It was observed through an
electronic microscope that the resin was elongated, so that the
pattern was no good.
Comparative Example 10
Evaluation for Imprinting on a Film
[0139] Sample 8 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 112.degree. C.), a
mold (pattern: pillar, diameter 0.75 .mu.m/depth 1 .mu.m) which was
preheated to a molding set temperature Tg+15.degree. C. (i.e.,
150.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 2000 N, it was held for 600 seconds
by that load. Thereafter, it was cooled to Tg-23.degree. C.
(112.degree. C.) while maintaining the displacement of the mold,
and after the completion of cooling, the mold was released from the
film at a speed of 10 .mu.m/second. It was observed through an
electronic microscope that the resin was elongated, so that the
pattern was no good.
Comparative Example 11
Evaluation for Imprinting on a Film
[0140] Sample 8 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 112.degree. C.), a
mold (pattern: L/S=1 .mu.m/1 .mu.m) which was preheated to a
molding set temperature Tg+30.degree. C. (i.e., 165.degree. C.) was
pressed against the surface of the film at a speed of 100
.mu.m/second, and when the load sensor attached to the upper part
of the mold reached 2000 N, it was held for 10 seconds by that
load. Thereafter, it was cooled to Tg-23.degree. C. (112.degree.
C.) while maintaining the displacement of the mold, and after the
completion of cooling, the mold was released from the film at a
speed of 10 .mu.m/second. It was observed through an electronic
microscope that the resin was elongated, so that the pattern was no
good.
Comparative Example 12
Evaluation for Imprinting on a Film
[0141] Sample 8 was fixed on a plate which was heated to a glass
transition temperature Tg-23.degree. C. (i.e., 112.degree. C.), a
mold (pattern: hole, diameter 1 .mu.m/depth 1 .mu.m) which was
preheated to a molding set temperature Tg+30.degree. C. (i.e.,
165.degree. C.) was pressed against the surface of the film at a
speed of 100 .mu.m/second, and when the load sensor attached to the
upper part of the mold reached 2000 N, it was held for 10 seconds
by that load. Thereafter, it was cooled to Tg-23.degree. C.
(112.degree. C.) while maintaining the displacement of the mold,
and after the completion of cooling, the mold was released from the
film at a speed of 10 .mu.m/second. It was observed through an
electronic microscope that the resin was elongated, so that the
pattern was no good.
Comparative Example 13
Evaluation for Imprinting on a Film
[0142] Sample 9 was fixed on a stainless plate which was heated to
a glass transition temperature Tg-5.degree. C. (i.e., 127.degree.
C.), a mold (pattern: pillar, diameter 0.5 .mu.m/depth 1 .mu.m)
which was preheated to a molding set temperature Tg+65.degree. C.
(i.e., 197.degree. C.) was pressed against the surface of the film
at a speed of 100 .mu.m/second, and when the load sensor attached
to the upper part of the mold reached 2000 N, it was held for 300
seconds by that load. Thereafter, it was cooled to Tg-5.degree. C.
(127.degree. C.) while maintaining the load, and after the
completion of cooling, the mold was released from the film at a
speed of 10 .mu.m/second. It was observed through an electronic
microscope that the resin was elongated and flaked off, so that the
pattern was no good.
Comparative Example 14
Evaluation for Imprinting on a Film
[0143] Sample 9 was fixed on a stainless plate which was heated to
a glass transition temperature Tg-5.degree. C. (i.e., 127.degree.
C), a mold (pattern: pillar, diameter 0.5 .mu.m/depth 1 .mu.m)
which was preheated to a molding set temperature Tg+65.degree. C.
(i.e., 197.degree. C.) was pressed against the surface of the film
at a speed of 100 .mu.m/second, and when the load sensor attached
to the upper part of the mold reached 1750 N, it was held for 300
seconds by that load. Thereafter, it was cooled to Tg-5.degree. C.
(127.degree. C.) while maintaining the load, and after the
completion of cooling, the mold was released from the film at a
speed of 10 .mu.m/second. It was observed through an electronic
microscope that the resin was elongated and flaked off, so that the
pattern was no good.
Comparative Example 15
Evaluation for Imprinting on a Film
[0144] Sample 9 was fixed on a stainless plate which was heated to
a glass transition temperature Tg-5.degree. C. (i.e., 127.degree.
C.), a mold (pattern: pillar, diameter 0.5 .mu.m/depth 1 .mu.m)
which was preheated to a molding set temperature Tg+65.degree. C.
(i.e., 197.degree. C.) was pressed against the surface of the film
at a speed of 100 .mu.m/second, and when the load sensor attached
to the upper part of the mold reached 1500 N, it was held for 300
seconds by that load. Thereafter, it was cooled to Tg-5.degree. C.
(127.degree. C.) while maintaining the load, and after the
completion of cooling, the mold was released from the film at a
speed of 10 .mu.m/second. It was observed through an electronic
microscope that the resin was elongated and flaked off, so that the
pattern was no good.
Comparative Example 16
Evaluation for Imprinting on a Film
[0145] Sample 9 was fixed on a stainless plate which was heated to
a glass transition temperature Tg-5.degree. C. (i.e., 127.degree.
C.), a mold (pattern: pillar, diameter 0.5 .mu.m/depth 1 .mu.m)
which was preheated to a molding set temperature Tg+55.degree. C.
(i.e., 187.degree. C.) was pressed against the surface of the film
at a speed of 100 .mu.m/second, and when the load sensor attached
to the upper part of the mold reached 1750 N, it was held for 300
seconds by that load. Thereafter, it was cooled to Tg-5.degree. C.
(127.degree. C.) while maintaining the load, and after the
completion of cooling, the mold was released from the film at a
speed of 10 .mu.m/second. It was observed through an electronic
microscope that the resin was elongated and flaked off, so that the
pattern was no good.
[0146] The above-mentioned results are summarized in Table 1.
TABLE-US-00001 TABLE 1 MOLD HOLD SAMPLE 1 SAMPLE 2 SAMPLE 3 SAMPLE
4 PATTERN SIZE TEMPERATURE LOAD TIME (Tg = 134.degree. C.) (Tg =
135.degree. C.) (Tg = 109.degree. C.) (Tg = 138.degree. C.) PILLAR
diameter 0.5 .mu.m/ Tg + 15 2000 N 600 s -- -- -- .largecircle.
depth 1 .mu.m (EXAMPLE 32) diameter 0.75 .mu.m/ -- -- --
.largecircle. depth 1 .mu.m (EXAMPLE 33) diameter 1 .mu.m/ -- -- --
-- depth 1 .mu.m diameter 0.5 .mu.m/ Tg + 30 10 s .largecircle. --
-- .largecircle. depth 1 .mu.m (EXAMPLE 1) (EXAMPLE 24) diameter
0.75 .mu.m/ .largecircle. -- -- .largecircle. depth 1 .mu.m
(EXAMPLE 2) (EXAMPLE 25) diameter 1 .mu.m/ .largecircle. -- --
.largecircle. depth 1 .mu.m (EXAMPLE 3) (EXAMPLE 26) diameter 0.5
.mu.m/ Tg + 35 500 N -- .largecircle. -- .largecircle. depth 1
.mu.m (EXAMPLE 12) (EXAMPLE 30) diameter 0.75 .mu.m/ --
.largecircle. -- .largecircle. depth 1 .mu.m (EXAMPLE 13) (EXAMPLE
31) diameter 1 .mu.m/ -- -- .largecircle. -- depth 1 .mu.m (EXAMPLE
20) diameter 0.5 .mu.m/ 2000 N -- .largecircle. -- .largecircle.
depth 1 .mu.m (EXAMPLE 9) (EXAMPLE 27) diameter 0.75 .mu.m/ --
.largecircle. -- .largecircle. depth 1 .mu.m (EXAMPLE 10) (EXAMPLE
28) diameter 1 .mu.m/ -- .largecircle. .largecircle. .largecircle.
depth 1 .mu.m (EXAMPLE 11) (EXAMPLE 19) (EXAMPLE 29) diameter 0.5
.mu.m/ Tg + 55 1750 N 300 s -- -- -- .largecircle. depth 1 .mu.m
(EXAMPLE 36) Tg + 65 1500 N -- -- -- .largecircle. (EXAMPLE 35)
1750 N -- -- -- -- 2000 N -- -- -- .largecircle. (EXAMPLE 34)
diameter 1 .mu.m/ 1500 N -- -- .largecircle. -- depth 1 .mu.m
(EXAMPLE 21) L/S 1 .mu.m/1 .mu.m Tg + 30 2000 N 10 s .largecircle.
-- -- .largecircle. (EXAMPLE 4) (EXAMPLE 37) Tg + 35 500 N
.largecircle. .largecircle. -- -- (EXAMPLE 5) (EXAMPLE 15) 300 s
.largecircle. .largecircle. -- .largecircle. (EXAMPLE 6) (EXAMPLE
16) (EXAMPLE 38) 2000 N 10 s -- .largecircle. -- -- (EXAMPLE 14) Tg
+ 55 1500 N 300 s -- -- -- .largecircle. (EXAMPLE 41) 1750 N -- --
-- -- Tg + 65 1500 N -- -- .largecircle. -- (EXAMPLE 22) 1750 N --
-- -- .largecircle. (EXAMPLE 40) 2000 N -- -- -- .largecircle.
(EXAMPLE 39) HOLE diameter 1 .mu.m/ Tg + 30 2000 N 10 s
.largecircle. -- -- .largecircle. depth 1 .mu.m (EXAMPLE 7)
(EXAMPLE 42) Tg + 35 500 N .largecircle. .largecircle. -- --
(EXAMPLE 8) (EXAMPLE 18) 750 N -- -- .largecircle. (EXAMPLE 43)
2000 N -- .largecircle. -- -- (EXAMPLE 17) Tg + 55 1750 N 300 s --
-- -- .largecircle. (EXAMPLE 46) Tg + 65 1500 N -- -- .largecircle.
.largecircle. (EXAMPLE 23) (EXAMPLE 45) 2000 N -- -- --
.largecircle. (EXAMPLE 44) MOLD SAMPLE 5 SAMPLE 6 SAMPLE 7 PATTERN
SIZE TEMPERATURE LOAD HOLD TIME (Tg = 136.degree. C.) (Tg =
105.degree. C.) (Tg = 135.degree. C.) PILLAR diameter 0.5 .mu.m/ Tg
+ 15 2000 N 600 s -- -- -- depth 1 .mu.m diameter 0.75 .mu.m/ -- --
-- depth 1 .mu.m diameter 1 .mu.m/ -- .largecircle. -- depth 1
.mu.m (EXAMPLE 50) diameter 0.5 .mu.m/ Tg + 30 10 s -- -- -- depth
1 .mu.m diameter 0.75 .mu.m/ -- -- -- depth 1 .mu.m diameter 1
.mu.m/ -- -- -- depth 1 .mu.m diameter 0.5 .mu.m/ Tg + 35 500 N --
-- -- depth 1 .mu.m diameter 0.75 .mu.m/ -- -- -- depth 1 .mu.m
diameter 1 .mu.m/ -- .largecircle. -- depth 1 .mu.m (EXAMPLE 49)
diameter 0.5 .mu.m/ 2000 N -- -- -- depth 1 .mu.m diameter 0.75
.mu.m/ -- -- -- depth 1 .mu.m diameter 1 .mu.m/ -- .largecircle.
.largecircle. depth 1 .mu.m (EXAMPLE 48) (EXAMPLE 56) diameter 0.5
.mu.m/ Tg + 55 1750 N 300 s -- .largecircle. -- depth 1 .mu.m
(EXAMPLE 51) Tg + 65 1500 N -- -- -- 1750 N -- -- -- 2000 N
.largecircle. -- -- (EXAMPLE 47) diameter 1 .mu.m/ 1500 N -- -- --
depth 1 .mu.m L/S 1 .mu.m/1 .mu.m Tg + 30 2000 N 10 s -- -- -- Tg +
35 500 N -- -- -- 300 s -- -- -- 2000 N 10 s -- .largecircle. --
(EXAMPLE 52) Tg + 55 1500 N 300 s -- -- -- 1750 N -- .largecircle.
-- (EXAMPLE 53) Tg + 65 1500 N -- -- -- 1750 N -- -- -- 2000 N --
-- -- HOLE diameter 1 .mu.m/ Tg + 30 2000 N 10 s -- -- -- depth 1
.mu.m Tg + 35 500 N -- -- -- 750 N -- -- -- 2000 N -- .largecircle.
-- (EXAMPLE 54) Tg + 55 1750 N 300 s -- .largecircle. -- (EXAMPLE
55) Tg + 65 1500 N -- -- -- 2000 N -- -- -- MOLD HOLD SAMPLE 8
SAMPLE 9 PATTERN SIZE TEMPERATURE LOAD TIME (Tg = 135.degree. C.)
(Tg = 132.degree. C.) PILLAR diameter 0.5 .mu.m/ Tg + 15 2000 N 600
s X -- depth 1 .mu.m (COMPARATIVE EXAMPLE 9) diameter 0.75 .mu.m/ X
-- depth 1 .mu.m (COMPARATIVE EXAMPLE 10) diameter 1 .mu.m/ -- --
depth 1 .mu.m diameter 0.5 .mu.m/ Tg + 30 10 s X -- depth 1 .mu.m
(COMPARATIVE EXAMPLE 1) diameter 0.75 .mu.m/ X -- depth 1 .mu.m
(COMPARATIVE EXAMPLE 2) diameter 1 .mu.m/ X -- depth 1 .mu.m
(COMPARATIVE EXAMPLE 3) diameter 0.5 .mu.m/ Tg + 35 500 N X --
depth 1 .mu.m (COMPARATIVE EXAMPLE 7) diameter 0.75 .mu.m/ X --
depth 1 .mu.m (COMPARATIVE) EXAMPLE 8) diameter 1 .mu.m/ -- --
depth 1 .mu.m diameter 0.5 .mu.m/ 2000 N X -- depth 1 .mu.m
(COMPARATIVE EXAMPLE 4) diameter 0.75 .mu.m/ X -- depth 1 .mu.m
(COMPARATIVE EXAMPLE 5) diameter 1 .mu.m/ X -- depth 1 .mu.m
(COMPARATIVE EXAMPLE 6) diameter 0.5 .mu.m/ Tg + 55 1750 N 300 s --
X depth 1 .mu.m (COMPARATIVE EXAMPLE 16) Tg + 65 1500 N -- X
(COMPARATIVE EXAMPLE 15) 1750 N -- X (COMPARATIVE EXAMPLE 14) 2000
N -- X (COMPARATIVE EXAMPLE 13) diameter 1 .mu.m/ 1500 N -- --
depth 1 .mu.m L/S 1 .mu.m/1 .mu.m Tg + 30 2000 N 10 s X --
(COMPARATIVE EXAMPLE 11) Tg + 35 500 N -- -- 300 s -- -- 2000 N 10
s -- -- Tg + 55 1500 N 300 s -- -- 1750 N -- -- Tg + 65 1500 N --
-- 1750 N -- -- 2000 N -- -- HOLE diameter 1 .mu.m/ Tg + 30 2000 N
10 s X -- depth 1 .mu.m (COMPARATIVE EXAMPLE 12) Tg + 35 500 N --
-- 750 N -- -- 2000 N -- -- Tg + 55 1750 N 300 s -- -- Tg + 65 1500
N -- -- 2000 N -- --
[0147] It becomes apparent from table 1 that the film manufactured
from a cyclic-olefin-based thermoplastic resin having a specific
correlation (indicated by equation 1) between a glass transition
temperature Tg (.degree. C.) and MFR at 260.degree. C. has a
superior thermal imprint characteristic at a low temperature and a
low pressure, and can provide a good transferred pattern.
Furthermore, it becomes apparent that the film manufactured from a
cyclic-olefin-based thermoplastic resin which does not have a
specific correlation (indicated by equation 1) between a glass
transition temperature Tg (.degree. C.) and MFR at 260.degree. C.
can't provide a good transferred pattern only because the film
formed a stretching or distortion of pattern.
* * * * *