U.S. patent application number 13/425098 was filed with the patent office on 2012-07-12 for photocurable composition and method for producing molded product with fine pattern.
This patent application is currently assigned to ASAHI GLASS COMPANY, LIMITED. Invention is credited to Yasuhide KAWAGUCHI, Kentaro Tsunozaki.
Application Number | 20120175821 13/425098 |
Document ID | / |
Family ID | 40156091 |
Filed Date | 2012-07-12 |
United States Patent
Application |
20120175821 |
Kind Code |
A1 |
KAWAGUCHI; Yasuhide ; et
al. |
July 12, 2012 |
PHOTOCURABLE COMPOSITION AND METHOD FOR PRODUCING MOLDED PRODUCT
WITH FINE PATTERN
Abstract
To provide a photocurable composition from which a cured product
excellent in mold release characteristics and mechanical strength
can be obtained, and a method for producing a molded product
excellent in durability, with a fine pattern having a reverse
pattern of a mold precisely transferred on its surface. A
photocurable composition 20 comprising from 15 to 60 mass % of a
compound (A) which is an aromatic compound having at least two
rings or an alicyclic compound having at least two rings and which
has two (meth)acryloyloxy groups, from 5 to 40 mass % of a compound
(B) having a fluorine atom and having at least one carbon-carbon
unsaturated double bond (excluding the compound (A)), from 10 to 55
mass % of a compound (C) having one (meth)acryloyloxy group
(excluding the compound (B)) and from 1 to 12 mass % of a
photopolymerization initiator (D) (provided that
(A)+(B)+(C)+(D)=100 mass %) is used.
Inventors: |
KAWAGUCHI; Yasuhide;
(Chiyoda-ku, JP) ; Tsunozaki; Kentaro;
(Chiyoda-ku, JP) |
Assignee: |
ASAHI GLASS COMPANY,
LIMITED
Chiyoda-ku
JP
|
Family ID: |
40156091 |
Appl. No.: |
13/425098 |
Filed: |
March 20, 2012 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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12542086 |
Aug 17, 2009 |
8163813 |
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13425098 |
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PCT/JP2008/052373 |
Feb 13, 2008 |
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12542086 |
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Current U.S.
Class: |
264/447 |
Current CPC
Class: |
G02B 5/1857 20130101;
G03F 7/0048 20130101; C08F 220/18 20130101; B82Y 10/00 20130101;
C08F 220/22 20130101; C08F 220/20 20130101; G02B 5/1852 20130101;
G03F 7/027 20130101; G03F 7/0002 20130101; G03F 7/033 20130101;
G03F 7/0046 20130101; C08F 220/22 20130101; B82Y 40/00 20130101;
C08F 220/22 20130101; C08F 220/18 20130101; C08F 222/1006 20130101;
C08F 220/18 20130101; C08F 222/1006 20130101 |
Class at
Publication: |
264/447 |
International
Class: |
B29C 59/16 20060101
B29C059/16 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 20, 2007 |
JP |
2007-162466 |
Claims
1-10. (canceled)
11. A method for producing a resist having a surface with a fine
pattern, which comprises: contacting a photocurable composition
with a surface of a mold having a pattern reverse of the fine
pattern, wherein the photocurable composition comprises: a compound
(A) which is an aromatic compound having at least two rings or an
alicyclic compound having at least two rings and which has two
(meth)acryloyloxy groups, a compound (B) having a fluorine atom and
having at least one carbon-carbon unsaturated double bond excluding
the compound (A), a compound (C) having one (meth)acryloyloxy group
excluding the compound (B) and a photopolymerization initiator (D),
wherein the amount of the compound (A) is from 15 to 60 mass %, the
amount of the compound (B) is from 5 to 40 mass %, the amount of
the compound (C) is from 10 to 55 mass %, and the amount of the
photopolymerization initiator (D) is from 1 to 12 mass % based on
the total amount 100 mass % of the compound (A), the compound (B),
the compound (C) and the photopolymerization initiator (D);
irradiating the photocurable composition with light while the
photocurable composition is in contact with the surface having the
pattern reverse to cure the photocurable composition and to thereby
obtain a cured product; and separating the mold from the cured
product to obtain the resist having the surface with the fine
pattern.
12. The method of claim 11, further comprising: disposing the
photocurable composition to the surface of a substrate; and
pressing the mold while the pattern reverse of the mold is in
contact with the photocurable composition; wherein the irradiating
is carried out while the photocurable composition is pressed with
the mold; and wherein during the separating at least one of the
mold and the substrate and the mold, is separated from the cured
product to obtain the resist having the surface with the fine
pattern.
13. The method of claim 11, further comprising: disposing the
photocurable composition to the surface of the mold having the
pattern reverse of the fine pattern; and pressing a substrate on
the photocurable composition while the photocurable composition is
in contact with the pattern reverse of the mold; wherein the
irradiating is carried out while the photocurable composition is
pressed with the substrate; and wherein during the separating at
least one of the mold and the substrate and the mold is separated
from the cured product to obtain the resist having the surface with
the fine pattern.
14. The method of claim 11, further comprising: bringing a
substrate and the surface of the mold having the pattern reverse of
the fine pattern close together or into contact with each other so
that the reverse pattern of the mold is on the substrate side; and
filling the photocurable composition between the substrate and the
mold; wherein the irradiating is carried out while the photocurable
composition is between the substrate and the mold and while the
substrate and the mold are close together or in contact with each
other; and wherein during the separating at least one of the mold
and the substrate and the mold is separated from the cured product
to obtain the resist having the surface with the fine pattern.
15. The method of claim 11, wherein the resist having the surface
with the fine pattern has a relative value dry etching resistance
of at most 0.6.
16. The method of claim 11, wherein the resist having the surface
with the fine pattern has a fine pattern with at least one of a
fine convex portion and a fine concave portion, and features having
at least one of a height, length and width from 1 nm to 10
.mu.m.
17. The method of claim 11, wherein the photocurable composition
contains substantially no solvent.
18. The method of claim 11, wherein the compound (A) is an
alicyclic compound having at least two rings and having two
(meth)acryloyloxy groups.
19. The method of claim 11, wherein the photocurable composition
further comprises a compound (E) having two (meth)acryloyloxy
groups, excluding the compounds (A) and (B), in an amount of from 5
to 30 parts by mass per 100 parts by mass of the total amount of
the compound (A), the compound (B), the compound (C) and the
photopolymerization initiator (D).
20. The method of claim 11, wherein the photocurable composition
further comprises a compound (F) having at least three
(meth)acryloyloxy groups, excluding the compound (B), in an amount
of from 5 to 90 parts by mass per 100 parts by mass of the total
amount of the compound (A), the compound (B), the compound (C) and
the photopolymerization initiator (D).
21. The method of claim 11, wherein the photocurable composition
further comprises a fluoropolymer (H) in an amount of from 5 to 25
parts by mass per 100 parts by mass of the total amount of the
compound (A), the compound (B), the compound (C) and the
photopolymerization initiator (D), and wherein the amount of the
compound (B) is from 0.5 to 100 times the total mass of the
fluoropolymer (H).
22. The method of claim 11, wherein the compound (A) is at least
one selected from the group consisting of ##STR00007##
23. The method of claim 11, wherein the compound (B) at least one
selected from the group consisting of
CH.sub.2.dbd.CHCOOCH.sub.2CH.sub.2(CF.sub.2).sub.6F and
CF.sub.2.dbd.CFCF.sub.2C(CF.sub.3)(OH)CH.sub.2CH.dbd.CH.sub.2.
24. The method of claim 11, wherein the compound (C) is at least
one selected from the group consisting of ##STR00008##
Description
TECHNICAL FIELD
[0001] The present invention relates to a photocurable composition
and a method for producing a molded product with a fine pattern on
its surface.
BACKGROUND ART
[0002] As a method of forming a fine pattern in a short time in
production of optical members, recording media, semiconductor
apparatus, etc., a method (a nanoimprint method) has been known of
pressing a mold having a pattern reverse of the fine pattern on its
surface on a photocurable composition disposed on the surface of a
substrate and irradiating the photocurable composition with light
to cure the photocurable composition thereby to form a fine pattern
on the surface of the substrate (Patent Documents 1 and 2).
[0003] However, in this method, since the cured product of the
photocurable composition is attached to the mold, it is difficult
to separate the cured product and the mold. Accordingly, it is
necessary to apply a mold release agent to the surface of the mold.
However, it will be difficult to precisely transfer the reverse
pattern of the mold due to the thickness of the mold release agent
itself, uneven coating of the mold release agent, etc.
[0004] As a photocurable composition from which a cured product
with fine mold release characteristics can be formed, the following
has been proposed.
[0005] (1) A photocurable composition comprising a fluorinated
monomer, a monomer containing no fluorine, a fluorinated surfactant
or a fluoropolymer, and a polymerization initiator (Patent Document
3).
[0006] However, a cured product of the photocurable composition (1)
contains a fluoromonomer and a fluorinated surfactant or a
fluoropolymer and thereby has low mechanical strength. In order to
obtain a molded product having a fine pattern in nanometer order,
durability with which the pattern shape is maintained is required.
Accordingly, a photocurable composition from which a cured product
with high mechanical strength can be obtained has been required.
Further, in production of semiconductor apparatus also, a resist is
required to have high dry etching resistance and in addition,
particularly for a fine pattern at the nano level, a photocurable
composition from which a cured product with high mechanical
strength to maintain the pattern shape can be obtained has been
required. [0007] Patent Document 1: U.S. Pat. No. 6,696,220 [0008]
Patent Document 2: JP-A-2004-071934 [0009] Patent Document 3:
WO2006/114958
DISCLOSURE OF THE INVENTION
Object to be Accomplished by the Invention
[0010] The object of the present invention is to provide a
photocurable composition from which a cured product excellent in
mold release characteristics and mechanical strength can be
obtained, and a method for producing a molded product excellent in
durability, with a fine pattern having a reverse pattern of a mold
precisely transferred on its surface.
Means to Accomplish the Object
[0011] The photocurable composition of the present invention is
characterized by comprising a compound (A) which is an aromatic
compound having at least two rings or an alicyclic compound having
at least two rings and which has two (meth)acryloyloxy groups, a
compound (B) having a fluorine atom and having at least one
carbon-carbon unsaturated double bond (excluding the compound (A)),
a compound (C) having one (meth)acryloyloxy group (excluding the
compound (B)) and a photopolymerization initiator (D), in amounts
of the compound (A) of from 15 to 60 mass %, the compound (B) of
from 5 to 40 mass %, the compound (C) of from 10 to 55 mass % and
the photopolymerization initiator (D) of from 1 to 12 mass % based
on the total amount (100 mass %) of the compound (A), the compound
(B), the compound (C) and the photopolymerization initiator
(D).
[0012] The photocurable composition of the present invention
preferably contains substantially no solvent.
[0013] The photocurable composition of the present invention
preferably further contains a compound (E) having two
(meth)acryloyloxy groups (excluding the compounds (A) and (B)) in
an amount of from 5 to 30 parts by mass per 100 parts by mass of
the total amount of the compound (A), the compound (B), the
compound (C) and the photopolymerization initiator (D).
[0014] The photocurable composition of the present invention
preferably further contains a compound (F) having at least three
(meth)acryloyloxy groups (excluding the compound (B)) in an amount
of from 5 to 90 parts by mass per 100 parts by mass of the total
amount of the compound (A), the compound (B), the compound (C) and
the photopolymerization initiator (D).
[0015] The photocurable composition of the present invention
preferably further contains a fluorinated surfactant (G) in an
amount of from 0.1 to 3 parts by mass per 100 parts by mass of the
total amount of the compound (A), the compound (B), the compound
(C) and the photopolymerization initiator (D), the amount of the
compound (B) being from 0.5 to 100 times the total mass of the
fluorinated surfactant (G).
[0016] The photocurable composition of the present invention
preferably further contains a fluoropolymer (H) in an amount of
from 5 to 25 parts by mass per 100 parts by mass of the total
amount of the compound (A), the compound (B), the compound (C) and
the photopolymerization initiator (D), the amount of the compound
(B) being from 0.5 to 100 times the total mass of the fluoropolymer
(H).
[0017] The method for producing a molded product with a fine
pattern on its surface of the present invention is characterized by
comprising a step of bringing the photocurable composition of the
present invention into contact with the surface with a pattern
reverse of the fine pattern of a mold having the reverse pattern
formed on its surface, a step of irradiating the photocurable
composition with light in a state where the photocurable
composition is in contact with the surface of the mold to cure the
photocurable composition thereby to obtain a cured product, and a
step of separating the mold from the cured product to obtain the
molded product with a fine pattern on its surface.
[0018] The method for producing a molded product with a fine
pattern on its surface of the present invention is characterized by
comprising a step of disposing the photocurable composition of the
present invention to the surface of a substrate, a step of pressing
a mold having a pattern reverse of the fine pattern on its surface
on the photocurable composition so that the reverse pattern of the
mold is in contact with the photocurable composition, a step of
irradiating the photocurable composition with light in a state
where the mold is pressed on the photocurable composition to cure
the photocurable composition thereby to obtain a cured product, and
a step of separating the mold, or the substrate and the mold, from
the cured product to obtain the molded product with a fine pattern
on its surface.
[0019] The method for producing a molded product with a fine
pattern on its surface of the present invention is characterized by
comprising a step of disposing the photocurable composition of the
present invention to the surface with a pattern reverse of the fine
pattern of a mold having the reverse pattern formed on its surface,
a step of pressing a substrate on the photocurable composition, a
step of irradiating the photocurable composition with light in a
state where the substrate is pressed on the photocurable
composition to cure the photocurable composition thereby to obtain
a cured product, and a step of separating the mold, or the
substrate and the mold, from the cured product to obtain the molded
product with a fine pattern on its surface.
[0020] The method for producing a molded product with a fine
pattern on its surface of the present invention is characterized by
comprising a step of bringing a substrate and a mold having a
pattern reverse of the fine patter on its surface into close to or
into contact with each other so that the reverse pattern of the
mold is on the substrate side, a step of filling the photocurable
composition of the present invention between the substrate and the
mold, a step of irradiating the photocurable composition with light
in a state where the substrate and the mold are close to or in
contact with each other to cure the photocurable composition
thereby to obtain a cured product, and a step of separating the
mold, or the substrate and the mold, from the cured product to
obtain the molded product with a fine pattern on its surface.
Effects of the Invention
[0021] According to photocurable composition of the present
invention, a cured product excellent in mold release
characteristics and mechanical strength can be obtained.
[0022] According to the method for producing a molded product with
a fine pattern on its surface, a molded product excellent in
durability, with a fine pattern having a reverse pattern of a mold
precisely transferred on its surface, can be produced.
BRIEF DESCRIPTION OF THE DRAWINGS
[0023] FIG. 1 is a cross section illustrating one example of the
method for producing a molded product with a fine pattern on its
surface.
[0024] FIG. 2 is a cross section illustrating another example of a
method for producing a molded product with a fine pattern on its
surface.
[0025] FIG. 3 is a cross section illustrating one example of a
molded product with a fine pattern on its surface.
[0026] FIG. 4 is a cross section illustrating another example of a
molded product with a fine pattern on its surface.
MEANINGS OF SYMBOLS
[0027] 10: mold [0028] 12: reverse pattern [0029] 20: photocurable
composition [0030] 30: substrate [0031] 40: molded product [0032]
42: cured product [0033] 44: fine pattern
BEST MODE FOR CARRYING OUT THE INVENTION
[0034] In the present specification, a compound represented by the
formula (A1) will be referred to as a compound (A1). The same
applies to compounds represented by other formulae. Further, in the
present specification, a (meth)acryloyloxy group means an
acryloyloxy group or a methacryloyloxy group. Further, in the
present specification, a (meth)acrylate means an acrylate or a
methacrylate.
(Photocurable Composition)
[0035] The photocurable composition of the present invention is a
composition comprising compound (A) to (C) and a
photopolymerization initiator (D) and as the case requires, further
containing a compound (E), a compound (F), a fluorinated surfactant
(G), a fluoropolymer (H) or other additives.
[0036] Compound (A): A compound which is an aromatic compound
having at least two rings or an alicyclic compound having at least
two rings and which has two (meth)acryloyloxy groups.
[0037] Compound (B): A compound having a fluorine atom and having
at least one carbon-carbon unsaturated double bond (excluding the
compound (A)).
[0038] Compound (C): A compound having one (meth)acryloyloxy group
(excluding the compound (B)).
[0039] Compound (E): A compound having two (meth)acryloyloxy groups
(excluding the compounds (A) and (B)).
[0040] Compound (F): A compound having at least three
(meth)acryloyloxy groups (excluding the compound (B)).
[0041] The viscosity of the photocurable composition of the present
invention at 25.degree. C. is preferably from 0.1 to 300 mPas,
particularly preferably from 1 to 200 mPas. When the viscosity of
the photocurable composition is within this range, the photocurable
composition and the surface with a reverse pattern of a mold can
easily be contacted without any special operation (for example, an
operation of heating the photocurable composition to high
temperature to make it have a low viscosity).
[0042] The photocurable composition of the present invention
preferably contains substantially no solvent. When the photocurable
composition contains substantially no solvent, curing of the
photocurable composition can easily be carried out without any
special operation excluding irradiation with light (for example, an
operation of heating the photocurable composition to high
temperature to remove the solvent).
[0043] The solvent is a compound other than the compounds (A) to
(C), the photopolymerization initiator (D), the compound (E), the
compound (F), the fluorinated surfactant (G), the fluoropolymer (H)
and other additives and is a compound capable of dissolving any of
the compounds (A) to (C), the photopolymerization initiator (D),
the compound (E), the compound (F), the fluorinated surfactant (G),
the fluoropolymer (H) and other additives.
[0044] Containing substantially no solvent means a case where no
solvent is contained at all, or a case where a solvent only in an
amount of preferably at most 1 mass %, particularly at most 0.7
mass % is contained in the photocurable composition (100 mass %).
Particularly in the present invention, the solvent used in
preparation of the photocurable composition may be contained as the
remaining solvent, but even in such a case, the remaining solvent
is preferably removed as far as possible, and its amount is
preferably at most 1 mass % in the photocurable composition (100
mass %).
(Compound (A))
[0045] The aromatic compound having at least two rings is a
compound having at least two benzene rings, and the at least two
benzene rings may form a condensed ring (e.g. a naphthalene ring or
an anthracene ring). The aromatic compound may, for example, be a
compound having a bisphenol skeleton, a compound having a
naphthalene skeleton or a compound having a fluorene skeleton.
[0046] The alicyclic compound having at least two rings is a
compound having at least two hydrocarbon rings with no aromaticity,
and may be a polycyclic compound having a bridge formed in one
ring. Such a polycyclic compound may, for example, be a compound
having a tricyclodecane skeleton containing an adamantane skeleton,
a compound having a decalin skeleton, a compound having a
norbornene skeleton or a compound having an isobornyl skeleton.
[0047] As the compound (A), the following compounds may be
mentioned.
[0048] Bisphenol (A) di(meth)acrylate, modified bisphenol (A)
di(meth)acrylate (e.g. ethoxylated bisphenol (A) di(meth)acrylate,
propoxylated bisphenol A di(meth)acrylate, propoxylated ethoxylated
bisphenol (A) di(meth)acrylate, bisphenol A glycerolate
di(meth)acrylate or bisphenol (A) propoxylate glycerolate
di(meth)acrylate), ethoxylated bisphenol F di(meth)acrylate,
tricyclodecanedimethanol di(meth)acrylate, fluorene
di(meth)acrylate, etc.
[0049] As the compound (A), in view of compatibility, particularly
preferred is tricyclodecanedimethanol di(meth)acrylate, modified
bisphenol A di(meth)acrylate (e.g. ethoxylated bisphenol A
di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate,
propoxylated ethoxylated bisphenol A di(meth)acrylate, bisphenol A
glycerolate di(meth)acrylate or bisphenol A propoxylate glycerolate
di(meth)acrylate) or ethoxylated bisphenol F di(meth)acrylate.
[0050] The compounds (A) may be used alone or in combination of two
or more.
[0051] The content of the compound (A) is from 15 to 60 mass %,
preferably from 20 to 45 mass % based on the total amount (100 mass
%) of the compound (A), the compound (B), the compound (C) and the
photopolymerization initiator (D). When the content of the compound
(A) is at least 15 mass %, a cured product excellent in mechanical
strength will be obtained. When the content of the compound (A) is
at most 60 mass %, a cured product will not be fragile.
(Compound (B))
[0052] The compound (B) may, for example, be a
fluoro(meth)acrylate, a fluorodiene, a fluorovinyl ether or a
fluorocyclic monomer, and in view of compatibility, preferred is a
fluoro(meth)acrylate or a fluorodiene.
[0053] As the fluoro(meth)acrylate, the following compounds may be
mentioned. [0054] 3-(Perfluoro-3-methylbutyl)-2-hydroxypropyl(meth)
acrylate, 2,2,2-trifluoro-1-(trifluoromethyl)ethyl(meth)acrylate,
[0055] CH.sub.2.dbd.CHCOO(CH.sub.2).sub.2(CF.sub.2).sub.10F, [0056]
CH.sub.2.dbd.CHCOO(CH.sub.2).sub.2(CF.sub.2).sub.8F, [0057]
CH.sub.2.dbd.CHCOO(CH.sub.2).sub.2(CF.sub.2).sub.6F, [0058]
CH.sub.2.dbd.C(CH.sub.3)COO(CH.sub.2).sub.2(CF.sub.2).sub.10F,
[0059]
CH.sub.2.dbd.C(CH.sub.3)COO(CH.sub.2).sub.2(CF.sub.2).sub.8F,
[0060]
CH.sub.2.dbd.C(CH.sub.3)COO(CH.sub.2).sub.2(CF.sub.2).sub.6F,
[0061] CH.sub.2.dbd.CHCOOCH.sub.2(CF.sub.2).sub.6F, [0062]
CH.sub.2.dbd.C(CH.sub.3)COOCH.sub.2(CF.sub.2).sub.6F, [0063]
CH.sub.2.dbd.CHCOOCH.sub.2(CF.sub.2).sub.7F, [0064]
CH.sub.2.dbd.C(CH.sub.3)COOCH.sub.2(CF.sub.2).sub.7F, [0065]
CH.sub.2.dbd.CHCOOCH.sub.2CF.sub.2CF.sub.2H, [0066]
CH.sub.2.dbd.CHCOOCH.sub.2(CF.sub.2CF.sub.2).sub.2H, [0067]
CH.sub.2.dbd.CHCOOCH.sub.2(CF.sub.2CF.sub.2).sub.4H, [0068]
CH.sub.2.dbd.C(CH.sub.3)COOCH.sub.2(CF.sub.2CF.sub.2)H, [0069]
CH.sub.2.dbd.C(CH.sub.3)COOCH.sub.2(CF.sub.2CF.sub.2).sub.2H,
[0070]
CH.sub.2.dbd.C(CH.sub.3)COOCH.sub.2(CF.sub.2CF.sub.2).sub.4H,
[0071]
CH.sub.2.dbd.CHCOOCH.sub.2CF.sub.2OCF.sub.2CF.sub.2OCF.sub.3,
[0072]
CH.sub.2.dbd.CHCOOCH.sub.2CF.sub.2O(CF.sub.2CF.sub.2O).sub.3CF.sub.3,
[0073]
CH.sub.2.dbd.C(CH.sub.3)COOCH.sub.2CF.sub.2OCF.sub.2CF.sub.2OCF.su-
b.3, [0074]
CH.sub.2.dbd.C(CH.sub.3)COOCH.sub.2CF.sub.2O(CF.sub.2CF.sub.2O).sub.3CF.s-
ub.3, [0075] CH.sub.2.dbd.CHCOOCH.sub.2CF(CF.sub.3)OCF.sub.2CF
(CF.sub.3)O(CF.sub.2).sub.3F, [0076]
CH.sub.2.dbd.CHCOOCH.sub.2CF(CF.sub.3)O(CF.sub.2CF(CF.sub.3)O).sub.2(CF.s-
ub.2).sub.3F, [0077]
CH.sub.2.dbd.C(CH.sub.3)COOCH.sub.2CF(CF.sub.3)OCF.sub.2CF(CF.sub.3)O(CF.-
sub.2).sub.3F, [0078]
CH.sub.2.dbd.C(CH.sub.3)COOCH.sub.2CF(CF.sub.3)O(CF.sub.2CF(CF.sub.3)O).s-
ub.2(CF.sub.2).sub.3F, [0079]
CH.sub.2.dbd.CFCOOCH.sub.2CH(OH)CH.sub.2(CF.sub.2).sub.6CF(CF.sub.3).sub.-
2, [0080]
CH.sub.2.dbd.CFCOOCH.sub.2CH(CH.sub.2OH)CH.sub.2(CF.sub.2).sub.6-
CF(CF.sub.3).sub.2, [0081]
CH.sub.2.dbd.CFCOOCH.sub.2CH(OH)CH.sub.2(CF.sub.2).sub.10F, [0082]
CH.sub.2.dbd.CFCOOCH.sub.2CH(CH.sub.2OH)CH.sub.2(CF.sub.2).sub.10F,
[0083]
CH.sub.2.dbd.CHCOOCH.sub.2CF.sub.2(OCF.sub.2CF.sub.2).sub.nOCF.sub-
.2CH.sub.2OCOCH.dbd.CH.sub.2 (where n is an integer of from 4 to
20), etc.
[0084] As the fluoro(meth)acrylate, in view of compatibility and
environmental characteristics, preferred is a compound (B1):
##STR00001##
wherein R.sup.1 is a hydrogen atom or a methyl group, each of
R.sup.2 and R.sup.3 is a hydrogen atom or a C.sub.1-4 alkyl group,
each of R.sup.4 and R.sup.5 is a fluorine atom, a C.sub.1-4
perfluoroalkyl group or a C.sub.1-4 perfluoroalkoxy group, R.sup.6
is a hydrogen atom or a fluorine atom, m is an integer of from 1 to
4, and n is an integer of from 1 to 16. n is preferably an integer
of from 1 to 10 in view of compatibility, more preferably an
integer of from 3 to 6 in view of environmental
characteristics.
[0085] As the fluorodiene, the following compounds may be
mentioned. [0086] CF.sub.2.dbd.CFOCF.sub.2CF.dbd.CF.sub.2, [0087]
CF.sub.2.dbd.CFOCF.sub.2CF.sub.2CF.dbd.CF.sub.2, [0088]
CF.sub.2.dbd.CFCF.sub.2CF.dbd.CF.sub.2, [0089]
CF.sub.2.dbd.CFCF.sub.2CH.dbd.CH.sub.2, [0090]
CF.sub.2.dbd.CFCF.sub.2C(CF.sub.3)(OH)CH.sub.2CH.dbd.CH.sub.2,
[0091] CF.sub.2.dbd.CFCF.sub.2C(CF.sub.3)(OH)CH.dbd.CH.sub.2,
[0092]
CF.sub.2.dbd.CFCH.sub.2CH(CH.sub.2C(CF.sub.3).sub.2OH)CH.sub.2CH.dbd.CH.s-
ub.2, etc.
[0093] As the fluorovinyl ether, the following compounds may be
mentioned. [0094] CF.sub.2.dbd.CFO(CF.sub.2).sub.3F, [0095]
CF.sub.2.dbd.CFO(CF.sub.2).sub.3COOCH.sub.3, etc.
[0096] As the fluorocyclic monomer, the following compounds may be
mentioned.
##STR00002##
[0097] The compounds (B) may be used alone or in combination of two
or more.
[0098] The content of the compound (B) is from 5 to 40 mass %,
preferably from 15 to 35 mass % based on the total amount (100 mass
%) of the compound (A), the compound (B), the compound (C) and the
photopolymerization initiator (D). When the content of the compound
(B) is at least 5 mass %, a cured product excellent in mold release
characteristics will be obtained, and foaming of the photocurable
composition will be suppressed. When the foaming of the
photocurable composition can be suppressed, filtration will easily
be carried out at the time of preparation, and defects of the
pattern shape due to inclusion of bubbles can be eliminated at the
time of nanoimprinting. When the content of the compound (B) is at
most 40 mass %, uniform mixing will be carried out, whereby a cured
product excellent in mechanical strength will be obtained.
(Compound (C))
[0099] The compound (C) is a component to dissolve other components
and is a component which improves compatibility between the
compound (A) and the compound (B). When the compound (A) and the
compound (B) are highly compatible with each other, preparation of
the photocurable composition will be easy since foaming at the time
of preparation of the photocurable composition will be suppressed,
whereby filtration through a filter will easily be carried out, and
further, a uniform photocurable composition will be obtained.
Further, a homogeneous cured product will be obtained, whereby
sufficient mold release characteristics and mechanical strength
will be obtained.
[0100] The viscosity of the compound (C) at 25.degree. C. is
preferably from 0.1 to 200 mPas. When the viscosity of the compound
(C) is within this range, the viscosity of the photocurable
composition will easily be adjusted to be low.
[0101] As the compound (C), the following compounds may be
mentioned.
[0102] Phenoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl
(meth)acrylate, phenoxyethylene glycol (meth)acrylate,
phenoxydiethylene glycol (meth)acrylate, benzyl (meth)acrylate,
methoxytriethylene glycol (meth)acrylate, methoxypolyethylene
glycol (meth)acrylate, 2-(meth)acryloyloxyethylhexahydrophthalic
acid, behenyl (meth)acrylate, 2-(meth)acryloyloxyethylsuccinic
acid, stearyl (meth)acrylate, isostearyl (meth)acrylate, lauryl
(meth)acrylate, 2-ethylhexyl (meth)acrylate,
3-(trimethoxysilyl)propyl (meth)acrylate, butyl (meth)acrylate,
ethoxyethyl (meth)acrylate, methoxyethyl (meth)acrylate, glycidyl
(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, allyl
(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl
(meth)acrylate, N,N-diethylaminoethyl (meth)acrylate,
N,N-dimethylaminoethyl (meth)acrylate, dimethylaminoethyl
(meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate,
2-ethyl-2-adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl
(meth)acrylate, 1-adamantyl (meth)acrylate, isobornyl
(meth)acrylate, .beta.-carboxyethyl (meth)acrylate, octyl
(meth)acrylate, decyl (meth)acrylate, 2-(tert-butylamino)ethyl
(meth)acrylate, 1,2,2,6,6-pentamethyl-4-piperidyl (meth)acrylate,
n-butyl (meth)acrylate, tert-butyl (meth)acrylate,
4-tert-butylcyclohexyl (meth)acrylate, etc.
[0103] The compounds (C) may be used alone or in combination of two
or more.
[0104] The content of the compound (C) is from 10 to 55 mass %,
preferably from 15 to 45 mass % based on the total amount (100 mass
%) of the compound (A), the compound (B), the compound (C) and the
photopolymerization initiator (D). When the content of the compound
(C) is at least 10 mass %, the viscosity of the photocurable
composition can be adjusted to be low, and the compound (A) and the
compound (B) will be highly compatible. When the content of the
compound (C) is at most 55 mass %, the sensitivity will be
favorable, and the crosslinking density will increase, whereby a
cured product excellent in mechanical strength will be
obtained.
(Photopolymerization Initiator (D))
[0105] The photopolymerization initiator (D) may, for example, be
an acetophenone photopolymerization initiator, a benzoin
photopolymerization initiator, a benzophenone photopolymerization
initiator, a thioxantone photopolymerization initiator, an
.alpha.-aminoketone photopolymerization initiator, an
.alpha.-hydroxyketone photopolymerization initiator, an
.alpha.-acyloxime ester,
benzyl-(o-ethoxycarbonyl)-.alpha.-monooxime, acylphosphine oxide,
glyoxyester, 3-ketocoumarin, 2-ethylanthraquinone, camphorquinone,
tetramethylthiuram sulfide, azobisisobutyronitrile, benzoyl
peroxide, dialkyl peroxide or tert-butyl peroxypivalate, and in
view of sensitivity and compatibility, preferred is an acetophenone
photopolymerization initiator, a benzoin photopolymerization
initiator, an .alpha.-aminoketone photopolymerization initiator or
a benzophenone photopolymerization initiator.
[0106] As the acetophenone photopolymerization initiator, the
following compounds may be mentioned.
[0107] Acetophenone, p-(tert-butyl)1',1',1'-trichloroacetophenone,
chloroacetophenone, 2',2'-diethoxyacetophenone,
hydroxyacetophenone, 2,2-dimethoxy-2'-phenylacetophenone,
2-aminoacetophenone, dialkylaminoacetophenone, etc.
[0108] As the benzoin photopolymerization initiator, the following
compounds may be mentioned.
[0109] Benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether,
benzoin isopropyl ether, benzoin isobutyl ether,
1-hydroxycyclohexyl phenyl ketone,
2-hydroxy-2-methyl-1-phenyl-2-methylpropan-1-one,
1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, benzyl
dimethyl ketal, etc.
[0110] As the .alpha.-aminoketone photopolymerization initiator,
the following compounds may be mentioned.
[0111]
2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-
-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, etc.
[0112] As the benzophenone photopolymerization initiator, the
following compounds may be mentioned.
[0113] Benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate,
methyl-o-benzoylbenzoate, 4-phenylbenzophenone,
hydroxybenzophenone, hydroxypropylbenzophenone, acrylbenzophenone,
4,4'-bis(dimethylamino)benzophenone, etc.
[0114] The photopolymerization initiators (D) may be used alone or
in combination of two or more.
[0115] The content of the photopolymerization initiator (D) is from
1 to 12 mass %, preferably from 4 to 10 mass % based on the total
amount (100 mass %) of the compound (A), the compound (B), the
compound (C) and the photopolymerization initiator (D). When the
content of the photopolymerization initiator (D) is at least 1 mass
%, a cured product will easily be obtained without an operation
such as heating. When the content of the photopolymerization
initiator (D) is at most 12 mass %, uniform mixing is possible,
whereby the amount of the photopolymerization initiator (D)
remaining in a cured product will be small, and accordingly a
decrease in physical properties of the cured product will be
suppressed.
(Compound (E))
[0116] The compound (E) is a component to dissolve other components
and to improve mechanical strength of a cured product. When the
compound (E) is a glycol compound, flexibility of the cured product
will improve in addition.
[0117] As the compound (E), the following compounds may be
mentioned.
[0118] Ethylene glycol di(meth)acrylate, dipropylene glycol
di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol
di(meth)acrylate, glycerol 1,3-diglycerolate di(meth)acrylate,
1,6-hexanediol ethoxylate di(meth)acrylate, 1,6-hexanediol
propoxylate di(meth)acrylate, 1,6-hexanediol di(meth)acrylate,
3-hydroxy-2,2-dimethylpropionate di(meth)acrylate, 1,9-nonanediol
di(meth)acrylate, 1,10-decanediol di(meth)acrylate, diethylene
glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate,
neopentyl glycol propoxylate di(meth)acrylate, polyethylene glycol
di(meth)acrylate, propylene glycol di(meth)acrylate, glycerol
di(meth)acrylate, propylene glycol glycerolate di(meth)acrylate,
polypropylene glycol di(meth)acrylate, polyoxyethylene glycol
di(meth)acrylate, tripropylene glycol di(meth)acrylate, triethylene
glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate,
tripropylene glycol glycerolate di(meth)acrylate,
2-hydroxy-3-acryloyloxypropyl (meth)acrylate,
2-methyl-1,3-propanediol diacrylate, trimethylolpropanebenzoate
di(meth)acrylate, pentaerythritol di(meth)acrylate monostearate,
trimethylolpropane ethoxylate methyl ether di(meth)acrylate,
diurethane di(meth)acrylate,
1,3-bis(3-methacryloyloxypropyl)-1,1,3,3-tetramethyldicyloxane,
etc.
[0119] The compounds (E) may be used alone or in combination of two
or more.
[0120] The content of the compound (E) is preferably from 5 to 30
parts by mass, more preferably from 10 to 25 parts by mass per 100
parts by mass of the total amount of the compound (A), the compound
(B), the compound (C) and the photopolymerization initiator (D).
When the content of the compound (E) is at least 5 parts by mass,
sensitivity of the photocurable composition will improve. When the
content of the compound (E) is at most 30 parts by mass,
compatibility of the respective components will be favorable.
(Compound (F))
[0121] The compound (F) is a component to improve mechanical
strength (hardness) of a cured product.
[0122] As the compound (F), the following compounds may be
mentioned.
[0123] Tri(meth)acrylate: trimethylolpropane tri(meth)acrylate,
trimethylolpropane ethoxy tri(meth)acrylate, polyether
tri(meth)acrylate, glycerol propoxy tri(meth)acrylate,
pentaerythritol tri(meth)acrylate, ethoxylated isocyanurate
triacrylate, ethoxylated trimethylolpropane triacrylate,
propoxylated trimethylolpropane triacrylate, etc.
[0124] Tetra(meth)acrylate: pentaerythritol tetra(meth)acrylate,
pentaerythritolethoxy tetra(meth)acrylate, ditrimethylolpropane
tetra(meth)acrylate, propoxylated pentaerythritol tetraacrylate,
etc.
[0125] Dipentaerythritol hexa(meth)acrylate, aromatic urethane
tri(meth)acrylate, aromatic urethane tetra(meth)acrylate, aromatic
urethane hexa(meth)acrylate, etc.
[0126] The compounds (F) may be used alone or in combination of two
or more.
[0127] The content of the compound (F) is preferably from 5 to 90
parts by mass, more preferably from 10 to 80 parts by mass per 100
parts by mass of the total amount of the compound (A), the compound
(B), the compound (C) and the photopolymerization initiator (D).
When the content of the compound (F) is at least 5 parts by mass,
mechanical strength of a cured product will improve. When the
content of the compound (F) is at most 90 parts by mass, the
viscosity of the photocurable composition can be suppressed
low.
[0128] The total amount of the compound (E) and the compound (F) is
preferably from 5 to 110 parts by mass, more preferably from 10 to
65 parts by mass per 100 parts by mass of the total amount of the
compound (A), the compound (B), the compound (C) and the
photopolymerization initiator (D).
(Fluorinated Surfactant (G))
[0129] The fluorinated surfactant (G) is a component to improve
mold release characteristics of a cured product.
[0130] The fluorinated surfactant (G) is preferably a fluorinated
surfactant having a fluorine content of from 10 to 70 mass %, more
preferably a fluorinated surfactant having a fluorine content of
from 10 to 40 mass %. The fluorinated surfactant may be water
soluble or oil soluble.
[0131] The fluorinated surfactant (G) is preferably an anionic
fluorinated surfactant, a cationic fluorinated surfactant, an
amphoteric fluorinated surfactant or a nonionic fluorinated
surfactant, more preferably a nonionic fluorinated surfactant in
view of compatibility in the photocurable composition and
dispersibility in the cured product.
[0132] The anionic fluorinated surfactant is preferably a
polyfluoroalkyl carboxylate, a polyfluoroalkyl phosphate or a
polyfluoroalkyl sulfonate.
[0133] Specific examples of the anionic fluorinated surfactant
include Surflon S-111 (tradename, manufactured by Seimi Chemical
Co., Ltd.), Fluorad FC-143 (tradename, manufactured by Sumitomo 3M
Limited) and MEGAFACE F-120 (tradename, manufactured by DAINIPPON
INK AND CHEMICALS, INCORPORATED).
[0134] The cationic fluorinated surfactant is preferably a
trimethylammonium salt of a polyfluoroalkyl carboxylate or a
trimethylammonium salt of a polyfluoroalkyl sulfonamide.
[0135] Specific examples of the cationic fluorinated surfactant
include Surflon S-121 (tradename, manufactured by Seimi Chemical
Co., Ltd.), Fluorad FX-134 (tradename, manufactured by Sumitomo 3M
Limited) and MEGAFACE F-150 (tradename, manufactured by DAINIPPON
INK AND CHEMICALS, INCORPORATED).
[0136] The amphoteric fluorinated surfactant is preferably
polyfluoroalkylbetain.
[0137] Specific examples of the amphoteric fluorinated surfactant
include Surflon S-132 (tradename, manufactured by Seimi Chemical
Co., Ltd.), Fluorad FX-172 (tradename, manufactured by Sumitomo 3M
Limited) and MEGAFACE F-120 (tradename, manufactured by DAINIPPON
INK AND CHEMICALS, INCORPORATED).
[0138] The nonionic fluorinated surfactant is preferably a
polyfluoroalkylamine oxide or a polyfluoroalkyl/alkylene oxide
addition product.
[0139] Specific examples of the nonionic fluorinated surfactant
include Surflon S-145 (tradename, manufactured by Seimi Chemical
Co., Ltd.), Surflon S-393 (tradename, manufactured by Seimi
Chemical Co., Ltd.), Surflon KH-20 (tradename, manufactured by
Seimi Chemical Co., Ltd.), Surflon KH-40 (tradename, manufactured
by Seimi Chemical Co., Ltd.), Fluorad FX-170 (tradename,
manufactured by Sumitomo 3M Limited), Fluorad FC-430 (tradename,
manufactured by Sumitomo 3M Limited) and MEGAFACE F-141 (tradename,
manufactured by DAINIPPON INK AND CHEMICALS, INCORPORATED).
[0140] The fluorinated surfactants (G) may be used alone or in
combination of two or more.
[0141] The content of the fluorinated surfactant (G) is preferably
from 0.1 to 3 parts by mass, more preferably from 0.5 to 1 part by
mass per 100 parts by mass of the total amount of the compound (A),
the compound (B), the compound (C) and the photopolymerization
initiator (D). When the content of the fluorinated surfactant (G)
is at least 0.1 part by mass, mold release characteristics will
improve. When the content of the fluorinated surfactant (G) is at
most 3 parts by mass, inhibition of curing of the photocurable
composition will be suppressed, and phase separation of a cured
product will be suppressed.
[0142] The amount of the compound (B) is preferably from 0.5 to 100
times, particularly preferably from 10 to 75 times the total mass
of the fluorinated surfactant (G). When the amount of the compound
(B) is within this range, mold release characteristics by the
compound (B) and the fluorinated surfactant (G) can synergistically
be obtained. If the amount of the compound (B) is less than 0.5
times, the components will not be uniformly compatible, thus
causing foaming. If the amount of the compound (B) exceeds 100
times, the effect of mold release characteristics by the
fluorinated surfactant (G) will not be obtained.
(Fluoropolymer (H))
[0143] The fluoropolymer (H) is a component to adjust the viscosity
of the photocurable composition.
[0144] The mass average molecular weight of the fluoropolymer (H)
is preferably from 500 to 2,000,000, more preferably from 1,000 to
1,000,000 particularly preferably from 3,000 to 500,000. When the
mass average molecular weight of the fluoropolymer (H) is within
this range, compatibility with other components will be
favorable.
[0145] The fluorine content of the fluoropolymer (H) is preferably
from 30 to 70 mass %, more preferably from 45 to 70 mass %. When
the fluorine content of the fluoropolymer (H) is within this range,
it will be uniformly dissolved in the photocurable composition,
whereby the viscosity of the photocurable composition will easily
be adjusted.
[0146] The fluoropolymer (H) is preferably a fluoropolymer having a
hetero atom, more preferably a fluoropolymer having a nitrogen
atom, an oxygen atom, a sulfur atom or a phosphorus atom,
furthermore preferably a fluoropolymer having a hydroxyl group, an
etheric oxygen atom, an ester group, an alkoxycarbonyl group, a
sulfonyl group, a phosphate group, an amino group, a nitro group or
a ketones group, and in view of compatibility, particularly
preferably a fluoropolymer having a hydroxyl group, an etheric
oxygen atom, an ester group or an alkoxycarbonyl group. The
fluoropolymer having a hetero atom has high compatibility with
other components, whereby a uniform photocurable composition will
easily be prepared.
[0147] As the fluoropolymer (H), the following fluoropolymers (H1)
to (H4) may be mentioned, and the fluoropolymer (H4) is preferred
in view of compatibility.
[0148] Fluoropolymer (H1): A fluoropolymer obtained by polymerizing
a compound (h1):
CF.sub.2.dbd.CR.sup.11-Q-CF.sup.12.dbd.CH.sub.2 (h1)
wherein each of R.sup.11 and R.sup.12 is a hydrogen atom, a
fluorine atom, a C.sub.1-3 alkyl group or a C.sub.1-3 fluoroalkyl
group, Q is an oxygen atom, --NR.sup.13-- or a bivalent organic
group which may have a functional group, and R.sup.13 is a hydrogen
atom, a C.sub.1-6 alkyl group, an alkylcarbonyl group or a tosyl
group.
[0149] Fluoropolymer (H2): A fluoropolymer having fluoroolefin
units and hydrocarbon monomer units.
[0150] As the fluoroolefin units, vinyl fluoride, vinylidene
fluoride, trifluoroethylene, tetrafluoroethylene,
pentafluoropropylene or hexafluoropropylene may, for example, be
mentioned. As the hydrocarbon monomer units, a vinyl ether, a vinyl
ester, an allyl ether, a hydrocarbon olefin, an acrylate or a
methacrylate may, for example, be mentioned.
[0151] Fluoropolymer (H3): A fluoropolymer having fluoroethylene
units and fluoro(meth)acrylate units.
[0152] As the fluoroethylene units, tetrafluoroethylene or
CF.sub.2.dbd.CFCl may, for example, be mentioned. As the
fluoro(meth)acrylate units, 2-(perfluorohexyl)ethyl methacrylate,
2-(perfluorohexyl)ethyl acrylate, 2-(perfluorooctyl)ethyl
methacrylate or 2-(perfluorooctyl)ethyl acrylate may, for example,
be mentioned.
[0153] Fluoropolymer (H4): A fluoropolymer having fluoroethylene
units and compound (h4) units:
CHR.sup.17.dbd.CH--O--R.sup.18 (h4)
wherein R.sup.17 is a hydrogen atom, a C.sub.1-4 alkyl group, a
phenyl group or a benzyl group, R.sup.18 is a C.sub.1-18 alkyl
group, an alkyl group or phenyl group having at most 10 carbon
atoms containing an aromatic ring, an alkyl group or phenyl group
having at most 10 carbon atoms containing a hydroxyl group, an
alkyl group or phenyl group having at most 10 carbon atoms
containing a fluorine atom, or an alkyl group or phenyl group
having at most 10 carbon atoms containing a carboxylic acid or an
ester group.
[0154] The fluoropolymers (H) may be used alone or in combination
of two or more.
[0155] The content of the fluoropolymer (H) is preferably from 5 to
25 parts by mass, more preferably from 7 to 20 parts by mass per
100 parts by mass of the total amount of the compound (A), the
compound (B), the compound (C) and the photopolymerization
initiator (D). When the content of the fluoropolymer (H) is at
least 5 parts by mass, an effect of adjusting the viscosity of the
photocurable composition will be obtained. When the content of the
fluoropolymer (H) is at most 25 parts by mass, inhibition of curing
of the photocurable composition will be suppressed, and phase
separation of the cured product will be suppressed.
[0156] The amount of the compound (B) based on the total mass of
the fluoropolymer (H) is preferably from 0.5 to 100 times,
particularly preferably from 2 to 50 times. When the amount of the
compound (B) is within this range, a uniform photocurable
composition will be obtained without phase separation. If the
amount of the compound (B) is less than 0.5 times, no effect of
mold release characteristics will be obtained. If the amount of the
compound (B) exceeds 100 times, phase separation will occur.
[0157] The total amount of the fluorinated surfactant (G) and the
fluoropolymer (H) is preferably from 0.1 to 35 parts by mass, more
preferably from 0.5 to 25 parts by mass per 100 parts by mass of
the total amount of the compound (A), the compound (B), the
compound (C) and the photopolymerization initiator (D).
[0158] The total amount of the compound (E), the compound (F), the
fluorinated surfactant (G) and the fluoropolymer (H) is preferably
from 0.1 to 125 parts by mass, more preferably from 0.5 to 85 parts
by mass per 100 parts by mass of the total amount of the compound
(A), the compound (B), the compound (C) and the photopolymerization
initiator (D).
(Other Additives)
[0159] The photocurable composition may contain other additives
excluding the compounds (A) to (C), the photopolymerization
initiator (D), the compound (E), the compound (F), the fluorinated
surfactant (G) and the fluoropolymer (H).
[0160] As other additives, a photosensitizer, another resin, fine
metal oxide particles, a carbon compound, fine metal particles or
another organic compound may, for example, be mentioned.
[0161] The photosensitizer may, for example, be an amine compound
such as n-butylamine, di-n-butylamine, tri-n-butylphosphine,
allylthiourea, s-benzylisothiuronium-p-toluene sulfinate,
triethylamine, diethylaminoethyl methacrylate, triethylenetetramine
or 4,4'-bis(dialkylamino)benzophenone.
[0162] Another resin may, for example, be a polyester, a polyester
oligomer, a polycarbonate or a poly(meth)acrylate.
[0163] The fine metal oxide particles may, for example, be titania
or silica.
[0164] The carbon compound may, for example, be carbon nanotubes or
fullerene.
[0165] The fine metal particles may, for example, be fine particles
of copper or platinum.
[0166] Another organic compound may, for example, be porphyrin or
metal-containing porphyrin.
[0167] The total amount of other additives is preferably at most 20
mass % in the photocurable composition (100 mass %). When the total
amount of other additives is at most 20 mass %, the photocurable
composition will be uniformly mixed, whereby a homogeneous
photocurable composition will be obtained.
[0168] From the above-described photocurable composition of the
present invention, which contains the compound (A), a cured product
excellent in mechanical strength can be obtained. Further, since it
contains the compound (B), a cured product excellent in mold
release characteristics can be obtained. Further, since it contains
the compound (C), compatibility between the compound (A) and the
compound (B) is excellent and as a result, mold release
characteristics and mechanical strength of the cured product will
further improve.
(Method for Producing Molded Product with Fine Pattern on its
Surface)
[0169] The method for producing a molded product with a fine
pattern on its surface of the present invention comprises the
following steps (1) to (3).
[0170] (1) A step of bringing the photocurable composition of the
present invention into contact with the surface with a pattern
reverse of a fine pattern of a mold having the reverse pattern
formed on its surface.
[0171] (2) A step of irradiating the photocurable composition with
light in a state where the photocurable composition is in contact
with the surface of the mold to cure the photocurable composition
thereby to obtain a cured product.
[0172] (3) A step of separating the mold from the cured product to
obtain a molded product with a fine pattern on its surface.
[0173] As the method for producing a molded product with a fine
pattern on its surface of the present invention, more specifically,
the following methods (a) to (c) may be mentioned.
Method (a):
[0174] A method comprising the following steps (a-1) to (a-4).
[0175] (a-1) A step of disposing a photocurable composition 20 to
the surface of a substrate 30 as shown in FIG. 1.
[0176] (a-2) A step of pressing a mold 10 on the photocurable
composition 20 so that a reverse pattern 12 of the mold 10 is in
contact with the photocurable composition 20 as shown in FIG.
1.
[0177] (a-3) A step of irradiating the photocurable composition 20
with light in a state where the mold 10 is pressed on the
photocurable composition 20 to cure the photocurable composition 20
thereby to obtain a cured produce.
[0178] (a-4) A step of separating the mold 10, or the substrate 30
and the mold 10, from the cured product to obtain a molded product
with a fine pattern on its surface.
Method (b):
[0179] A method comprising the following steps (b-1) to (b-4).
[0180] (b-1) A step of disposing a photocurable composition 20 to
the surface of a reverse pattern 12 of a mold 10 as shown in FIG.
2.
[0181] (b-2) A step of pressing a substrate 30 on the photocurable
composition 20 on the surface of the mold 10 as shown in FIG.
2.
[0182] (b-3) A step of irradiating the photocurable composition 20
with light in a state where the substrate 30 is pressed on the
photocurable composition 20 to cure the photocurable composition 20
thereby to obtain a cured product.
[0183] (b-4) A step of separating the mold 10, or the substrate 30
and the mold 10, from the cured product to obtain a molded product
with a fine pattern on its surface.
Method (c):
[0184] A method comprising the following steps (c-1) to (c-4).
[0185] (c-1) A step of bringing a substrate 30 and a mold 10 into
close to or into contact with each other so that a reverse pattern
12 of the mold 10 is on the substrate 30 side as shown in FIG.
1.
[0186] (c-2) A step of filling a photocurable composition 20
between the substrate 30 and the mold 10 as shown in FIG. 1.
[0187] (c-3) A step of irradiating the photocurable composition 20
with light in a state where the substrate 30 and mold 10 are close
to or in contact with each other to cure the photocurable
composition 20 thereby to obtain a cured product.
[0188] (c-4) A step of separating the mold 10, or the substrate 30
and the mold 10, from the cured product to obtain a molded product
with a fine pattern on its surface.
[0189] The substrate may be a substrate made of an inorganic
material or a substrate made of an organic material.
[0190] The inorganic material may, for example, be silicon wafer,
glass, quartz glass, a metal (such as aluminum, nickel or copper),
a metal oxide (such as alumina), silicon nitride, aluminum nitride
or lithium niobate.
[0191] The organic material may, for example, be a fluororesin, a
silicone resin, an acrylic resin, a polycarbonate, a polyester
(such as polyethylene terephthalate), a polyimide, a polypropylene,
a polyethylene, a nylon resin, a polyphenylene sulfide or a cyclic
polyolefin.
[0192] As the substrate, a surface-treated substrate may be used,
which is excellent in adhesion to the photocurable composition. The
surface treatment may, for example, be primer coating treatment,
ozone treatment or plasma etching treatment. The primer may, for
example, be a silane coupling agent or a silazane.
[0193] The mold may be a mold made of a non-translucent material or
a mold made of a translucent material.
[0194] The non-translucent material may, for example, be silicon
wafer, nickel, copper, stainless steel, titanium, SiC or mica.
[0195] The translucent material may, for example, be quartz, glass,
polydimethylsiloxane, a cyclic polyolefin, a polycarbonate, a
polyethylene terephthalate or a transparent fluororesin.
[0196] At least one of the substrate and the mold is made of a
material which is transparent to at least 40% of light having a
wavelength at which the photopolymerization initiator (D) acts.
[0197] The mold has a reverse pattern on its surface. The reverse
pattern is a reverse pattern corresponding to the fine pattern on
the surface of the molded product.
[0198] The reverse pattern has a fine convex portion and/or a
concave portion.
[0199] The convex portion may, for example, be a continuous convex
extending on the surface of the mold or protrusions dotted on the
surface.
[0200] The concave portion may, for example, be a continuous groove
extending on the surface of the mold or pores dotted on the
surface.
[0201] The shape of the convex or the groove may, for example, be a
straight line, a curve or a bent line. A plurality of convexes or
grooves may be present in parallel with each other to form
stripes.
[0202] The cross-sectional shape of the convex or the groove in a
direction at right angles to the longitudinal direction may, for
example, be rectangular, trapezoidal, triangular or
semi-circular.
[0203] The shape of the protrusions or the pores may be triangular
prism, quadrangular prism, hexagonal column, cylindrical column,
triangular pyramid, quadrangular pyramid, six-sided pyramid,
circular cone, hemisphere or polyhedron.
[0204] The width of the convex or the groove is preferably from 1
nm to 100 .mu.m on an average, more preferably from 10 nm to 10
.mu.m. The width of the convex means the length of the base in the
cross section in a direction at right angles to the longitudinal
direction. The width of the groove means the length of the upper
side in the cross section in a direction at right angles to the
longitudinal direction.
[0205] The width of the protrusions or the pores is preferably from
1 nm to 100 .mu.m on an average, more preferably from 10 nm to 10
.mu.m. The width of the protrusions means, in a case where the
bottom face is elongated, the length of the base in the cross
section in a direction at right angles to the longitudinal
direction, and in other cases, the maximum length at the bottom
face of the protrusions. The width of the pores means, in a case
where the opening is elongated, the length of the upper side in the
cross section in a direction at right angles to the longitudinal
direction, and in other cases, the maximum length at the opening of
the protrusions.
[0206] The height of the convex portion is preferably from 1 nm to
100 .mu.m on an average, more preferably from 10 nm to 10
.mu.m.
[0207] The depth of the concave portion is preferably from 1 nm to
100 .mu.m on an average, more preferably from 10 nm to 10
.mu.m.
[0208] In a region where the reverse pattern is present at high
density, the distance between adjacent convex portions (or concave
portions) is preferably from 1 nm to 500 .mu.m on an average, more
preferably from 1 nm to 50 .mu.m. The distance between adjacent
convex portions means a distance from the terminal of the base of
the cross section of a convex portion to the start point of the
base of the cross section of the adjacent convex portion. The
distance between adjacent concave portions means a distance between
the terminal of the upper side of the cross section of a concave
portion and the start point of the upper side of the cross section
of the adjacent concave portion.
[0209] The minimum dimension of the convex portion is preferably
from 1 nm to 50 .mu.m, more preferably from 1 nm to 500 nm,
particularly preferably from 1 nm to 50 nm. The minimum dimension
means the minimum dimension among the width, the length and the
height of the convex portion.
[0210] The minimum dimension of the concave portion is preferably
from 1 nm to 50 .mu.m, more preferably from 1 nm to 500 nm,
particularly preferably from 1 nm to 50 nm. The minimum dimension
means the minimum dimension among the width, the length and the
depth of the concave portion.
Step (a-1):
[0211] The method of disposing the photocurable composition may,
for example, be an ink jet method, a potting method, a spin coating
method, a roll coating method, a casting method, a dip coating
method, a die coating method, a Langmuir Blodgett method or a
vacuum vapor deposition method.
[0212] The photocurable composition may be disposed on the entire
surface of the substrate, or may be disposed on a part of the
substrate.
Step (a-2):
[0213] The pressing pressure (gauge pressure) at the time of
pressing the mold on the photocurable composition is preferably
higher than 0 and at most 10 MPa, more preferably from 0.1 to 5
MPa. The temperature at the time of pressing the mold on the
photocurable composition is preferably from 0 to 100.degree. C.,
more preferably from 10 to 60.degree. C.
Step (b-1):
[0214] The method of disposing the photocurable composition may,
for example, be an ink jet method, a potting method, a spin coating
method, a roll coating method, a casting method, a dip coating
method, a die coating method, a Langmuir Blodgett method or a
vacuum vapor deposition method.
[0215] The photocurable composition may be disposed on the entire
surface of the reverse pattern of the mold or may be disposed on a
part of the reverse pattern, and is preferably disposed on the
entire surface of the reverser pattern.
Step (b-2):
[0216] The pressing pressure (gauge pressure) at the time of
pressing the substrate on the photocurable composition is
preferably higher than 0 and at most 10 MPa, more preferably from
0.1 to 5 MPa. The temperature at the time of pressing the substrate
on the photocurable composition is preferably from 0 to 100.degree.
C., more preferably from 10 to 60.degree. C.
Step (c-2):
[0217] As a method of filling the photocurable composition between
the substrate and the mold, a method of sucking the photocurable
composition in the gap by a capillary action may be mentioned.
[0218] The temperature at the time of filling the photocurable
composition is preferably from 0 to 100.degree. C., more preferably
from 10 to 60.degree. C.
Steps (a-3), (b-3) and (c-3):
[0219] The light irradiation method may be a light irradiation
method using a mold made of a translucent material from the mold
side, or a light irradiation method using a substrate made of a
translucent material from the substrate side. The wavelength of
light is preferably from 200 to 500 nm. At the time of light
irradiation, the photocurable composition may be heated to
accelerate curing.
[0220] The temperature at the time of light irradiation is
preferably from 0 to 100.degree. C., more preferably from 10 to
60.degree. C.
Steps (a-4), (b-4) and (c-4):
[0221] The temperature at the time of separating the mold, or the
substrate and the mold, from the cured product is preferably from 0
to 100.degree. C., more preferably from 10 to 60.degree. C.
[0222] When the substrate and the mold are separated from the cured
product, as shown in FIG. 3, a molded product 40 with a fine
pattern 44 on its surface consisting only of a cured product 42
with a surface having the reverse pattern of the mold transferred,
is obtained.
[0223] When only the mold is separated from the cured product, as
shown in FIG. 4, a molded product 40 (laminate) with a fine pattern
44 on its surface, comprising a cured product 42 with a surface
having the reverse pattern of the mold transferred and a substrate
30, is obtained.
[0224] As a molded product with a fine pattern on its surface, the
following articles may be mentioned.
[0225] Optical elements: A microlens array, an optical waveguide
element, an optical switching element (such as a grid polarizing
element or a wave plate), a fresnel zone plate element, a binary
optical element, a blaze optical element, a photonics crystal,
etc.
[0226] Anti-reflection components: AR (anti reflection) coating
member, etc.
[0227] Chips: Biochips, chips for .mu.-TAS (micro-total analysis
systems), microreactor chips, etc.
[0228] Others: A recording medium, a display material, a carrier
for a catalyst, a filter, a sensor component, a resist to be used
for production of a semiconductor apparatus, a daughter mold for
nanoimprinting, etc.
[0229] When it is used as a resist, a fine pattern can be formed on
a substrate by etching the substrate using the molded product with
a fine pattern as a mask.
[0230] In the above-described method for producing a molded product
with a fine pattern on its surface of the present invention, since
the photocurable composition of the present invention from which a
cured product excellent in mold release characteristics and
mechanical strength can be obtained is used, a molded product
excellent in durability, with a fine pattern having a reverse
pattern of a mold precisely transferred on its surface, can be
produced.
EXAMPLES
[0231] Now, the present invention will be described in further
detail with reference to Examples, but the present invention is by
no means restricted to such specific Examples.
[0232] Examples 1 to 10 and 19 to 27 are Examples, and Examples 11
to 18 are Comparative Examples.
(Mass Average Molecular Weight)
[0233] The mass averse molecular weight of the fluoropolymer (H)
was measured by using a GPC analyzer (manufactured by TOSOH
CORPORATION, HLC-8220).
(Viscosity)
[0234] The viscosity of the photocurable composition at 25.degree.
C. was measured by using a viscometer (manufactured by Toki Sangyo
Co., Ltd.). The viscometer is one calibrated with a standard fluid
(JS50 (33.17 mPaS at 25.degree. C.)). The viscosity was judged to
be favorable when it was at most 300 mPaS.
(Sensitivity)
[0235] The sensitivity of the photocurable composition was
determined as follows.
[0236] The photocurable composition was formed into a film with a
thickness of about 1.5 .mu.m by a spin coating method, and the
coating film was irradiated with light from a high pressure mercury
lamp (a light source having dominant wavelengths at 255, 315 and
365 nm at from 1.5 to 2.0 kHz) to determine the accumulated
quantity of light until complete curing, which was regarded as the
sensitivity. Whether the photocurable composition was completely
cured was judged by measuring an IR spectrum and from the presence
or absence of absorption of an olefin at the acrylic moiety. The
sensitivity was judged to be favorable with a value of at most 500
mJ/cm.sup.2.
(Volume Shrinkage Ratio)
[0237] The volume shrinkage ratio was determined as follows.
[0238] The photocurable composition was sealed in a test tube (made
of glass) to a height of L1 at 25.degree. C., the photocurable
composition was irradiated with light from a high pressure mercury
lamp (a light source having dominant wavelengths at 255, 315 and
365 nm at from 1.5 to 2.0 kHz) for 15 seconds, and the height L2 of
the obtained cured product was measured. The volume shrinkage ratio
was determined from the following formula. The volume shrinkage
ratio was judged to be favorable when it was at most 15%.
Volume shrinkage ratio(%)=(L1-L2)/L1.times.100
(Contact Angle)
[0239] The contact angle of the cured product against water was
measured as follows.
[0240] The photocurable composition was irradiated with light from
a high pressure mercury lamp (a light source having dominant
wavelengths at 255, 315 and 365 nm at from 1.5 to 2.0 kHz) for 15
seconds to obtain a cured product.
[0241] With respect to the cured product, 4 .mu.L of water was
dropped on the surface of the cured product for measurement by
using a contact angle meter (manufactured by Kyowa Interface
Science Co., Ltd., model CA-X150).
[0242] The contact angle is a measure of mold release
characteristics of the cured product. The contact angle was judged
to be favorable when it was at least 75.degree..
(Pencil Hardness)
[0243] The pencil hardness of the cured product was measured as
follows.
[0244] The photocurable composition was irradiated with light from
a high pressure mercury lamp (a light source having dominant
wavelengths at 255, 315 and 365 nm at from 1.5 to 2.0 kHz) for 15
seconds to obtain a cured produce.
[0245] The pencil hardness of the cured product was determined in
accordance with JIS K5400 (old JIS) under a load of 1 kg.
[0246] The pencil hardness is a measure of mechanical strength of
the cured product. The pencil hardness was judged to be favorable
when the result was F or higher.
(Dry Etching Resistance)
[0247] The dry etching resistance was determined as follows.
[0248] The photocurable composition was applied to a substrate
(silicon wafer), and then the photocurable composition was
irradiated with light from a high pressure mercury lamp (a light
source having dominant wavelengths at 255, 315 and 365 nm at from
1.5 to 2.0 kHz) for 15 seconds to obtain a cured product. The
substrate on which the cured product was formed and a substrate to
which polymethyl methacrylate (hereinafter referred to as PMMA) was
applied were prepared, and etching treatment was carried out
simultaneously using RIE-10NR (manufactured by SAMCO) under
conditions of CF.sub.4/O.sub.2 (40/10 sccm) under a pressure of 5
Pa at an output of 70 W for 120 seconds. The etching rate were
calculated from differences in thickness as between before and
after the etching treatment, and the relative etching rate of the
cured product when the etching rate of PMMA was 1, was determined,
which was regarded as the drying etching resistance. The dry
etching resistance was judged to be favorable when the relative
value was at most 0.6.
##STR00003##
wherein each of q and r is an integer of from 1 to 3.
##STR00004##
(Photopolymerization Initiator (D1))
[0249] Photopolymerization initiator (D1): Tradename: IRGACURE 651,
manufactured by Ciba Geigy Specialty
##STR00005##
(Fluorinated Surfactant (G1))
[0250] Fluorinated surfactant (G1): Nonionic fluorinated
surfactant, tradename: Surflon S-393, manufactured by Seimi
Chemical Co., Ltd.
(Fluoropolymer (H11))
[0251] 9.00 g of the compound (B2) and 38.37 g of 1,4-dioxane were
charged in a pressure reactor (internal capacity: 50 mL, made of
glass), and then 0.71 g of diisopropyl peroxydicarbonate was
charged. The reactor was freeze deaerated, and then the internal
temperature was maintained at 40.degree. C., followed by
polymerization for 18 hours. Then, the content in the reactor was
dropped in hexane. The agglomerated solid content was recovered and
vacuum dried at 110.degree. C. for 40 hours to obtain 6.33 g of a
white powdery amorphous fluoropolymer having the following
repeating units (fluorine content: 56.3 mass %) (hereinafter
referred to as a fluoropolymer (H11)). The fluoropolymer (H11) had
a glass transition temperature of 118.degree. C., a number average
molecular weight of 2,600 and a mass average molecular weight of
4,800:
##STR00006##
[0252] Fluoropolymer (H41): Tradename: LUMIFLON LF710, manufactured
by Asahi Glass Company, Limited, mass average molecular weight:
40,000.
Example 1
[0253] In a vial (internal capacity: 6 mL), 1.52 g of the compound
(A1), 0.88 g of the compound (B11) and 1.44 g of the compound (C1)
were added, then 0.16 g of the photopolymerization initiator (D1)
was mixed, and the mixture was subjected to filtration through a
0.2 .mu.m filter made of polyethylene terephthalate (hereinafter
referred to as PTFE) to obtain a photocurable composition. The
composition of the photocurable is composition is shown in Table 1,
and the evaluation results are shown in Table 2.
Example 2
[0254] In a vial (internal capacity: 6 mL), 1.52 g of the compound
(A2), 0.88 g of the compound (B11) and 1.44 g of the compound (C1)
were added, then 0.16 g of the photopolymerization initiator (D1)
was mixed, and the mixture was subjected to filtration through a
0.2 .mu.m filter made of PTFE to obtain a photocurable composition.
The composition of the photocurable composition is shown in Table
1, and the evaluation results are shown in Table 2.
Example 3
[0255] In a vial (internal capacity: 6 mL), 1.52 g of the compound
(A3), 0.88 g of the compound (B11) and 1.44 g of the compound (C1)
were added, then 0.16 g of the photopolymerization initiator (D1)
was mixed, and the mixture was subjected to filtration through a
0.2 .mu.m filter made of PTFE to obtain a photocurable composition.
The composition of the photocurable composition is shown in Table
1, and the evaluation results are shown in Table 2.
Example 4
[0256] In a vial (internal capacity: 6 mL), 1.52 g of the compound
(A2), 0.88 g of the compound (B2) and 1.44 g of the compound (C1)
were added, then 0.16 g of the photopolymerization initiator (D1)
was mixed, and the mixture was subjected to filtration through a
0.2 .mu.m filter made of PTFE to obtain a photocurable composition.
The composition of the photocurable composition is shown in Table
1, and the evaluation results are shown in Table 2.
Example 5
[0257] In a vial (internal capacity: 6 mL), 1.52 g of the compound
(A2), 0.88 g of the compound (B11) and 1.44 g of the compound (C2)
were added, then 0.16 g of the photopolymerization initiator (D1)
was mixed, and the mixture was subjected to filtration through a
0.2 .mu.m filter made of PTFE to obtain a photocurable composition.
The composition of the photocurable composition is shown in Table
1, and the evaluation results are shown in Table 2.
Example 6
[0258] In a vial (internal capacity: 6 mL), 1.32 g of the compound
(A2), 0.80 g of the compound (B11), 1.32 g of the compound (C1) and
0.40 g of the compound (E1) were added, then 0.16 g of the
photopolymerization initiator (D1) was mixed, and the mixture was
subjected to filtration through a 0.2 .mu.m filter made of PTFE to
obtain a photocurable composition. The composition of the
photocurable composition is shown in Table 1, and the evaluation
results are shown in Table 2.
Example 7
[0259] In a vial (internal capacity: 6 mL), 1.20 g of the compound
(A2), 0.80 g of the compound (B11), 1.20 g of the compound (C1),
0.32 g of the compound (E1) and 0.32 g of the compound (F1) were
added, then 0.16 g of the photopolymerization initiator (D1) was
mixed, and the mixture was subjected to filtration through a 0.2
.mu.m filter made of PTFE to obtain a photocurable composition. The
composition of the photocurable composition is shown in Table 1,
and the evaluation results are shown in Table 2.
Example 8
[0260] In a vial (internal capacity: 6 mL), 1.20 g of the compound
(A2), 0.80 g of the compound (B11), 1.20 g of the compound (C1),
0.28 g of the compound (E1), 0.28 g of the compound (F1) and 0.08 g
of the fluorinated surfactant (G1) were added, then 0.16 g of the
photopolymerization initiator (D1) was mixed, and the mixture was
subjected to filtration through a 0.2 .mu.m filter made of PTFE to
obtain a photocurable composition. The composition of the
photocurable composition is shown in Table 1, and the evaluation
results are shown in Table 2.
Example 9
[0261] In a vial (internal capacity: 6 mL), 1.20 g of the compound
(A2), 0.80 g of the compound (B11), 1.20 g of the compound (C1),
0.28 g of the compound (E1), 0.08 g of the fluorinated surfactant
(G1) and 0.28 g of the fluoropolymer (H11) were added, then 0.16 g
of the photopolymerization initiator (D1) was mixed, and the
mixture was subjected to filtration through a 0.2 .mu.m filter made
of PTFE to obtain a photocurable composition. The composition of
the photocurable composition is shown in Table 1, and the
evaluation results are shown in Table 2.
Example 10
[0262] In a vial (internal capacity: 6 mL), 1.20 g of the compound
(A2), 0.80 g of the compound (B11), 1.20 g of the compound (C1),
0.28 g of the compound (E1), 0.08 g of the fluorinated surfactant
(G1) and 0.28 g of the fluoropolymer (H41) were added, then 0.16 g
of the photopolymerization initiator (D1) was mixed, and the
mixture was subjected to filtration through a 0.2 .mu.m filter made
of PTFE to obtain a photocurable composition. The composition of
the photocurable composition is shown in Table 1, and the
evaluation results are shown in Table 2.
Example 11
[0263] In a vial (internal capacity: 6 mL), 0.28 g of the compound
(A1), 1.56 g of the compound (B11) and 0.20 g of the compound (C1)
were added, then 0.16 g of the photopolymerization initiator (D1)
was mixed, and the mixture was subjected to filtration through a
0.2 .mu.m filter made of PTFE to obtain a photocurable composition.
The composition of the photocurable composition is shown in Table
1, and the evaluation results are shown in Table 2.
Example 12
[0264] In a vial (internal capacity: 6 mL), 3.00 g of the compound
(A1), 0.40 g of the compound (B11) and 0.44 g of the compound (C1)
were added, then 0.16 g of the photopolymerization initiator (D1)
was mixed, and the mixture was subjected to filtration through a
0.2 .mu.m filter made of PTFE to obtain a photocurable composition.
However, the cured product was hard and fragile and was difficult
to handle as a self-supporting membrane. The composition of the
photocurable composition is shown in Table 1, and the evaluation
results are shown in Table 2.
Example 13
[0265] In a vial (internal capacity: 6 mL), 1.84 g of the compound
(A1), 0.12 g of the compound (B11) and 1.88 g of the compound (C1)
were added, then 0.16 g of the photopolymerization initiator (D1)
was mixed, and the mixture was subjected to filtration through a
0.2 .mu.m filter made of PTFE to obtain a photocurable composition.
The composition of the photocurable composition is shown in Table
1, and the evaluation results are shown in Table 2.
Example 14
[0266] In a vial (internal capacity: 6 mL), 0.80 g of the compound
(A1), 2.20 g of the compound (B11) and 0.84 g of the compound (C1)
were added, and then 0.16 g of the photopolymerization initiator
(D1) was mixed, but they were not uniformly mixed, and phase
separation occurred. The composition of the obtained composition is
shown in Table 1.
Example 15
[0267] In a vial (internal capacity: 6 mL), 1.96 g of the compound
(A1), 1.60 g of the compound (B11) and 0.28 g of the compound (C1)
were added, and then 0.16 g of the photopolymerization initiator
(D1) was mixed, but they were not uniformly mixed, and phase
separation occurred. The composition of the obtained composition is
shown in Table 1.
Example 16
[0268] In a vial (internal capacity: 6 mL), 0.60 g of the compound
(A1), 0.24 g of the compound (B11) and 3.00 g of the compound (C1)
were added, then 0.16 g of the photopolymerization initiator (D1)
was mixed, and the mixture was subjected to filtration through a
0.2 .mu.m filter made of PTFE to obtain a photocurable composition.
However, the cured product was fragile and was difficult to handle
as a self-supporting membrane. The composition of the photocurable
composition is shown in Table 1, and the evaluation results are
shown in Table 2.
Example 17
[0269] In a vial (internal capacity: 6 mL), 1.60 g of the compound
(A1), 0.96 g of the compound (B11) and 1.42 g of the compound (C1)
were added, then 0.02 g of the photopolymerization initiator (D1)
was mixed, and the mixture was subjected to filtration through a
0.2 .mu.m filter made of PTFE to obtain a photocurable composition.
However, even after light irradiation, the amount of an uncured
portion was large, and no cured product could be obtained. The
composition of the obtained composition is shown in Table 1, and
the evaluation results are shown in Table 2.
Example 18
[0270] In a vial (internal capacity: 6 mL), 1.20 g of the compound
(A1), 0.72 g of the compound (B11) and 1.28 g of the compound (C1)
were added, and then 0.80 g of the photopolymerization initiator
(D1) was mixed, but the photopolymerization initiator (D1) was not
completely dissolved, whereby no uniform composition could be
obtained. The composition of the obtained composition is shown in
Table 1.
Example 19
[0271] In a vial (internal capacity: 6 mL), 1.44 g of the compound
(A1), 0.88 g of the compound (B11), 1.44 g of the compound (C1) and
0.08 g of the compound (E1) were added, then 0.16 g of the
photopolymerization initiator (D1) was mixed, and the mixture was
subjected to filtration through a 0.2 .mu.m filter made of PTFE to
obtain a photocurable composition. The composition of the
photocurable composition is shown in Table 1, and the evaluation
results are shown in Table 2.
Example 20
[0272] In a vial (internal capacity: 6 mL), 1.08 g of the compound
(A1), 0.56 g of the compound (B11), 1.20 g of the compound (C1) and
1.00 g of the compound (E1) were added, then 0.16 g of the
photopolymerization initiator (D1) was mixed, and the mixture was
subjected to filtration through a 0.2 .mu.m filter made of PTFE to
obtain a photocurable composition. The composition of the
photocurable composition is shown in Table 1, and the evaluation
results are shown in Table 2.
Example 21
[0273] In a vial (internal capacity: 6 mL), 1.32 g of the compound
(A2), 0.88 g of the compound (B11), 1.40 g of the compound (C1),
0.20 g of the compound (E1) and 0.04 g of Compound (F1) were added,
then 0.16 g of the photopolymerization initiator (D1) was mixed,
and the mixture was subjected to filtration through a 0.2 .mu.m
filter made of PTFE to obtain a photocurable composition. The
composition of the photocurable composition is shown in Table 1,
and the evaluation results are shown in Table 2.
Example 22
[0274] In a vial (internal capacity: 6 mL), 0.64 g of the compound
(A2), 0.40 g of the compound (B11), 0.72 g of the compound (C1),
0.26 g of the compound (E1) and 1.82 g of the Compound (F1) were
added, then 0.16 g of the photopolymerization initiator (D1) was
mixed, and the mixture was subjected to filtration through a 0.2
.mu.m filter made of PTFE to obtain a photocurable composition. The
composition of the photocurable composition is shown in Table 1,
and the evaluation results are shown in Table 2.
Example 23
[0275] In a vial (internal capacity: 6 mL), 1.20 g of the compound
(A2), 0.20 g of the compound (B11), 1.24 g of the compound (C1),
0.80 g of the compound (E1), 0.40 g of the compound (F1) and 0.002
g of the fluorinated surfactant (G1) were added, then 0.16 g of the
photopolymerization initiator (D1) was mixed, and the mixture was
subjected to filtration through a 0.2 .mu.m filter made of PTFE to
obtain a photocurable composition. The composition of the
photocurable composition is shown in Table 1, and the evaluation
results are shown in Table 2.
Example 24
[0276] In a vial (internal capacity: 6 mL), 1.08 g of the compound
(A2), 0.88 g of the compound (B11), 1.08 g of the compound (C1),
0.68 g of the compound (E1) and 0.12 g of the fluorinated
surfactant (G1) were added, then 0.16 g of the photopolymerization
initiator (D1) was mixed, and the mixture was subjected to
filtration through a 0.2 .mu.m filter made of PTFE to obtain a
photocurable composition. The composition of the photocurable
composition is shown in Table 1, and the evaluation results are
shown in Table 2.
Example 25
[0277] In a vial (internal capacity: 6 mL), 1.28 g of the compound
(A2), 0.80 g of the compound (B11), 1.28 g of the compound (C1),
0.280 g of the compound (E1), 0.08 g of the fluorinated surfactant
(G1) and 0.12 g of the fluoropolymer (H11) were added, then 0.16 g
of the photopolymerization initiator (D1) was mixed, and the
mixture was subjected to filtration through a 0.2 .mu.m filter made
of PTFE to obtain a photocurable composition. The composition of
the photocurable composition is shown in Table 1, and the
evaluation results are shown in Table 2.
Example 26
[0278] In a vial (internal capacity: 6 mL), 0.96 g of the compound
(A2), 0.68 g of the compound (B11), 1.00 g of the compound (C1),
0.20 g of the compound (E1), 0.08 g of the fluorinated surfactant
(G1) and 0.84 g of the fluoropolymer (H11) were added, then 0.24 g
of the photopolymerization initiator (D1) was mixed, and the
mixture was subjected to filtration through a 0.2 .mu.m filter made
of PTFE to obtain a photocurable composition. The composition of
the photocurable composition is shown in Table 1, and the
evaluation results are shown in Table 2.
TABLE-US-00001 TABLE 1 Mass % based on 100 mass % of (A) + (B) +
(C) + (D) (A) (B) (C) (D) Example 1 38.0 22.0 36.0 4.0 Example 2
38.0 22.0 36.0 4.0 Example 3 38.0 22.0 36.0 4.0 Example 4 38.0 22.0
36.0 4.0 Example 5 38.0 22.0 36.0 4.0 Example 6 36.7 22.2 36.7 4.4
Example 7 35.7 23.8 35.7 4.8 Example 8 35.7 23.8 35.7 4.8 Example 9
35.7 23.8 35.7 4.8 Example 10 35.7 23.8 35.7 4.8 Example 11 7.0
39.0 50.0 4.0 Example 12 65.0 16.0 15.0 4.0 Example 13 45.9 3.0
47.1 4.0 Example 14 20.0 55.0 21.0 4.0 Example 15 49.0 40.0 7.0 4.0
Example 16 15.0 6.0 75.0 4.0 Example 17 40.0 24.0 35.5 0.5 Example
18 35.0 18.0 32.0 15.0 Example 19 36.7 22.4 36.7 4.1 Example 20
36.0 18.7 40.0 5.3 Example 21 35.1 23.4 37.2 4.3 Example 22 33.3
20.8 37.5 8.3 Example 23 42.8 7.2 44.3 5.7 Example 24 33.8 27.5
33.8 5.0 Example 25 36.4 22.7 36.4 4.5 Example 26 33.3 23.6 34.7
8.3 Parts by mass per 100 parts by mass of (A) + (B) + (C) + (D)
(E) (F) (G) (H) Example 1 -- -- -- -- Example 2 -- -- -- -- Example
3 -- -- -- -- Example 4 -- -- -- -- Example 5 -- -- -- -- Example 6
11.1 -- -- -- Example 7 9.5 9.5 -- -- Example 8 8.3 8.3 2.4 --
Example 9 8.3 -- 2.4 8.3 Example 10 8.3 -- 2.4 8.3 Example 11 -- --
-- -- Example 12 -- -- -- -- Example 13 -- -- -- -- Example 14 --
-- -- -- Example 15 -- -- -- -- Example 16 -- -- -- -- Example 17
-- -- -- -- Example 18 -- -- -- -- Example 19 2.0 -- -- -- Example
20 33.3 -- -- -- Example 21 5.3 1.1 -- -- Example 22 13.5 94.8 --
-- Example 23 28.6 14.3 0.071 -- Example 24 21.3 -- 3.8 -- Example
25 8.0 -- 2.3 3.4 Example 26 6.9 -- 2.8 29.2
TABLE-US-00002 TABLE 2 Dry etching Volume resistance Viscosity
Sensitivity shrinkage Contact Pencil (relative rate (mPa s)
(mJ/cm.sup.2) ratio (%) angle (.degree.) hardness when PMMA = 1)
Ex. 1 80 441 9 78 H 0.5 Ex. 2 41 315 10 79 H 0.5 Ex. 3 32 315 9 85
H 0.6 Ex. 4 37 315 12 82 H 0.5 Ex. 5 35 315 10 79 H 0.6 Ex. 6 40
284 9 80 H 0.5 Ex. 7 66 284 9 80 2H 0.4 Ex. 8 62 284 9 97 2H 0.4
Ex. 9 109 284 8 93 H 0.5 Ex. 10 116 284 7 91 H 0.5 Ex. 11 22 567 13
79 4B 0.9 Ex. 12 76 252 11 77 -- -- Ex. 13 45 378 12 69 H 0.4 Ex.
14 -- -- -- -- -- -- Ex. 15 -- -- -- -- -- -- Ex. 16 15 1260 22 71
-- -- Ex. 17 45 Uncured -- -- -- -- Ex. 18 -- -- -- -- -- -- Ex. 19
39 315 10 77 H 0.5 Ex. 20 37 252 13 76 F 0.6 Ex. 21 40 284 9 79 H
0.5 Ex. 22 215 284 14 78 4H 0.3 Ex. 23 72 252 9 75 2H 0.4 Ex. 24 35
315 9 91 F 0.5 Ex. 25 82 284 9 97 H 0.5 Ex. 26 298 378 7 93 F
0.6
Example 27
[0279] At 25.degree. C., one drop of the photocurable composition
in Example 2 was dropped on a silicon wafer, to obtain a silicon
wafer uniformly coated with the composition. A quartz mold having a
concave portion with a width of 800 nm, a depth of 180 nm and a
length of 10 .mu.m on its surface was pressed on the photocurable
composition on the silicon wafer and then pressed under 0.5 MPa
(gauge pressure) as it was.
[0280] Then, at 25.degree. C., the photocurable composition was
irradiated with light from a high pressure mercury lamp (a light
source having dominant wavelengths at 255, 315 and 365 nm at from
1.5 to 2.0 kHz) for 15 seconds from the mold side to obtain a cured
product of the photocurable composition. At 25.degree. C., the mold
was separated from the silicon wafer to obtain a molded product
comprising a cured product having a convex portion reverse of the
concave portion of the mold on its surface, formed on the surface
of the silicon wafer. The height from the bottom face of the convex
portion to the top face was from 178 to 180 nm.
INDUSTRIAL APPLICABILITY
[0281] A molded product with a fine pattern on its surface
obtainable by the production method of the present invention is
useful as an optical element, an anti-reflection component,
biochips, microreactor chips, a recording medium, a carrier for a
catalyst, a replica mold for production, a resist, etc.
[0282] The entire disclosure of Japanese Patent Application No.
2007-162466 filed on Jun. 20, 2007 including specification, claims,
drawings and summary is incorporated herein by reference in its
entirety.
* * * * *