U.S. patent application number 17/178474 was filed with the patent office on 2021-07-08 for curable composition and cured product obtained by curing the same.
This patent application is currently assigned to ENEOS CORPORATION. The applicant listed for this patent is ENEOS CORPORATION. Invention is credited to Atsushi KAMEYAMA, Takashi SEKI, Hisashi SONE, Shohei TAKATA, Ryuichi UENO.
Application Number | 20210206916 17/178474 |
Document ID | / |
Family ID | 1000005450883 |
Filed Date | 2021-07-08 |
United States Patent
Application |
20210206916 |
Kind Code |
A1 |
KAMEYAMA; Atsushi ; et
al. |
July 8, 2021 |
CURABLE COMPOSITION AND CURED PRODUCT OBTAINED BY CURING THE
SAME
Abstract
The present invention discloses a curable composition
comprising: an epoxy compound represented by the following Formula
(1); and one selected from the group consisting of: a thermal
cationic polymerization initiator, an acid anhydride-based curing
agent and a curing accelerator, and a photo-cationic polymerization
initiator as well as the cured product therefrom. The above
described curable composition is useful in that it allows for the
production of a cured product having a high heat resistance.
##STR00001## (In the Formula (1), A represents CR.sup.17R.sup.18; B
represents CR.sup.19R.sup.20; R.sup.1 to R.sup.20 each
independently represents a substituent selected from the group
consisting of a hydrogen atom, an alkyl group and an alkoxy group;
and n represents 0 or 1, with the proviso that when n is 0, m
represents 1, and when n is 1, m represents 0.)
Inventors: |
KAMEYAMA; Atsushi; (Tokyo,
JP) ; UENO; Ryuichi; (Tokyo, JP) ; SONE;
Hisashi; (Tokyo, JP) ; TAKATA; Shohei; (Tokyo,
JP) ; SEKI; Takashi; (Tokyo, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ENEOS CORPORATION |
Tokyo |
|
JP |
|
|
Assignee: |
ENEOS CORPORATION
Tokyo
JP
|
Family ID: |
1000005450883 |
Appl. No.: |
17/178474 |
Filed: |
February 18, 2021 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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16086101 |
Sep 18, 2018 |
10961345 |
|
|
PCT/JP2017/011465 |
Mar 22, 2017 |
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17178474 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08G 65/2603
20130101 |
International
Class: |
C08G 65/26 20060101
C08G065/26 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 23, 2016 |
JP |
2016-059069 |
Mar 23, 2016 |
JP |
2016-059079 |
Mar 29, 2016 |
JP |
2016-066376 |
Mar 29, 2016 |
JP |
2016-066399 |
May 30, 2016 |
JP |
2016-107736 |
Sep 27, 2016 |
JP |
2016-188872 |
Sep 27, 2016 |
JP |
2016-188873 |
Sep 27, 2016 |
JP |
2016-188874 |
Sep 27, 2016 |
JP |
2016-188876 |
Sep 27, 2016 |
JP |
2016-188879 |
Claims
1-15. (canceled)
16. A curable composition comprising: an epoxy compound represented
by the following Formula (1): ##STR00019## (wherein A represents
CR.sup.15R.sup.16; B represents CR.sup.17R.sup.18; R.sup.1 to
R.sup.18 each independently represents a substituent selected from
the group consisting of a hydrogen atom, an alkyl group and an
alkoxy group; and n represents 1); and a thermal cationic
polymerization initiator, or a combination of an acid
anhydride-based curing agent and a curing accelerator.
17. The curable composition according to claim 16, further
comprising one kind, or two or more kinds selected from the group
consisting of an epoxy compound other than the epoxy compound
represented by the Formula (1), an oxetane compound and a vinyl
ether.
18. The curable composition according to claim 16, wherein the
thermal cationic polymerization initiator is selected from the
group consisting of aromatic sulfonium salt-based thermal cationic
polymerization initiators, aromatic iodonium salt-based thermal
cationic polymerization initiators and aluminum complex-based
thermal cationic polymerization initiators.
19. The curable composition according to claim 18, wherein the
thermal cationic polymerization initiator is an aromatic sulfonium
salt-based thermal cationic polymerization initiator.
20. The curable composition according to claim 17, wherein, in
cases where the curable composition does not contain any of the
epoxy compound other than the epoxy compound represented by the
Formula (1), the oxetane compound or the vinyl ether, the content
of the thermal cationic polymerization initiator is from 0.1 to 15
parts by mass with respect to 100 parts by mass of the epoxy
compound represented by the Formula (1) contained in the curable
composition; and in cases where the curable composition contains
one kind, or two or more kinds selected from the group consisting
of the epoxy compound other than the epoxy compound represented by
the Formula (1), the oxetane compound and the vinyl ether, the
content of the thermal cationic polymerization initiator is from
0.1 to 15 parts by mass with respect to 100 parts by mass of the
total amount of the epoxy compound represented by the Formula (1),
the epoxy compound other than the epoxy compound represented by the
Formula (1), the oxetane compound and the vinyl ether.
21. The curable composition according to claim 17, wherein, in
cases where the curable composition does not contain the epoxy
compound other than the epoxy compound represented by the Formula
(1), the content of the acid anhydride-based curing agent is from
0.6 to 1.2 equivalent with respect to one equivalent of the epoxy
compound represented by the Formula (1) contained in the curable
composition; and in cases where the curable composition contains
the epoxy compound other than the epoxy compound represented by the
Formula (1), the content of the acid anhydride-based curing agent
is from 0.6 to 1.2 equivalent with respect to one equivalent of a
mixture of epoxy compounds composed of the epoxy compound
represented by the Formula (1) and the epoxy compound other than
the epoxy compound represented by the Formula (1).
22. The curable composition according to claim 17, wherein, in
cases where the curable composition does not contain the epoxy
compound other than the epoxy compound represented by the Formula
(1), the content of the curing accelerator is from 0.1 to 10 parts
by mass with respect to 100 parts by mass of the epoxy compound
represented by the Formula (1) contained in the curable
composition; and in cases where the curable composition contains
the epoxy compound other than the epoxy compound represented by the
Formula (1), the content of the curing accelerator is from 0.1 to
10 parts by mass with respect to 100 parts by mass of the total
amount of the epoxy compound represented by the Formula (1) and the
epoxy compound other than the epoxy compound represented by the
Formula (1).
23. The curable composition according to claim 16, wherein the
curing accelerator is an imidazole-based curing accelerator.
24. The curable composition according to claim 18, wherein the
content of the epoxy compound represented by the Formula (1) is
from 10 to 99% by mass.
25. The curable composition according to claim 17, wherein the
epoxy compound other than the epoxy compound represented by the
Formula (1) is selected from the group consisting of glycidyl
ether-type epoxides, glycidyl ester-type epoxides and alicyclic
epoxides.
26. The curable composition according to claim 16, further
comprising a compound containing a hydroxyl group.
27. A method of producing a cured product, the method comprising
the step of curing the curable composition according to claim
16.
28. A cured product from the curable composition according to claim
16.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present patent application is based upon and claims the
benefit of priority from previously filed Japanese Patent
Application No. 2016-59069 (filed on Mar. 23, 2016), Japanese
Patent Application No. 2016-59079 (filed on Mar. 23, 2016),
Japanese Patent Application No. 2016-66376 (filed on Mar. 29,
2016), Japanese Patent Application No. 2016-66399 (filed on Mar.
29, 2016), Japanese Patent Application No. 2016-107736 (filed on
May 30, 2016), Japanese Patent Application No. 2016-188872 (filed
on Sep. 27, 2016), Japanese Patent Application No. 2016-188873
(filed on Sep. 27, 2016), Japanese Patent Application No.
2016-188874 (filed on Sep. 27, 2016), Japanese Patent Application
No. 2016-188876 (filed on Sep. 27, 2016), and Japanese Patent
Application No. 2016-188879 (filed on Sep. 27, 2016). The entire
disclosures of the above described patent applications are
incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to a curable composition, and
a cured product obtained by curing the same.
BACKGROUND OF THE INVENTION
[0003] Curable compositions containing epoxy compounds are used as
materials for surface protective films for semiconductor devices
and organic thin film elements (such as organic electro-luminescent
elements and organic thin film solar cell elements), interlayer
insulators, protective insulating films for printed alignment
substrates, and fiber-reinforced composite materials and the like.
Among these epoxy compounds, epoxy compounds containing an aromatic
ring have been used as compounds which allow for the production of
cured products having an excellent heat resistance and the
like.
[0004] However, compounds containing an aromatic ring generally
have a high dielectric constant due to having a high electron
density, and accordingly, in the applications as described above,
there has been a problem for use in the field of electronic
materials. Further, these compounds are also associated with a
problem that coloration and the like thereof lead to a reduction in
the light transmittance of the resulting resin. In view of the
above, alicyclic diamine compounds having no aromatic ring are
drawing attention, in recent years. In addition, curable
compositions for use in the applications as described above are
required to be able to produce cured products having a high
moisture resistance and heat resistance.
[0005] Among epoxy compounds, epoxy compounds having an alicyclic
skeleton are known as compounds which allow for the production of
cured products having an excellent heat resistance and the like.
For example, Patent Document 1 discloses an epoxy compound which
has an alicyclic skeleton with a specific structure and which
allows for the production of a resin having an excellent heat
resistance and the like.
[0006] Further, among these epoxy compounds, epoxy compounds having
two or more alicyclic skeletons within the molecule are known as
compounds which allow for the production of cured products having
an excellent heat resistance, transparency and the like. For
example, Patent Document 2 discloses a curable composition
containing dicyclopentadiene diepoxide or tricyclopentadiene
diepoxide. In addition, Patent Document 3 discloses a curable
composition containing a diepoxybicyclohexyl compound. However, the
epoxy compounds having alicyclic skeletons which are proposed in
Patent Documents 2 and 3 have room fora further improvement, from
the viewpoint of improving the heat resistance of the resulting
cured products and decreasing the weight reduction upon curing.
PRIOR ART DOCUMENTS
Patent Documents
[0007] Patent Document 1: JP S49-126658 A [0008] Patent Document 2:
JP 2004-143362 A [0009] Patent Document 3: JP 2008-31424 A
SUMMARY OF THE INVENTION
Problems to be Solved by the Invention
[0010] The present inventors have found out that, by incorporating
into a curable composition: an epoxy compound represented by the
following Formula (1); and one selected from the group consisting
of: a thermal cationic polymerization initiator, an acid
anhydride-based curing agent and a curing accelerator, and a
photo-cationic polymerization initiator; it is possible to
dramatically improve the heat resistance of a cured product
obtained from the curable composition. The present invention has
been made based on the above finding, and an object of the
invention is to provide a curable composition which allows for the
production of a cured product having an excellent heat
resistance.
[0011] Further, the present inventors have found out that, by using
an epoxy compound represented by the following Formula (1) and a
thermal cationic polymerization initiator in combination, in a
curable composition, it is possible to dramatically improve the
heat resistance of a cured product obtained therefrom, as well as
to decrease a reduction in weight upon curing the curable
composition to an extremely low level, The present invention has
been made based on the above finding, and it is another object of
the present invention to provide a curable composition which has an
excellent heat resistance, and in which the reduction in weight
upon curing is reduced.
[0012] Still further, the present inventors have found out that, by
incorporating into a curable composition an epoxy compound
represented by the following Formula (1), and an acid
anhydride-based curing agent and a curing accelerator, in
combination, it is possible to dramatically improve the moisture
resistance and the heat resistance of a cured product obtained
therefrom. The present invention has been made based on the above
finding, and it is still another object of the present invention to
provide a curable composition which allows for the production of a
cured product having an excellent moisture resistance and heat
resistance.
Means for Solving the Problems
[0013] In other words, the present invention encompasses the
following inventions.
(1) A curable composition comprising:
[0014] an epoxy compound represented by the following Formula
(1):
##STR00002##
(wherein A represents CR.sup.17R.sup.18; B represents
CR.sup.19R.sup.20; R.sup.1 to R.sup.20 each independently
represents a substituent selected from the group consisting of a
hydrogen atom, an alkyl group and an alkoxy group; and n represents
0 or 1, with the proviso that when n is 0, m represents 1, and when
n is 1, m represents 0); and
[0015] one selected from the group consisting of: a thermal
cationic polymerization initiator, an acid anhydride-based curing
agent and a curing accelerator, and a photo-cationic polymerization
initiator.
(2) The curable composition according to (1), further comprising
one kind, or two or more kinds selected from the group consisting
of an epoxy compound other than the epoxy compound represented by
the Formula (1), an oxetane compound and a vinyl ether. (3) The
curable composition according to (1) or (2), wherein the thermal
cationic polymerization initiator is selected from the group
consisting of aromatic sulfonium salt-based thermal cationic
polymerization initiators, aromatic iodonium salt-based thermal
cationic polymerization initiators and aluminum complex-based
thermal cationic polymerization initiators. (4) The curable
composition according to (3), wherein the thermal cationic
polymerization initiator is an aromatic sulfonium salt-based
thermal cationic polymerization initiator. (5) The curable
composition according to any one of (2) to (4), wherein, in cases
where the curable composition does not include any of the epoxy
compound other than the epoxy compound represented by the Formula
(1), the oxetane compound or the vinyl ether, the content of the
thermal cationic polymerization initiator is from 0.1 to 15 parts
by mass with respect to 100 parts by mass of the epoxy compound
represented by the Formula (1) contained in the curable
composition; and in cases where the curable composition includes
one kind, or two or more kinds selected from the group consisting
of the epoxy compound other than the epoxy compound represented by
the Formula (1), the oxetane compound and the vinyl ether; the
content of the thermal cationic polymerization initiator is from
0.1 to 15 parts by mass with respect to 100 parts by mass of the
total amount of the epoxy compound represented by the Formula (1),
the epoxy compound other than the epoxy compound represented by the
Formula (1), the oxetane compound and the vinyl ether. (6) The
curable composition according to (2), wherein, in cases where the
curable composition does not include the epoxy compound other than
the epoxy compound represented by the Formula (1), the content of
the acid anhydride-based curing agent is from 0.6 to 1.2 equivalent
with respect to one equivalent of the epoxy compound represented by
the Formula (1) contained in the curable composition; and in cases
where the curable composition includes the epoxy compound other
than the epoxy compound represented by the Formula (1), the content
of the acid anhydride-based curing agent is from 0.6 to 1.2
equivalent with respect to one equivalent of a mixture of epoxy
compounds composed of the epoxy compound represented by the Formula
(1) and the epoxy compound other than the epoxy compound
represented by the Formula (1). (7) The curable composition
according to (2) or (6), wherein, in cases where the curable
composition does not include the epoxy compound other than the
epoxy compound represented by the Formula (1), the content of the
curing accelerator is from 0.1 to 10 parts by mass with respect to
100 parts by mass of the epoxy compound represented by the Formula
(1) contained in the curable composition; and in cases where the
curable composition includes the epoxy compound other than the
epoxy compound represented by the Formula (1), the content of the
curing accelerator is from 0.1 to 10 parts by mass with respect to
100 parts by mass of the total amount of the epoxy compound
represented by the Formula (1) and the epoxy compound other than
the epoxy compound represented by the Formula (1). (8) The curable
composition according to (1), (6) or (7), wherein the curing
accelerator is an imidazole-based curing accelerator. (9) The
curable composition according to any one of (3) to (8), wherein the
content of the epoxy compound represented by the Formula (1) is
from 10 to 99% by mass. (10) The curable composition according to
(1) or (2), wherein the photo-cationic polymerization initiator is
an aromatic sulfonium salt-based photo-cationic polymerization
initiator. (11) The curable composition according to (2) or (10),
wherein, in cases where the curable composition does not include
any of the epoxy compound other than the epoxy compound represented
by the Formula (1), the oxetane compound or the vinyl ether, the
content of the photo-cationic polymerization initiator is from 0.1
to 20 parts by mass with respect to 100 parts by mass of the epoxy
compound represented by the Formula (1) contained in the curable
composition; and in cases where the curable composition includes
one kind, or two or more kinds selected from the group consisting
of the epoxy compound other than the epoxy compound represented by
the Formula (1), the oxetane compound and the vinyl ether, the
content of the photo-cationic polymerization initiator is from 0.1
to 20 parts by mass with respect to 100 parts by mass of the total
amount of the epoxy compound represented by the Formula (1), the
epoxy compound other than the epoxy compound represented by the
Formula (1), the oxetane compound and the vinyl ether. (12) The
curable composition according to (10) or (11), wherein the content
of the epoxy compound represented by the Formula (1) is from 1 to
50% by mass. (13) The curable composition according to any one of
(2) to (12), wherein the epoxy compound other than the epoxy
compound represented by the Formula (1) is selected from the group
consisting of glycidyl ether-type epoxides, glycidyl ester-type
epoxides and alicyclic epoxides. (14) A method of producing a cured
product, the method comprising the step of curing the curable
composition according to any one of (1) to (13), (15) A cured
product from the curable composition according to any one of (1) to
(13).
Effect of the Invention
[0016] The present invention provides a curable composition which
allows for the production of a cured product having a high heat
resistance.
[0017] Further, the present invention provides a curable
composition capable of producing a cured product having a high heat
resistance. According to the curable composition of the present
invention, a reduction in weight which occurs upon curing the
curable composition can be decreased to an extremely low level.
[0018] Still further, the present invention provides a curable
composition which allows for obtaining a cured product with a
dramatically improved heat resistance.
[0019] Yet still further, the present invention provides a curable
composition which allows for the production of a cured product
having a high moisture resistance and heat resistance.
BRIEF DESCRIPTION OF THE DRAWINGS
[0020] FIG. 1 shows a .sup.13C-NMR chart of an epoxy compound (A-1)
produced in Preparation Example 1.
[0021] FIG. 2 shows a .sup.13C-NMR chart of an epoxy compound (A-2)
produced in Preparation Example 2.
DETAILED DESCRIPTION OF THE INVENTION
1. Definition
[0022] In the present specification, the terms "part(s)", "%" and
the like used to describe the composition are represented on a mass
basis, unless otherwise specified.
[0023] In the present specification, the term "epoxy equivalent" is
defined by the mass of an epoxy compound containing one equivalent
of epoxy groups. In the case of a mixture composed of m kinds
(wherein m is an integer of 2 or more) of epoxy compounds, the
epoxy equivalent of the mixture is represented by the following
equation;
Epoxy equivalent of mixture of epoxy compounds = n = 1 n Mass of
epoxy compound n n = 1 n Mass of epoxy compound n Epoxy equivalent
of epoxy compound n [ Equation . 1 ] ##EQU00001##
The epoxy equivalent of an epoxy compound can be measured in
accordance with JIS K7236.
2. Curable Composition
[0024] The curable composition according to the present invention
is characterized in that it comprises:
[0025] an epoxy compound represented by the following Formula (1);
and
[0026] one selected from the group consisting of: a thermal
cationic polymerization initiator, an acid anhydride-based curing
agent and a curing accelerator, and a photo-cationic polymerization
initiator.
##STR00003##
(In the Formula (1),
[0027] A represents CR.sup.1517R.sup.18; B represents
CR.sup.19R.sup.20; R.sup.1 to R.sup.20 each independently
represents a substituent selected from the group consisting of a
hydrogen atom, an alkyl group and an alkoxy group; and n represents
0 or 1, with the proviso that when n is 0, m represents 1, and when
n is 1, m represents 0.)
[0028] In a curable composition obtained by using dicyclopentadiene
diepoxide, which is an epoxy compound having a similar alicyclic
skeleton, in combination with a thermal cationic polymerization
initiator, a large reduction in weight occurs upon curing, making
the curable composition difficult to handle. In contrast, when the
epoxy compound represented by the above described Formula (1) is
used in combination with a thermal cationic polymerization
initiator, a reduction in weight: which occurs upon curing the
resulting curable composition can be decreased to an extremely low
level.
[0029] Further, dicyclopentadiene diepoxide, which is an epoxy
compound having a similar alicyclic skeleton, has a low curability,
even if used in combination with an acid anhydride-based curing
agent and a curing accelerator, and thus it is difficult to obtain
a cured product from the resulting curable composition. In
contrast, when the epoxy compound represented by the above
described Formula (1) is used in combination with an acid
anhydride-based curing agent and a curing accelerator, it is
possible to easily produce a cured product from the resulting
curable composition, as well as to obtain a cured product with a
dramatically improved heat resistance.
[0030] The combined use of the epoxy compound represented by the
above described Formula (1) with a thermal cationic polymerization
initiator, in a curable composition, enables to dramatically
improve the heat resistance of a cured product obtained by curing
the resulting curable composition.
[0031] Further, the combined use of the epoxy compound represented
by the above described Formula (1), with an acid anhydride-based
curing agent and a curing accelerator, in a curable composition,
enables to dramatically improve the moisture resistance and the
heat resistance of a cured product obtained by curing the resulting
curable composition.
[0032] In a cured product obtained by curing a curable composition
containing dicyclopentadiene diepoxide, which is an epoxy compound
having a similar alicyclic skeleton, and a photo-cationic
polymerization initiator, there is room for improvement in the heat
resistance. In contrast, when the epoxy compound represented by the
above described Formula (1) and a photo-cationic, polymerization
initiator are incorporated into a curable composition in
combination, the heat resistance of the resulting cured product can
be dramatically improved. Further, the combined use thereof allows
for improving the transparency of the resulting cured product.
Still further, since the time required for curing can be markedly
reduced as compared to the case of using a thermal cationic
polymerization initiator, the productivity can also be
improved.
(1) Epoxy Compound
[0033] The epoxy compound to be contained in the curable
composition according to the present invention is preferably one
wherein, in the above described Formula (1), A and B each
independently represents CR.sup.15R.sup.16; R.sup.1 to R.sup.16
each independently represents a substituent selected from the group
consisting of a hydrogen atom, an alkyl group and an alkoxy group;
n represents 0 or 1, and in cases where n is 0, a cross-linked
structure is not formed; and the alkyl group preferably has from 1
to 10 carbon atoms, and more preferably 1 to 5 carbon atoms.
Further, the alkyl group may be a linear alkyl group or a branched
alkyl group. The alkoxy group preferably has from 1 to 10 carbon
atoms, and more preferably from 1 to 5 carbon atoms. It is
particularly preferred that R.sup.1 to R.sup.16 be all hydrogen
atoms. Further, the curable composition according to the present
invention may contain two or more epoxy compounds represented by
the above described Formula (1).
[0034] In the case of a curable composition containing the epoxy
compound represented by the Formula (1) and a thermal cationic
polymerization initiator, or a curable composition containing the
epoxy compound represented by the Formula (1), an acid
anhydride-based curing agent and a curing accelerator, the epoxy
compound represented by the Formula (1) contained in the curable
composition preferably has an epoxy equivalent of from 85 to 600
g/eq, more preferably from 90 to 600 g/eq, still more preferably
from 85 to 300 g/eq, still more preferably from 90 to 300 g/eq, and
still more preferably from 90 to 200 g/eq. The curable composition
according to the present invention may further contain any of other
compounds to be described later. However, the content of the epoxy
compound represented by the Formula (1) contained in the curable
composition according to the present invention is preferably from
10 to 99% by mass, more preferably from 10 to 80% by mass, still
more preferably from 15 to 99% by mass, and still more preferably
from 15 to 60% by mass, from the viewpoint of preventing a
reduction in the heat resistance of the resulting cured product
and/or a reduction in weight upon curing.
[0035] In the case of a curable composition containing the epoxy
compound represented by the Formula (1) and a photo-cationic
polymerization initiator, the epoxy equivalent of the epoxy
compound represented by the Formula (1) contained in the curable
composition is preferably from 85 to 600 g/eq, more preferably from
85 to 300 g/eq, and still more preferably from 85 to 200 g/eq. The
curable composition according to the present invention may further
contain any of other compounds to be described later. However, the
content of the epoxy compound represented by the Formula (1)
contained in the curable composition according to the present
invention is preferably from 1 to 50% by mass, and more preferably
from 5 to 40% by mass, from the viewpoint of improving the heat
resistance of the resulting cured product. In one embodiment, it is
preferred that the curable composition according to the present
invention further contain an epoxy compound other than the epoxy
compound represented by the Formula (1) and/or an oxetane
compound.
(2) Method of Producing Epoxy Compound
[0036] An epoxy compound satisfying the above described Formula (1)
to be contained in the curable composition according to the present
invention can be synthesized by allowing a diolefin compound
represented by the following Formula (2) with a peracid, such as
hydrogen peroxide, peracetic acid or perbenzoic acid.
##STR00004##
[0037] In one embodiment, an epoxy compound represented by the
following Formula (4) can be obtained as the compound satisfying
the above described Formula (1), by allowing a diolefin compound
represented by the following Formula (3) as the diolefin compound
satisfying the above described Formula (2) to react with
meta-chloroperoxybenzoic acid. The compound represented by the
following Formula (3) can be synthesized by the Diels-Alder
reaction of butadiene and dicyclopentadiene.
##STR00005##
[0038] Further, in one embodiment, an epoxy compound represented by
the following Formula (6) can be obtained as the compound
satisfying the above described Formula (1), by allowing a diolefin
compound represented by the following Formula (5) as the diolefin
compound satisfying the above described Formula (2) to react with
meta-chloroperoxybenzoic acid. The compound represented by the
following Formula (5) can be synthesized by the Diels-Alder
reaction of cyclopentadiene and dicyclopentadiene.
##STR00006##
(3) Thermal Cationic Polymerization Initiator
[0039] Examples of cationic polymerization initiators which can be
contained in the curable composition according to the present
invention include thermal cationic polymerization initiators
(initiators capable of generating cationic active species by the
application of thermal energy thereto) and photo-cationic
polymerization initiators (initiators capable of generating
cationic active species by the irradiation of light or an electron
beam thereto). The combined use of the epoxy compound represented
by the above described Formula (1) with a thermal cationic
polymerization initiator enables to improve the heat resistance of
the resulting cured product to an even higher level, as well as to
decrease the reduction in the weight thereof which occurs upon
curing. The above combination also enables to improve the
transparency of the resulting cured product.
[0040] The thermal cationic polymerization initiator may be, for
example: (i) an aromatic sulfonium salt-based thermal cationic
polymerization initiator; (ii) a phosphonium salt-based thermal
cationic polymerization initiator; (iii) a quaternary ammonium
salt-based thermal cationic polymerization initiator; (iv) an
aluminum complex-based thermal cationic polymerization initiator;
(v) an aromatic iodonium salt-based thermal cationic polymerization
initiator; (vi) an aromatic diazonium salt-based thermal cationic
polymerization initiator; or (vii) a pyridinium-based thermal
cationic polymerization initiator.
[0041] Examples of the aromatic sulfonium salt-based thermal
cationic polymerization initiator include: hexafluoroantimonate
salts such as
(2-ethoxy-1-methyl-2-oxoethyl)methyl-2-naphthalenylsulfonium
hexafluoroantimonate,
4-(methoxycarbonyloxy)phenylbenzylmethylsulfonium
hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium
hexafluoroantimonate, 4-hydroxyphenylbenzylmethylsulfonium
hexafluoroantimonate,
4-hydroxyphenyl(o-methylbenzyl)methylsulfonium
hexafluoroantimonate,
4-hydroxyphenyl(.alpha.-naphthylmethyl)methysulfonium
hexafluoroantimonate, diphenyl-4-(phenylthio)phenylsulfonium
hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate,
bis[4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl]sulfide
bishexafluoroantimonate, and bis[4-(diphenylsulfonio)phenyl]sulfide
bishexafluoroantimonate; hexafluorophosphate salts such as
(2-ethoxy-1-methyl-2-oxoethyl)methyl-2-naphthalenysulfonium
hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium
hexafluorophosphate, 4-hydroxyphenyl(o-methylbenzyl)methylsulfonium
hexafluorophosphate,
4-hydroxyphenyl(.alpha.-naphthylmethyl)methylsulfonium
hexafluorophosphate, diphenyl-4-(phenylthio)phenylsulfonium
hexafluorophosphate, triphenylsulfonium hexafluorophosphate,
bis[4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl]sulfide
bishexafluorophosphate, and bis[4-(diphenylsulfonio)phenyl]sulfide
bishexafluorophosphate; hexafluoroarsenate salts such as
4-hydroxyphenyl(o-methylbenzyl)methylsulfonium hexafluoroarsenate,
and 4-hydroxyphenylbenzylmethylsulfonium hexafluoroarsenate;
tetrafluoroborate salts such as
(2-ethoxy-1-methyl-2-oxoethyl)methyl-2-naphthalenysulfonium
tetrafluoroborate, 4-hydroxyphenyl(o-methylbenzyl)methylsulfonium
tetrafluoroborate, 4-hydroxyphenylbenzylmethylsufonium
tetrafluoroborate, diphenyl-4-(phenylthio)phenylsulfonium
tetrafluoroborate, triphenylsulfonium tetrafluoroborate,
bis[4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl]sulfide
bistetrafluoroborate, and bis[4-(diphenylsulfonio)phenyl]sulfide
bistetrafluoroborate; trifluoromethanesulfonate salts such as
4-hydroxyphenyl(o-methylbenzyl)methylsulfonium
trifluoromethanesulfonate, and 4-hydroxyphenylbenzylmethylsulfonium
trifluoromethanesulfonate; trifluoromethanesulfonate salts such as
diphenyl-4-(phenylthio)phenylsulfonium trifluoromethanesulfonate;
bis(trifluoromethanesulfone)imide salts such as
4-hydroxyphenyl(.alpha.-naphthylmethyl)methylsulfonium
bis(trifluoromethanesulfone)imide, and
4-hydroxyphenylbenzylmethylsulfonium
bis(trifluoromethanesulfone)imide;
tetrakis(pentafluorophenyl)borate salts such as
(2-ethoxy-1-methyl-2-oxoethyl)methyl-2-naphthalenylsulfonium
tetrakis(pentafluorophenyl)borate,
4-(methoxycarbonyloxy)phenylbenzylmethylsulfonium
tetrakis(pentafluorophenyl)borate,
4-hydroxyphenyl(o-methylbenzyl)methylsulfonium
tetrakis(pentafluorophenyl)borate,
4-hydroxyphenyl(.alpha.-naphthylmethyl)methylsulfonium
tetrakis(pentafluorophenyl)borate,
4-hydroxyphenylbenzylmethylsulfonium
tetrakis(pentafluorophenyl)borate,
diphenyl-4-(phenylthio)phenylsulfonium
tetrakis(pentafluorophenyl)borate, triphenylsulfonium
tetrakis(pentafluorophenyl)borate,
bis[4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl]sulfide
tetrakis(pentafluorophenyl)borate, and
bis[4-(diphenylsulfonio)phenyl]sulfide
tetrakis(pentafluorophenyl)borate.
[0042] Examples of (ii) the phosphonium salt-based thermal cationic
polymerization initiator include ethyltriphenylphosphonium
hexafluoroantimonate, and tetrabutylphosphonium
hexafluoroantimonate.
[0043] Examples of (ii) the quaternary ammonium salt-based thermal
cationic polymerization initiator Include
N,N-dimethyl-N-benzylanilinium hexafluoroantimonate,
N,N-diethyl-N-benzylanilinium tetrafluoroborate,
N,N-dimethyl-N-benzylpyridinium hexafluoroantimonate,
N,N-diethyl-N-benzylpyridinium trifluoromethanesulfonic acid,
N,N-dimethyl-N-(4-methoxybenzyl)pyridinium hexafluoroantimonate,
N,N-diethyl-N-(4-methoxybenzyl)pyridinium hexafluoroantimonate,
N,N-diethyl-N-(4-methoxybenzyl)toluidinium hexafluoroantimonate,
and N,N-dimethyl-N-(4-methoxybenzyl)toluidinium
hexafluoroantimonate.
[0044] Examples of (lv) the aluminum complex-based thermal cationic
polymerization initiator Include aluminum carboxylates; aluminum
alkoxide, aluminium chloride, aluminum (alkoxide) acetoacetic acid
chelate, acetoacetonato aluminum, and ethylacetoacetato
aluminum.
[0045] Examples of (v) the aromatic iodonium salt-based thermal
cationic polymerization initiator include phenyliodonium
hexafluorophosphate, diphenyliodonium hexafluoroantimonate,
diphenyliodonium tetrafluoroborate, diphenyliodonium
tetrakis(pentafluorophenyl)borate, diphenyliodonium
hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate,
bis(dodecylphenyl)iodonium hexafluorophosphate,
bis(dodecylphenyl)iodonium hexafluoroantimonate,
bis(dodecylphenyl)iodonium tetrafluoroborate,
bis(dodecylphenyl)iodonium tetrakis(pentafluorophenyl)borate,
4-methylphenyl-4-(1-methylethyl)phenyliodonium hexafluorophosphate,
4-methylphenyl-4-(1-methylethyl)phenyliodonium
hexafluoroantimonate,
4-methylphenyl-4-(1-methylethyl)phenyliodonium tetrafluoroborate,
and 4-methylphenyl-4-(1-methylethy)phenyliodonium
tetrakis(pentafluorophenyl)borate.
[0046] Examples of (vi) the aromatic diazonium salt-based thermal
cationic polymerization initiator include phenyldiazonium
hexafluorophosphate, phenyldiazonium hexafluoroantimonate,
phenyldiazonium tetrafluoroborate and phenyldiazonium
tetrakis(pentafluorophenyl)borate.
[0047] Examples of (vii) the pyridinium-based thermal cationic
polymerization initiator include 1-benzyl-2-cyanopyridinium
hexafluorophosphate, 1-benzyl-2-cyanopyridinium
hexafluoroantimonate, 1-benzyl-2-cyanopyridinium tetrafluoroborate,
1-benzyl-2-cyanopyridinium tetrakis(pentafluorophenyl)borate,
1-(naphthylmethyl)-2-cyanopyridinium hexafluorophosphate,
1-(naphthylmethyl)-2-cyanopyridinium hexafluoroantimonate,
1-(naphthylmethyl)-2-cyanopyridinium tetrafluoroborate, and
1-(naphthylmethyl)-2-cyanopyridinium
tetrakis(pentafluorophenyl)borate.
[0048] These thermal cationic polymerization initiators may be used
alone, or as a mixture of two or more kinds thereof.
[0049] Among these, an aromatic sulfonium salt-based thermal
cationic polymerization initiator is more preferred, and a
monoaryl-based thermal cationic polymerization initiator, such as
4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, is
particularly preferred. The combined use of any of these specific
thermal cationic polymerization initiators with the epoxy compound
represented by the Formula (1) enables to improve the heat
resistance of the resulting cured product to an even higher level,
as well as to further decrease the reduction in the weight thereof
which occurs upon curing. The above combination also enables to
improve the transparency of the resulting cured product.
[0050] In cases where the curable composition according to the
present invention does not contain any of an epoxy compound other
than the epoxy compound represented by the Formula (1) to be
described later, an oxetane compound to be described later or a
vinyl ether to be described later, the content of the thermal
cationic polymerization initiator in the curable composition is
preferably from 0.1 to 15 parts by mass, and more preferably from
0.3 to 7 parts by mass with respect to 100 parts by mass of the
epoxy compound represented by the Formula (1) contained in the
curable composition. Further, in cases where the curable
composition according to the present invention contains one kind,
or two or more kinds selected from the group consisting of the
epoxy compound other than the epoxy compound represented by the
Formula (1), the oxetane compound and the vinyl ether, the content
of the thermal cationic polymerization initiator in the curable
composition is preferably from 0.1 to 15 parts by mass, and more
preferably from 0.3 to 7 parts by mass with respect to 100 parts by
mass of the total amount of the epoxy compound represented by the
Formula (1), the epoxy compound other than the epoxy compound
represented by the Formula (1), the oxetane compound and the vinyl
ether. When the content of the thermal cationic polymerization
initiator is adjusted within the above described numerical range,
the heat resistance of the resulting cured product can be improved
to an even higher level. Further, the weight reduction of the cured
product upon curing can further be decreased. In addition, the
transparency of the cured product can be further improved.
[0051] The cationic polymerization initiator to be contained in the
curable composition according to the present invention is more
preferably selected from the group consisting of aromatic sulfonium
salt-based thermal cationic polymerization initiators, aromatic
iodonium salt-based thermal cationic polymerization initiators and
aluminum complex-based thermal cationic polymerization initiators.
Further, the cationic polymerization initiator to be contained in
the curable composition according to the present invention is still
more preferably an aromatic sulfonium salt-based thermal cationic
polymerization initiator.
(4) Aid Anhydride-Based Curing Agent
[0052] Examples of the acid anhydride-based curing agent to be
contained in the curable composition according to the present
invention include hexahydrophthalic anhydride,
methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride,
methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic
anhydride, methylnadic anhydride, methylbutenyltetrahydrophthalic
anhydride, hydrogenated methylnadic anhydride,
trialkyltetrahydrophthalic anhydride, cyclohexanetricarboxylic
anhydride, methylcyclohexenedicarboxylic anhydride,
methylcyclohexanetetracarboxylic acid dianhydride, maleic
anhydride, phthalic anhydride, succinic anhydride,
dodecenylsuccinic anhydride, octenylsuccinic anhydride,
pyromellitic anhydride, trimellitic anhydride, alkylstyrene-maleic
anhydride copolymer, chlorendic anhydride, polyazelaic anhydride,
benzophenone tetracarboxylic anhydride, ethylene glycol
bisanhydrotrimellitate, glycerol tristrimellitate, glycerin
bis(anhydrotrimellitate) monoacetate, benzophenonetetracarboxylic
acid, polyadipic anhydride, polysebacic anhydride,
poly(ethyloctadecanedioic acid) anhydride,
poly(phenylhexadecanedioic acid) anhydride, HET anhydride, and
norbornane-2,3-dicarboxylic anhydride.
[0053] Among these, hexahydrophthalic anhydride and
methylhexahydrophthalic anhydride are preferred, because the
combined use of any of these with the epoxy compound represented by
the Formula (1) allows for improving the heat resistance and the
transparency of the resulting cured product to an even higher
level. The curable composition according to the present invention
can contain one kind, or two or more kinds of the acid
anhydride-based curing agents described above.
[0054] From the viewpoint of improving the heat resistance of the
resulting cured product, the content of the acid anhydride-based
curing agent in the curable composition according to the present
invention, in cases where the curable composition does not contain
the epoxy compound other than the epoxy compound represented by the
Formula (1) to be described later, is preferably from 0.5 to 1.5
equivalent, more preferably from 0.6 to 1.2 equivalent, and still
more preferably from 0.8 to 1.2 equivalent with respect to one
equivalent of the epoxy compound represented by the Formula (1)
contained in the curable composition. Further, in cases where the
curable composition according to the present invention contains the
epoxy compound other than the epoxy compound represented by the
Formula (1), the content of the acid anhydride-based curing agent
in the curable composition is preferably from 0.5 to 1.5
equivalent, more preferably from 0.6 to 1.2 equivalent, and still
more preferably from 0.8 to 1.2 equivalent with respect to one
equivalent of a mixture of epoxy compounds composed of the epoxy
compound represented by the Formula (1) and the epoxy compound
other than the epoxy compound represented by the Formula (1).
(5) Curing Accelerator
[0055] Examples of the curing accelerator to be contained in the
curable composition according to the present invention include:
phosphines and quaternary salts thereof, such as
triphenylphosphine, triphenylbenzylphosphonium tetraphenylborate,
tetrabutylphosphonium diethylphosphorodithioate,
tetraphenylphosphonium bromide, tetrabutylphosphonium acetate,
tetra-n-butylphosphonium bromide, tetra-n-butylphosphonium
benzotriazolate, tetra-n-butylphosphonium tetrafluoroborate,
tetra-n-butylphosphonium tetraphenylborate,
methyltriphenylphosphonium bromide, ethyltriphenylphosphonium
bromide, ethyltriphenylphosphonium iodide,
ethyltriphenylphosphonium acetate, methyltri-n-butylphosphonium
dimethylphosphate, n-butyltriphenylphosphonium bromide,
benzyltriphenylphosphonium chloride, and tetraphenylphosphonium
tetraphenylborate; imidazoles such as 2-ethyl-4-methylimidazole,
1,2-dimethylimidazole, 1-benzyl-2-phenylimidazole,
2-methylimidazole, 2-phenylimidazole,
1-(2-cyanoethyl)-2-ethyl-4-methylimidazole,
2,4-diamino-6-[2-methylimidazolyl-(1)]ethyl-s-triazine,
2-phenylimidazoline, and
2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole; tertiary amines and
quaternary salts thereof such as, tris(dimethylaminomethyl)phenol,
benzyldimethylamine, and tetrabutylammonium bromide; super strong
basic organic compounds such as 1,8-diazabicyclo(5,4,0)undecene-7
and 1,5-diazabicyclo(4,3,0)nonene-5; organic metal carboxylates
such as zinc octylate, zinc laurate, zinc stearate, and tin
octylate; metal-organic chelate compounds such as benzoylacetone
zinc chelate, dibenzoylmethane zinc chelate and ethyl acetoacetate
zinc chelate; and tetra-n-butylsulfonium-o,o-diethyl
phosphorodithionate.
[0056] Among these, an imidazole-based curing accelerator is
particularly preferred, because the combined use thereof with the
epoxy compound represented by the Formula (1) allows for improving
the heat resistance of the resulting cured product to an even
higher level.
[0057] The curable composition according to the present invention
may contain one kind, or two or more kinds of the curing
accelerators as described above.
[0058] From the viewpoint of improving the heat resistance of the
resulting cured product, the content of the curing accelerator in
the curable composition according to the present invention, in
cases where the curable composition does not contain the epoxy
compound other than the epoxy compound represented by the Formula
(1) to be described later, is preferably from 0.1 to 10 parts by
mass, more preferably from 0.2 to 8 parts by mass, and still more
preferably from 0.5 to 6 parts by mass with respect to 100 parts by
mass of the epoxy compound represented by the Formula (1). Further,
in cases where the curable composition according to the present
invention contains the epoxy compound other than the epoxy compound
represented by the Formula (1), the content of the curing
accelerator in the curable composition is preferably from 0.1 to 10
parts by mass, more preferably from 0.2 to 8 parts by mass, and
still more preferably from 0.5 to 6 parts by mass with respect to
100 parts by mass of the total amount of the epoxy compound
represented by the Formula (1) and the epoxy compound other than
the epoxy compound represented by the Formula (1).
(6) Photo-Cationic Polymerization Initiator
[0059] The photo-cationic polymerization initiator to be contained
in the curable composition according to the present invention is
one which generates cationic species or Lewis acid when irradiated
with an active energy ray such as a visible ray, UV light, an X ray
or an electron beam, thereby initiating a polymerization reaction
of a cationically polymerizable compound. As the photo-cationic
polymerization initiator to be contained in the curable composition
according to the present invention, it is possible to use, for
example, a compound such as an onium salt, a metallocene complex,
or an iron-allene complex. Examples of the onium salt which can be
used include aromatic sulfonium salts, aromatic iodonium salts,
aromatic diazonium salts, aromatic phosphonium salts and aromatic
selenium salts. As the counter ions for these salts, anions such as
CF.sub.3SO.sub.3.sup.-, BF.sub.4.sup.-, PF.sub.6.sup.-,
AsF.sub.6.sup.-, and SbF.sub.6.sup.- are used. Among these, it is
more preferred to use an aromatic sulfonium salt-based
photo-cationic polymerization initiator, since it exhibits an
excellent curing performance due to having UV absorption properties
even in the wavelength range of 300 nm or more, and allows for
providing a cured product having a good mechanical strength and
adhesion strength. The curable composition according to the present
invention may contain two or more kinds of the photo-cationic
polymerization initiators.
[0060] Examples of the aromatic sulfonium salt include
diphenyl-4-(phenylthio)phenylsulfonium hexafluorophosphate,
4,4'-bis(diphenylsulfonio)diphenylsulfide bishexafluorophosphate,
4,4'-bis[di(.beta.-hydroxyethoxy)phenylsulfonio]diphenylsulfide
bishexafluoroantimonate,
4,4'-bis[di(.beta.-hydroxyethoxy)phenylsulfonio]diphenylsulfide
bishexafluorophosphate,
7-[di(p-toluyl)sulfonio]-2-isopropylthioxanthone
hexafluoroantimonate,
7-[di(p-toluyl)sulfonio]-2-isopropylthioxanthone
tetrakis(pentafluorophenyl)borate,
4-phenylcarbonyl-4'-diphenylsulfonio-diphenylsulfide
hexafluorophosphate,
4-(p-tert-butylphenylcarbonyl)-4'-diphenylsulfonio-diphenylsulfide
hexafluoroantimonate,
4-(p-tert-butylphenylcarbonyl)-4'-di(p-toluyl)sulfonio-diphenylsulfide
tetrakis(pentafluorophenyl)borate,
diphenyl-4-(phenylthio)phenylsulfonium hexafluoroantimonate,
triphenylsulfonium trifluoromethanesulfonate,
bis[4-(diphenylsulfonio)phenyl]sulfide bishexafluoroantimonate, and
(4-methoxyphenyl)diphenylsulfonium hexafluoroantimonate.
[0061] Examples of the aromatic iodonium salt include
diphenyliodonium tetrakis(pentafluorophenyl)borate,
diphenyliodonium hexafluorophosphate, diphenyliodonium
hexafluoroantimonate, di(4-nonylphenyl)iodonium
hexafluorophosphate, (4-methoxyphenyl)phenyliodonium
hexafluoroantimonate, and bis(4-t-butylphenyl)iodonium
hexafluorophosphate.
[0062] Examples of the aromatic diazonium salt include
benzenediazonium hexafluoroantimonate, benzenediazonium
hexafluorophosphate, benzenediazonium tetrafluoroborate, and
4-chlorobenzenediazonium hexafluorophosphate.
[0063] Examples of the aromatic phosphonium salt include
benzyltriphenylphosphonium hexafluoroantimonate.
[0064] Examples of the aromatic selenium salt include
triphenylselenium hexafluorophosphate.
[0065] Examples of the iron-allene complex include
xylene-cyclopentadienyl iron (II) hexafluoroantimonate,
cumene-cyclopentadienyl iron (II) hexafluorophosphate, and
xylene-cyclopentadienyl iron (II)
tris(trifluoromethylsulfonyl)methanaide.
[0066] In cases where the curable composition according to the
present invention does not contain any of the epoxy compound other
than the epoxy compound represented by the Formula (1) to be
described later, the oxetane compound to be described later, or the
vinyl ether to be described later, the content of the
photo-cationic polymerization initiator in the curable composition
is preferably from 0.1 to 20 parts by mass, and more preferably
from 0.3 to 15 parts by mass with respect to 100 parts by mass of
the epoxy compound represented by the Formula (1) contained in the
curable composition. Further, in cases where the curable
composition according to the present invention contains one kind,
or two or more kinds selected from the group consisting of the
epoxy compound other than the epoxy compound represented by the
Formula (1), the oxetane compound and the vinyl ether, the content
of the photo-cationic polymerization initiator in the curable
composition is preferably from 0.1 to 20 parts by mass, and more
preferably from 0.3 to 15 parts by mass with respect to 100 parts
by mass of the total amount of the epoxy compound represented by
the Formula (1), the epoxy compound other than the epoxy compound
represented by the Formula (1), the oxetane compound and the vinyl
ether. When the content of the photo-cationic polymerization
initiator is adjusted within the above described numerical range,
the heat resistance of the resulting cured product can be improved
to an even higher level. In addition, the transparency of the cured
product can further be improved.
(7) Epoxy Compound Other than Epoxy Compound Represented by the
Formula (1)
[0067] The curable composition according to the present invention
may contain an epoxy compound other than the epoxy compound
represented by the Formula (1) (in the present specification,
sometimes also referred to as "the other epoxy compound"),
depending on the application. Examples of the epoxy compound other
than the epoxy compound represented by the Formula (1) include
glycidyl ether-type epoxides, glycidyl ester-type epoxides,
glycidyl amine-type epoxides and alicyclic epoxides; as well as
oligomers and polymers therefrom.
[0068] Examples of the glycidyl ether-type epoxide include:
glycidyl ethers of divalent phenols such as bisphenol A diglycidyl
ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether,
tetramethyl biphenol diglycidyl ether, hydrogenated bisphenol A
diglycidyl ether, and brominated bisphenol A diglycidyl ether;
glycidyl ethers of polyvalent phenols such as dihydroxynaphthyl
cresol triglycidyl ether, tris(hydroxyphenyl)methane triglycidyl
ether, tetrakis(hydroxyphenyl)ethane tetraglycidyl ether,
dinaphthyltriol triglycidyl ether, phenol novolac glycidyl ether,
cresol novolac glycidyl ether, xylylene skeleton-containing phenol
novolac glycidyl ethers, dicyclopentadiene skeleton-containing
phenol novolac glycidyl ethers, biphenyl skeleton-containing phenol
novolac glycidyl ethers, terpene skeleton-containing phenol novolac
glycidyl ethers, bisphenol A novolac glycidyl ether, bisphenol F
novolac glycidyl ether, bisphenol S novolac glycidyl ether,
bisphenol AP novolac glycidyl ether, bisphenol C novolac glycidyl
ether, bisphenol E novolac glycidyl ether, bisphenol Z novolac
glycidyl ether, biphenol novolac glycidyl ether, tetramethyl
bisphenol A novolac glycidyl ether, dimethyl bisphenol A novolac
glycidyl ether, tetramethyl bisphenol F novolac glycidyl ether,
dimethyl bisphenol F novolac glycidyl ether, tetramethyl bisphenol
S novolac glycidyl ether, dimethyl bisphenol S novolac glycidyl
ether, tetramethyl-4,4'-biphenol novolac glycidyl ether,
trishydroxyphenylmethane novolac glycidyl ether, resorcinol novolac
glycidyl ether, hydroquinone novolac glycidyl ether, pyrogallol
novolac glycidyl ether, diisopropylidene novolac glycidyl ether,
1,1-di-4-hydroxyphenylfluorene novolac glycidyl ether, phenolated
polybutadiene novolac glycidyl ether, ethylphenol novolac glycidyl
ether, butylphenol novolac glycidyl ether, octylphenol novolac
glycidyl ether, naphthol novolac glycidyl ether, and hydrogenated
phenol novolac glycidyl ether; glycidyl ethers of divalent alcohols
such as ethylene glycol diglycidyl ether, propylene glycol
diglycidyl ether, tetramethylene glycol diglycidyl ether,
1,6-hexanediol diglycidyl ether, cyclohexanedimethylol diglycidyl
ether, polyethylene glycol diglycidyl ether, and polypropylene
glycol diglycidyl ether; glycidyl ethers of polyols such as
trimethylolpropane triglycidyl ether, glycerin triglycidyl ether,
pentaerythritol tetraglycidyl ether, sorbitol hexaglycidyl ether,
and polyglycerin polyglycidyl ether; and triglycidyl
isocyanurate.
[0069] Examples of the glycidyl ester-type epoxide include:
glycidyl esters of carboxylic acids such as glycidyl methacrylate,
phthalic acid diglycidyl ester, isophthalic acid diglycidyl ester,
terephthalic acid diglycidyl ester, cyclohexanedicarboxylic acid
diglycidyl ester, and trimellitic acid triglycidyl ester; and
glycidyl ester-type polyepoxides.
[0070] Examples of the glycidyl amine-type epoxide include:
glycidyl aromatic amines such as N,N-diglycidylaniline,
N,N-diglycidyltoluidine,
N,N,N',N'-tetraglycidyldiaminodiphenylmethane,
N,N,N',N'-tetraglycidyldiaminodiphenylsulfone, and
N,N,N',N'-tetraglycidyldiethyldiphenylmethane; and glycidyl
heterocyclic amines such as
bis(N,N-diglycidylaminocyclohexyl)methane (hydride of
N,N,N',N'-tetraglycidyldlaminodiphenylmethane),
N,N,N',N'-tetraglycidyl-1,3-(bisaminomethyl)cyclohexane (hydride of
N,N,N',N'-tetraglycidylxylylene diamine), trisglycidylmelamine,
triglycidyl-p-aminophenol, N-glycidyl-4-glycidyloxypyrrolidone.
[0071] Examples of the alicyclic epoxide include vinyl cyclohexene
dioxide, limonene dioxide, dicyclopentadiene dioxide,
bis(2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxy
dicyclopentyl ether, 3,4-epoxy-6-methylcyclohexylmethyl
3',4'-epoxy-6'-methylcyclohexane carboxylate,
3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate,
3,4-epoxy-1-methylcyclohexyl 3,4-epoxy-1-methylhexane carboxylate,
3,4-epoxy-3-methylcyclohexylmethyl 3,4-epoxy-3-methylhexane
carboxylate, 3,4-epoxy-5-methylcyclohexylmethyl
3,4-epoxy-5-methylcyclohexane carboxylate,
2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-metadioxane,
methylenebis(3,4-epoxycyclohexane),
(3,3',4,4'-diepoxy)bicyclohexyl, 1,2-epoxy-(2-oxiranyl)cyclohexane
adduct of 2,2-bis(hydroxymethyl)-1-butanol, and tetrahydroindene
diepoxide. The curable composition according to the present
invention may contain one kind, or two or more kinds of epoxy
compounds other than the epoxy compound represented by the Formula
(1), such as those as described above.
[0072] The content of the above described epoxy compound other than
the epoxy compound represented by the Formula (1) is preferably
from 1 to 90% by mass, and more preferably from 5 to 85% by mass
with respect to the amount of curable composition, from the
viewpoint of improving the heat resistance of the resulting cured
product.
[0073] In one preferred embodiment, the epoxy compound other than
the epoxy compound represented by the Formula (1) contained in the
curable composition according to the present invention is selected
from the group consisting of glycidyl ether-type epoxides, glycidyl
ester-type epoxides and alicyclic epoxides.
(8) Reactive Diluent
[0074] The curable composition according to the present invention
may further contain a reactive diluent in order to reduce the
viscosity. Examples of the reactive diluent include a monoepoxy
compound produced by the method described in Preparation Example 4,
butyl glycidyl ether, 2-ethylhexyl glycidyl ether, glycidyl ether
of a mixture of C12 and C13 alcohols, and
1,2-epoxy-4-vinylcyclohexane. The curable composition may contain
one kind, or two or more kinds of the reactive diluents as
described above. The mixing ratio of the reactive diluent may be
adjusted as appropriate such that the curable composition
containing the reactive diluent has a desired viscosity.
(9) Oxetane Compound
[0075] The curable composition according to the present invention
may contain an oxetane compound. Examples of the oxetane compound
include 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene,
3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(phenoxymethyl)oxetane,
di[(3-ethyl-3-oxetanyl)methyl] ether,
3-ethyl-3-(2-ethylhexyloxymethyl)oxetane,
3-ethyl-3-(cyclohexyloxymethyl)oxetane, phenol novolac oxetane,
1,3-bis[(3-ethyloxetan-3-yl)]methoxybenzene, oxetanyl
silsesquioxane, oxetanyl silicate, bis[1-ethyl(3-oxetanyl)]methyl
ether, 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl,
4,4'-bis(3-ethyl-3-oxetanylmethoxy)biphenyl, ethylene glycol
(3-ethyl-3-oxetanylmethyl) ether, diethylene glycol
bis(3-ethyl-3-oxetanylmethyl) ether, bis(3-ethyl-3-oxetanylmethyl)
diphenoate, trimethylolpropane propane
tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol
tetrakis(3-ethyl-3-oxetanylmethyl) ether, and phenol novolac-type
oxetane compounds. The curable composition according to the present
invention may contain one kind, or two or more kinds of the oxetane
compounds as described above.
[0076] The content of the oxetane compound in the curable
composition according to the present invention is preferably from 1
to 90% by mass, and more preferably from 5 to 85% by mass, from the
viewpoint of improving the heat resistance of the resulting cured
product.
(10) Vinyl Ether Compound
[0077] The curable composition according to the present invention
may contain a vinyl ether compound. Examples of the vinyl ether
compound include: monofunctional vinyl ethers such as methyl vinyl
ether, ethyl vinyl ether, propyl vinyl ether, and butyl vinyl
ether; polyfunctional vinyl ethers such as ethylene glycol divinyl
ether, butanediol divinyl ether, cyclohexanedimethanol divinyl
ether, cyclohexanediol divinyl ether, trimethylolpropane trivinyl
ether, pentaerythritol tetravinyl ether, glycerol trivinyl ether,
triethylene glycol divinyl ether, and diethylene glycol divinyl
ether; vinyl ether compounds containing a hydroxyl group such as
hydroxyethyl vinyl ether, hydroxybutyl vinyl ether,
cyclohexanedimethanol monovinyl ether, cyclohexanediol monovinyl
ether, 9-hydroxynonyl vinyl ether, propylene glycol monovinyl
ether, neopentyl glycol monovinyl ether, glycerol divinyl ether,
glycerol monovinyl ether, trimethylolpropane divinyl ether,
trimethylolpropane monovinyl ether, pentaerythritol monovinyl
ether, pentaerythritol divinyl ether, pentaerythritol trivinyl
ether, diethylene glycol monovinyl ether, triethylene glycol
monovinyl ether, tetraethylene glycol monovinyl ether,
tricyclodecanediol monovinyl ether, and tricyclodecane dimethanol
monovinyl ether; and vinyl ethers containing different types of
functional groups, such as 2-(2-vinyloxyethoxy)ethyl acrylate, and
2-(2-vinyloxyethoxy)ethyl methacrylate. The curable composition
according to the present invention may contain one kind, or two or
more kinds of the vinyl ether compounds as described above.
[0078] The content of the vinyl ether compound in the curable
composition according to the present invention is preferably from 1
to 90% by mass, and more preferably from 5 to 85% by mass, from the
viewpoint of improving the heat resistance of the resulting cured
product.
(11) Compound Containing Hydroxyl Group
[0079] The curable composition according to the present invention
may further contain a compound containing a hydroxyl group.
Incorporation of a compound containing a hydroxyl group into the
curable composition allows a moderate curing reaction to proceed.
Examples of the compound containing a hydroxyl group include
ethylene glycol, diethylene glycol, and glycerin. The curable
composition according to the present invention may contain one
kind, or two or more kinds of the compounds containing a hydroxyl
group, such as those described above.
[0080] The content of the compound containing a hydroxyl group in
the curable composition according to the present invention is
preferably from 0.1 to 10% by mass, and more preferably from 0.2 to
8% by mass, from the viewpoint of improving the heat resistance of
the resulting cured product.
(12) Other Components
[0081] The curable composition according to the present invention
may further contain a solvent. Examples of the solvent include
methyl ethyl ketone, ethyl acetate, toluene, methanol, and
ethanol.
[0082] The curable composition according to the present invention
may contain various types of additives to the extent that the
properties of the composition are not impaired. Examples of the
additives include fillers, silane coupling agents, mold release
agents, coloring agents, flame retardants, antioxidants,
photostabilizers and plasticizers, antifoaming agents,
photostabilizers, coloring agents such as pigments and dyes,
plasticizers, pH adjusting agents, coloration inhibitors, matting
agents, deodorants, weather resistant agents, antistatic agents,
yarn friction reducing agents, slip agents, and ion exchangers.
[0083] (13) Production of Curable Composition
[0084] The curable composition according to the present invention
can be produced in accordance with technical common knowledge
widely known to those skilled in the art, and the method of
producing the curable composition and the components to be further
included in the curable composition can be selected as
appropriate.
3. Cured Product
(1) Conditions for Curing
[0085] The cured product according to the present invention is
obtained by curing the above described curable composition
according to the present invention. The method of curing the
curable composition is not particularly limited, and the
composition can be cured by heating or irradiation of light, as
appropriate.
[0086] In cases where the curable composition is cured by heating,
the heating of the curable composition is preferably carried out in
multiple stages, taking into consideration the degree of reactivity
of the epoxy compound. This allows for a sufficient curing reaction
to proceed. For example, the curing reaction can be carried out by
performing a first heating at a temperature of from 100 to
130.degree. C. for 10 to 150 minutes, a second heating at 140 to
160.degree. C. for 10 to 150 minutes, a third heating at 170 to
200.degree. C. for 60 to 180 minutes, and a fourth heating at 210
to 250.degree. C. for 10 to 150 minutes. Alternatively, the curing
reaction can also be carried out, for example, by performing a
first heating at a temperature of from 100 to 130.degree. C. for 10
to 150 minutes, a second heating at 140 to 200.degree. C. for 10 to
150 minutes, and a third heating at 210 to 250.degree. C. for 10 to
150 minutes. Still alternatively, the curing reaction can also be
carried out, for example, by performing a first heating at a
temperature of from 80 to 100.degree. C. for 10 to 150 minutes, a
second heating at 110 to 120.degree. C. for 10 to 150 minutes, a
third heating at 130 to 140.degree. C. for 60 to 180 minutes, a
fourth heating at 150 to 170.degree. C. for 10 to 150 minutes, a
fifth heating at 180 to 200.degree. C. for 60 to 180 minutes and a
sixth heating at 210 to 230.degree. C. for 60 to 240 minutes. Still
alternatively, the curing reaction can be carried out, for example,
by performing a first heating at a temperature of from 100 to
110.degree. C. for 10 to 150 minutes, a second heating at 120 to
150.degree. C. for 10 to 150 minutes, a third heating at 160 to
220.degree. C. for 10 to 150 minutes, and a fourth heating at 230
to 250.degree. C. for 10 to 150 minutes. However, the heating
conditions are not limited to those described above, and the
heating is preferably carried out varying the conditions as
appropriate, in view of the content of the epoxy compound and the
properties of other compounds and the like contained in the curable
composition.
[0087] In cases where the curable composition is cured by the
irradiation of an active energy ray, such as a visible ray, UV
light, an X ray or an electron beam, the type of the active energy
ray used and the conditions for irradiation are preferably selected
as appropriate, depending on the composition of the curable
composition. In one embodiment, it is preferred that the
irradiation of UV light is carried out such that the accumulated
amount of light, which is represented as the product of the
irradiation intensity and the irradiation time, is adjusted within
the range of from 10 to 5,000 mJ/cm.sup.2. When the accumulated
amount of light irradiated to the curable composition is adjusted
within the above described numerical range, it is possible to allow
active species derived from the photo-cationic polymerization
initiator to be generated sufficiently. This also allows for an
improvement in the productivity.
(2) Applications of Cured Product
[0088] Specific examples of the application of the curable
composition according to the present invention and the cured
product obtained therefrom include: coating materials for coating
on substrates such as metals, resin films, glass, paper and wood,
surface protective films for semiconductor devices and organic thin
film elements (for example, organic electroluminescent elements and
organic thin film solar cell elements), hard coating agents,
anti-fouling films and antireflection films; adhesive agents, tacky
materials; various types of optical members such as lenses, prisms,
filters, image display materials, lens arrays, sealing materials
and reflector materials for optical semiconductor devices, sealing
materials for semiconductor devices, optical waveguides, light
guide plates, light diffusion plates, diffraction elements and
optical adhesive agents; and materials such as casting materials,
interlayer insulators, insulating films for printed alignment
substrates and fiber-reinforced composite materials.
[0089] Aspect I of the present invention, which is one preferred
aspect of the present invention, encompasses the following
inventions.
(1) A curable composition comprising:
[0090] an epoxy compound represented by the following Formula
(1):
##STR00007##
(wherein A represents CR.sup.17R.sup.18; B represents
CR.sup.9R.sup.20; R.sup.1 to R.sup.20 each independently represents
a substituent selected from the group consisting of a hydrogen
atom, an alkyl group and an alkoxy group; n represents 1; and m
represents 0); and
[0091] a thermal cationic polymerization initiator.
(2) The curable composition according to (1), further comprising
one kind, or two or more kinds selected from the group consisting
of an epoxy compound other than the epoxy compound represented by
the Formula (1), an oxetane compound and a vinyl ether. (3) The
curable composition according to (1) or (2), wherein the cationic
polymerization initiator is selected from the group consisting of
aromatic sulfonium salt-based thermal cationic polymerization
initiators, aromatic iodonium salt-based thermal cationic
polymerization initiators and aluminum complex-based thermal
cationic polymerization initiators. (4) The curable composition
according to any one of (1) to (3), wherein the cationic
polymerization initiator is an aromatic sulfonium salt-based
thermal cationic polymerization initiator. (5) The curable
composition according to any one of (1) to (4), wherein the content
of the epoxy compound represented by the Formula (1) is from 10 to
99% by mass. (6) The curable composition according to any one of
(1) to (5), wherein, in cases where the curable composition does
not include any of the epoxy compound other than the epoxy compound
represented by the Formula (1), the oxetane compound or the vinyl
ether, the content of the thermal cationic polymerization initiator
is from 0.1 to 15 parts by mass with respect to 100 parts by mass
of the epoxy compound represented by the Formula (1) contained in
the curable composition; and in cases where the curable composition
includes one kind, or two or more kinds selected from the group
consisting of the epoxy compound other than the epoxy compound
represented by the Formula (1), the oxetane compound and the vinyl
ether, the content of the thermal cationic polymerization initiator
is from 0.1 to 15 parts by mass with respect to 100 parts by mass
of the total amount of the epoxy compound represented by the
Formula (1), the epoxy compound other than the epoxy compound
represented by the Formula (1), the oxetane compound and the vinyl
ether. (7) The curable composition according to (2), wherein the
epoxy compound other than the epoxy compound represented by the
Formula (1) is selected from the group consisting of glycidyl
ether-type epoxides, glycidyl ester-type epoxides and alicyclic
epoxides. (8) A cured product from the curable composition
according to any one of (1) to (7).
[0092] According to Aspect I of the present invention, it is
possible to provide a curable composition capable of producing a
cured product having a high heat resistance. Further, according to
the curable composition of the present invention, a reduction in
weight which occurs upon curing the curable composition can be
decreased to an extremely low level.
[0093] According to Aspect I of the present invention, the epoxy
compound represented by the Formula (1) contained in the curable
composition according to the present invention preferably has an
epoxy equivalent of from 90 to 600 g/eq, more preferably from 90 to
300 g/eq, and still more preferably from 90 to 200 g/eq. The
curable composition according to the present invention may contain
any of other compounds to be described later. However, the content
of the epoxy compound represented by the Formula (1) contained in
the curable composition according to the present invention is
preferably from 10 to 99% by mass, and more preferably from 15 to
99% by mass, from the viewpoint of improving the heat resistance of
the resulting cured product and decreasing the weight reduction
upon curing.
[0094] Aspect II of the present invention, which is one preferred
aspect of the present invention, encompasses the following
inventions.
(1) A curable composition comprising:
[0095] an epoxy compound represented by the following Formula
(1):
##STR00008##
(wherein A represents CR.sup.17R.sup.18; B represents
CR.sup.19R.sup.20; R.sup.1 to R.sup.20 each independently
represents a substituent selected from the group consisting of a
hydrogen atom, an alkyl group and an alkoxy group; n represents 1;
and m represents 0);
[0096] an acid anhydride-based curing agent; and
[0097] a curing accelerator.
(2) The curable composition according to (1), further comprising an
epoxy compound other than the epoxy compound represented by the
Formula (1). (3) The curable composition according (2), wherein, in
cases where the curable composition does not include the epoxy
compound other than the epoxy compound represented by the Formula
(1), the content of the acid anhydride-based curing agent is from
0.6 to 1.2 equivalent with respect to one equivalent of the epoxy
compound represented by the Formula (1) contained in the curable
composition; and in cases where the curable composition includes
the epoxy compound other than the epoxy compound represented by the
Formula (1), the content of the acid anhydride-based curing agent
is from 0.6 to 1.2 equivalent with respect to one equivalent of a
mixture of epoxy compounds composed of the epoxy compound
represented by the Formula (1) and the epoxy compound other than
the epoxy compound represented by the Formula (1). (4) The curable
composition according to (2) or (3), wherein, in cases where the
curable composition does not include the epoxy compound other than
the epoxy compound represented by the Formula (1), the content of
the curing accelerator is from 0.1 to 10 parts by mass with respect
to 100 parts by mass of the epoxy compound represented by the
Formula (1) contained in the curable composition; and in cases
where the curable composition includes the epoxy compound other
than the epoxy compound represented by the Formula (1), the content
of the curing accelerator is from 0.1 to 10 parts by mass with
respect to 100 parts by mass of a mixture of epoxy compounds
composed of the epoxy compound represented by the Formula (1) and
the epoxy compound other than the epoxy compound represented by the
Formula (1). (5) The curable composition according to any one of
(1) to (4), wherein the curing accelerator is an imidazole-based
curing accelerator. (6) The curable composition according to (2),
wherein the epoxy compound other than the epoxy compound
represented by the Formula (1) is selected from the group
consisting of glycidyl ether-type epoxides, glycidyl ester-type
epoxides and alicyclic epoxides. (7) A cured product from the
curable composition according to any one of (1) to (6).
[0098] According to Aspect II of the present invention, it Is
possible to provide a curable composition which allows for the
production of a cured product having a high heat resistance.
[0099] According to Aspect II of the present invention, the epoxy
compound represented by the Formula (1) contained in the curable
composition according to the present invention preferably has an
epoxy equivalent of from 90 to 600 g/eq, more preferably from 90 to
300 g/eq, and still more preferably from 90 to 200 g/eq. The
content of the epoxy compound represented by the Formula (1) in the
curable composition according to the present invention is
preferably from 10 to 80% by mass, and more preferably from 15 to
60% by mass.
[0100] Aspect III of the present invention, which is one preferred
aspect of the present invention, encompasses the following
inventions.
(1) A curable composition comprising:
[0101] an epoxy compound represented by the following Formula
(1):
##STR00009##
(wherein A represents CR.sup.17R.sup.18; B represents
CR.sup.19R.sup.20; R.sup.1 to R.sup.20 each independently
represents a substituent selected from the group consisting of a
hydrogen atom, an alkyl group and an alkoxy group; n represents 0;
and m represents 1); and
[0102] a thermal cationic polymerization initiator.
(2) The curable composition according to (1), further comrising one
kind, or two or more kinds selected from the group consisting of an
epoxy compound other than the epoxy compound represented by the
Formula (1), an oxetane compound and a vinyl ether. (3) The curable
composition according to (1) or (2), wherein the cationic
polymerization initiator is selected from the group consisting of
aromatic sulfonium salt-based thermal cationic polymerization
initiators, aromatic iodonium salt-based thermal cationic
polymerization initiators and aluminum complex-based thermal
cationic polymerization initiators. (4) The curable composition
according to any one of (1) to (3), wherein the cationic
polymerization initiator is an aromatic sulfonium salt-based
thermal cationic polymerization initiator. (5) The curable
composition according to any one of (1) to (4), wherein the content
of the epoxy compound represented by the Formula (1) is from 10 to
99% by mass. (6) The curable composition according to any one of
(2) to (5), wherein, in cases where the curable composition does
not include any of the epoxy compound other than the epoxy compound
represented by the Formula (1), the oxetane compound or the vinyl
ether, the content of the thermal cationic polymerization initiator
is from 0.1 to 15 parts by mass with respect to 100 parts by mass
of the epoxy compound represented by the Formula (1) contained in
the curable composition; and in cases where the curable composition
includes one kind, or two or more kinds selected from the group
consisting of the epoxy compound other than the epoxy compound
represented by the Formula (1), the oxetane compound and the vinyl
ether, the content of the thermal cationic polymerization initiator
is from 0.1 to 15 parts by mass with respect to 100 parts by mass
of the total amount of the epoxy compound represented by the
Formula (1), the epoxy compound other than the epoxy compound
represented by the Formula (1), the oxetane compound and the vinyl
ether. (7) The curable composition according to any one of (2) to
(7), wherein the epoxy compound other than the epoxy compound
represented by the Formula (1) is selected from the group
consisting of glycidyl ether-type epoxides, glycidyl ester-type
epoxides and alicyclic epoxides. (8) A cured product from the
curable composition according to any one of (1) to (7).
[0103] According to Aspect III of the present invention, it is
possible to provide a curable composition which allows for
obtaining a cured product with a dramatically improved heat
resistance.
[0104] According to Aspect III of the present invention, the epoxy
compound represented by the Formula (1) contained in the curable
composition according to the present invention preferably has an
epoxy equivalent of from 85 to 600 g/eq, more preferably from 85 to
300 g/eq, and still more preferably from 85 to 150 g/eq. The
curable composition according to the present invention may contain
any of other compounds to be described later. However, the content
of the epoxy compound represented by the Formula (1) contained in
the curable composition according to the present invention is
preferably from 10 to 99% by mass, and more preferably from 15 to
99% by mass, from the viewpoint of improving the heat resistance of
the resulting cured product.
[0105] Aspect IV of the present invention, which is one preferred
aspect of the present invention, encompasses the following
inventions.
(1) A curable composition comprising:
[0106] an epoxy compound represented by the following Formula
(1):
##STR00010##
(wherein A represents CR.sup.17R.sup.18; B represents
CR.sup.19R.sup.20; R.sup.1 to R.sup.20 each independently
represents a substituent selected from the group consisting of a
hydrogen atom, an alkyl group and an alkoxy group; n represents 0;
and m represents 1); and
[0107] an acid anhydride-based curing agent; and
[0108] a curing accelerator.
(2) The curable composition according to (1), further comprising an
epoxy compound other than the epoxy compound represented by the
Formula (1). (3) The curable composition according (2), wherein, in
cases where the curable composition does not include the epoxy
compound other than the epoxy compound represented by the Formula
(1), the content of the acid anhydride-based curing agent is from
0.6 to 1.2 equivalent with respect to one equivalent of the epoxy
compound represented by the Formula (1) contained in the curable
composition; and in cases where the curable composition includes
the epoxy compound other than the epoxy compound represented by the
Formula (1), the content of the acid anhydride-based curing agent
is from 0.6 to 1.2 equivalent with respect to one equivalent of a
mixture of epoxy compounds composed of the epoxy compound
represented by the Formula (1) and the epoxy compound other than
the epoxy compound represented by the Formula (1). (4) The curable
composition according to (2) or (3), wherein, in cases where the
curable composition does not include the epoxy compound other than
the epoxy compound represented by the Formula (1), the content of
the curing accelerator is from 0.1 to 10 parts by mass with respect
to 100 parts by mass of the epoxy compound represented by the
Formula (1) contained in the curable composition; and in cases
where the curable composition includes the epoxy compound other
than the epoxy compound represented by the Formula (1), the content
of the curing accelerator is from 0.1 to 10 parts by mass with
respect to 100 parts by mass of a mixture of epoxy compounds
composed of the epoxy compound represented by the Formula (1) and
the epoxy compound other than the epoxy compound represented by the
Formula (1). (5) The curable composition according to any one of
(1) to (4), wherein the curing accelerator is an imidazole-based
curing accelerator. (6) The curable composition according to any
one of (2) to (5), wherein the epoxy compound other than the epoxy
compound represented by the Formula (1) is selected from the group
consisting of glycidyl ether-type epoxides, glycidyl ester-type
epoxides and alicyclic epoxides. (7) A cured product from the
curable composition according to any one of (1) to (6).
[0109] According to Aspect IV of the present invention, it is
possible to provide a curable composition which allows for the
production of a cured product having a high moisture resistance and
heat resistance.
[0110] According to Aspect IV of the present invention, the epoxy
compound represented by the Formula (1) contained in the curable
composition according to the present invention preferably has an
epoxy equivalent of from 85 to 600 g/eq, more preferably from 85 to
300 g/eq, and still more preferably from 85 to 150 g/eq. The
content of the epoxy compound represented by the Formula (1) in the
curable composition according to the present invention is
preferably from 10 to 80% by mass, and more preferably from 15 to
60% by mass.
[0111] Aspect V of the present invention, which is one preferred
aspect of the present invention, encompasses the following
inventions.
(1) A curable composition comprising:
[0112] an epoxy compound represented by the following Formula
(1):
##STR00011##
(wherein A represents CR.sup.17R.sup.18; B represents
CR.sup.19R.sup.20; R.sup.1 to R.sup.20 each independently
represents a substituent selected from the group consisting of a
hydrogen atom, an alkyl group and an alkoxy group; and n represents
0 or 1, with the proviso that when n is 0, m represents 1, and when
n is 1, m represents 0); and
[0113] a photo-cationic polymerization initiator.
(2) The curable composition according to (1), further comprising
one kind, or two or more kinds selected from the group consisting
of an epoxy compound other than the epoxy compound represented by
the Formula (1), an oxetane compound and a vinyl ether. (3) The
curable composition according to (1) or (2), wherein the
photo-cationic polymerization initiator is an aromatic sulfonium
salt-based photo-cationic polymerization initiator. (4) The curable
composition according to any one of (1) to (3), wherein the content
of the epoxy compound represented by the Formula (1) is from 1 to
50% by mass. (5) The curable composition according to any one of
(2) to (4), wherein the epoxy compound other than the epoxy
compound represented by the Formula (1) is selected from the group
consisting of glycidyl ether-type epoxides, glycidyl ester-type
epoxides and alicyclic epoxides. (6) The curable composition
according to any one of (2) to (5) wherein, in cases where the
curable composition does not include any of the epoxy compound
other than the epoxy compound represented by the Formula (1), the
oxetane compound or the vinyl ether, the content of the
photo-cationic polymerization initiator is from 0.1 to 20 parts by
mass with respect to 100 parts by mass of the epoxy compound
represented by the Formula (1) contained in the curable
composition; and in cases where the curable composition includes
one kind, or two or more kinds selected from the group consisting
of the epoxy compound other than the epoxy compound represented by
the Formula (1), the oxetane compound and the vinyl ether, the
content of the photo-cationic polymerization initiator is from 0.1
to 20 parts by mass with respect to 100 parts by mass of the total
amount of the epoxy compound represented by the Formula (1), the
epoxy compound other than the epoxy compound represented by the
Formula (1), the oxetane compound and the vinyl ether. (7) A cured
product from the curable composition according to any one of (1) to
(6).
[0114] According to Aspect V of the present invention, it is
possible to provide a curable composition which allows for
obtaining a cured product with a dramatically improved heat
resistance.
[0115] According to Aspect V of the present invention, the epoxy
compound represented by the Formula (1) contained in the curable
composition according to the present invention preferably has an
epoxy equivalent of from 85 to 600 g/eq, more preferably from 85 to
300 g/eq, and still more preferably from 85 to 200 g/eq. The
curable composition according to the present invention may further
contain any of other compounds to be described later. However, the
content of the epoxy compound represented by the Formula (1)
contained in the curable composition according to the present
invention is preferably from 1 to 50% by mass, and more preferably
from 5 to 40% by mass, from the viewpoint of improving the heat
resistance the resulting cured product. In one embodiment, it is
preferred that the curable composition according to the present
invention further contain the epoxy compound other than the epoxy
compound represented by the Formula (1) and/or the oxetane
compound.
EXAMPLES
[0116] The present invention will now be described in further
detail by way of Examples. However, the present invention is in no
way limited by these Examples.
1. Preparation Example 1: Production of Epoxy Compound (A-1)
Satisfying Formula (1)
[0117] Into a reaction vessel equipped with a thermometer, an
agitator, a reflux tube and a dropping device, 23.5 kg of
chloroform, and 1.6 kg of a compound represented by the following
Formula (3) and satisfying the above described Formula (2) were
charged. To the reactor, 4.5 kg of meta-chloroperoxybenzoic acid
was added dropwise while stirring at 0.degree. C. The temperature
was then raised to room temperature, and a reaction was allowed to
proceed for 12 hours.
[0118] Subsequently, by-produced meta-chlorobenzoic acid was
removed by filtration, and the filtrate was then washed with a 1N
aqueous solution of sodium hydroxide three times, followed by
washing with saturated saline. After drying the organic layer with
magnesium sulfate, the magnesium sulfate was removed by filtration
to concentrate the filtrate, thereby obtaining a coarse
product.
[0119] A quantity of 2 kg of toluene was added to the coarse
product, to dissolve the coarse product at room temperature. To the
resultant, 6 kg of heptane was added dropwise to allow
crystallization to occur. The resultant was matured at 5.degree. C.
for one hour. The resulting crystallization product was filtered,
and washed with hexane. Thereafter, the crystallization product was
dried under reduced pressure for 24 hours, to obtain 1.4 kg of an
epoxy compound (A-1) which is represented by the following Formula
(4) and which satisfies the above described Formula (1), as a white
solid. The epoxy equivalent of the thus obtained epoxy compound
(A-1) was measured in accordance with JIS K7236, and it was
determined to be 122 g/eq. The structure of the resulting epoxy
compound (A-1) was analyzed by .sup.13C-NMR, to confirm that the
epoxy compound (A-1) of interest had been obtained. The
.sup.13C-NMR chart of the epoxy compound (A-1) is shown in FIG.
1.
##STR00012##
2. Preparation Example 2: Synthesis of Epoxy Compound (A-2)
Satisfying Formula (1)
[0120] Into a reaction vessel equipped with a thermometer, an
agitator, a reflux tube and a dropping device, 59.2 kg of
chloroform, and 4.0 kg of a compound represented by the following
Formula (5) and satisfying the above described Formula (2) were
charged. To the reactor, 10.6 kg of meta-chloroperoxybenzoic acid
was added dropwise while stirring at -10.degree. C. The temperature
was then raised to room temperature, and a reaction was allowed to
proceed for 12 hours.
[0121] Subsequently, by-produced meta-chlorobenzoic acid was
removed by filtration, and the filtrate was then washed with 42.0
kg of a 5% aqueous solution of sodium sulfite. The organic layer
was further washed with 41.6 kg of a 1N aqueous solution of sodium
hydroxide four times, followed by washing with 48.0 kg of saturated
saline. After drying the organic layer with magnesium sulfate, the
magnesium sulfate was removed by filtration to concentrate the
filtrate, thereby obtaining 5.1 kg of a coarse product.
[0122] A quantity of 3.5 kg of toluene was added to the coarse
product, to dissolve the coarse product at room temperature. To the
resultant, 13.7 kg of heptane was added dropwise to allow
crystallization to occur. The resultant was matured at 5.degree. C.
for one hour. The resulting crystallization product was filtered,
and washed with heptane. Thereafter, the crystallization product
was dried under reduced pressure at 35.degree. C. for 12 hours, to
obtain 2.8 kg of an epoxy compound (A-2) which is represented by
the following Formula (6) and which satisfies the above described
Formula (1), as a white solid. The epoxy equivalent of the thus
obtained epoxy compound (A-2) was measured in accordance with JIS
K7236, and it was determined to be 180 g/eq. Note, however, that
since the measured value (180 g/eq) of the epoxy equivalent of the
resulting epoxy compound (A-2) did not coincide with the
theoretical value (115 g/eq) of the epoxy equivalent of the epoxy
compound (A-2) calculated from the chemical structure of the epoxy
compound (A-2), the theoretical value 115 g/eq was used as the
epoxy equivalent of the epoxy compound (A-2), when determining the
content of an acid anhydride-based curing agent to be used. The
structure of the resulting epoxy compound (A-2) was analyzed by
1.sup.3C-NMR, to confirm that the epoxy compound (A-2) of interest
had been obtained. The .sup.13C-NMR chart of the epoxy compound
(A-2) is shown in FIG. 2.
##STR00013##
3. Preparation Example 3: Synthesis of Epoxy Compound (A-3)
Satisfying Formula (1)
[0123] Into a reaction vessel equipped with a thermometer, an
agitator, a reflux tube and a dropping device, 59.2 kg of
chloroform, and 4.0 kg of a compound represented by the following
Formula (3) and satisfying the above described Formula (2) were
charged. To the reactor, 10.6 kg of meta-chloroperoxybenzoic acid
was added dropwise while stirring at -10.degree. C. The temperature
was then raised to room temperature, and a reaction was allowed to
proceed for 12 hours.
[0124] Subsequently, by-produced meta-chlorobenzoic acid was
removed by filtration, and the filtrate was then washed with 42.0
kg of a 5% aqueous solution of sodium sulfite. The organic layer
was further washed with 41.6 kg of a 1N aqueous solution of sodium
hydroxide four times, followed by washing with 48.0 kg of saturated
saline. After drying the organic layer with magnesium sulfate, the
magnesium sulfate was removed by filtration to concentrate the
filtrate, thereby obtaining 5.1 kg of a coarse product.
[0125] A quantity of 3.5 kg of toluene was added to the coarse
product, to dissolve the coarse product at room temperature. To the
resultant, 13.7 kg of heptane was added dropwise to allow
crystallization to occur. The resultant was matured at 5.degree. C.
for one hour. The resulting crystallization product was filtered,
and washed with heptane. Thereafter, the crystallization product
was dried under reduced pressure at 35.degree. C. for 12 hours, to
obtain 2.8 kg of an epoxy compound (A-3) which is represented by
the following Formula (4) and which satisfies the above described
Formula (1), as a white solid.
##STR00014##
4. Preparation Example 4: Production of Monoepoxy Compound as
Reactive Diluent
Production Example of Monoepoxy Compound
[0126] Into a reaction vessel equipped with a thermometer, an
agitator, a reflux tube and a dropping device, 3,132 g of a
diolefin compound represented by the following Formula (7), 3,132 g
of toluene and sodium acetate were charged. To the reactor, 3,783 g
of a 38% aqueous solution of peracetic acid was added dropwise over
five hours, while stirring at -5.degree. C. While continuing to
stir the mixture at -5.degree. C., a reaction was allowed to
proceed for 17 hours.
[0127] Subsequently, a 10% aqueous solution of sodium sulfite was
used to carry out a neutralization treatment, followed by a liquid
separation operation. The resultant was then subjected to
distillation at a pressure of 2 hPa and a bottom temperature of
from 130 to 140.degree. C., to obtain 2,109 g of a colorless
transparent liquid. In the .sup.13C-NMR spectrum and the precise
mass measurement by LC-MS, the [M+H].sup.+ of the thus obtained
liquid was determined to be 191.1439, which corresponds to the
theoretical structure. Accordingly, it was confirmed that the
resulting liquid was a monoepoxy compound of interest satisfying
the following Formula (8). The viscosity of the resulting monoepoxy
compound was measured using a Type E viscometer, to be 11.0
mPas.
##STR00015##
I. Examples of Aspect I of the Present Invention
I-1. Examples I 1: Preparation of Curable Compositions Containing
Epoxy Compound (A-2) and Evaluation Thereof (Part 1: Combination
with the Other Epoxy Compounds and Thermal Cationic Polymerization
Initiator, and Comparison with Dicyclopentadiene Diepoxide (the
Other Epoxy Compound (I B-1)))
(1) Example I 1-1
Production of Curable Composition
[0128] Tricyclopentadiene diepoxide obtained as the epoxy compound
(A-2) by the method described in the above Preparation Example 2,
the other epoxy compound (I B-2) and a thermal cationic
polymerization initiator were mixed to achieve the following
composition, to obtain a curable composition.
<Composition of Curable Composition>
[0129] Epoxy compound (A-2) 75 parts by mass (tricyclopentadiene
diepoxide obtained by the method described in the above Preparation
Example 2) [0130] the other epoxy compound (I B-2) 25 parts by mass
(bisphenol A-type liquid epoxy resin, manufactured by Nippon Steel
& Sumikin Chemical Co., Ltd., trade name YD-128) [0131] Thermal
cationic polymerization initiator (I D-1) 2 parts by mass (an
aromatic sulfonium salt: 4-acetoxyphenyldimethylsulfonium
hexafluoroantimonate, manufactured by Sanshin Chemical Industry
Co., Ltd., trade name: SI-150L)
<Evaluation of Physical Properties>
(Weight Reduction Rate)
[0132] The curable composition obtained as described above was
heated in a hot air circulating oven at 130.degree. C. for one
hour, at 150.degree. C. for one hour, at 190.degree. C. for two
hours, and then at 240.degree. C. for one hour, to obtain a cured
product. The weight reduction rate of the resulting cured product
was calculated as follows, and summarized in Tables I-1 and
I-2.
Weight reduction rate (%)=(weight of curable composition-weight of
cured product from curable composition)/weight of curable
composition.times.100
(Heat Resistance)
[0133] The glass transition temperature of the cured product
obtained as described above was measured by increasing the
temperature from 30 to 300.degree. C. at a rate of 10.degree.
C./min, using a differential scanning calorimeter, DSC7020,
manufactured by Hitachi High-Tech Science Corporation, and the thus
measured value was taken as the heat resistance of the cured
product. The glass transition temperature as used herein refers to
a value measured in accordance with JIS K7121, based on "Midpoint
Glass Transition Temperature: T.sub.mg" described in the section of
"Method for Measuring Transition Temperature of Plastics". The
measurement results are summarized in Tables I-1 and I-2.
(Overall Evaluation)
[0134] The overall evaluation of the curable composition obtained
in the above described Example was carried out according to the
following evaluation criteria. The evaluation results are
summarized in Tables I-1 and I-2.
.smallcircle.: The resulting cured product has a weight reduction
rate of less than 5% and a heat resistance of 230.degree. C. or
higher. x: The resulting cured product has a weight reduction rate
of 5% or more and/or a heat resistance of less than 230.degree. C.,
and thus has problems in practical use.
(2) Example I 1-2
[0135] A curable composition was obtained in the same manner as in
Example I 1-1, except that the composition of the curable
composition was changed as described below.
<Composition of Curable Composition>
[0136] Epoxy compound (A-2) 60 parts by mass (tricyclopentadiene
diepoxide obtained by the method described in the above Preparation
Example 2) [0137] the other epoxy compound (I B-3) 40 parts by mass
(3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate,
manufactured by Daicel Corporation, trade name: CELLOXIDE 2021P,
epoxy equivalent: 131 g/eq) [0138] Thermal cationic polymerization
initiator (I D-1) 2 parts by mass (an aromatic sulfonium salt:
4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, manufactured
by Sanshin Chemical Industry Co., Ltd., trade name: SI-150L)
[0139] The curable composition obtained as described above was
heated in the same manner as in Example I 1-1, to obtain a cured
product.
[0140] The weight reduction rate and the glass transition
temperature of the thus obtained cured product were measured In the
same manner as in Example I 1-1. The measurement results are
summarized in Tables I-1 and I-2.
(3) Example I 1-3
[0141] A curable composition was obtained in the same manner as in
Example I 1-1, except that the composition of the curable
composition was changed as shown in Tables I-1 and I-2, to obtain a
curable composition.
[0142] The curable composition obtained as described above was
heated in the same manner as in Example I 1-1, to obtain a cured
product.
[0143] The weight reduction rate and the glass transition
temperature of the thus obtained cured product were measured in the
same manner as in Example I 1-1. The measurement results are
summarized in Tables I-1 and I-2.
(4) Examples I 1-4 to I 1-7
[0144] Curable compositions were obtained in the same manner as in
Example I 1-1, except that the compositions of the curable
compositions were changed to those shown in Tables I-1 and I-2.
[0145] The curable compositions obtained as described above were
heated in a hot air circulating oven at 140.degree. C. for one
hour, at 180.degree. C. for one hour, and then at 220.degree. C.
for two hours, to obtain cured products.
[0146] The weight reduction rate and the glass transition
temperature of each of the thus obtained cured products were
measured in the same manner as in Example I 1-1. The measurement
results are summarized in Tables I-1 and I-2.
(5) Comparative Example I 1-1
[0147] A curable composition was obtained in the same manner as in
Example I 1-1, except that the composition of the curable
composition was changed as shown in Tables I-1 and I-2, to obtain a
curable composition.
[0148] The curable composition obtained as described above was
heated in a hot air circulating oven at 140.degree. C. for one
hour, at 160.degree. C. for one hour, at 180.degree. C. for one
hour, at 220.degree. C. for one hour, and then at 240.degree. C.
for two hours, to obtain a cured product.
[0149] The weight reduction rate and the glass transition
temperature of the thus obtained cured product were measured in the
same manner as in Example I 1-1. The measurement results are
summarized in Tables I-1 and I-2.
(6) Comparative Examples I 1-2 to I 1-4
[0150] Curable compositions were obtained in the same manner as in
Example I 1-1, except that the compositions of the curable
compositions were changed to those shown in Tables I-1 and I-2.
[0151] The curable compositions obtained as described above were
heated in a hot air circulating oven at 130.degree. C. for one
hour, at 150.degree. C. for one hour, at 180.degree. C. for one
hour, and then at 200.degree. C. for two hours, to obtain cured
products.
[0152] The weight reduction rate and the glass transition
temperature of each of the thus obtained cured products were
measured in the same manner as in Example I 1-1. The measurement
results are summarized in Tables I-1 and I-2.
(7) Comparative Example I 1-5
[0153] A curable composition was obtained in the same manner as in
Example I 1-1, except that the composition of the curable
composition was changed as shown in Tables I-1 and I-2, to obtain a
curable composition.
[0154] The curable composition obtained as described above was
heated in a hot air circulating oven at 110.degree. C. for one
hour, at 180.degree. C. for one hour, at then at 220.degree. C. for
two hours, to obtain a cured product.
[0155] The weight reduction rate and the glass transition
temperature of the thus obtained cured product were measured in the
same manner as in Example I 1-1. The measurement results are
summarized in Tables I-1 and I-2.
(8) Comparative Example I 1-6
[0156] A curable composition was obtained in the same manner as in
Example I 1-1, except that dicyclopentadiene diepoxide (the other
epoxy compound (I B-1)) represented by the following Formula was
used instead of tricyclopentadiene diepoxide (epoxy compound (A-2))
in the curable composition.
##STR00016##
[0157] The curable composition obtained as described above was
heated in a hot air circulating oven at 130.degree. C. for one
hour, at 140.degree. C. for one hour, at 160.degree. C. for one
hour, at 190.degree. C. for one hour, and then at 240.degree. C.
for two hours, to obtain a cured product.
[0158] The weight reduction rate and the glass transition
temperature of the thus obtained cured product were measured in the
same manner as in Example I 1-1. The measurement results are
summarized in Tables I-1 and 1-2.
(9) Comparative Examples I 1-7 to I 1-10
[0159] Curable compositions were obtained in the same manner as in
Example I 1-1, except that the compositions of the curable
compositions were changed to those shown in Tables I-1 and I-2.
[0160] The curable compositions obtained as described above were
heated in a hot air circulating oven at 130.degree. C. for one
hour, at 140.degree. C. for one hour, at 160.degree. C. for one
hour, at 190.degree. C. for one hour, and then at 240.degree. C.
for two hours, to obtain cured products.
[0161] The weight reduction rate and the glass transition
temperature of each of the thus obtained cured products were
measured in the same manner as in Example I 1-1. The measurement
results are summarized in Tables I-1 and I-2.
(Overall Evaluation)
[0162] The overall evaluation of each of the curable compositions
obtained in the above described Examples I 1-2 to I 1-7 and
Comparative Examples I 1-1 to I 1-10 was carried out according to
the evaluation criteria described in Example I 1-1. The evaluation
results are summarized in Tables I-1 and I-2.
TABLE-US-00001 TABLE 1 Ex- Ex- Ex- Ex- Ex- Ex- Ex- am- am- am- am-
am- am- am- ple ple ple ple ple ple ple Table I-1 I 1-1 I 1-2 I 1-3
I 1-4 I 1-5 I 1-6 I 1-7 Composi- Epoxy com- 75 60 50 25 75 50 25
tion pound (A-2) of curable the other 25 50 75 composi- epoxy com-
tion pound (I B-2) (parts by the other 40 25 50 75 mass) epoxy com-
pound (I B-3) Thermal 2 2 2 2 2 2 2 cationic polymeriza- tion
initiator (I D-1) Weight reduction rate 0 3 0 0 0 1 0 of cured
product (%) Heat resistance (.degree. C.) 247 253 257 258 245 247
234 Overall evaluation .smallcircle. .smallcircle. .smallcircle.
.smallcircle. .smallcircle. .smallcircle. .smallcircle.
TABLE-US-00002 TABLE 2 Com- Com- Com- Com- Com- Com- Com- Com- Com-
Com- para- para- para- para- para- para- para- para- para- para-
tive tive tive tive tive tive tive tive tive tive Exam- Exam- Exam-
Exam- Exam- Exam- Exam- Exam- Exam- Exam- ple ple ple ple ple ple
ple ple ple ple Table I-2 I 1-1 I 1-2 I 1-3 I 1-4 I 1-5 I 1-6 I 1-7
I 1-8 I 1-9 I 1-10 Composition Epoxy compound (A-2) of curable the
other epoxy 75 50 25 75 50 composition compound (I B-1) (parts by
the other epoxy 100 75 50 25 25 50 75 mass) compound (I B-2) the
other epoxy 25 50 75 100 25 75 compound (I B-3) Thermal cationic 2
2 2 2 1 2 2 2 2 2 polymerization initiator (I D-1) Weight reduction
rate of 1 0 1 1 1 19 15 8 7 5 cured product (%) Heat resistance
(.degree. C.) 188 220 157 188 175 262 248 239 264 161 Overall
evaluation x x x x x x x x x x
I-2. Examples I 2: Preparation of Curable Compositions Containing
Epoxy Compound (A-2) and Evaluation Thereof (Part 2: Combination
with the Other Epoxy Compounds, Oxetane Compound, and Thermal
Cationic Polymerization Initiator)
(1) Example I 2-1
Production of Curable Composition
[0163] Tricyclopentadiene diepoxide (epoxy compound (A-2)) obtained
in in the above described Preparation Example 2, an oxetane
compound and a thermal cationic polymerization initiator were mixed
to achieve the following composition, to obtain a curable
composition.
<Composition of Curable Composition>
[0164] Epoxy compound (A-2) 75 parts by mass (tricyclopentadiene
diepoxide obtained by the method described in the above Preparation
Example 2) [0165] Oxetane compound (I C-1) 25 parts by mass
(1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, manufactured by
Toagosel Co., Ltd., trade name: ARONE OXETANE OXT-121) [0166]
Thermal cationic polymerization Initiator (I D-1) 2 parts by mass
(an aromatic sulfonium salt, 4-acetoxyphenyldimethylsulfonium
hexafluoroantimonate, manufactured by Sanshin Chemical Industry
Co., Ltd., trade name: SI-150L)
[0167] The curable composition obtained as described above was
heated in a hot air circulating oven at 100.degree. C. for one
hour, at 130.degree. C. for one hour, at 160.degree. C. for one
hour, and then at 230.degree. C. for two hours, to obtain a cured
product.
[0168] The glass transition temperature of the thus obtained cured
product was measured in the same manner as in Example I 1-1. The
measurement results are summarized in Table I-3.
(2) Examples I 2-2 to I 2-3
[0169] Curable compositions were obtained in the same manner as in
Example I 2-1, except that the compositions of the curable
compositions were changed to those shown in Table I-3.
[0170] The curable compositions obtained as described above were
heated in the same manner as in Example I 2-1, to obtain cured
products.
[0171] The glass transition temperature of each of the thus
obtained cured products was measured in the same manner as in
Example I 2-1. The measurement results are summarized in Table
I-3.
(3) Comparative Examples I 2-1 to I 2-3
[0172] Curable compositions were obtained in the same manner as in
Example I 2-1, except that the compositions of the curable
compositions were changed to those shown in Table I-3.
[0173] The curable compositions obtained as described above were
heated in a hot air circulating oven at 130.degree. C. for one
hour, at 150.degree. C. for one hour, at then at 180.degree. C. for
two hours, to obtain cured products.
[0174] The glass transition temperature of each of the thus
obtained cured products was measured in the same manner as in
Example I 2-1. The measurement results are summarized in Table
I-3.
(4) Comparative Examples I 2-4 and I 2-5
[0175] Curable compositions were obtained in the same manner as in
Example I 2-1, except that the compositions of the curable
compositions were changed to those shown in Table I-3.
[0176] The curable compositions obtained as described above were
heated in a hot air circulating oven at 120.degree. C. for one
hour, at 140.degree. C. for one hour, and then at 220.degree. C.
for two hours, to obtain cured products.
[0177] The glass transition temperature of each of the thus
obtained cured products was measured in the same manner as In
Example I 1-1. The measurement results are summarized in Table
I-3.
(5) Comparative Example I 2-6
[0178] A curable composition was obtained in the same manner as in
Example I 2-1, except that the composition of the curable
composition was changed to that shown in Table I-3.
[0179] The curable composition obtained as described above was
heated in a hot air circulating oven at 110.degree. C. for one
hour, at 130.degree. C. for one hour, and then at 240.degree. C.
for two hours, to obtain a cured product.
[0180] The glass transition temperature of the thus obtained cured
product was measured in the same manner as in Example I 1-1. The
measurement results are summarized in Table I-3.
TABLE-US-00003 TABLE 3 Com- Com- Com- Com- Com- Com- para- para-
para- para- para- para- tive tive tive tive tive tive Exam- Exam-
Exam- Exam- Exam- Exam- Exam- Exam- Exam- ple ple ple ple ple ple
ple ple ple Table I-3 I 2-1 I 2-2 I 2-3 I 2-1 I 2-2 I 2-3 I 2-4 I
2-5 I 2-6 Composition Epoxy compound 75 50 25 of curable (A-2)
composition the other epoxy 75 75 (parts by mass) compound (I B-2)
the other epoxy 75 50 75 compound (I B-3) the other epoxy 75
compound (I B-14) Oxetane 25 50 75 25 25 50 25 25 25 compound (I
C-1) Thermal cationic 2 2 2 2 2 2 2 2 2 Polymerization Initiator (I
D-1) Heat resistance (.degree. C.) 185 181 180 166 96 120 175 160
153
I-3 Examples I 3: Preparation of Curable Compositions Containing
Epoxy Compound (A-2) and Evaluation Thereof (Part 3: Combination
with the Other Epoxy Compounds and Thermal Cationic Polymerization
Initiator)
(1) Examples I 3-1 to I 3-7 and Comparative Examples I 3-1 to I
3-7
[0181] Curable compositions were prepared in the same manner as in
Example I 1-1, except that the following components were used at
the compositions shown in Tables I-4 and I-5.
(i) Epoxy Compound (A-2)
[0182] Tricyclopentadiene diepoxide obtained by the method
described in the above Preparation Example 2 was used.
(ii) The Other Epoxy Compound (I B-1)
[0183] Dicyclopentadiene diepoxide described in the above
Comparative Example I 1-6 was used.
(iii) The Other Epoxy Compound (I B-2)
[0184] A bisphenol A-type liquid epoxy resin, manufactured by
Nippon Steel & Sumikin Chemical Co., Ltd., trade name: YD-128,
was used.
(iv) The Other Epoxy Compound (I B-3)
[0185] 3',4'-Epoxycyclohexylmethyl 3,4-epoxycyclohexane
carboxylate, manufactured by Daicel Corporation, trade name:
CELLOXIDE 2021P, was used.
(v) The Other Epoxy Compound (I B-6)
[0186] A bisphenol F-type liquid epoxy resin, manufactured by
Nippon Steel & Sumikin Chemical Co., Ltd., trade name: YDF-170,
was used.
(vi) The Other Epoxy Compound (I B-8)
[0187] Triglycidyl isocyanurate, manufactured by Nissan Chemical
Industries, Ltd., trade name: TEPIC-S, was used.
(vii) The Other Epoxy Compound (I B-10)
[0188] Cyclohexanedicarboxylic acid diglycidyl ester, a reagent
manufactured by Tokyo Chemical Industry Co., Ltd., was used.
(viii) The Other Epoxy Compound (I B-12)
[0189] 1,2-Epoxy-(2-oxiranyl)cyclohexane adduct of
2,2-bis(hydroxymethyl)-1-butanol, manufactured by Daicel
Corporation, trade name: EHPE 3150, was used.
(ix) The Other Epoxy Compound (I B-15)
[0190] An epoxy compound produced by the method described in
Example 3 in JP 49-126658 A was used.
(x) The Other Epoxy Compound (I B-16)
[0191] Tetrahydroindene diepoxide produced by the method described
in JP 2012-116390 A was used.
(xi) The Other Epoxy Compound (I B-17)
[0192] 1,2-Epoxy-4-vinylcyclohexane, manufactured by Dacel
Corporation, trade name: CELLOXIDE 2000, was used.
(xii) Thermal Cationic Polymerization Initiator (I D-1)
[0193] 4-Acetoxyphenyidimethylsulfonium hexafluoroantimonate,
manufactured by Sanshin Chemical Industry Co., Ltd., trade name:
SI-150L, was used.
(2) Evaluation of Physical Properties
[0194] (Weight Reduction Rate of Cured Product from Curable
Composition)
[0195] Each of the curable compositions obtained as described above
was heated under each of the following conditions, to obtain a
cured product.
(a) Example I 3-1
[0196] The curable composition obtained as described above was
heated in a hot air circulating oven at 170.degree. C. for one
hour, at 190.degree. C. for one hour, and then at 220.degree. C.
for two hours, to obtain a cured product.
(b) Example I 3-2
[0197] The curable composition obtained as described above was
heated in a hot air circulating oven at 110.degree. C. for one
hour, at 140.degree. C. for one hour, and then at 220.degree. C.
for two hours, to obtain a cured product.
(c) Example I 3-3
[0198] The curable composition obtained as described above was
heated in a hot air circulating oven at 120.degree. C. for one
hour, at 180.degree. C. for one hour, and then at 230.degree. C.
for two hours, to obtain a cured product.
(d) Example I 3-4
[0199] The curable composition obtained as described above was
heated in a hot air circulating oven at 150.degree. C. for one
hour, at 170.degree. C. for one hour, and then at 220.degree. C.
for two hours, to obtain a cured product.
(e) Example I 3-5
[0200] The curable composition obtained as described above was
heated in a hot air circulating oven at 160.degree. C. for one
hour, and then at 220.degree. C. for two hours, to obtain a cured
product.
(f) Example I 3-6
[0201] The curable composition obtained as described above was
heated in a hot air circulating oven at 150.degree. C. for one
hour, at 180.degree. C. for one hour, and then at 220.degree. C.
for two hours, to obtain a cured product.
(g) Example I 3-7
[0202] The curable composition obtained as described above was
heated in a hot air circulating oven at 140.degree. C. for one
hour, at 160.degree. C. for one hour, and then at 220.degree. C.
for two hours, to obtain a cured product.
(a') Comparative Example I 3-1
[0203] The curable composition obtained as described above was
heated in a hot air circulating oven at 110.degree. C. for one
hour, and then at 240.degree. C. for two hours, to obtain a cured
product.
(b') Comparative Example 13-2
[0204] The curable composition obtained as described above was
heated in a hot air circulating oven at 110.degree. C. for one
hour, at 170.degree. C. for one hour, and then at 220.degree. C.
for two hours, to obtain a cured product.
(d') Comparative Example I 3-3
[0205] The curable composition obtained as described above was
heated in a hot air circulating oven at 130.degree. C. for one
hour, at 190.degree. C. for one hour, and then at 230.degree. C.
for two hours, to obtain a cured product.
(c') Comparative Example I 3-4
[0206] The curable composition obtained as described above was
heated in a hot air circulating oven at 120.degree. C. for one
hour, at 140.degree. C. for one hour, and then at 220.degree. C.
for two hours, to obtain a cured product.
(d') Comparative Example I 3-5
[0207] The curable composition obtained as described above was
heated in a hot air circulating oven at 150.degree. C. for one
hour, at 170.degree. C. for one hour, and then at 210.degree. C.
for two hours, to obtain a cured product.
(e') Comparative Example I 3-6
[0208] The curable composition obtained as described above was
heated in a hot air circulating oven at 130.degree. C. for one
hour, at 150.degree. C. for one hour, at 180.degree. C. for one
hour, and then at 220.degree. C. for three hours, to obtain a cured
product.
(f') Comparative Example I 3-7
[0209] The curable composition obtained as described above was
heated in a hot air circulating oven at 120.degree. C. for one
hour, at 130.degree. C. for one hour, and then at 190.degree. C.
for two hours, to obtain a cured product.
[0210] The weight reduction rate of each of the cured products
obtained as described above was calculated in the same manner as in
Example I 1-1. The measurement results are summarized in Tables I-4
and I-5.
(Heat Resistance of Cured Product from Curable Composition)
[0211] The heat resistance of each of the cured products obtained
as described above was measured in the same manner as in Example I
1-1. The measurement results are summarized in Tables I-4 and
I-5.
(Overall Evaluation)
[0212] The overall evaluation of each of the curable compositions
obtained in the above described Examples was carried out according
to the following evaluation criteria. The evaluation results are
summarized in Tables I-4 and I-5.
.smallcircle.: The resulting cured product has a weight reduction
rate of 5% or less and a heat resistance of 220.degree. C. or
higher. x: The resulting cured product has a weight reduction rate
of more than 5% and/or a heat resistance of less than 220.degree.
C., and thus has problems in practical use.
TABLE-US-00004 TABLE 4 Compar- Compar- Compar- Compar- ative ative
ative ative Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- ple ple
ple ple ple ple ple ple Table I-4 I 3-1 I 3-2 I 3-3 I 3-4 I 3-1 I
3-2 I 3-3 I 3-4 Composition Epoxy compound (A-2) 25 50 50 50 of
curable the other epoxy 25 25 37.5 50 50 87.5 composition compound
(I B-3) (parts by the other epoxy 50 100 mass) compound (I B-6) the
other epoxy 50 50 compound (I B-8) the other epoxy 25 50 compound
(I B-12) the other epoxy 12.5 12.5 compound (I B-17) Thermal
cationic 2 2 2 2 2 2 2 2 polymerization initiator (I D-1) Weight
reduction rate of 0 0 0 2 7 0 2 2 cured product (%) Heat resistance
(.degree. C.) 237 226 252 238 134 199 144 200 Overall evaluation
.smallcircle. .smallcircle. .smallcircle. .smallcircle. x x x x
TABLE-US-00005 TABLE 5 Compar- Compar- Compar- ative ative ative
Exam- Exam- Exam- Exam- Exam- Exam- ple ple ple ple ple ple Table
I-5 I 3-5 I 3-6 I 3-7 I 3-5 I 3-6 I 3-7 Composition Epoxy compound
(A-2) 50 50 50 of curable the other epoxy 50 composition compound
(I B-1) (parts by the other epoxy 25 mass compound (I B-2) the
other epoxy 50 100 compound (I B-10) the other epoxy 25 100
compound (I B-15) the other epoxy 50 50 compound (I B-16) Thermal
cationic polymerization initiator 2 2 2 2 2 2 (I D-1) Weight
reduction rate of 0 1 5 1 1 7 cured product (%) Heat resistance
(.degree. C.) 225 223 232 90 198 197 Overall evaluation
.smallcircle. .smallcircle. .smallcircle. x x x
I-4. Examples I 4: Preparation of Curable Compositions Containing
Epoxy Compound (A-2) and Evaluation Thereof (Part 4: Combination
with Various Types of Thermal Cationic Polymerization
Initiators)
(1) Example I 4-1 to I 4-5 and Comparative Examples I 4-1 to I
4-5
[0213] Curable compositions were prepared in the same manner as in
Example I 1-1, except that the following components were used at
the compositions shown in Tables I-6 and I-7.
(i) Epoxy Compound (A-2)
[0214] Tricyclopentadiene diepoxide obtained by the method
described in the above Preparation Example 2 was used.
(ii) The Other Epoxy Compound (I B-1)
[0215] Dicyclopentadiene diepoxide described in the above
Comparative Example I 1-6 was used.
(iii) The Other Epoxy Compound (I B-2)
[0216] A bisphenol A-type liquid epoxy resin, manufactured by
Nippon Steel & Sumikin Chemical Co., Ltd., trade name: YD-128,
was used.
(iv) The Other Epoxy Compound (I B-3)
[0217] 3',4'-Epoxycyclohexylmethyl 3,4-epoxycyclohexane
carboxylate, manufactured by Daicel Corporation, trade name:
CELLOXIDE 2021P, was used.
(v) Thermal Cationic Polymerization Initiator (I D-3)
[0218] Bis[4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl]sulfide
bishexafluoroantimonate, manufactured by ADEKA CORPORATION, ADEKA
ARKLS SP-170, was used.
(vi) Thermal Cationic Polymerization Initiator (I D-4)
[0219] Diphenyl-4-(phenylthio)phenylsulfonium hexafluoroantimonate,
manufactured by San-Apro Ltd., CPI-101A, was used.
(vii) Thermal Cationic Polymerization Initiator (I D-5)
[0220] 4-Methylphenyl-4-(1-methylethyl)phenyliodonium
tetrakis(pentafluorophenyl)borate, a reagent manufactured by Tokyo
Chemical Industry Co., Ltd., was used.
(2) Evaluation of Physical Properties
(Weight Reduction Rate of Cured Product of Curable Composition)
[0221] Each of the curable compositions obtained as described above
was heated under each of the following conditions, to obtain a
cured product.
(a) Example I 4-1
[0222] The curable composition obtained as described above was
heated in a hot air circulating oven at 70.degree. C. for one hour,
at 130.degree. C. for one hour, and then at 240.degree. C. for two
hours, to obtain a cured product.
(b) Example I 4-2
[0223] The curable composition obtained as described above was
heated in a hot air circulating oven at 80.degree. C. for one hour,
at 140.degree. C. for one hour, and then at 180.degree. C. for two
hours, to obtain a cured product.
(c) Example I 4-3
[0224] The curable composition obtained as described above was
heated in a hot air circulating oven at 140.degree. C. for one
hour, at 160.degree. C. for one hour, and then at 220.degree. C.
for two hours, to obtain a cured product.
(d) Example I 4-4
[0225] The curable composition obtained as described above was
heated in a hot air circulating oven at 70.degree. C. for one hour,
at 140.degree. C. for one hour, and then at 200.degree. C. for two
hours, to obtain a cured product.
(e) Example I 4-5
[0226] The curable composition obtained as described above was
heated in a hot air circulating oven at 90.degree. C. for one hour,
and then at 240.degree. C. for two hours, to obtain a cured
product.
(a') Comparative Example I 4-1
[0227] The curable composition obtained as described above was
heated in a hot air circulating oven at 70.degree. C. for one hour,
at 130.degree. C. for one hour, and then at 170.degree. C. for two
hours, to obtain a cured product.
(b') Comparative Example 14-2
[0228] The curable composition obtained as described above was
heated in a hot air circulating oven at 80.degree. C. for one hour,
at 140.degree. C. for one hour, and then at 180.degree. C. for two
hours, to obtain a cured product.
(c') Comparative Example I 4-3
[0229] The curable composition obtained as described above was
heated in a hot air circulating oven at 130.degree. C. for one
hour, at 150.degree. C. for one hour, and then at 230.degree. C.
for two hours, to obtain a cured product.
(d') Comparative Example 14-4
[0230] The curable composition obtained as described above was
heated in a hot air circulating oven at 80.degree. C. for one hour,
at 120.degree. C. for one hour, and then at 240.degree. C. for two
hours, to obtain a cured product.
(e') Comparative Example I 4-5
[0231] The curable composition obtained as described above was
heated in a hot air circulating oven at 120.degree. C. for one
hour, and then at 140.degree. C. for two hours, to obtain a cured
product.
[0232] The weight reduction rate of each of the cured products
obtained as described above was calculated in the same manner as in
Example I 1-1. The measurement results are summarized in Tables I-6
and I-7.
(Heat Resistance of Cured Product from Curable Composition)
[0233] The heat resistance of each of the cured products obtained
as described above was measured in the same manner as in Example I
1-1. The measurement results are summarized in Tables I-6 and
I-7.
(Overall Evaluation)
[0234] The overall evaluation of each of the curable compositions
obtained in the above described Examples was carried out according
to the following evaluation criteria. The evaluation results are
summarized in Tables I-6 and I-7.
.smallcircle.: The resulting cured product has a weight reduction
rate of 5% or less and a heat resistance of 130.degree. C. or
higher. x: The resulting cured product has a weight reduction rate
of more than 5% and/or a heat resistance of less than 130.degree.
C., and thus has problems in practical use.
TABLE-US-00006 TABLE 6 Compar- Compar- Compar- ative ative ative
Exam- Exam- Exam- Exam- Exam- Exam- ple ple ple ple ple ple Table
I-6 I 4-1 I 4-2 I 4-3 I 4-1 I 4-2 I 4-3 Composition Epoxy compound
(A-2) 50 50 50 of curable the other epoxy compound 100 composition
(I B-1) (parts by mass) the other epoxy compound 50 (I B-2) the
other epoxy compound 50 50 100 100 (I B-3) Thermal cationic 2 2 2 2
polymerization initiator (I D-4) Thermal cationic 2 2
polymerization initiator (I D-5) Weight reduction rate of cured
product (%) 0 0 0 0 0 11 Heat resistance (.degree. C.) 261 239 134
123 110 87 Overall evaluation .smallcircle. .smallcircle.
.smallcircle. x x x
TABLE-US-00007 TABLE 7 Com- Com- par- par- ative ative Exam- Exam-
Exam- Exam- ple ple ple ple Table I-7 I 4-4 I 4-5 I 4-4 I 4-5
Composition of Epoxy compound 50 50 curable composi- (A-2) tion
(parts by the other epoxy 50 100 mass) compound (I B-2) the other
epoxy 50 100 compound (I B-3) Thermal cationic 2 2 2 2
polymerization initiator (I D-3) Weight reduction rate of cured 0 3
3 7 product (%) Heat resistance (.degree. C.) 133 248 109 230
Overall evaluation .smallcircle. .smallcircle. x x
I-5. Examples I 5: Preparation of Curable Compostions Containing
Epoxy Compound (A-2) and Evaluation Thereof (Part 5: Combination
with Various Types of Oxetane Compounds and Thermal Cationic
Polymerization Initiator)
(1) Examples I 5-1 and I 5-2, and Comparative Examples I 5-1 to I
5-5
[0235] Curable compositions were obtained in the same manner as in
Example I 1-1, except that the following components were used at
the compositions shown in Table I-8.
(i) Epoxy Compound (A-2)
[0236] Tricyclopentadiene diepoxide obtained by the method
described in the above Preparation Example 2 was used.
(ii) The Other Epoxy Compound (I B-2)
[0237] A bisphenol A-type liquid epoxy resin, manufactured by
Nippon Steel & Sumikin Chemical Co., Ltd., trade name: YD-128,
was used.
(iii) The Other Epoxy Compound (I B-3)
[0238] 3',4'-Epoxycyclohexylmethyl 3,4-epoxycyclohexane
carboxylate, manufactured by Dalcel Corporation, trade name:
CELLOXIDE 2021P, was used.
(iv) The Other Epoxy Compound (I B-14)
[0239] (3,3',4,4'-Diepoxy)bicyclohexyl produced by the method
described in JP 2004-099467 A was used.
(v) Oxetane Compound (I C-2)
[0240] 3-Ethyl-3-hydroxymethyloxetane, manufactured by Toagosel
Co., Ltd., trade name: ARONE OXETANE OXT-101, was used.
(vi) Oxetane Compound (I C-3)
[0241] Di[(3-ethyl-3-oxetanyl)methyl]ether, manufactured by
Toagosel Co., Ltd., trade name: ARONE OXETANE OXT-221, was
used.
(vii) Oxetane Compound (I C-4)
[0242] 3-Ethyl-3-(2-ethylhexyloxymethyl)oxetane, manufactured by
Toagosei Co., Ltd., trade name: ARONE OXETANE OXT-212, was
used.
(viii) Thermal Cationic Polymerization Initiator (I D-1)
[0243] 4-Acetoxyphenyldimethylsulfonium hexafluoroantimonate,
manufactured by Sanshin Chemical Industry Co., Ltd., trade name:
SI-150L, was used.
(2) Evaluation of Physical Properties
[0244] (Weight Reduction Rate of Cured Product from Curable
Composition)
[0245] Each of the curable compositions obtained as described above
was heated under each of the following conditions, to obtain a
cured product.
(a) Example I 5-1
[0246] The curable composition obtained as described above was
heated in a hot air circulating oven at 130.degree. C. for one
hour, at 140.degree. C. for one hour, at 180.degree. C. for one
hour, at 220.degree. C. for one hour, and then at 240.degree. C.
for two hours, to obtain a cured product.
(b) Example I 5-2
[0247] The curable composition obtained as described above was
heated in a hot air circulating oven at 140.degree. C. for one
hour, at 170.degree. C. for one hour, and then at 220.degree. C.
for two hours, to obtain a cured product.
(a') Comparative Example I 5-1
[0248] The curable composition obtained as described above was
heated in a hot air circulating oven at 110.degree. C. for one
hour, at 130.degree. C. for one hour, and then at 220.degree. C.
for two hours, to obtain a cured product.
(b') Comparative Example I 5-2
[0249] The curable composition obtained as described above was
heated in a hot air circulating oven at 110.degree. C. for one
hour, at 140.degree. C. for one hour, and then at 240.degree. C.
for two hours, to obtain a cured product.
(c') Comparative Example I 5-3
[0250] The curable composition obtained as described above was
heated in a hot air circulating oven at 110.degree. C. for one
hour, at 120.degree. C. for one hour, and then at 220.degree. C.
for two hours, to obtain a cured product.
(d') Comparative Example 15-4
[0251] The curable composition obtained as described above was
heated in a hot air circulating oven at 70.degree. C. for one hour,
at 120.degree. C. for one hour, at 150.degree. C. for one hour, and
then at 230.degree. C. for two hours, to obtain a cured
product.
(e') Comparative Example I 5-5
[0252] The curable composition obtained as described above was
heated in a hot air circulating oven at 130.degree. C. for one
hour, at 170.degree. C. for one hour, and then at 220.degree. C.
for two hours, to obtain a cured product.
[0253] The weight reduction rate of each of the cured products
obtained as described above was calculated in the same manner as in
Example I 1-1. The measurement results are summarized in Table
I-8.
(Heat Resistance of Cured Product of Curable Composition)
[0254] The heat resistance of each of the cured products obtained
as described above was measured in the same manner as in Example I
1-1. The measurement results are summarized in Table I-8.
(Overall Evaluation)
[0255] The overall evaluation of each of the curable compositions
obtained in the above described Examples was carried out according
to the following evaluation criteria. The evaluation results are
summarized in Table I-8.
.smallcircle.: The resulting cured product has a weight reduction
rate of 5% or less and a heat resistance of 180.degree. C. or
higher. x: The resulting cured product has a weight reduction rate
of more than 5% and/or a heat resistance of less than 180.degree.
C., and thus has problems in practical use.
TABLE-US-00008 TABLE 8 Compar- Compar- Compar- Compar- Compar-
ative ative ative ative ative Exam- Exam- Exam- Exam- Exam- Exam-
Exam- ple ple ple ple ple ple ple Table I-8 I 5-1 I 5-2 I 5-1 I 5-2
I 5-3 I 5-4 I 5-5 Composition Epoxy compound 75 75 of curable (A-2)
composition the other epoxy 75 75 75 (parts compound (I B-2) by
mass) the other epoxy 75 compound (I B-3) the other epoxy 75
compound (I B-14) Oxetane compound 25 (I C-2) Oxetane compound 25
25 25 25 (I C-3) Oxetane compound 25 25 (I C-4) Thermal cationic 2
2 2 2 2 2 2 polymerization initiator (I D-1) Weight reduction rate
of cured 2 5 2 2 2 11 8 product (%) Heat resistance (.degree. C.)
185 235 160 116 137 145 124 Overall evaluation .smallcircle.
.smallcircle. x x x x x
II. Examples of Aspect II of the Present Invention
II-1. Examples II 1: Preparation of Curable Compositions Containing
Epoxy Compound (A-2) and Evaluation Thereof (Part 1: Evaluation in
the Case of Using Acid Anhydride-Based Curing Agent)
(1) Example II 1-1
Production of Curable Composition
[0256] The epoxy compound (A-2) (tricyclopentadiene diepoxide)
obtained as described above, the other epoxy compound (II B-2), an
acid anhydride-based curing agent, a curing accelerator and a
polymerization initiator were mixed to achieve the following
composition, to obtain a curable composition.
<Composition of Curable Composition>
[0257] Epoxy compound (A-2) 50 parts by mass (tricyclopentadiene
diepoxide obtained by the method described in the above Preparation
Example 2) [0258] the other epoxy compound (II B-2) 50 parts by
mass (bisphenol A-type liquid epoxy resin, manufactured by Nippon
Steel & Sumikin Chemical Co., Ltd., trade name YD-128) [0259]
Acid anhydride-based curing agent 106 parts by mass (a mixture of
4-methylhexahydrophthalic anhydride and hexahydrophthalic
anhydride, manufactured by New Japan Chemical Co., Ltd., trade
name: MH-700; an amount corresponding to 0.9 equivalent with
respect to one equivalent of the epoxy compound (A-2)
(tricyclopentadiene diepoxide)) [0260] Curing accelerator (II C-1)
1 part by mass (2-ethyl-4-methylimidazole, manufactured by Shikoku
Chemicals Corporation, trade name: 2E4MZ) [0261] Compound
containing a hydroxyl group 5 parts by mass (ethylene glycol, a
reagent manufactured by Wako Pure Chemical Industries, Ltd.)
[0262] The curable composition obtained as described above was
heated in a hot air circulating oven at 120.degree. C. for two
hours, at 190.degree. C. for one hour, and then at 240.degree. C.
for two hours, to obtain a cured product.
[0263] The glass transition temperature of the cured product
obtained as described above was measured by increasing the
temperature from 30 to 300.degree. C. at a rate of 10.degree.
C./min, using a differential scanning calorimeter, DSC7020,
manufactured by Hitachi High-Tech Science Corporation, and the thus
measured value was taken as the heat resistance of the cured
product. The glass transition temperature as used herein refers to
a value measured in accordance with JIS K7121, based on "Midpoint
Glass Transition Temperature: T.sub.mg" described in the section of
"Method for Measuring Transition Temperature of Plastics". The
measurement results are summarized in Table II-1.
(2) Comparative Example II 1-1
[0264] A curable composition was obtained in the same manner as in
Example II 1-1, except that the composition of the curable
composition was changed to that shown in Table II-1.
[0265] The curable composition obtained as described above was
heated in a hot air circulating oven at 100.degree. C. for two
hours, and then at 160.degree. C. for four hours, to obtain a cured
product.
[0266] The glass transition temperature of the thus obtained cured
product was measured in the same manner as in Example II 1-1. The
measurement results are summarized in Table 11-1.
(3) Comparative Example II 1-2
[0267] A curable composition was obtained in the same manner as in
Comparative Example II 1-1, except that a curing accelerator (II
C-2) (tetra-n-butysulfonium-o,o-diethyl phosphorodithionate,
manufactured by Nippon Chemical Industrial Co., Ltd., trade name:
HISHICOLIN PX-4ET) was used instead of the curing accelerator (II
C-1) in the curable composition.
[0268] The curable composition obtained as described above was
heated in the same manner as in Comparative Example II 1-1, to
obtain a cured product.
[0269] The glass transition temperature of the thus obtained cured
product was measured in the same manner as in Example II 1-1. The
measurement results are summarized in Table II-1.
(4) Comparative Examples II 1-3
[0270] A curable composition was obtained in the same manner as in
Example II 1-1, except that 34 parts by mass of an amine-based
curing agent (1,3-bisaminomethylcyclohexane; a reagent manufactured
by Tokyo Chemical Industry Co., Ltd.) was used instead of the acid
anhydride-based curing agent in the curable composition, and that
no curing accelerator was used.
[0271] The curable composition obtained as described above was
heated in a hot air circulating oven at 100.degree. C. for one
hour, at 120.degree. C. for one hour, and then at 150.degree. C.
for one hour to cure the composition. However, a curing failure
occurred due to the volatilization of the curing agent during the
heating, and the composition had problems in practical use.
(5) Comparative Example II 1-4
[0272] A curable composition was obtained in the same manner as in
Example II 1-1, except that a phenol-based curing agent (a phenol
novolac resin, manufactured by DIC Corporation trade name: TD-2131)
was used instead of the acid anhydride-based curing agent, and a
curing accelerator (II C-9) was used instead of the curing
accelerator (II C-1), in the curable composition.
[0273] The curable composition obtained as described above was
heated in a hot air circulating oven at 100.degree. C. for one
hour, at 120.degree. C. for one hour, and then at 150.degree. C.
for one hour to cure the composition. However, the composition
could not be sufficiently cured, and had problems in practical
use.
II-2. Examples II 2: Preparation of Curable Compositions Containing
Epoxy Compound (A-2) and Evaluation Thereof (Part 2: Combination
with Acid Anhydride-Based Curing Agent and Various Types of Curing
Accelerators)
(1) Examples II 2-1 to II 2-11
Production of Curable Compositions
[0274] Curable compositions were obtained in the same manner as in
Example II 1-1, except that the compositions of the curable
compositions were changed to those shown in Tables II-2 and
II-3.
[0275] The curable compositions obtained as described above were
heated in a hot air circulating oven at 100.degree. C. for one
hour, at 110.degree. C. for one hour, at 120.degree. C. for two
hours, at 190.degree. C. for one hour, and then at 240.degree. C.
for two hours, to obtain cured products.
[0276] The glass transition temperature of each of the thus
obtained cured products was measured in the same manner as in
Example II 1-1. The measurement results are summarized in Tables
II-2 and II-3.
(2) Examples II 2 to II 12
Production of Curable Compositions
[0277] Curable compositions were obtained in the same manner as in
Example II 1-1, except that the compositions of the curable
compositions were changed to those shown in Tables II-2 and
II-3.
[0278] The curable compositions obtained as described above were
heated in a hot air circulating oven at 120.degree. C. for two
hours, at 190.degree. C. for one hour, and then at 240.degree. C.
for two hours, to obtain cured products.
[0279] The glass transition temperature of each of the thus
obtained cured products was measured in the same manner as in
Example II 1-1. The measurement results are summarized in Tables
II-2 and II-3.
(3) Comparative Examples II 2-1 and II 2-2
Production of Curable Compositions
[0280] Curable compositions were obtained in the same manner as in
Example II 1-1, except that the compositions of the curable
compositions were changed to those shown in Tables II-2 and
II-3.
[0281] The curable compositions obtained as described above were
heated in a hot air circulating oven at 100.degree. C. for two
hours, and then at 160.degree. C. for six hours, to obtain cured
products.
[0282] The glass transition temperature of each of the thus
obtained cured products was measured in the same manner as in
Example II 1-1. The measurement results are summarized in Tables
II-2 and II-3.
(4) Comparative Example II 2-3
[0283] A curable composition was obtained in the same manner as in
Example II 2-1, except that dicyclopentadiene diepoxide (the other
epoxy compound (II B-1)) represented by the following Formula was
used instead of the epoxy compound (A-2) (tricyclopentadiene
diepoxide) in the curable composition. Note, however, that since
the measured value (170 g/eq) of the epoxy equivalent of the epoxy
compound (II B-1) did not coincide with the theoretical value (82
g/eq) of the epoxy equivalent of the epoxy compound (II B-1)
calculated from the chemical structure of the epoxy compound (II
B-1), the theoretical value 82 g/eq was used as the epoxy
equivalent of the epoxy compound (II B-1), when determining the
content of the acid anhydride-based curing agent.
##STR00017##
[0284] The curable composition obtained as described above was
heated in a hot air circulating oven at 100.degree. C. for two
hours, and then at 160.degree. C. for six hours to cure the
composition. However, the composition was not cured and remained in
a state of liquid.
II-3. Examples II 3: Preparation of Curable Compositions Containing
Epoxy Compound (A-2) and Evaluation Thereof (Part 3: Comparison
with the Case in which Epoxy Compound (A-2) and Compound Containing
Hydroxyl Group are not Incorporated)
(1) Example II 3-1
[0285] A curable composition was obtained in the same manner as in
Example II 1-1, except that the composition of the curable
composition was changed to that shown in Table II-4.
[0286] The curable composition obtained as described above was
heated in a hot air circulating oven at 120.degree. C. for two
hours, at 190.degree. C. for one hour, and then at 240.degree. C.
for two hours, to obtain a cured product.
[0287] The glass transition temperature of the thus obtained cured
product was measured in the same manner as in Example II 1-1. The
measurement results are summarized in Table II-4.
(2) Comparative Example II 3-1
[0288] A curable composition was obtained in the same manner as in
Example II 1-1, except that the composition of the curable
composition was changed to that shown in Table II-4.
[0289] The curable composition obtained as described above was
heated in a hot air circulating oven at 110.degree. C. for two
hours, at 180.degree. C. for four hours, and then at 220.degree. C.
for two hours, to obtain a cured product.
[0290] The glass transition temperature of the thus obtained cured
product was measured in the same manner as in Example II 1-1. The
measurement results are summarized in Table II-4.
TABLE-US-00009 TABLE 9 Com- Com- Com- Com- par- par- par- par-
ative ative ative ative Ex- Ex- Ex- Ex- Ex- am- am- am- am- am- ple
ple ple ple ple Table II-1 II 1-1 II 1-1 II 1-2 II 1-3 II 1-4
Composi- Epoxy com- 50 100 100 tion of pound (A-2) curable the
other epoxy 50 100 100 composi- compound tion (II B-2) (parts by
Acid 106 81 81 mass) anhydride-based curing agent Amine-based 34
curing agent Phenol-based 81 curing agent Curing 1 1 accelerator
(II C-1) Curing 1 accelerator (II C-2) Curing 2 accelerator (II
C-9) Compound 5 containing hydroxyl group Heat resistance (.degree.
C.) 164 158 148 -- --
TABLE-US-00010 TABLE 10 Exam- Exam- Exam- Exam- Exam- Exam- Exam-
ple ple ple ple ple ple ple Table II-2 II 2-1 II 2-2 II 2-3 II 2-4
II 2-5 II 2-6 II 2-7 Composition Epoxy compound (A-2) 100 100 100
100 100 100 100 of curable Acid anhydride-based 131 131 131 131 131
131 131 composition curing agent (0.9 (0.9 (0.9 (0.9 (0.9 (0.9 (0.9
(parts by equi- equi- equi- equi- equi- equi- equi- mass) valent)
valent) valent) valent) valent) valent) valent) Curing accelerator
1 (II C-1) Curing accelerator 1 (II C-2) Curing accelerator 1 (II
C-3) Curing accelerator 1 (II C-4) Curing accelerator 1 (II C-5)
Curing accelerator 1 (II C-6) Curing accelerator 1 (II C-7)
Compound containing 5 5 5 5 5 5 5 hydroxyl group Heat resistance
(.degree. C.) 253 248 246 254 251 245 236
TABLE-US-00011 TABLE 11 Compar- Compar- Compar- ative ative ative
Exam- Exam- Exam- Exam- Exam- Exam- Exam- ple ple ple ple ple ple
ple Table II-3 II 2-8 II 2-9 II 2-10 II 2-11 II 2-1 II 2-2 II 2-3
Composition Epoxy compound (A-2) 100 100 100 50 of curable the
other epoxy compound 100 composition (II B-1) (parts by the other
epoxy compound 50 100 100 mass) (II B-3) Acid anhydride-based 131
131 131 123 115 115 184 curing agent (0.9 (0.9 (0.9 (0.9 (0.9 (0.9
(0.9 equi- equi- equi- equi- equi- equi- equi- valent) valent)
valent) valent) valent) valent) valent) Curing accelerator (II C-1)
1 1 1 Curing accelerator (II C-2) 1 Curing accelerator (II C-8) 1
Curing accelerator (II C-9) 1 Curing accelerator (II C-10) 1
Compound containing 5 5 5 hydroxyl group Heat resistance ( .degree.
C.) 247 252 257 222 199 192 --
TABLE-US-00012 TABLE 12 Com- para- tive Exam- Exam- ple ple Table
II-4 II 3-1 II 3-1 Composition Epoxy compound (A-2) 50 of curable
the other epoxy compound (II B-4) 50 100 composition Acid
anhydride-based 103 74 (parts by curing agent (0.9 (0.9 mass) equi-
equi- valent) valent) Curing accelerator (II C-1) 1 1 Compound
containing 5 hydroxyl group Heat resistance (.degree. C.) 194
185
[0291] The respective components used for the preparation of the
respective curable compositions shown in Tables II-2 to 11-4 are as
follows.
[0292] the other epoxy compound (II B-3): 3,4-epoxycyclohexylmethyl
3,4-epoxycyclohexane carboxylate, manufactured by Dalcel
Corporation, trade name: CELLOXIDE 2021P
[0293] the other epoxy compound (II B-4): a cresol novolac type
epoxy resin, manufactured by DIC Corporation, trade name: EPICLON
N-660
[0294] Curing accelerator (II C-3): 1,2-dimethylimidazole,
manufactured by Shikoku Chemicals Corporation, trade name:
1.2DMZ
[0295] Curing accelerator (II C-4): 1-benzyl-2-phenylimidazole,
manufactured by Shikoku Chemicals Corporation, trade name:
1B2PZ
[0296] Curing accelerator (II C-5):
1-cyanoethyl-2-ethyl-4-methylimidazole, manufactured by Shikoku
Chemicals Corporation, trade name: 2E4MZ-CN
[0297] Curing accelerator (II C-6):
1,8-diazabicyclo(5,4,0)undecene-7, a reagent manufactured by Tokyo
Chemical Industry Co., Ltd.
[0298] Curing accelerator (II C-7): tetrabutylammonium bromide, a
reagent manufactured by Tokyo Chemical Industry Co., Ltd.
[0299] Curing accelerator (II C-8): methyltri-n-butylphosphonium
dimethylphosphate, manufactured by Nippon Chemical Industrial Co.,
Ltd., trade name: HISHICOLIN PX-4MP
[0300] Curing accelerator (II C-9): triphenylphosphine, a reagent
manufactured by Tokyo Chemical Industry Co., Ltd.
[0301] Curing accelerator (II C-10): 2-methylimidazole,
manufactured by Shikoku Chemicals Corporation, trade name: 2MI
II-4. Examples II 4: Preparation of Curable Compositions Containing
Epoxy Compound (A-2) and Evaluation Thereof (Part 4: Combination
with Various Types of the Other Epoxy Compound and Acid
Anhydride-Based Curing Agent)
(1) Examples II 4-1 to II 4-13 and Comparative Examples II 4-1 to
II 4-14
[0302] Curable compositions were obtained in the same manner as in
Example II 1-1, except that the following components were used at
the compositions shown in Tables II-5 to II-7.
(i) Epoxy Compound (A-2)
[0303] Tricyclopentadiene diepoxide obtained by the method
described in the above Preparation Example 2 was used.
(ii) The Other Epoxy Compound (II B-2)
[0304] A bisphenol A-type liquid epoxy resin, manufactured by
Nippon Steel & Sumikin Chemical Co., Ltd., trade name: YD-128,
was used.
(iii) The Other Epoxy Compound (II B-3)
[0305] 3',4'-Epoxycyclohexylmethyl 3,4-epoxycyclohexane
carboxylate, manufactured by Dalcel Corporation, trade name:
CELLOXIDE 2021P, was used.
(iv) The Other Epoxy Compound (II B-5)
[0306] A phenol novolac type epoxy resin, manufactured by Nippon
Steel & Sumikin Chemical Co., Ltd., trade name: YDPN-638, was
used.
(v) The Other Epoxy Compound (II B-6)
[0307] A bisphenol F-type liquid epoxy resin, manufactured by
Nippon Steel & Sumikin Chemical Co., Ltd., trade name: YDF-170,
was used.
(vi) The Other Epoxy Compound (II B-7)
[0308] A hydrogenated bisphenol A-type liquid epoxy resin,
manufactured by Mitsubishi Chemical Corporation, trade name:
YX8000, was used.
(vii) The Other Epoxy Compound (II B-8)
[0309] Triglycidyl isocyanurate, manufactured by Nissan Chemical
Industries, Ltd., trade name: TEPIC-S, was used.
(viii) The Other Epoxy Compound (II B-9)
[0310] Tetramethylene glycol diglycidyl ether, a reagent
manufactured by Tokyo Chemical Industry Co., Ltd., was used.
(ix) The Other Epoxy Compound (II B-10)
[0311] Cyclohexanedicarboxylic acid diglycidyl ester, a reagent
manufactured by Tokyo Chemical Industry Co., Ltd., was used.
(x) The Other Epoxy Compound (II B-11)
[0312] Vinyl cyclohexene dioxide, a reagent manufactured by
Sigma-Aldrich Co., was used.
(xi) The Other Epoxy Compound (II B-12)
[0313] 1,2-Epoxy-(2-oxiranyl)cyclohexane adduct of
2,2-bis(hydroxymethyl)-1-butanol, manufactured by Dalcel
Corporation, trade name: EHPE 3150, was used.
(xii) The Other Epoxy Compound (II B-13)
[0314] Limonene dioxide, a reagent manufactured by Sigma-Aldrich
Co., was used.
(xii) The Other Epoxy Compound (II B-14)
[0315] (3,3',4,4'-Diepoxy)bicyclohexyl, manufactured by Daicel
Corporation, trade name: CELLOXIDE 8000, was used.
(xiv) The Other Epoxy Compound (II B-15)
[0316] An epoxy compound produced by the method described in
Example 3 in JP 49-126658 A was used.
(xv) The Other Epoxy Compound (II B-16)
[0317] Tetrahydroindene diepoxide produced by the method described
in JP 2012-116390 A was used.
(xvi) The Other Epoxy Compound (II B-18)
[0318] The monoepoxy compound produced by the method described in
Preparation Example 4 was used.
(xvii) Acid Anhydride-Based Curing Agent
[0319] A mixture of 4-methylhexahydrophthalic anhydride and
hexahydrophthalic anhydride, manufactured by New Japan Chemical
Co., Ltd., trade name: MH-700, was used.
(xviii) Curing Accelerator (II C-1)
[0320] 2-Ethyl-4-methylimidazole, manufactured by Shikoku Chemicals
Corporation, trade name: 2E4MZ, was used.
(xix) Curing Accelerator (II C-6)
[0321] 1,8-Diazabicyclo(5,4,0)undecene-7, a reagent manufactured by
Tokyo Chemical Industry Co., Ltd., was used.
(xx) Compound Containing Hydroxyl Group
[0322] Ethylene glycol, a reagent manufactured by Wako Pure
Chemical Industries, Ltd., was used.
(2) Evaluation of Physical Properties
[0323] (Heat Resistance of Cured Product from Curable
Composition)
[0324] Each of the curable compositions obtained as described above
was heated under each of the following conditions, to obtain a
cured product.
(a) Example II 4-1
[0325] The curable composition obtained as described above was
heated in a hot air circulating oven at 120.degree. C. for one
hour, at 150.degree. C. for one hour, and then at 220.degree. C.
for two hours, to obtain a cured product.
(b) Example II 4-2
[0326] The curable composition obtained as described above was
heated in a hot air circulating oven at 90.degree. C. for one hour,
at 140.degree. C. for one hour, and then at 180.degree. C. for two
hours, to obtain a cured product.
(c) Example II 4-3
[0327] The curable composition obtained as described above was
heated in a hot air circulating oven at 90.degree. C. for one hour,
at 130.degree. C. for one hour, and then at 160.degree. C. for two
hours, to obtain a cured product.
(d) Example II 4-4
[0328] The curable composition obtained as described above was
heated in a hot air circulating oven at 90.degree. C. for one hour,
at 130.degree. C. for one hour, and then at 170.degree. C. for two
hours, to obtain a cured product.
(e) Example II 4-5
[0329] The curable composition obtained as described above was
heated in a hot air circulating oven at 100.degree. C. for one
hour, at 140.degree. C. for one hour, and then at 240.degree. C.
for two hours, to obtain a cured product.
(f) Example II 4-6
[0330] The curable composition obtained as described above was
heated in a hot air circulating oven at 60.degree. C. for one hour,
at 110.degree. C. for one hour, at 160.degree. C. for one hour, and
then at 240.degree. C. for two hours, to obtain a cured
product.
(g) Example II 4-7
[0331] The curable composition obtained as described above was
heated in a hot air circulating oven at 90.degree. C. for one hour,
at 130.degree. C. for one hour, and then at 160.degree. C. for two
hours, to obtain a cured product.
(h) Example II 4-8
[0332] The curable composition obtained as described above was
heated in a hot air circulating oven at 60.degree. C. for one hour,
at 120.degree. C. for one hour, at 160.degree. C. for one hour, and
then at 210.degree. C. for two hours, to obtain a cured
product.
(i) Example II 4-9
[0333] The curable composition obtained as described above was
heated in a hot air circulating oven at 70.degree. C. for one hour,
at 130.degree. C. for one hour, and then at 240.degree. C. for two
hours, to obtain a cured product.
(j) Example II 4-10
[0334] The curable composition obtained as described above was
heated in a hot air circulating oven at 90.degree. C. for one hour,
at 140.degree. C. for one hour, at 180.degree. C. for one hour, and
then at 240.degree. C. for two hours, to obtain a cured
product.
(k) Example II 4-11
[0335] The curable composition obtained as described above was
heated in a hot air circulating oven at 90.degree. C. for one hour,
at 140.degree. C. for one hour, and then at 240.degree. C. for two
hours, to obtain a cured product.
(l) Example II 4-12
[0336] The curable composition obtained as described above was
heated in a hot air circulating oven at 90.degree. C. for one hour,
at 140.degree. C. for one hour, and then at 240.degree. C. for two
hours, to obtain a cured product.
(m) Example II 4-13
[0337] The curable composition obtained as described above was
heated in a hot air circulating oven at 90.degree. C. for one hour,
and then at 180.degree. C. for two hours, to obtain a cured
product.
(a') Comparative Example II 4-1
[0338] The curable composition obtained as described above was
heated in a hot air circulating oven at 120.degree. C. for one
hour, at 150.degree. C. for one hour, and then at 170.degree. C.
for two hours, to obtain a cured product.
(b') Comparative Example II 4-2
[0339] The curable composition obtained as described above was
heated in a hot air circulating oven at 90.degree. C. for one hour,
at 140.degree. C. for one hour, and then at 180.degree. C. for two
hours, to obtain a cured product.
(c') Comparative Example II 4-3
[0340] The curable composition obtained as described above was
heated in a hot air circulating oven at 90.degree. C. for one hour,
at 130.degree. C. for one hour, and then at 160.degree. C. for two
hours, to obtain a cured product.
(d') Comparative Example II 4-4
[0341] The curable composition obtained as described above was
heated in a hot air circulating oven at 80.degree. C. for one hour,
at 130.degree. C. for one hour, and then at 170.degree. C. for two
hours, to obtain a cured product.
(e') Comparative Example II 4-5
[0342] The curable composition obtained as described above was
heated in a hot air circulating oven at 100.degree. C. for one
hour, at 140.degree. C. for one hour, and then at 240.degree. C.
for two hours, to obtain a cured product.
(f') Comparative Example II 4-6
[0343] The curable composition obtained as described above was
heated in a hot air circulating oven at 60.degree. C. for one hour,
at 110.degree. C. for one hour, at 160.degree. C. for one hour, and
then at 240.degree. C. for two hours, to obtain a cured
product.
(g') Comparative Example II 4-7
[0344] The curable composition obtained as described above was
heated in a hot air circulating oven at 80.degree. C. for one hour,
at 120.degree. C. for one hour, and then at 150.degree. C. for two
hours, to obtain a cured product.
(h') Comparative Example II 4-8
[0345] The curable composition obtained as described above was
heated in a hot air circulating oven at 70.degree. C. for one hour,
at 100.degree. C. for one hour, at 190.degree. C. for one hour, and
then at 240.degree. C. for two hours, to obtain a cured
product.
(i') Comparative Example II 4-9
[0346] The curable composition obtained as described above was
heated in a hot air circulating oven at 70.degree. C. for one hour,
at 130.degree. C. for one hour, and then at 240.degree. C. for two
hours, to obtain a cured product.
(j') Comparative Example II 4-10
[0347] The curable composition obtained as described above was
heated in a hot air circulating oven at 110.degree. C. for one
hour, at 120.degree. C. for one hour, at 130.degree. C. for one
hour, at 150.degree. C. for one hour, and then at 240.degree. C.
for one hour, to obtain a cured product.
(k') Comparative Example II 4-11
[0348] The curable composition obtained as described above was
heated in a hot air circulating oven at 90.degree. C. for one hour,
at 140.degree. C. for one hour, and then at 240.degree. C. for two
hours, to obtain a cured product.
(l') Comparative Example II 4-12
[0349] The curable composition obtained as described above was
heated in a hot air circulating oven at 90.degree. C. for one hour,
at 140.degree. C. for one hour, and then at 180.degree. C. for two
hours, to obtain a cured product.
(m') Comparative Example II 4-13
[0350] The curable composition obtained as described above was
heated in a hot air circulating oven at 90.degree. C. for one hour,
at 140.degree. C. for one hour, and then at 180.degree. C. for two
hours, to obtain a cured product.
(n') Comparative Example II 4-14
[0351] The curable composition obtained as described above was
heated in a hot air circulating oven at 90.degree. C. for one hour,
and then at 180.degree. C. for two hours, to obtain a cured
product.
[0352] The heat resistance of each of the cured products obtained
as described above was measured in the same manner as in Example II
1-1. The measurement results are summarized in Tables II-5 to
II-7.
TABLE-US-00013 TABLE 13 Com- Com- Com- Com- Com- para- para- para-
para- para- tive tive tive tive tive Exam- Exam- Exam- Exam- Exam-
Exam- Exam- Exam- Exam- Exam- ple ple ple ple ple ple ple ple ple
ple Table II-5 II 4-1 II 4-2 II 4-3 II 4-4 II 4-5 II 4-1 II 4-2 II
4-3 II 4-4 II 4-5 Composition Epoxy compound 50 50 50 50 50 of
curable (A-2) composition the other epoxy 25 50 (parts by compound
(II B-3) mass) the other epoxy 50 100 compound (II B-5) the other
epoxy 50 100 compound (II B-6) the other epoxy 50 100 compound (II
B-7) the other epoxy 50 100 compound (II B-8) the other epoxy 25 50
compound (II B-12) Acid 108 104 141 115 110 84 76 151 99 89
anhydride-based curing agent Curing 2 2 2 2 2 2 2 2 2 2 accelerator
(II C-1) Compound 5 5 5 5 5 5 containing hydroxyl group Heat
resistance (.degree. C.) 160 232 270 275 135 113 220 209 232 92
TABLE-US-00014 TABLE 14 Compar- Compar- Compar- ative ative ative
Exam- Exam- Exam- Exam- Exam- Exam- ple ple ple ple ple ple Table
II-6 II 4-6 II 4-7 II 4-8 II 4-6 II 4-7 II 4-8 Composition Epoxy
compound (A-2) 50 50 50 of curable the other epoxy compound 50 100
composition (II B-10) (parts by the other epoxy compound 50 100
mass) (II B-11) the other epoxy compound 50 100 (II B-16) Acid
anhydride-based 174 119 159 216 106 187 curing agent Curing
accelerator (II C-1) 2 2 2 2 2 Curing accelerator 2 (II C-6)
Compound containing 5 5 5 hydroxyl group Heat resistance (.degree.
C.) 174 265 233 137 102 126
TABLE-US-00015 TABLE 15 Com- Com- Com- Com- Com- Com- para- para-
para- para- para- para- tive tive tive tive tive tive Exam- Exam-
Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- ple ple ple
ple ple ple ple ple ple ple ple Table II-7 II 4-9 II 4-10 II 4-11
II 4-12 II 4-13 II 4-9 II 4-10 II 4-11 II 4-12 II 4-13 II 4-14
Composi- Epoxy compound 50 50 50 67 50 tion of (A-2) curable the
other epoxy 67 composi- compound (II B-2) tion the other epoxy 67
(parts compound (II B-3) by mass) the other epoxy 50 100 compound
(II B-9) the other epoxy 50 100 compound (II B-13) the other epoxy
50 100 compound (II B-14) the other epoxy 50 100 compound (II B-15)
the other epoxy 33 33 33 compound (II B-18) Acid 144 134 140 114
156 156 137 150 80 104 180 anhydride-based curing agent Curing 2 2
2 2 2 1 2 2 2 2 accelerator (II C-1) Curing 2 accelerator (II C-6)
Compound 5 5 5 5 5 2 5 5 5 5 containing hydroxyl group Heat
resistance (.degree. C.) 219 200 105 169 82 152 181 86 101 105
57
III. Examples of Aspect III of the Present Invention
III-1. Examples III 1: Preparation of Curable Compositions
Containing Epoxy Compound (A-1) and Evaluation Thereof (Part 1:
Combination with the Other Epoxy Compounds and Thermal Cationic
Polymerization Initiator)
(1) Example III 1-1
Production of Curable Composition
[0353] The epoxy compound (A-1) obtained as described above and a
thermal cationic polymerization initiator were mixed to achieve the
following composition, to obtain a curable composition.
<Composition of Curable Composition>
[0354] Epoxy compound (A-1) 100 parts by mass (the compound
obtained by the method described in Preparation Example 1) [0355]
Thermal cationic polymerization initiator (III D-1) 2 parts by mass
(an aromatic sulfonium salt: 4-acetoxyphenyldimethylsulfonium
hexafluoroantimonate, manufactured by Sanshin Chemical Industry
Co., Ltd., trade name: SI-150L)
[0356] The curable composition obtained as described above was
injected into a metal mold having a size of 3 mm.times.30
mm.times.130 mm, and heated in a hot air circulating oven at
100.degree. C. for one hour, at 110.degree. C. for one hour, at
130.degree. C. for one hour, at 150.degree. C. for one hour, at
180.degree. C. for two hours, and then at 220.degree. C. for three
hours, to obtain a cured product.
[0357] The glass transition temperature of the cured product
obtained as described above was measured by increasing the
temperature from 30 to 300.degree. C. at a rate of 10.degree.
C./min, using a thermomechanical analyzer (manufactured by Hitachi
High-Tech Science Corporation, trade name: TMA 7100), and the thus
measured value was taken as the heat resistance of the cured
product. Note that the glass transition temperature as used herein
refers to the value at the intersection of a straight tangential
line on the low temperature side and a straight tangential line on
the high temperature side. The measurement results are summarized
in Table III-1.
(2) Example III 1-2
[0358] A curable composition was obtained in the same manner as in
Example III 1-1, except that the composition of the curable
composition was changed as described below.
<Composition of Curable Composition>
[0359] Epoxy compound (A-1) 75 parts by mass (the compound obtained
by the method described in Preparation Example 1) [0360] the other
epoxy compound (III B-1) 25 parts by mass (a bisphenol A-type
liquid epoxy resin, manufactured by Nippon Steel & Sumikin
Chemical Co., Ltd., trade name: YD-128) [0361] Thermal cationic
polymerization initiator (III D-1) 2 parts by mass (an aromatic
sulfonium salt: 4-acetoxyphenyldimethylsulfonium
hexafluoroantimonate, manufactured by Sanshin Chemical Industry
Co., Ltd., trade name: SI-150L)
[0362] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 100.degree. C. for
one hour, at 110.degree. C. for one hour, at 130.degree. C. for one
hour, at 150.degree. C. for one hour, at 180.degree. C. for one
hour, and then at 220.degree. C. for five hours, to obtain a cured
product.
[0363] The glass transition temperature of the thus obtained cured
products was measured in the same manner as in Example III 1-1. The
measurement results are summarized in Table III-1.
(3) Examples III 1-3 and III 1-4
[0364] Curable compositions were obtained in the same manner as in
Example III 1-1, except that the compositions of the curable
compositions were changed to those shown in Table III-1.
[0365] The curable compositions obtained as described above were
heated in the same manner as in Example III 1-2 to obtain cured
products.
[0366] The glass transition temperature of each of the thus
obtained cured products was measured in the same manner as in
Example III 1-1. The measurement results are summarized in Table
III-1.
(4) Example III 1-5
[0367] A curable composition was obtained in the same manner as in
Example III 1-1, except that the composition of the curable
composition was changed as described below.
<Composition of Curable Composition>
[0368] Epoxy compound (A-1) 75 parts by mass (the compound obtained
by the method described in Preparation Example 1) [0369] the other
epoxy compound (III B-2) 25 parts by mass
(3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate,
manufactured by Daicel Corporation, trade name: CELLOXIDE 2021P)
[0370] Thermal cationic polymerization initiator (III D-1) 1 part
by mass (an aromatic sulfonium salt:
4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, manufactured
by Sanshin Chemical Industry Co., Ltd., trade name: SI-150L)
[0371] The curable composition obtained as described above was
heated in the same manner as in Example III 1-1 to obtain a cured
product.
[0372] The glass transition temperature of the thus obtained cured
product was measured in the same manner as in Example III 1-1. The
measurement results are summarized in Table III-1.
(5) Examples III 1-6 and III 1-7
[0373] Curable compositions were obtained in the same manner as in
Example III 1-1, except that the compositions of the curable
compositions were changed to those shown in Table III-1.
[0374] The curable compositions obtained as described above were
heated in the same manner as in Example III 1-1, to obtain cured
products.
[0375] The glass transition temperature of each of the thus
obtained cured products was measured in the same manner as in
Example III 1-1. The measurement results are summarized in Table
III-1.
(6) Comparative Examples III 1-1 to III 1-3
[0376] Curable compositions were obtained in the same manner as in
Example III 1-1, except that the compositions of the curable
compositions were changed to those shown in Table III-1.
[0377] The curable compositions obtained as described above were
heated in the same manner as in Example III 1-2, to obtain cured
products.
[0378] The glass transition temperature of each of the thus
obtained cured products was measured in the same manner as in
Example III 1-1. The measurement results are summarized in Table
III-1.
(7) Comparative Examples III 1-4 and III 1-5
[0379] Curable compositions were obtained in the same manner as in
Example III 1-1, except that the compositions of the curable
compositions were changed to those shown in Table III-1.
[0380] The curable compositions obtained as described above were
heated in the same manner as in Example III 1-1, to obtain cured
products.
[0381] The glass transition temperature of each of the thus
obtained cured products was measured in the same manner as in
Example III 1-1. The measurement results are summarized in Table
III-1.
TABLE-US-00016 TABLE 16 Com- Com- Com- Com- Com- para- para- para-
para- para- tive tive tive tive tive Exam- Exam- Exam- Exam- Exam-
Exam- Exam- Exam- Exam- Exam- Exam- Exam- ple ple ple ple ple ple
ple ple ple ple ple ple Table III-1 III 1-1 III 1-2 III 1-3 III 1-4
III 1-5 III 1-6 III 1-7 III 1-1 III 1-2 III 1-3 III 1-4 III 1-5
Composition Epoxy 100 75 50 25 75 50 25 of curable compound
composition (A-1) (parts by the other 25 50 75 25 50 75 100 mass)
epoxy compound (III B-1) the other 25 50 75 75 50 25 100 epoxy
compound (III B-2) Thermal 2 2 2 2 1 1 1 2 2 2 2 1 cationic
polymeriza- tion initiator (III D-1) Heat resistance (.degree.
C.).sup.1) 236 239 187 165 230 226 212 166 162 155 150 179 Note
.sup.1)Heat resistance was measured by the method described in
Example III 1-1.
III-2. Examples III 2: Preparation of Curable Compositions
Containing Epoxy Compound (A-1) and Evaluation Thereof (Part 2:
Combination with Various Types of the Other Epoxy Compounds and
Thermal Cationic Polymerization Initiator)
(1) Example III 2-1
[0382] A curable composition was obtained in the same manner as in
Example III 1-1, except that the composition of the curable
composition was changed as described below.
<Composition of Curable Composition>
[0383] Epoxy compound (A-1) 50 parts by mass (the compound obtained
by the method described in Preparation Example 1) [0384] the other
epoxy compound (III B-3) 50 parts by mass (a cresol novolac type
epoxy resin, manufactured by DIC Corporation, trade name: N-660)
[0385] Thermal cationic polymerization initiator (III D-1) 2 parts
by mass (an aromatic sulfonium salt:
4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, manufactured
by Sanshin Chemical Industry Co., Ltd., trade name: SI-150L)
[0386] The curable composition obtained as described above was
heated in a hot air circulating oven at 110.degree. C. for one
hour, at 130.degree. C. for one hour, at 150.degree. C. for one
hour, at 180.degree. C. for two hours, and then at 220.degree. C.
for three hours, to obtain a cured product.
[0387] The glass transition temperature of the thus obtained cured
product was measured by increasing the temperature from 30 to
300.degree. C. at a rate of 10.degree. C./min, using a differential
scanning calorimeter DSC7000X manufactured by Hitachi High-Tech
Science Corporation, and the thus measured value was taken as the
heat resistance of the cured product. The glass transition
temperature as used herein refers to a value measured in accordance
with JIS K7121, based on "Midpoint Glass Transition Temperature:
T.sub.mg" described in the section of "Method for Measuring
Transition Temperature of Plastics". The measurement results are
summarized in Table III-2.
(2) Example III 2-2
[0388] A curable composition was obtained in the same manner as in
Example III 1-1, except that the composition of the curable
composition was changed as described below.
<Composition of Curable Composition>
[0389] Epoxy compound (A-1) 50 parts by mass (the compound obtained
by the method described in Preparation Example 1) [0390] the other
epoxy compound (III B-4) 50 parts by mass (a phenol novolac type
epoxy resin, manufactured by Nippon Steel & Sumikin Chemical
Co., Ltd., trade name: YDPN-638) [0391] Thermal cationic
polymerization Initiator (III D-1) 2 parts by mass (an aromatic
sulfonium salt: 4-acetoxyphenyldimethylsulfonium
hexafluoroantimonate, manufactured by Sanshin Chemical Industry
Co., Ltd., trade name: SI-150L)
[0392] The curable composition obtained as described above was
heated in the same manner as in Example III 2-1, to obtain a cured
product.
[0393] The glass transition temperature of the thus obtained cured
product was measured in the same manner as in Example III 2-1. The
measurement results are summarized in Table III-2.
(3) Comparative Examples III 2-1 to III 2-4
[0394] Curable compositions were obtained in the same manner as in
Example III 1-1, except that the compositions of the curable
compositions were changed to those shown in Table III-2.
[0395] The curable compositions obtained as described above were
heated in the same manner as in Example III 2-1, to obtain cured
products.
[0396] The glass transition temperature of each of the thus
obtained cured products was measured in the same manner as in
Example III 2-1. The measurement results are summarized in Table
III-2.
TABLE-US-00017 TABLE 17 Compar- Compar- Compar- Compar- ative ative
ative ative Exam- Exam- Exam- Exam- Exam- Exam- ple ple ple ple ple
ple Table III-2 III 2-1 III 2-2 III 2-1 III 2-2 III 2-3 III 2-4
Composition Epoxy compound (A-1) 50 50 of curable the other epoxy
50 50 composition compound(III B-1) (parts by the other epoxy 50 50
mass) compound (III B-2) the other epoxy 50 50 50 compound (III
B-3) the other epoxy 50 50 50 compound (III B-4) Thermal cationic
polymerization initiator 2 2 2 2 2 2 (III D-1) Heat resistance
(.degree. C.).sup.1) 193 188 169 172 169 175 Note .sup.1)Heat
resistance was measured by the method described in Example III
2-1.
III-3. Examples III 3: Preparation of Curable Compositions
Containing Epoxy Compound (A-1) and Evaluation Thereof (Part 3:
Combination with Oxetane Compound and Thermal Cationic
Polymerization Initiator)
(1) Example III 3-1
[0397] A curable composition was obtained in the same manner as in
Example III 1-1, except that the composition of the curable
composition was changed as described below.
<Composition of Curable Composition>
[0398] Epoxy compound (A-1) 50 parts by mass (the compound obtained
by the method described in Preparation Example 1) [0399] Oxetane
compound (III C-1) 50 parts by mass
(1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, manufactured by
Toagosel Co., Ltd., trade name: ARONE OXETANE OXT-121) [0400]
Thermal cationic polymerization initiator (III D-1) 1 part by mass
(an aromatic sulfonium salt: 4-acetoxyphenyldimethylsulfonium
hexafluoroantimonate, manufactured by Sanshin Chemical Industry
Co., Ltd., trade name: SI-150L)
[0401] The curable composition obtained as described above was
injected into a metal mold having a size of 3 mm.times.30
mm.times.130 mm, and heated in a hot air circulating oven at
110.degree. C. for one hour, at 130.degree. C. for one hour, at
150.degree. C. for one hour, at 180.degree. C. for two hours, and
then at 220.degree. C. for three hours, to obtain a cured
product.
[0402] The glass transition temperature of the thus obtained cured
product was measured in the same manner as in Example III 1-1. The
measurement results are summarized in Table III-3.
(2) Comparative Examples III 3-1 and III 3-2
[0403] Curable compositions were obtained in the same manner as in
Example III 1-1, except that the compositions of the curable
compositions were changed to those shown in Table III-3.
[0404] The curable compositions obtained as described above were
heated in the same manner as in Example III 3-1, to obtain cured
products.
[0405] The glass transition temperature of each of the thus
obtained cured products was measured in the same manner as in
Example III 1-1. The measurement results are summarized in Table
III-3.
TABLE-US-00018 TABLE 18 Compar- Compar- Exam- ative ative ple
Example Example Table III-3 III 3-1 III 3-1 III 3-2 Composition
Epoxy compound (A-1) 50 of curable the other epoxy 50 composition
compound (III B-1) (parts by the other epoxy 50 mass) compound (III
B-2) Oxetane compound 50 50 50 (III C-1) Thermal cationic 1 1 1
polymerization initiator (III D-1) Heat resistance (.degree.
C.).sup.1) 203 140 149 Note .sup.1)Heat resistance was measured by
the method described in Example III 1-1.
III-4. Examples III 4: Preparation of Curable Compositions
Containing Epoxy-Compound (A-1) and Evaluation Thereof (Part 4:
Combination with Various Types of the Other Epoxy Compounds and
Thermal Cationic Polymerization Initiator)
(1) Example III 4-1 to III 4-5 and Comparative Example III 4-1 to 4
III-5
[0406] Curable compositions were obtained in the same manner as in
Example III 1-1, except that the following components were used at
the compositions shown in Table III-4.
(i) Epoxy Compound (A-1)
[0407] The epoxy compound (A-1) obtained by the method described in
Preparation Example 1 was used.
(ii) The Other Epoxy Compound (III B-2)
[0408] 3',4'-Epoxycyclohexylmethyl 3,4-epoxycyclohexane
carboxylate, manufactured by Daicel Corporation, trade name:
CELLOXIDE 2021P, was used.
(iii) The Other Epoxy Compound (III B-5)
[0409] A bisphenol F-type liquid epoxy resin, manufactured by
Nippon Steel & Sumikin Chemical Co., Ltd., trade name: YDF-170,
was used.
(iv) The Other Epoxy Compound (III B-6)
[0410] A hydrogenated bisphenol A-type liquid epoxy resin,
manufactured by Mitsubishi Chemical Corporation, trade name:
YX8000, was used.
(v) The Other Epoxy Compound (III B-7)
[0411] Triglycidyl isocyanurate, manufactured by Nissan Chemical
Industries, Ltd., trade name: TEPIC-S, was used.
(vi) The Other Epoxy Compound (III B-11)
[0412] 1,2-Epoxy-(2-oxiranyl)cyclohexane adduct of
2,2-bis(hydroxymethyl)-1-butanol, manufactured by Dalcel
Corporation, trade name: EHPE 3150, was used.
(vii) The Other Epoxy Compound (III B-15)
[0413] 1,2-Epoxy-4-vinylcyclohexane, manufactured by Daicel
Corporation, trade name: CELLOXIDE 2000, was used.
(viii) Thermal Cationic Polymerization Initiator (III D-1)
[0414] An aromatic sulfonium salt: 4-acetoxyphenyldimethylsulfonium
hexafluoroantimonate, manufactured by Sanshin Chemical Industry
Co., Ltd., trade name: SI-150L, was used.
(2) Evaluation of Physical Properties
[0415] Each of the curable compositions obtained as described above
was heated under each of the following conditions, to obtain a
cured product.
(a) Example III 4-1
[0416] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 120.degree. C. for
one hour, at 170.degree. C. for one hour, and then at 220.degree.
C. for two hours, to obtain a cured product.
(b) Example III 4-2
[0417] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 160.degree. C. for
one hour, at 180.degree. C. for one hour, and then at 220.degree.
C. for two hours, to obtain a cured product.
(c) Example III 4-3
[0418] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 120.degree. C. for
one hour, at 140.degree. C. for one hour, and then at 220.degree.
C. for two hours, to obtain a cured product.
(d) Example III 4-4
[0419] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 120.degree. C. for
one hour, at 170.degree. C. for one hour, and then at 230.degree.
C. for two hours, to obtain a cured product.
(e) Example III 4-5
[0420] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 120.degree. C. for
one hour, at 140.degree. C. for one hour, and then at 220.degree.
C. for two hours, to obtain a cured product.
(a') Comparative Example III 4-1
[0421] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 120.degree. C. for
one hour, and then at 220.degree. C. for two hours, to obtain a
cured product.
(b') Comparative Example III 4-2
[0422] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 110.degree. C. for
one hour, and then at 240.degree. C. for two hours, to obtain a
cured product.
(c') Comparative Example III 4-3
[0423] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 110.degree. C. for
one hour, at 170.degree. C. for one hour, and then at 220.degree.
C. for two hours, to obtain a cured product.
(d') Comparative Example III 4-4
[0424] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 130.degree. C. for
one hour, at 190.degree. C. for one hour, and then at 230.degree.
C. for two hours, to obtain a cured product.
(e') Comparative Example III 4-5
[0425] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 120.degree. C. for
one hour, at 140.degree. C. for one hour, and then at 220.degree.
C. for two hours, to obtain a cured product.
[0426] The glass transition temperature of each of the thus
obtained cured products was measured in the same manner as in
Example II 2-1. The measurement results are summarized in Table
III-4.
TABLE-US-00019 TABLE 19 Compar- Compar- Compar- Compar- Compar-
Exam- Exam- Exam- Exam- Exam- ative ative ative ative ative ple ple
ple ple ple Example Example Example Example Example Table III-4 III
4-1 III 4-2 III 4-3 III 4-4 III 4-5 III 4-1 III 4-2 III 4-3 III 4-4
III 4-5 Composition of Epoxy compound 50 25 50 50 50 curable
composition (A-1) (parts by mass) the other epoxy 25 25 37.5 50 50
87.5 compound (III B-2) the other epoxy 50 100 compound (III B-5)
the other epoxy 50 100 compound (III B-6) the other epoxy 50 50
compound (III B-7 the other epoxy 25 50 compound (III B-11) the
other epoxy 12.5 12.5 compound (III B-15) Thermal cationic 2 2 2 2
2 2 2 2 2 2 polymerization initiator (III D-1) Heat resistance
(.degree.C.).sup.1) 263 250 241 249 232 148 134 199 144 200 Note
.sup.1)Heat resistance was measured by the method described in
Example III 2-1.
III-5. Examples III 5: Preparation of Curable Compositions
Containing Epoxy Compound (A-1) and Evaluation Thereof (Part 5:
Combination with Various Types of the Other Epoxy Compounds,
Various Types of Oxetane Compounds, and Thermal Cationic
Polymerization Initiator)
(1) Examples III 5-1 to III 5-4 and Comparative Examples III 5-1 to
III 5-10
[0427] Curable compositions were obtained in the same manner as in
Example III 1-1, except that the following components were used at
the compositions shown in Tables III-5 and III-6.
(i) Epoxy Compound (A-1)
[0428] The epoxy compound (A-1) obtained by the method described in
Preparation Example 1 was used.
(ii) The Other Epoxy Compound (III B-1)
[0429] A bisphenol A-type liquid epoxy resin, manufactured by
Nippon Steel & Sumikin Chemical Co., Ltd., trade name: YD-128,
was used.
(iii) The Other Epoxy Compound (III B-2)
[0430] 3',4'-Epoxycyclohexylmethyl 3,4-epoxycyclohexane
carboxylate, manufactured by Daicel Corporation, trade name:
CELLOXIDE 2021P, was used.
(iv) The Other Epoxy Compound (III B-13)
[0431] (3,3',4,4'-Diepoxy)bicyclohexyl, manufactured by Daicel
Corporation, trade name: CELLOXIDE 8000, was used.
(v) Oxetane Compound (III C-1)
[0432] 1,4-Bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene,
manufactured by Toagosei Co., Ltd., trade name: ARONE OXETANE
OXT-121, was used.
(vi) Oxetane Compound (III C-2)
[0433] 3-Ethyl-3-hydroxymethyloxetane, manufactured by Toagosel
Co., Ltd., trade name: ARONE OXETANE OXT-101, was used.
(vii) Oxetane Compound (III C-3)
[0434] Di[(3-ethyl-3-oxetanyl)methyl]ether, manufactured by
Toagosei Co., Ltd., trade name: ARONE OXETANE OXT-221, was
used.
(viii) Oxetane Compound (III C-4)
[0435] 3-Ethyl-3-(2-ethylhexyloxymethyl)oxetane, manufactured by
Toagosel Co., Ltd., trade name: ARONE OXETANE OXT-212, was
used.
(ix) Thermal Cationic Polymerization Initiator (III D-1)
[0436] An aromatic sulfonium salt: 4-acetoxyphenyldimethylsulfonium
hexafluoroantimonate, manufactured by Sanshin Chemical Industry
Co., Ltd., trade name: SI-150L, was used.
(2) Evaluation of Physical Properties
[0437] Each of the curable compositions obtained as described above
was heated under each of the following conditions, to obtain a
cured product.
(a) Example III 5-1
[0438] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 70.degree. C. for
one hour, at 120.degree. C. for one hour, at 150.degree. C. for one
hour, and then at 230.degree. C. for two hours, to obtain a cured
product.
(b) Example III 5-2
[0439] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 70.degree. C. for
one hour, at 120.degree. C. for one hour, at 150.degree. C. for one
hour, and then at 230.degree. C. for two hours, to obtain a cured
product.
(c) Example III 5-3
[0440] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 70.degree. C. for
one hour, at 120.degree. C. for one hour, at 150.degree. C. for one
hour, and then at 230.degree. C. for two hours, to obtain a cured
product.
(d) Example III 5-4
[0441] The curable composition obtained as described above was
Injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 120.degree. C. for
one hour, at 140.degree. C. for one hour, and then at 220.degree.
C. for two hours, to obtain a cured product.
(a') Comparative Example III 5-1
[0442] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 120.degree. C. for
one hour, at 140.degree. C. for one hour, and then at 220.degree.
C. for two hours, to obtain a cured product.
(b') Comparative Example III 5-2
[0443] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 120.degree. C. for
one hour, at 140.degree. C. for one hour, and then at 220.degree.
C. for two hours, to obtain a cured product.
(c') Comparative Example III 5-3
[0444] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 110.degree. C. for
one hour, at 130.degree. C. for one hour, and then at 240.degree.
C. for two hours, to obtain a cured product.
(d') Comparative Example III 5-4
[0445] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 110.degree. C. for
one hour, at 130.degree. C. for one hour, and then at 220.degree.
C. for two hours, to obtain a cured product.
(e') Comparative Example III 5-5
[0446] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 110.degree. C. for
one hour, at 140.degree. C. for one hour, and then at 240.degree.
C. for two hours, to obtain a cured product.
(f') Comparative Example III 5-6
[0447] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 110.degree. C. for
one hour, at 120.degree. C. for one hour, and then at 220.degree.
C. for two hours, to obtain a cured product.
(g') Comparative Example III 5-7
[0448] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 70.degree. C. for
one hour, at 120.degree. C. for one hour, at 150.degree. C. for one
hour, and then at 230.degree. C. for two hours, to obtain a cured
product.
(h') Comparative Example III 5-8
[0449] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 70.degree. C. for
one hour, at 120.degree. C. for one hour, at 150.degree. C. for one
hour, and then at 230.degree. C. for two hours, to obtain a cured
product.
(I') Comparative Example III 5-9
[0450] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 130.degree. C. for
one hour, at 170.degree. C. for one hour, and then at 220.degree.
C. for two hours, to obtain a cured product.
(j') Comparative Example III 5-10
[0451] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 125.degree. C. for
one hour, and then at 220.degree. C. for two hours, to obtain a
cured product.
[0452] The glass transition temperature of each of the thus
obtained cured products was measured in the same manner as in
Example III 2-1. The measurement results are summarized in Tables
III-5 and III-6.
TABLE-US-00020 TABLE 20 Compar- Compar- Compar- Compar- Compar-
Compar- ative ative ative ative ative ative Exam- Exam- Exam- Exam-
Exam- Exam- Exam- Exam- ple ple ple ple ple ple ple ple Table III-5
III 5-1 III 5-2 III 5-1 III 5-2 III 5-3 III 5-4 III 5-5 III 5-6
Composition of Epoxy compound 75 75 curable (A-1) composition the
other epoxy 75 75 (parts by mass) compound (III B-1) the other
epoxy 75 75 compound III B-2) the other epoxy 75 75 compound (III
B-13) Oxetane 25 25 25 25 compound (III C-1) Oxetane 25 25 25 25
compound (III C-3) Thermal cationic 2 2 2 2 2 2 2 2 polymerization
initiator (III D-1) Heat resistance (.degree. C.).sup.1) 255 241
175 160 153 160 116 137 Note .sup.1)Heat resistance was measured by
the method described in Example III 2-1
TABLE-US-00021 TABLE 21 Compar- Compar- Compar- Compar- ative ative
ative ative Exam- Exam- Exam- Exam- Exam- Exam- ple ple ple ple ple
ple Table III-6 III 5-3 III 5-4 III 5-7 III 5-8 III 5-9 III 5-10
Composition of Epoxy compound (A-1) 75 75 curable composition the
other epoxy compound 75 75 (parts by mass) (III B-1) the other
epoxy compound 75 75 (III B-2) Oxetane compound (III C-2) 25 25 25
Oxetane compound (III C-4) 25 25 25 Thermal cationic polymerization
2 2 2 2 2 2 initiator (III D-1) Heat resistance (.degree.
C.).sup.1) 253 258 145 245 124 257 Note .sup.1)Heat resistance was
measured by the method described in Example III 2-1.
III-6. Examples III 6: Preparation of Curable Compositions
Containing Epoxy Compound (A-1) and Evaluation Thereof (Part 6:
Combination with Various Types of Thermal Cationic Polymerization
Initiators)
(1) Examples III 6-1 to III 6-4 Comparative Examples III 6-1 to III
6-4
[0453] Curable compositions were obtained in the same manner as in
Example III 1-1, except that the following components were used at
the compositions shown in Table III-7.
(i) Epoxy Compound (A-1)
[0454] The epoxy compound (A-1) obtained by the method described in
Preparation Example 1 was used.
(ii) The Other Epoxy Compound (III B-1)
[0455] A bisphenol A-type liquid epoxy resin, manufactured by
Nippon Steel & Sumikin Chemical Co., Ltd., trade name: YD-128,
was used.
(ii) The Other Epoxy Compound (III B-2)
[0456] 3',4'-Epoxycyclohexylmethyl 3,4-epoxycyclohexane
carboxylate, manufactured by Dalcel Corporation, trade name:
CELLOXIDE 2021P, was used.
(iv) Thermal Cationic Polymerization Initiator (III D-4)
[0457] Diphenyl-4-(phenylthio)phenylsulfonium hexafluoroantimonate,
manufactured by San-Apro Ltd., CPI-101A, was used.
(v) Thermal Cationic Polymerization Initiator (III D-5)
[0458] 4-Methylphenyl-4-(1-methylethyl)phenyliodonium
tetrakis(pentafluorophenyl)borate, a reagent manufactured by Tokyo
Chemical Industry Co., Ltd., was used.
(2) Evaluation of Physical Properties
[0459] Each of the curable compositions obtained as described above
was heated under each of the following conditions, to obtain a
cured product.
(a) Example III 6-1
[0460] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 60.degree. C. for
one hour, at 90.degree. C. for one hour, at 190.degree. C. for one
hour, and then at 240.degree. C. for two hours, to obtain a cured
product.
(b) Example III 6-2
[0461] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 60.degree. C. for
one hour, at 140.degree. C. for one hour, at 200.degree. C. for one
hour, and then at 240.degree. C. for two hours, to obtain a cured
product.
(c) Example III 6-3
[0462] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 100.degree. C. for
one hour, at 140.degree. C. for one hour, and then at 200.degree.
C. for two hours, to obtain a cured product.
(d) Example III 6-4
[0463] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 140.degree. C. for
one hour, and then at 210.degree. C. for two hours, to obtain a
cured product.
(a') Comparative Example III 6-1
[0464] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 70.degree. C. for
one hour, at 130.degree. C. for one hour, and then at 170.degree.
C. for two hours, to obtain a cured product.
(b') Comparative Example III 6-2
[0465] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 80.degree. C. for
one hour, at 140.degree. C. for one hour, and then at 180.degree.
C. for two hours, to obtain a cured product.
(c') Comparative Example III 6-3
[0466] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 130.degree. C. for
one hour, at 150.degree. C. for one hour, and then at 230.degree.
C. for two hours, to obtain a cured product.
(d') Comparative Example III 6-4
[0467] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 140.degree. C. for
one hour, at 160.degree. C. for one hour, and then at 240.degree.
C. for two hours, to obtain a cured product.
[0468] The glass transition temperature of each of the thus
obtained cured products was measured in the same manner as in
Example III 2-1. The measurement results are summarized in Table
III-7.
TABLE-US-00022 TABLE 22 Compar- Compar- Compar- Compar- ative ative
ative ative Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- ple ple
ple ple ple ple ple ple Table III-7 III 6-1 III 6-2 III 6-3 III 6-4
III 6-1 III 6-2 III 6-3 III 6-4 Composition of Epoxy compound (A-1)
50 50 50 50 curable composition the other epoxy 50 50 100 100
(parts by mass) compound (III B-1) the other epoxy 50 50 100 100
compound (III B-2) Thermal cationic 2 2 2 2 polymerization
initiator (III D-4) Thermal cationic 2 2 2 2 polymerization
initiator (III D-5) Heat resistance (.degree. C.).sup.1) 165 164
128 213 123 110 87 198 Note .sup.1)Heat resistance was measured by
the method described in Example III 2-1.
III-7. Examples III 7: Preparation of Curable Compostions
Containing Epoxy Compound (A-1) and Evaluation Thereof (Part 7:
Combination with Various Types of the Other Epoxy Compounds and
Various Types of Thermal Cationic Polymerization Initiators)
(1) Examples III 7-1 to III 7-8 nd Comparative Examples III 7-1 to
III 7-8
[0469] Curable compositions were obtained in the same manner as in
Example III 1-1, except that the following components were used at
the compositions shown in Tables III-8 and III-9.
(i) Epoxy Compound (A-1)
[0470] The epoxy compound (A-1) obtained by the method described in
Preparation Example 1 was used.
(ii) The Other Epoxy Compound (III B-1)
[0471] A bisphenol A-type liquid epoxy resin, manufactured by
Nippon Steel & Sumikin Chemical Co., Ltd., trade name: YD-128,
was used.
(iii) The Other Epoxy Compound (III B-2)
[0472] 3',4'-Epoxycyclohexylmethyl 3,4-epoxycyclohexane
carboxylate, manufactured by Dalcel Corporation, trade name:
CELLOXIDE 2021P, was used.
(iv) the Other Epoxy Compound (III B-8)
[0473] Tetramethylene glycol diglycidyl ether, a reagent
manufactured by Tokyo Chemical Industry Co., Ltd., was used.
(v) The Other Epoxy Compound (III B-9)
[0474] Cyclohexanedicarboxylic acid diglycidyl ester, a reagent
manufactured by Tokyo Chemical Industry Co., Ltd., was used.
(vi) The Other Epoxy Compound (III B-10)
[0475] Vinyl cyclohexene dioxide, a reagent manufactured by
Sigma-Aldrich Co., was used.
(vii) The Other Epoxy Compound (III B-14)
[0476] Tetrahydroindene diepoxide produced by the method described
in JP 2012-116390 A was used.
(viii) The Other Epoxy Compound (III B-16)
[0477] The monoepoxy compound produced by the method described in
Preparation Example 4 was used.
(ix) Thermal Cationic Polymerization Initiator (III D-1)
[0478] An aromatic sulfonium salt: 4-acetoxyphenyldimethylsulfonium
hexafluoroantimonate, manufactured by Sanshin Chemical Industry
Co., Ltd., trade name: SI-150L, was used.
(x) Thermal Cationic Polymerization Initiator (III D-2)
[0479] 4-Hydroxyphenylbenzylmethylsulfonium hexafluoroantimonate,
manufactured by Sanshin Chemical Industry Co., Ltd., trade name:
SI-100L, was used.
(xi) Thermal Cationic Polymerization Initiator (III D-3)
[0480] Bis[4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl]sulfide
bishexafluoroantimonate, manufactured by ADEKA CORPORATION, ADEKA
ARKLS SP-170, was used.
(2) Evaluation of Physical Properties
[0481] Each of the curable compositions obtained as described above
was heated under each of the following conditions, to obtain a
cured product.
(a) Example III 7-1
[0482] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 120.degree. C. for
one hour, at 150.degree. C. for one hour, and then at 200.degree.
C. for two hours, to obtain a cured product.
(b) Example III 7-2
[0483] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 110.degree. C. for
one hour, at 130.degree. C. for one hour, and then at 220.degree.
C. for two hours, to obtain a cured product.
(c) Example III 7-3
[0484] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 100.degree. C. for
one hour, and then at 240.degree. C. for two hours, to obtain a
cured product.
(d) Example III 7-4
[0485] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 150.degree. C. for
one hour, at 180.degree. C. for one hour, and then at 210.degree.
C. for two hours, to obtain a cured product.
(e) Example III 7-5
[0486] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 120.degree. C. for
one hour, and then at 210.degree. C. for two hours, to obtain a
cured product.
(f) Example III 7-6
[0487] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 120.degree. C. for
one hour, at 160.degree. C. for one hour, and then at 220.degree.
C. for two hours, to obtain a cured product.
(g) Example III 7-7
[0488] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 70.degree. C. for
one hour, at 120.degree. C. for one hour, and then at 220.degree.
C. for two hours, to obtain a cured product.
(h) Example III 7-8
[0489] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 120.degree. C. for
one hour, at 190.degree. C. for one hour, and then at 240.degree.
C. for two hours, to obtain a cured product.
(a') Comparative Example III 7-1
[0490] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 150.degree. C. for
one hour, at 170.degree. C. for one hour, and then at 210.degree.
C. for two hours, to obtain a cured product.
(b') Comparative Example III 7-2
[0491] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 120.degree. C. for
one hour, at 130.degree. C. for one hour, and then at 190.degree.
C. for two hours, to obtain a cured product.
(c') Comparative Example III 7-3
[0492] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 115.degree. C. for
one hour, at 130.degree. C. for one hour, at 190.degree. C. for one
hour, and then at 240.degree. C. for two hours, to obtain a cured
product.
(d') Comparative Example III 7-4
[0493] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 170.degree. C. for
one hour, and then at 210.degree. C. for two hours, to obtain a
cured product.
(e') Comparative Example III 7-5
[0494] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 120.degree. C. for
one hour, and then at 220.degree. C. for two hours, to obtain a
cured product.
(f') Comparative Example III 7-6
[0495] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 120.degree. C. for
one hour, and then at 220.degree. C. for two hours, to obtain a
cured product.
(g') Comparative Example III 7-7
[0496] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 80.degree. C. for
one hour, at 120.degree. C. for one hour, at 240.degree. C. for one
hour, and then at 240.degree. C. for two hours, to obtain a cured
product.
(h') Comparative Example III 7-8
[0497] The curable composition obtained as described above was
injected into a metal mold in the same manner as in Example III
1-1, and heated in a hot air circulating oven at 120.degree. C. for
one hour, and then at 140.degree. C. for two hours, to obtain a
cured product.
[0498] The glass transition temperature of each of the thus
obtained cured products was measured in the same manner as in
Example III 2-1. The measurement results are summarized in Tables
III-8 and III-9.
TABLE-US-00023 TABLE 23 Compar- Compar- Compar- Compar- ative ative
ative ative Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- ple ple
ple ple ple ple ple ple Table III-8 III 7-1 III 7-2 III 7-3 III 7-4
III 7-1 III 7-2 III 7-3 III 7-4 Composition Epoxy compound 50 50 50
50 of curable (A-1) composition the other epoxy 50 100 (parts by
mass) compound III B-1 100 the other epoxy 50 compound (III B-8)
the other epoxy 50 100 compound (III B-9) the other epoxy 50 100
compound (III B-14) Thermal cationic 2 2 2 2 2 2 polymerization
initiator (III D-1) Thermal cationic 2 2 polymerization initiator
(III D-2) Heat resistance (.degree. C.).sup.1) 119 230 253 186 90
197 158 76 Note .sup.1)Heat resistance was measured by the method
described in Example III 2-1
TABLE-US-00024 TABLE 24 Compar- Compar- Compar- Compar- ative ative
ative ative Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- ple ple
ple ple ple ple ple ple Table III-9 III 7-5 III 7-6 III 7-7 III 7-8
III 7-5 III 7-6 III 7-7 III 7-8 Composition of Epoxy compound (A-1)
50 50 50 50 curable the other epoxy compound 50 100 composition
(III B-1) (parts by mass) the other epoxy compound 37.5 50 87.5 100
(III B-2) the other epoxy compound 50 100 (III B-10) the other
epoxy compound 12.5 12.5 (III B-16) Thermal cationic 2 2 2 2
polymerization initiator (III D-1) Thermal cationic 2 2 2 2
polymerization initiator (III D-3) Heat resistance (.degree.
C.).sup.1) 246 227 161 239 236 211 109 230 Note .sup.1)Heat
resistance was measured by the method described in Example III
2-1.
IV. Examples of Aspect IV of the Present Invention
IV-1. Examples IV 1: Preparation of Curable Compositions Containing
Epoxy Compound (A-3) and Evaluation Thereof (Part 1: Evaluation in
the Case of Using Acid Anhydride-Type Curing Agent)
(1) Example IV 1-1
Production of Curable Composition
[0499] The epoxy compound (A-3) obtained as described above, the
other epoxy compound (IV B-1), an acid anhydride-based curing
agent, a curing accelerator and a compound containing a hydroxyl
group were mixed to achieve the following composition, to prepare a
curable composition.
<Composition of Curable Composition>
[0500] Epoxy compound (A-3) 75 parts by mass (the epoxy compound
(A-3) obtained by the method described in the above Preparation
Example 3 [0501] the other epoxy compound (IV B-1) 25 parts by mass
(a bisphenol A-type liquid epoxy resin, manufactured by Nippon
Steel & Sumikin Chemical Co., Ltd., trade name: YD-128) [0502]
Acid anhydride-based curing agent 123 parts by mass (a mixture of
4-methylhexahydrophthalic anhydride and hexahydrophthalic
anhydride, manufactured by New Japan Chemical Co., Ltd., trade
name: MH-700; an amount corresponding to 0.9 equivalent with
respect to one equivalent of the epoxy compound (A-3)) [0503]
Curing accelerator (IV C-1) 2 parts by mass
(2-ethyl-4-methylimidazole, manufactured by Shikoku Chemicals
Corporation, trade name: 2E4MZ) [0504] Compound containing a
hydroxyl group 5 parts by mass (ethylene glycol, a reagent
manufactured by Wako Pure Chemical Industries, Ltd.)
[0505] The curable composition obtained as described above was
heated in a hot air circulating oven at 110.degree. C. for one
hour, at 120.degree. C. for two hours, at 190.degree. C. for one
hour, and then at 240.degree. C. for two hours, to obtain a cured
product.
<<Performance-Evaluation>>
<Moisture Resistance>
[0506] The water absorption rate of the cured product obtained as
described above was measured in accordance with Method A described
in JIS K7209, and the moisture resistance of the cured product was
evaluated. The measurement results are summarized in Table
IV-1.
<Heat Resistance>
[0507] The glass transition temperature of the thus obtained cured
product was measured by increasing the temperature from 30 to
300.degree. C. at a rate of 10.degree. C./min, using a differential
scanning calorimeter (manufactured by Hitachi High-Tech Science
Corporation, trade name: DSC7020), and the thus measured value was
taken as the heat resistance of the cured product. The glass
transition temperature as used herein refers to a value measured in
accordance with JIS K7121, based on "Midpoint Glass Transition
Temperature: T.sub.mg" described in the section of "Method for
Measuring Transition Temperature of Plastics". The measurement
results are summarized in Table IV-1.
<Overall Evaluation>
[0508] The overall evaluation of the curable composition obtained
in the above described Example was carried out according to the
following evaluation criteria. The evaluation results are
summarized in Table IV-1.
.smallcircle.: The resulting cured product has a water absorption
rate of less than 0.50% and a heat resistance of 160.degree. C. or
higher. x: The resulting cured product has a water absorption rate
of 0.50% or more and/or a heat resistance of less than 160.degree.
C., and thus has problems in practical use.
(2) Examples IV 1-2 to IV 1-4
[0509] Curable compositions were obtained in the same manner as in
Example IV 1, except that the compositions of the curable
compositions were changed to those shown in Table IV-1.
[0510] Cured products were obtained in the same manner as in
Example IV 1 from the curable compositions prepared as described
above, and then the water absorption rate and the glass transition
temperature of each of the cured products were measured. The
measurement results are summarized in Table IV-1.
(3) Comparative Example IV 1-1
[0511] A curable composition was obtained in the same manner as in
Example IV 1, except that the composition of the curable
composition was changed to that shown in Table IV-1.
[0512] The curable composition obtained as described above was
heated in a hot air circulating oven at 100.degree. C. for two
hours, and then at 160.degree. C. for four hours, to obtain a cured
product.
[0513] The water absorption rate and the glass transition
temperature of the thus obtained cured product were measured. The
measurement results are summarized in Table IV-1.
(4) Comparative Example IV 1-2
[0514] A curable composition was obtained in the same manner as in
Example IV 1, except that the composition of the curable
composition was changed to that shown in Table IV-1.
[0515] The curable composition obtained as described above was
heated in a hot air circulating oven at 100.degree. C. for two
hours, at 160.degree. C. for two hours, and then at 220.degree. C.
for two hours, to obtain a cured product.
[0516] The water absorption rate and the glass transition
temperature of the thus obtained cured product were measured. The
measurement results are summarized in Table IV-1.
TABLE-US-00025 TABLE 25 Compar- Compar- ative ative Exam- Exam-
Exam- Exam- Exam- Exam- ple ple ple ple ple ple Table IV-1 IV 1-1
IV 1-2 IV 1-3 IV 1-4 IV 1-1 IV 1-2 Composition of Epoxy compound
(A-3) 75 50 75 50 curable composition the other epoxy compound 25
50 100 (parts by mass) (IV B-1) the other epoxy compound 25 50 100
(IV B-2) Acid anhydride-based curing agent 123 109 132 126 81 15
Curing accelerator 2 2 2 2 1 1 (IV C-1) Compound containing
hydroxyl group 5 5 5 5 Water absorption rate (%) 0.33 0.29 0.44
0.45 0.18 0.6 Heat resistance (.degree. C.) 179 161 197 191 158 233
Overall evaluation .smallcircle. .smallcircle. .smallcircle.
.smallcircle. x x
[0517] The respective components used for the preparation of the
respective curable compositions shown in Table IV-1 are as
follows.
the other epoxy compound (IV B-2): 3,4-epoxycyclohexymethyl
3,4-epoxycyclohexane carboxylate, manufactured by Daicel
Corporation, trade name: CELLOXIDE 2021P.
IV-2. Examples IV 2: Preparation of Curable Compositions Containing
Epoxy Compound (A-3) and Evaluation Thereof (Part 2: Combination
with Various Types of the Other Epoxy Compounds and Acid
Anhydride-Based Curing Agent)
(1) Examples IV 2-1 to IV 2-13 and Comparative Examples IV 2-1 to
IV 2-14
[0518] Curable compositions were obtained in the same manner as in
Example IV 1-1 except that the following components were used at
the compositions shown in Tables IV-2 to IV-4.
(i) Epoxy Compound (A-3)
[0519] The epoxy compound (A-3) obtained by the method described in
the above Preparation Example 3 was used.
(ii) The Other Epoxy Compound (IV B-1)
[0520] A bisphenol A-type liquid epoxy resin, manufactured by
Nippon Steel & Sumikin Chemical Co., Ltd., trade name: YD-128,
was used.
(iii) The Other Epoxy Compound (IV B-2)
[0521] 3,4'-Epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate,
manufactured by Daicel Corporation, trade name: CELLOXIDE 2021P,
was used.
(iv) The Other Epoxy Compound (IV B-3)
[0522] A cresol novolac type epoxy resin, manufactured by DIC
Corporation, trade name: N-660, was used.
(v) The Other Epoxy Compound (IV B-4)
[0523] A phenol novolac type epoxy resin, manufactured by Nippon
Steel & Sumikin Chemical Co., Ltd., trade name: YDPN-638, was
used.
(vi) The Other Epoxy Compound (IV B-5)
[0524] A bisphenol F-type liquid epoxy resin, manufactured by
Nippon Steel & Sumikin Chemical Co., Ltd., trade name: YDF-170,
was used.
(vii) The Other Epoxy Compound (IV B-6)
[0525] A hydrogenated bisphenol A-type liquid epoxy resin,
manufactured by Mitsubishi Chemical Corporation, trade name:
YX8000, was used.
(viii) The Other Epoxy Compound (IV B-7)
[0526] Triglycidyl isocyanurate, manufactured by Nissan Chemical
Industries, Ltd., trade name: TEPIC-S, was used.
(ix) The Other Epoxy Compound (IV B-8)
[0527] Tetramethylene glycol diglycidyl ether, a reagent
manufactured by Tokyo Chemical Industry Co., Ltd., was used.
(x) The Other Epoxy Compound (IV B-9)
[0528] Cyclohexanedicarboxylic acid diglycidyl ester, a reagent
manufactured by Tokyo Chemical Industry Co., Ltd., was used.
(xi) The Other Epoxy Compound (IV B-10)
[0529] Vinyl cyclohexene dioxide, a reagent manufactured by
Sigma-Aldrich Co., was used.
(xii) The Other Epoxy Compound (IV B-11)
[0530] 1,2-Epoxy-(2-oxiranyl)cyclohexane adduct of
2,2-bis(hydroxymethyl)-1-butanol, manufactured by Dace Corporation,
trade name: EHPE 3150, was used.
(xiii) The Other Epoxy Compound (IV B-12)
[0531] Limonene dioxide, a reagent manufactured by Sigma-Aldrich
Co., was used.
(xiv) The Other Epoxy Compound (IV 8-13)
[0532] (3,3',4,4'-Diepoxy)bicyclohexyl, manufactured by Daicel
Corporation, trade name: CELLOXIDE 8000, was used.
(xv) The Other Epoxy Compound (IV 8-14)
[0533] Tetrahydroindene diepoxide produced by the method described
in JP 2012-116390 A was used.
(xvi) The Other Epoxy Compound (IV 8-16)
[0534] The monoepoxy compound produced by the method described in
Preparation Example 4 was used.
(xvii) Acid Anhydride-Based Curing Agent
[0535] A mixture of 4-methylhexahydrophthalic anhydride and
hexahydrophthalic anhydride, manufactured by New Japan Chemical
Co., Ltd., trade name: MH-700, was used.
(xvii) Curing Accelerator (IV C-1)
[0536] 2-Ethyl-4-methylimidazole, manufactured by Shikoku Chemicals
Corporation, trade name: 2E4MZ, was used.
(xix) Curing Accelerator (IV C-2)
[0537] 1,8-Diazabicyclo(5,4,0)undecene-7, a reagent manufactured by
Tokyo Chemical Industry Co., Ltd. was used.
(xx) Compound Containing Hydroxyl Group
[0538] Ethylene glycol, a reagent manufactured by Wako Pure
Chemical Industries, Ltd. was used.
(2) Performance Evaluation
[0539] (Heat Resistance of Cured Product from Curable
Composition)
[0540] Each of the curable compositions obtained as described above
was heated under each of the following conditions, to obtain a
cured product.
(a) Example IV 2-1
[0541] The curable composition obtained as described above was
heated in a hot air circulating oven at 100.degree. C. for one
hour, at 170.degree. C. for one hour, and then at 240.degree. C.
for two hours, to obtain a cured product.
(b) Example IV 2-2
[0542] The curable composition obtained as described above was
heated in a hot air circulating oven at 100.degree. C. for one
hour, at 150.degree. C. for one hour, and then at 180.degree. C.
for two hours, to obtain a cured product.
(c) Example IV 2-3
[0543] The curable composition obtained as described above was
heated in a hot air circulating oven at 90.degree. C. for one hour,
at 140.degree. C. for one hour, and then at 180.degree. C. for two
hours, to obtain a cured product.
(d) Example IV 2-4
[0544] The curable composition obtained as described above was
heated in a hot air circulating oven at 90.degree. C. for one hour,
at 130.degree. C. for one hour, and then at 160.degree. C. for two
hours, to obtain a cured product.
(e) Example IV 2-5
[0545] The curable composition obtained as described above was
heated in a hot air circulating oven at 90.degree. C. for one hour,
at 130.degree. C. for one hour, and then at 170.degree. C. for two
hours, to obtain a cured product.
(f) Example IV 2-6
[0546] The curable composition obtained as described above was
heated in a hot air circulating oven at 100.degree. C. for one
hour, at 140.degree. C. for one hour, and then at 240.degree. C.
for two hours, to obtain a cured product.
(g) Example IV 2-7
[0547] The curable composition obtained as described above was
heated in a hot air circulating oven at 70.degree. C. for one hour,
at 120.degree. C. for one hour, at 170.degree. C. for one hour, and
then at 230.degree. C. for two hours, to obtain a cured
product.
(h) Example IV 2-8
[0548] The curable composition obtained as described above was
heated in a hot air circulating oven at 90.degree. C. for one hour,
at 130.degree. C. for one hour, and then at 160.degree. C. for two
hours, to obtain a cured product.
(i) Example IV 2-9
[0549] The curable composition obtained as described above was
heated in a hot air circulating oven at 70.degree. C. for one hour,
at 120.degree. C. for one hour, at 170.degree. C. for one hour, and
then at 210.degree. C. for two hours, to obtain a cured
product.
(j) Example IV 2-10
[0550] The curable composition obtained as described above was
heated in a hot air circulating oven at 70.degree. C. for one hour,
at 130.degree. C. for one hour, and then at 140.degree. C. for two
hours, to obtain a cured product.
(k) Example IV 2-11
[0551] The curable composition obtained as described above was
heated in a hot air circulating oven at 90.degree. C. for one hour,
at 140.degree. C. for one hour, and then at 240.degree. C. for two
hours, to obtain a cured product.
(l) Example IV 2-12
[0552] The curable composition obtained as described above was
heated in a hot air circulating oven at 90.degree. C. for one hour,
at 140.degree. C. for one hour, at 180.degree. C. for one hour, and
then at 240.degree. C. for two hours, to obtain a cured
product.
(m) Example IV 2-13
[0553] The curable composition obtained as described above was
heated in a hot air circulating oven at 90.degree. C. for one hour,
and then at 180.degree. C. for two hours, to obtain a cured
product.
(a') Comparative Example IV 2-1
[0554] The curable composition obtained as described above was
heated in a hot air circulating oven at 130.degree. C. for one
hour, at 160.degree. C. for one hour, and then at 180.degree. C.
for two hours, to obtain a cured product.
(b') Comparative Example IV 2-2
[0555] The curable composition obtained as described above was
heated in a hot air circulating oven at 120.degree. C. for one
hour, at 150.degree. C. for one hour, and then at 170.degree. C.
for two hours, to obtain a cured product.
(c') Comparative Example IV 2-3
[0556] The curable composition obtained as described above was
heated in a hot air circulating oven at 90.degree. C. for one hour,
at 140.degree. C. for one hour, and then at 180.degree. C. for two
hours, to obtain a cured product.
(d') Comparative Example IV 2-4
[0557] The curable composition obtained as described above was
heated in a hot air circulating oven at 90.degree. C. for one hour,
at 130.degree. C. for one hour, and then at 160.degree. C. for two
hours, to obtain a cured product.
(e') Comparative Example IV 2-5
[0558] The curable composition obtained as described above was
heated in a hot air circulating oven at 80.degree. C. for one hour,
at 130.degree. C. for one hour, and then at 170.degree. C. for two
hours, to obtain a cured product.
(f) Comparative Example IV 2-6
[0559] The curable composition obtained as described above was
heated in a hot air circulating oven at 100.degree. C. for one
hour, at 140.degree. C. for one hour, and then at 240.degree. C.
for two hours, to obtain a cured product.
(g') Comparative Example IV 2-7
[0560] The curable composition obtained as described above was
heated in a hot air circulating oven at 60.degree. C. for one hour,
at 110.degree. C. for one hour, at 160.degree. C. for one hour, and
then at 240.degree. C. for two hours, to obtain a cured
product.
(h') Comparative Example IV 2-8
[0561] The curable composition obtained as described above was
heated in a hot air circulating oven at 80.degree. C. for one hour,
at 120.degree. C. for one hour, and then at 150.degree. C. for two
hours, to obtain a cured product.
(i') Comparative Example IV 2-9
[0562] The curable composition obtained as described above was
heated in a hot air circulating oven at 70.degree. C. for one hour,
at 100.degree. C. for one hour, at 190.degree. C. for one hour, and
then at 240.degree. C. for two hours, to obtain a cured
product.
(j') Comparative Example IV 2-10
[0563] The curable composition obtained as described above was
heated in a hot air circulating oven at 70.degree. C. for one hour,
at 130.degree. C. for one hour, and then at 240.degree. C. for two
hours, to obtain a cured product.
(k') Comparative Example IV 2-11
[0564] The curable composition obtained as described above was
heated in a hot air circulating oven at 90.degree. C. for one hour,
at 140.degree. C. for one hour, and then at 240.degree. C. for two
hours, to obtain a cured product.
(l') Comparative Example IV 2-12
[0565] The curable composition obtained as described above was
heated in a hot air circulating oven at 90.degree. C. for one hour,
at 140.degree. C. for one hour, and then at 180.degree. C. for two
hours, to obtain a cured product.
(m') Comparative Example IV 2-13
[0566] The curable composition obtained as described above was
heated in a hot air circulating oven at 90.degree. C. for one hour,
at 140.degree. C. for one hour, and then at 180.degree. C. for two
hours, to obtain a cured product.
(n') Comparative Example IV 2-14
[0567] The curable composition obtained as described above was
heated in a hot air circulating oven at 90.degree. C. for one hour,
and then at 180.degree. C. for two hours, to obtain a cured
product.
[0568] The heat resistance (glass transition temperature) of each
of the thus obtained cured products was measured in the same manner
as in Example IV 1-1. The measurement results are summarized in
Tables IV-2 to IV-4.
TABLE-US-00026 TABLE 26 Compar- Compar- Compar- Compar- Compar-
ative ative ative ative ative Exam- Exam- Exam- Exam- Exam- Exam-
Exam- Exam- Exam- Exam- ple ple ple ple ple ple ple ple ple ple
Table IV-2 IV 2-1 IV 2-2 IV 2-3 IV 2-4 IV 2-5 IV 2-1 IV 2-2 IV 2-3
IV 2-4 IV 2-5 Composition of Epoxy compound 50 50 50 50 50 curable
(A-3) composition the other epoxy 25 50 (parts by mass) compound
(IV B-2) the other epoxy 50 100 compound (IV B-3) the other epoxy
50 100 compound (IV B-4) the other epoxy 50 100 compound (IV B-6)
the other epoxy 50 100 compound (IV B-7) the other epoxy 25 50
compound (IV B-11) Acid 106 111 107 144 118 74 84 76 151 99
anhydride-based curing agent Curing accelerator 2 2 2 2 2 2 2 2 2 2
(IV C-1) Compound 5 5 5 5 5 5 5 containing hydroxyl group Heat
resistance (.degree. C.) 186 132 257 253 283 149 113 220 209
232
TABLE-US-00027 TABLE 27 Compar- Compar- Compar- Compar- ative ative
ative ative Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- ple ple
ple ple ple ple ple ple Table IV-3 IV 2-6 IV 2-7 IV 2-8 IV 2-9 IV
2-6 IV 2-7 IV 2-8 IV 2-9 Composition of Epoxy compound 50 50 50 50
curable (A-3) composition the other epoxy 50 100 (parts by mass)
compound (IV B-5) the other epoxy 50 100 compound (IV B-9) the
other epoxy 50 100 compound (IV B-10) the other epoxy 50 100
compound (IV B-14) Acid 113 177 122 162 89 216 106 187
anhydride-based curing agent Curing accelerator 2 2 2 2 2 2 2 2 (IV
C-1) Compound 5 5 5 5 containing hydroxyl group Heat resistance
(.degree. C.) 120 158 276 268 92 137 102 126
TABLE-US-00028 TABLE 28 Compar- Compar- Compar- Compar- Compar-
ative ative ative ative ative Exam- Exam- Exam- Exam- Exam- Exam-
Exam- Exam- Exam- ple ple ple ple ple ple ple ple ple Table IV-4 IV
2-10 IV 2-11 IV 2-12 IV 2-13 IV 2-10 IV 2-11 IV 2-12 IV 2-13 IV
2-14 Composition of Epoxy compound 50 50 67 50 curable (A-3)
composition the other epoxy 67 (parts by mass) compound (IV B-1)
the other epoxy 67 compound (IV B-2) the other epoxy 50 100
compound (IV B-8) the other epoxy 50 100 compound (IV B-12) the
other epoxy 50 100 compound (IV B-13) the other epoxy 33 33 33
compound (IV B-16) Acid 147 144 118 159 156 150 80 104 180
anhydride-based curing agent Curing accelerator 2 2 2 2 2 2 2 (IV
C-1) Curing accelerator 2 2 (IV C-2) Compound 5 5 5 5 2 5 5 5
containing hydroxyl group Heat resistance (.degree. C.) 207 95 161
81 152 86 101 105 57
V. Examples of Aspect V of the Present Invention
V-1. Examples V 1: Preparation of Curable Compositions Containing
Epoxy Compound (A-1) or Epoxy Compound (A-2) and Evaluation Thereof
(Part 1: Comparison with the Other Epoxy Compounds)
(1) Example V 1-1
Production of Curable Composition
[0569] The epoxy compound (A-1) obtained as described above, a
photo-cationic polymerization initiator (V D-1) and the other epoxy
compound (V B-2) were mixed to achieve the following composition,
to prepare a curable composition.
<Composition of Curable Composition>
[0570] Epoxy compound (A-1) 25 parts by mass (the epoxy compound
produced by the method described in Preparation Example 1) [0571]
the other epoxy compound (V B-2) 75 parts by mass (a bisphenol
A-type liquid epoxy resin, manufactured by Nippon Steel &
Sumikin Chemical Co., Ltd., trade name: YD-128) [0572]
Photo-cationic polymerization initiator (V D-1) 10 parts by mass (a
50% propylene carbonate solution of an aromatic sulfonium salt:
diphenyl-4-(phenylthio)phenylsulfonium hexafluorophosphate,
manufactured by San-Apro Ltd., trade name: CPI-100P)
(2) Example V 1-2
Production of Curable Composition
[0573] A curable composition was obtained in the same manner as in
Example V 1-1, except that the epoxy compound (A-2) (the epoxy
compound produced by the method described in Preparation Example 2)
was used instead of the epoxy compound (A-1).
(3) Comparative Example V 1-1
[0574] A curable composition was obtained in the same manner as in
Example V 1-1, except that the epoxy compound (A-1) was not
incorporated, and the other epoxy compound (V B-2) was used in an
amount of 100 parts by mass in the composition.
(4) Comparative Example V 1-2
[0575] A curable composition was obtained in the same manner as in
Example V 1-1, except that that the epoxy compound (A-1) was not
incorporated, and 75 parts by mass of the other epoxy compound (V
B-2) and 25 parts by mass of the other epoxy compound (V B-3)
(3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate,
manufactured by Daicel Corporation, trade name: CELLOXIDE 2021P)
were used in the composition.
(5) Comparative Example V 1-3
[0576] A curable composition was obtained in the same manner as in
Example V 1-1, except that that the epoxy compound (A-1) was not
incorporated, and 25 parts by mass of the other epoxy compound (V
B-2) and 75 parts by mass of the other epoxy compound (V B-3) were
used in the composition.
(6) Comparative Example V 1-4
[0577] A curable composition was obtained in the same manner as in
Example V 1-1, except that the other epoxy compound (V B-1)
(dicyclopentadiene diepoxide) represented by the following Formula
was used instead of the epoxy compound (A-1).
##STR00018##
(7) Evaluation of Curable Compositions
<Heat Resistance (Weight Reduction Temperature)>
[0578] Each of the curable compositions obtained in the above
described Examples V 1-1 and V 1-2, and Comparative Examples V 1-1
to V 1-4 was coated on a glass substrate to a coating thickness of
50 .mu.m. Each coated substrate was irradiated with UV light at
room temperature (23.degree. C.) such that the accumulated amount
of light was 3,000 mJ/cm.sup.2. The curable composition was cured.
Next, the cured product was scraped off from each glass substrate,
and the measurement of the weight reduction temperature was carried
out using a simultaneous thermogravimetric analyzer (manufactured
by Hitachi High-Tech Science Corporation, trade name: TG/DTA 7200).
About 10 mg of the cured product was heated from room temperature
to 550.degree. C. at a constant temperature increase rate of
10.degree. C./min in dry air, and the 1% weight reduction
temperature, 3% weight reduction temperature, 5% weight reduction
temperature and 10% weight reduction temperature of each cured
product were measured. The measurement results are summarized in
Table V-1.
TABLE-US-00029 TABLE 29 Compar- Compar- Compar- Compar- ative ative
ative ative Exam- Exam- Exam- Exam- Exam- Exam- ple ple ple ple ple
ple Table V-1 V 1-1 V 1-2 V 1-1 V 1-2 V 1-3 V 1-4 Composition Epoxy
compound (A-1) 25 of curable Epoxy compound (A-2) 25 composition
the other epoxy compound (V B-1) 25 (parts by mass) the other epoxy
compound (V B-2) 75 75 100 75 25 75 the other epoxy compound (V
B-3) 25 75 Photo-cationic polymerization 10 10 10 10 10 10
initiator (V D-1) 1% Weight reduction temperature (.degree. C.) 135
141 112 115 110 100 3% Weight reduction temperature (.degree. C.)
230 235 172 180 190 134 5% Weight reduction temperature (.degree.
C.) 288 286 268 219 271 188 10% Weight reduction temperature
(.degree. C.) 320 319 325 261 313 288
V-2. Examples V 2: Preparation of Curable Compositions Containing
Epoxy Compound (A-1) or Epoxy Compound (A-2) and Evaluation Thereof
(Part 2: Comparison with the Other Epoxy Compounds)
(1) Example V 2-1
Production of Curable Composition
[0579] The epoxy compound (A-1) obtained as described above, the
photo-cationic polymerization initiator (V D-1) and the other epoxy
compound (V B-3) were mixed to achieve the following composition,
to prepare a curable composition.
<Composition of Curable Composition>
[0580] Epoxy compound (A-1) 25 parts by mass (the epoxy compound
produced by the method described in Preparation Example 1) [0581]
the other epoxy compound (V B-3) 75 parts by mass
(3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate,
manufactured by Daicel Corporation, trade name: CELLOXIDE 2021P)
[0582] Photo-cationic polymerization Initiator (V D-1) 10 parts by
mass (a 50% propylene carbonate solution of an aromatic sulfonium
salt: diphenyl-4-(phenylthio)phenylsulfonium hexafluorophosphate,
manufactured by San-Apro Ltd., trade name: CPI-100P)
(2) Example V 2-2
Production of Curable Composition
[0583] A curable composition was obtained in the same manner as in
Example V 2-1, except that the epoxy compound (A-2) (the epoxy
compound produced by the method described in Preparation Example 2)
was used instead of the epoxy compound (A-1).
(3) Comparative Example V 2-1
[0584] A curable composition was obtained in the same manner as in
Example V 2-1, except that the epoxy compound (A-1) was not
incorporated, and 100 parts by mass of the other epoxy resin (V
B-3) was used in the composition.
(4) Comparative Example V 2-2
[0585] A curable composition was obtained in the same manner as in
Example V 2-1, except that the other epoxy compound (V B-1)
(dicyclopentadiene diepoxide) was used instead of the epoxy
compound (A-1).
(5) Evaluation of Curable Compositions
<Heat Resistance (Weight Reduction Temperature)>
[0586] Each of the curable compositions obtained in the above
described Examples V 2-1 and V 2-2, and Comparative Examples V 2-1
and V 2-2 was coated on a glass substrate to a coating thickness of
50 .mu.m. Each coated substrate was irradiated with UV light at
room temperature (23.degree. C.) such that the accumulated amount
of light was 3,000 m/cm.sup.2. The curable composition was cured.
Next, the cured product was scraped off from each glass substrate,
and the measurement of the weight reduction temperature was carried
out using a simultaneous thermogravimetric analyzer (manufactured
by Hitachi High-Tech Science Corporation, trade name: TG/DTA 7200).
About 10 mg of the cured product was heated from room temperature
to 550.degree. C. at a constant temperature increase rate of
10.degree. C./min in dry air, and the 1% weight reduction
temperature, 3% weight reduction temperature, 5% weight reduction
temperature and 10% weight reduction temperature of each cured
product were measured. The measurement results are summarized in
Table V-2.
TABLE-US-00030 TABLE 30 Com- Com- para- para- tive tive Ex- Ex- Ex-
Ex- am- am- am- am- ple ple ple ple Table V-2 V 2-1 V 2-2 V 2-1 V
2-2 Composition of Epoxy compound 25 curable composition (A-1)
(parts by mass) Epoxy compound 25 (A-2) the other epoxy 25 compound
(V B-1) the other epoxy 75 75 100 75 compound (V B-3)
Photo-cationic 10 10 10 10 polymerization initiator (V D-1) 1%
Weight reduction temperature (.degree. C.) 142 139 120 110 3%
Weight reduction temperature (.degree. C.) 197 196 172 140 5%
Weight reduction temperature (.degree. C.) 240 227 197 164 10%
Weight reduction temperature (.degree. C.) 276 276 242 247
V-3. Examples V 3: Preparation of Curable Compositions Containing
Epoxy Compound (A-1) or Epoxy Compound (A-2) and Evaluation Thereof
(Part 3: Combination with Oxetane Compound and Photo-Cationic
Polymerization Initiator)
(1) Example V 3-1
Production of Curable Composition
[0587] The epoxy compound (A-1) obtained as described above, the
photo-cationic polymerization initiator (V D-1) and an oxetane
compound (V C-1) were mixed to achieve the following composition,
to prepare a curable composition.
<Composition of Curable Composition>
[0588] Epoxy compound (A-1) 25 parts by mass (the epoxy compound
produced by the method described in Preparation Example 1) [0589]
Oxetane compound (V C-1) 75 parts by mass
(1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, manufactured by
Toagosel Co., Ltd., trade name: ARONE OXETANE OXT-121) [0590]
Photo-cationic polymerization initiator (V D-1) 10 parts by mass (a
50% propylene carbonate solution of an aromatic sulfonium salt:
diphenyl-4-(phenylthio)phenylsulfonium hexafluorophosphate,
manufactured by San-Apro Ltd., trade name: CPI-100P)
(2) Example V-3-2
Production of Curable Composition
[0591] A curable composition was obtained in the same manner as in
Example V 3-1, except that the epoxy compound (A-2) (the epoxy
compound produced by the method described in Preparation Example 2)
was used instead of the epoxy compound (A-1).
(3) Comparative Example V 3-1
Production of Curable Composition
[0592] A curable composition was obtained in the same manner as in
Example V 3-1, except that the other epoxy compound (V B-2) was
used instead of the epoxy compound (A-1).
(4) Comparative Example V 3-2
Production of Curable Composition
[0593] A curable composition was obtained in the same manner as in
Example V 3-1, except that the other epoxy compound (V B-3) was
used instead of the epoxy compound (A-1).
(5) Evaluation of Curable Compositions
<Heat Resistance (Weight Reduction Temperature)>
[0594] Each of the curable compositions obtained in the above
described Examples V 3-1 and V 3-2, and Comparative Examples V 3-1
and V 3-2 was coated on a glass substrate to a coating thickness of
50 .mu.m. Each coated substrate was irradiated with UV light at
room temperature (23.degree. C.) such that the accumulated amount
of light was 3,000 m/cm.sup.2. The curable composition was cured.
Next, the cured product was scraped off from each glass substrate,
and the measurement of the weight reduction temperature was carried
out using a simultaneous thermogravimetric analyzer (manufactured
by Hitachi High-Tech Science Corporation, trade name: TG/DTA 7200).
About 10 mg of the cured product was heated from room temperature
to 550.degree. C. at a constant temperature increase rate of
10.degree. C./min in dry air, and the 1% weight reduction
temperature, 3% weight reduction temperature, 5% weight reduction
temperature and 10% weight reduction temperature of each cured
product were measured. The measurement results are summarized in
Table V-3.
TABLE-US-00031 TABLE 31 Com- Com- para- para- Ex- Ex- tive tive am-
am- Exam- Exam- ple ple ple ple Table V-3 V 3-1 V 3-2 V 3-1 V 3-2
Composition of Epoxy compound 25 curable composi- (A-1) tion (parts
by Epoxy compound 25 mass) (A-2) the other epoxy 25 compound (V
B-2) the other epoxy 25 compound (V B-3) Oxetane compound 75 75 75
75 (V C-1) Photo-cationic 10 10 10 10 polymerization initiator (V
D-1) 1% Weight reduction temperature 96 99 81 94 (.degree. C.) 3%
Weight reduction temperature 173 160 119 137 (.degree. C.) 5%
Weight reduction temperature 252 231 227 193 (.degree. C.) 10%
Weight reduction temperature 318 263 256 238 (.degree. C.)
V-4. Example V: Preparation of Curable Compostions Containing Epoxy
Compound (A-1) or Epoxy Compound (A-2) and Evaluation Thereof (Part
4: Combination with the Other Epoxy Compounds and Photo-Cationic
Polymerization Initiator)
(1) Example V 4-1
Production of Curable Composition
[0595] The epoxy compound (A-1) obtained as described above, the
photo-cationic polymerization Initiator (V D-1) and the other epoxy
compound (V B-16) were mixed to achieve the following composition,
to prepare a curable composition.
<Composition of Curable Composition>
[0596] Epoxy compound (A-1) 25 parts by mass (the epoxy compound
produced by the method described in Preparation Example 1) [0597]
the other epoxy compound (V B-16) 75 parts by mass
(1,2-epoxy-4-vinylcyclohexane, manufactured by Dalcel Corporation,
trade name: CELLOXIDE 2000) [0598] Photo-cationic polymerization
initiator (V D-1) 10 parts by mass (a 50% propylene carbonate
solution of an aromatic sulfonium salt:
diphenyl-4-(phenylthio)phenylsulfonium hexafluorophosphate,
manufactured by San-Apro Ltd., trade name: CPI-100P)
(2) Example V 4-2
Production of Curable Composition
[0599] A curable composition was obtained in the same manner as in
Example V 3-1, except that the epoxy compound (A-2) (the epoxy
compound produced by the method described in Preparation Example 2)
was used instead of the epoxy compound (A-1).
(3) Comparative Example V 4-1
Production of Curable Composition
[0600] A curable composition was obtained in the same manner as in
Example V 3-1, except that the other epoxy compound (V B-2) was
used instead of the epoxy compound (A-1).
(4) Comparative Example V 4-2
Production of Curable Composition
[0601] A curable composition was obtained in the same manner as in
Example V 3-1, except that the other epoxy compound (V B-3) was
used instead of the epoxy compound (A-1).
(5) Evaluation of Curable Compositions
<Heat Resistance (Weight Reduction Temperature)>
[0602] Each of the curable compositions obtained in the above
described Examples V 4-1 and V 4-2, and Comparative Examples V 4-1
and V 4-2 was coated on a glass substrate to a coating thickness of
50 .mu.m. Each coated substrate was irradiated with UV light at
room temperature (23.degree. C.) such that the accumulated amount
of light was 3,000 mJ/cm.sup.2. The curable composition was cured.
Next, the cured product was scraped off from each glass substrate,
and the measurement of the weight reduction temperature was carried
out using a simultaneous thermogravimetric analyzer (manufactured
by Hitachi High-Tech Science Corporation, trade name: TG/DTA 7200).
About 10 mg of the cured product was heated from room temperature
to 550.degree. C. at a constant temperature increase rate of
10.degree. C./min in dry air, and the 1% weight reduction
temperature, 3% weight reduction temperature, 5% weight reduction
temperature and 10% weight reduction temperature of each cured
product were measured. The measurement results are summarized in
Table V-4.
TABLE-US-00032 TABLE 32 Com- Com- para- para- tive tive Ex- Ex- Ex-
Ex- am- am- am- am- ple ple ple ple Table V-4 V 4-1 V 4-2 V 4-1 V
4-2 Composition of Epoxy compound 25 curable composi- (A-1) tion
(parts by Epoxy compound 25 mass) (A-2) the other epoxy 25 compound
(V B-2) the other epoxy 25 compound (V B-3) the other epoxy 75 75
75 75 compound (V B-16) Photo-cationic 10 10 10 10 polymerization
initiator (V D-1) 1% Weight reduction temperature 117 139 102 118
(.degree. C.) 3% Weight reduction temperature 182 214 138 155
(.degree. C.) 5% Weight reduction temperature 219 241 170 186
(.degree. C.) 10% Weight reduction temperature 264 284 250 246
(.degree. C.)
V-5. Examples V 5: Preparation of Curable Compositions Containing
Epoxy Compound (A-1) or Epoxy Compound (A-2) and Evaluation Thereof
(Part 5: Combination with Various Types of the Other Epoxy
Compounds and Photo-Cationic Polymerization Initiator)
(1) Examples V 5-1 to V 5-10 and Comparative Examples V5-1 to V
5-6
[0603] Curable compositions were obtained in the same manner as in
Example V 1-1, except that the following components were used, at
the compositions shown in Tables V-5 to V-7.
(i) Epoxy Compound (A-1)
[0604] The epoxy compound produced by the method described in
Preparation Example 1 was used.
(ii) Epoxy Compound (A-2)
[0605] The epoxy compound produced by the method described in
Preparation Example 2 was used.
(iii) The Other Epoxy Compound (V B-3)
[0606] 3',4'-Epoxycyclohexylmethyl 3,4-epoxycyclohexane
carboxylate, manufactured by Daicel Corporation, trade name:
CELLOXIDE 2021P, was used.
(iv) The Other Epoxy Compound (V B-6)
[0607] A bisphenol F-type liquid epoxy resin, manufactured by
Nippon Steel & Sumikin Chemical Co., Ltd., trade name: YDF-170,
was used.
(v) The Other Epoxy Compound (V B-7)
[0608] A hydrogenated bisphenol A-type liquid epoxy resin,
manufactured by Mitsubishi Chemical Corporation, trade name:
YX8000, was used.
(vi) The Other Epoxy Compound (V B-9)
[0609] Tetramethylene glycol diglycidyl ether, a reagent
manufactured by Tokyo Chemical Industry Co., Ltd., was used.
(vii) The Other Epoxy Compound (V B-10)
[0610] Cyclohexanedicarboxylic acid diglycidyl ester, a reagent
manufactured by Tokyo Chemical Industry Co., Ltd., was used.
(viii) The Other Epoxy Compound (V B-12)
[0611] 1,2-Epoxy-(2-oxiranyl)cyclohexane adduct of
2,2-bis(hydroxymethyl)-1-butanol, manufactured by Dalcel
Corporation, trade name: EHPE 3150, was used.
(ix) The Other Epoxy Compound (V B-17)
[0612] The monoepoxy compound produced by the method described in
Preparation Example 4 was used.
(x) Photo-Cationic Polymerization Initiator (V D-1)
[0613] A 50% propylene carbonate solution of
diphenyl-4-(phenylthio)phenylsulfonium hexafluorophosphate,
manufactured by San-Apro Ltd., trade name: CPI-100P, was used.
(2) Evaluation of Curable Compositions
<Heat Resistance (Weight Reduction Temperature)>
[0614] Each of the curable compositions obtained in the above
described Examples V 5-1 to V 5-10 and Comparative Examples V 5-1
to V 5-6 was coated on a glass substrate to a coating thickness of
50 .mu.m. Each coated substrate was irradiated with UV light at
room temperature (23.degree. C.) such that the accumulated amount
of light was 3,000 mJ/cm.sup.2. The curable composition was cured.
Next, the cured product was scraped off from each glass substrate,
and the measurement of the weight reduction temperature was carried
out using a simultaneous thermogravimetric analyzer (manufactured
by Hitachi High-Tech Science Corporation, trade name: TG/DTA 7200).
About 10 mg of the cured product was heated from room temperature
to 550.degree. C. at a constant temperature increase rate of
10.degree. C./min in dry air, and the 1% weight reduction
temperature, 3% weight reduction temperature, 5% weight reduction
temperature and 10% weight reduction temperature of each cured
product were measured. The measurement results are summarized in
Tables V-5 to V-7.
TABLE-US-00033 TABLE 33 Compar- Compar- ative ative Exam- Exam-
Exam- Exam- Exam- ple ple ple ple ple Table V-5 V 5-1 V 5-2 V 5-3 V
5-1 V 5-2 Composition Epoxy compound (A-1) 25 25 of curable Epoxy
compound (A-2) 25 composition the other epoxy compound (VB-6) 75
100 (parts by mass) the other epoxy compound (V B-7) 75 75 100
Photo-cationic polymerization initiator 10 10 10 10 10 (V D-1) 1%
Weight reduction temperature (.degree. C.) 100 96 95 98 78 3%
Weight reduction temperature (.degree. C.) 177 145 144 156 112 5%
Weight reduction temperature (.degree. C.) 263 226 234 263 201 10%
Weight reduction temperature (.degree. C.) 306 278 279 323 268
TABLE-US-00034 TABLE 34 Compar- Compar- ative ative Exam- Exam-
Exam- Exam- Exam- Exam- ple ple ple ple ple ple Table V-6 V 5-4 V
5-5 V 5-6 V 5-7 V 5-3 V 5-4 Composition Epoxy compound (A-1) 25
12.5 of curable Epoxy compound (A-2) 25 12.5 composition the other
epoxy compound 75 75 75 (parts by mass) (V B-3) the other epoxy
compound 75 75 100 (V B-9) the other epoxy compound 12.5 12.5 25 (V
B-10) Photo-cationic polymerization 10 10 10 10 10 10 initiator (V
D-1) 1% Weight reduction temperature (.degree. C.) 84 88 112 114 40
111 3% Weight reduction temperature (.degree. C.) 142 155 167 178
47 161 5% Weight reduction temperature (.degree. C.) 215 225 219
227 61 223 10% Weight reduction temperature (.degree. C.) 280 276
274 275 193 273
TABLE-US-00035 TABLE 35 Compar- Compar- ative ative Exam- Exam-
Exam- Exam- Exam- ple ple ple ple ple Table V-7 V 5-8 V 5-5 V 5-9 V
5-10 V 5-6 Composition Epoxy compound (A-1) 12.5 25 of curable
Epoxy compound (A-2) 25 composition the other epoxy compound (V
B-3) 75 75 25 (parts by mass) the other epoxy compound (V B-12)
12.5 25 the other epoxy compound (V B-17) 75 75 75 Photo-cationic
polymerization initiator 10 10 10 10 10 (V D-1) 1% Weight reduction
temperature (.degree. C.) 115 99 118 114 105 3% Weight reduction
temperature (.degree. C.) 163 148 235 170 152 5% Weight reduction
temperature (.degree. C.) 198 178 255 212 183 10% Weight reduction
temperature (.degree. C.) 238 208 289 270 241
V-6. Examples V-6: Preparation of Curable Compositions Containing
Epoxy Compound (A-1) or Epoxy Compound (A-2) and Evaluation Thereof
(Part 6: Combination with Various Types of Oxetane Compounds and
Photo-Cationic Polymerizaiton Initiator)
(1) Example V 6-1 and Comparative Example V 6-1
[0615] Curable compositions were obtained in the same manner as in
Example V 1-1, except that the following components were used, at
the compositions shown in Table V-8.
(i) Epoxy Compound (A-2)
[0616] The epoxy compound produced by the method described in
Preparation Example 2 was used.
(ii) The Other Epoxy Compound (V B-3)
[0617] 3',4'-Epoxycyclohexylmethyl-3,4-epoxycyclohexane
carboxylate, manufactured by Dalcel Corporation, trade name:
CELLOXIDE 2021P was used.
(iii) Oxetane Compound (V C-3) Di[(3-ethyl-3-oxetanyl)methyl]ether,
manufactured by Toagosel Co., Ltd., trade name: ARONE OXETANE
OXT-221, was used.
(iv) Photo-Cationic Polymerization Initiator (V D-1)
[0618] A 50% propylene carbonate solution of
diphenyl-4-(phenylthio)phenylsulfonium hexafluorophosphate,
manufactured by San-Apro Ltd., trade name: CPI-100P, was used.
(2) Evaluation of Curable Compositions
<Heat Resistance (Weight Reduction Temperature)>
[0619] Each of the curable compositions obtained in the above
described Example V 6-1 and Comparative Example V 6-1 was coated on
a glass substrate to a coating thickness of 50 .mu.m. Each coated
substrate was irradiated with UV light at room temperature
(23.degree. C.) such that the accumulated amount of light was 3,000
mJ/cm.sup.2. The curable composition was cured. Next, the cured
product was scraped off from each glass substrate, and the
measurement of the weight reduction temperature was carried out
using a simultaneous thermogravimetric analyzer (manufactured by
Hitachi High-Tech Science Corporation, trade name: TG/DTA 7200).
About 10 mg of the cured product was heated from room temperature
to 550.degree. C. at a constant temperature increase rate of
10.degree. C./min in dry air, and the 1% weight reduction
temperature, 3% weight reduction temperature, 5% weight reduction
temperature and 10% weight reduction temperature of each cured
product were measured. The measurement results are summarized in
Table V-8.
TABLE-US-00036 TABLE 36 Compar- ative Example Example Table V-8 V
6-1 V 6-1 Composition of Epoxy compound (A-2) 25 curable composi-
the other epoxy compound 25 tion (parts by (V B-3) mass) Oxetane
compound (V C-3) 75 75 Photo-cationic polymerization 10 10
initiator (V D-1) 1% Weight reduction temperature (.degree. C.) 145
109 3% Weight reduction temperature (.degree. C.) 204 178 5% Weight
reduction temperature (.degree. C.) 248 234 10% Weight reduction
temperature (.degree. C.) 283 263
V-7. Examples V 7: Preparation of Curable Compositions Containing
Epoxy Compound (A-1) or Epoxy Compound (A-2) and Evaluation Thereof
(Part 7: Combination with Various Types of Photo-Cationic
Polymerization Initiators)
(1) Examples V 7-1 to V 7-3. And Comparative Examples V 7-1 and V
7-2
[0620] Curable compositions were obtained in the same manner as in
Example V 1-1, except that the following components were used, at
the compositions shown in Table V-9.
(i) Epoxy Compound (A-1)
[0621] The epoxy compound produced by the method described in
Preparation Example 1 was used.
(ii) Epoxy Compound (A-2)
[0622] The epoxy compound produced by the method described in
Preparation Example 2 was used.
(iii) The Other Epoxy Compound (V B-3)
[0623] 3',4'-Epoxycyclohexylmethyl 3,4-epoxycyclohexane
carboxylate, manufactured by Daicel Corporation, trade name:
CELLOXIDE 2021P, was used.
(iv) Photo-Cationic Polymerization Initiator (V D-2)
[0624] Diphenyl-4-(phenylthio)phenylsulfonium hexafluoroantimonate,
manufactured by San-Apro Ltd., CPI-101A, was used.
(v) Photo-Cationic Polymerization Initiator (V D-3)
[0625] Bis[4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl]sulfide
bishexafluoroantimonate, manufactured by ADEKA CORPORATION, ADEKA
ARKLS SP-170, was used.
(2) Evaluation of Curable Compositions
<Heat Resistance (Weight Reduction Temperature)>
[0626] Each of the curable compositions obtained in the above
described Examples V 7-1 to V 7-3 and Comparative Examples V 7-1
and V 7-2 was coated on a glass substrate to a coating thickness of
50 .mu.m. Each coated substrate was irradiated with UV light at
room temperature (23.degree. C.) such that the accumulated amount
of light was 3,000 mJ/cm.sup.2. The curable composition was cured.
Next, the cured product was scraped off from each glass substrate,
and the measurement of the weight reduction temperature was carried
out using a simultaneous thermogravimetric analyzer (manufactured
by Hitachi High-Tech Science Corporation, trade name: TG/DTA 7200).
About 10 mg of the cured product was heated from room temperature
to 550.degree. C. at a constant temperature increase rate of
10.degree. C./min in dry air, and the 1% weight reduction
temperature, 3% weight reduction temperature, 5% weight reduction
temperature and 10% weight reduction temperature of each cured
product were measured. The measurement results are summarized in
Table V-9.
TABLE-US-00037 TABLE 37 Compar- Compar- ative ative Exam- Exam-
Exam- Exam- Exam- ple ple ple ple ple Table V-9 V 7-1 V 7-2 V 7-3 V
7-1 V 7-2 Composition Epoxy compound (A-1) 25 25 of curable Epoxy
compound (A-2) 25 composition the other epoxy compound 75 75 75 100
100 (parts by mass) (VB-3) Photo-cationic 10 10 polymerization
initiator (V D-2) Photo-cationic 10 10 10 polymerization initiator
(V D-3) 1% Weight reduction temperature (.degree. C.) 119 109 110
117 107 3% Weight reduction temperature (.degree. C.) 153 151 163
141 143 5% Weight reduction temperature (.degree. C.) 188 186 207
162 167 10% Weight reduction temperature (.degree. C.) 260 270 275
260 262
* * * * *