The present invention relates to a tetracarboxylic
dianhydride and a polyamic acid, a polyamic acid solution,
and a polyimide which are obtained by using the
tetracarboxylic dianhydride, as well as methods for
10 producing the tetracarboxylic dianhydride, the polyamic
acid, and the polyimide. Moreover, the present invention
relates to a polyimide solution, a film, a transparent
electrically conductive film, and a transparent electrode
substrate using the polyimide.
15 [Background Art]
In general, tetracarboxylic dianhydrides are useful
as raw materials for producing polyimide resins, as epoxy
curing agents, and as the like. Of the tetracarboxylic
dianhydrides, aromatic tetracarboxylic dianhydrides such
20 as pyromellitic dianhydride have been mainly used as raw
materials for polyimide resins used in the field of
electronic devices or the like , Then, as a polyimide
obtained by using such an aromatic tetracarboxylic
dianhydride, for example, a polyimide (trade name:
25 "Kapton") has been conventionally widely known which is
marketed by DU PONT-TORAY CO. , LTD. and which is a material
1
NOPF15-514
necessary for cutting-edge industries for aerospace and
aviation applications and the like. Conventional
polyimides obtained by using aromatic tetracarboxylic
dianhydrides have excellent physical properties in terms
5 of heat resistance; however, such polyimides are colored
{yellow to brown) , and cannot be used in the optical and
other applications where transparency is necessary. For
this reason, to produce a polyimide usable in the optical
or other applications, tetracarboxylic dianhydrides which
10 can be preferably used as monomers for producing polyimides
have been researched,
Conventionally, various types of compounds have been
disclosed as tetracarboxylic dianhydrides for producing
polyimides having high light transmittance . For example,
15 Japanese Unexamined Patent Application Publication No . Sho
55-36406 (PTL 1) discloses
5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexe
ne-1,2-dicarboxylic anhydride, and Japanese Unexamined
Patent Application Publication No. Sho 63-57589 (PTL 2)
20 discloses
bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic
dianhydride. Meanwhile, Japanese Unexamined Patent
Application Publication No. Hei 7-304868 (PTL 3) discloses
bicyclo[2-2.2]octanetetracarboxylic dianhydride as a rav;
25 material for a polyimide resin. Moreover, Japanese
Unexamined Patent Application Publication No, 2001-2670
2
NOPF15-514
(PTL 4) and Japanese Unexamined Patent Application
Publication No, 2002-255955 (PTL 5) disclose
1,2-bis(4'-oxa-3' ,5'-dioxotricyclo[5.2.1.02'6]decan-8' -
yloxy)ethane. Moreover, Japanese Unexamined Patent
5 Application Publication No. Hei10-310640(PTL 6) discloses
bicyclo[2.2.1]heptane-2,3,5 -tricarboxyl-5-acetic
2,3:5,5-acid dianhydride. However, when a polyimide is
produced by using a conventional tetracarboxylic
dianhydride described in any of PTLs 1 to 6, the obtained
10 polyimide has a sufficient light transmittance, but the
heat resistance of the polyimide is not sufficient. Hence ,
it is difficult to practically use such a polyimide in the
optical or other applications.
Meanwhile, studies on tetracarboxylic dianhydrides
15 have further conducted to solve the above-described
problems recently, and some tetracarboxylic dianhydrides
have been reported from which polyimides sufficiently
practical for use in the optical applications can be
produced. For example, International Publication No.
20 W02011/0 9 9518 (PTL 7) discloses a
norbornane-2-spiro-a-cycloalkanone-a'-spiro-2''-norbor
nane-5,5'',6,6''-tetracarboxylic dianhydride having a
specific structure, and reports that a polyimide having
a sufficiently high light transmittance and a sufficiently
25 high heat resistance can be produced by using such a
tetracarboxylic dianhydride,
3
NOPF15-514
Under such circumstances/ the development of a novel
tetracarboxylic dianhydride which has characteristics
(light transmittance, heat resistance, and the like) equal
to or superior to those of the above-described
5 tetracarboxylic dianhydride described in PTL 7, and which
can be produced more easily has been demanded in the field
of tetracarboxylic dianhydride.
[Citation List]
[Patent Literature]
ID [PTL 1] Japanese Unexamined Patent Application
Publication No. Sho 55-36406
[PTL 2] Japanese Unexamined Patent Application
Publication No. Sho 63-57589
[PTL 3] Japanese Unexamined Patent Application
15 Publication No. Hei 7-304863
[PTL 4] Japanese Unexamined Patent Application
Publication No. 2001-2670
[PTL 5] Japanese Unexamined Patent Application
Publication No. 2002-255955
20 [PTL 6] Japanese Unexamined Patent Application
Publication No. Hei 10-310640
[PTL 7] international Publication No. WO2011/099518
[Summary of Invention]
[Technical Problem]
25 The present invention has been made in view of the
above-described problems of the conventional techniques,
NOPF15-514
and an object of the present invention is to provide a
tetracarboxylic dianhydride which can be produced by a
simpler method, and which isusableasa raw material monomer
for producing a polyimide having a high light transmittance
5 and a sufficiently high heat resistance, as well as a
production method by which the tetracarboxylic dianhydride
can be produced efficiently and surely. In addition,
another object of the present invention is to provide a
polyamic acid which can be preferably used for producing
10 a polyimide having a high light transmittance and a
sufficiently high heat resistance and which can be produced
efficiently by using the above-described tetracarboxylic
dianhydride, as well as a method for producing the polyamic
acid and a polyamic acid solution comprising the polyamic
15 acid. Moreover, still another object of the present
invention is to provide a polyimide which can have a high
light transmittance and a sufficiently high heat resistance
and a method for producing a polyimide by which the polyimide
can be produced efficiently and surely, as well as a
20 polyimide solution, a film, a transparent electrically
conductive film, and a transparent electrode substrate
using the polyimide.
[Solution to Problem]
The present inventors have conducted intensive study
25 to achieve the above-described objects, and consequently
have first found that use of a tetracarboxylic dianhydride,
5
NOPF15-514
which is a compound represented by the following general
formula (1) , makes it possible to produce a poly imide having
a high light transmittance and a sufficiently high heat
resistance can be produced, by a simpler method with an
5 esterification step and the like omitted- This finding
has led to the completion of the present invention. In
addition, the present inventors have also found that the
use of a tetracarboxylic di anhydride , which is the compound
represented by the following general formula (1) , enables
10 efficient production even when an ester compound is used
as a raw material compound. This finding has led to the
completion of the present invention. Moreover, the
present inventors have found that when a polyimide
comprises a repeating unit represented by the following
15 general formula (4) , the poly imide has a high light
transmittance and a sufficiently high heat resistance.
This finding has led to the completion of the present
invention,
Specifically, first, a tetracarboxylic dianhydride
20 of the present invention is a compound represented by the
following general formula (1):
[Chem. 1]
6
NOPF15-514
CD
[in the formula (1) , A represents one selected from the
group consisting of optionally substituted divalent
aromatic groups in each of which the number of carbon atoms
5 forming an aromatic ring is 6 to 30, and multiple R1s each
independently represent one selected from the group
consisting of a hydrogen atom and alkyl groups having 1
to 10 carbon atoms],
In the above-described tetracarboxylic dianhydride
10 of the present invention; A in the general formula (1) is
preferably one selected from the group consisting of
optionally substituted phenylene groups, optionally
substituted biphenylene groups, optionally substituted
naphthylene groups, optionallysubstituted anthracenylene
15 groups, and optionally substituted terphenylene groups,
Meanwhile, a first method for producing a
tetracarboxylic dianhydride of the present invention
(hereinafter, sometimes simply referred to as "first
NOPF16-514
production method") comprises
reacting an acid anhydride represented by the
following general formula (2):
[Chem. 2]
10
15
(2)
[in the formula (2) , multiple R^-s each independently
represent one selected from the group consisting of a
hydrogen atom and alkyl groups having 1 to 10 carbon atoms]
with an aromatic compound represented by the following
general formula (3):
[Chem. 3]
R
R'
(3)
[in the formula (3) , A represents one selected from the
group consisting of optionally substituted divalent
aromatic groups in each of which the number of carbon atoms
forming an aromatic ring is 6 to 30, and R2 and R3 each
8
NOPF15-514
independently represent a leaving group] in a mixture
liquid containing at least one reducing agent selected from
the group consisting of formic acid, 2-propanol and
hydrogen, a base , a palladium catalyst, the acid anhydride,
and the aromatic compound, to thereby obtain a
tetracarboxylic dianhydride represented by the following
general formula (1) :
[Chem. 4]
(1)
10 [in the formula (1) , A represents one selected from the
group consisting of optionally substituted divalent
aromatic groups in each of which the number of carbon atoms
forming an aromatic ring is 6 to 30, and multiple R:s each
independently represent one selected from the group
15 consisting of a hydrogen atom and alkyl groups having 1
to 10 carbon atoms].
Meanwhile, a second method for producing a
tetracarboxylic dianhydride (hereinafter, sometimes
9
NOPF15-514
simply referred to as "second production method") of the
present invention comprises the steps of:
reacting a diester compound represented by the
following general formula (201}:
5 [Chem. 5]
15
OR10
OR10
O
(20 1)
[in the formula (2 01), multiple Rxs each independently
represent one selected from the group consisting of a
hydrogen atom and alkyl groups having 1 to 10 carbon atoms,
10 and multiple R10s each independently represent one selected
from the group consisting of alkyl groups having 1 to 5
carbon atoms] with an aromatic compound represented by the
following general formula (3) :
[Chem. 6]
(3)
[in the formula (3) , A represents one selected from the
group consisting of optionally substituted divalent
10
NOPF15-514
10
aromatic groups in each of which the number of carbon atoms
forming an aromatic ring is 6 to 30, and R2 and R3 each
independently represent a leaving group] in a mixture
liquid containing at least one reducing agent selected from
the group consisting of formic acid, 2-propanol and
hydrogen, a base, a palladium catalyst, the diester
compound, and the aromatic compound, to thereby obtain a
tetraester compound represented by the following general
formula (101):
[Chem. 7]
(1 01)
[in the formula (101) , A represents one selected from the
group consisting of optionally substituted divalent
aromatic groups in each of which the number of carbon atoms
15 forming an aromatic ring is 6 to 3 0, multiple RLs each
independently represent one selected from the group
consisting of a hydrogen atom and alkyl groups having 1
to 10 carbon atoms, and multiple R10s each independently
represent one selected from the group consisting of alkyl
11
NOPF15-514
groups having 1 to 5 carbon atoms]; and
heating the tetraester compound in a carboxylic acid
having 1 to 5 carbon atoms with an acid catalyst being used,
to thereby obtain a tetracarboxylic dianhydride
represented by the following general formula (1}:
[Chem. 8]
(D
[in the formula (1), A represents one selected from the
group consisting of optionally substituted divalent
10 aromatic groups in each of which the number of carbon atoms
forming an aromatic ring is 6 to 30, and multiple Rxs each
independently represent one selected from the group
consisting of a hydrogen atom and alkyl groups having 1
to 10 carbon atoms].
15 In addition, the above-described second method
(second product ion method) for producing a tetracarboxylic
dianhydride of the present invention preferably further
comprises the step of reacting an alcohol represented by
12
NOPF15-514
a general formula: R10-OH (in the formula, R10 represents
one selected from the group consisting of alkyl groups
having 1 to 5 carbon atoms) with an acid anhydride
represented by the following general formula (2):
5 [Chem. 93
O
[in the formula (2) , multiple R2s each independently
represent one selected from the group consisting of a
hydrogen atom and alkyl groups having 1 to 10 carbon atoms] ,
10 to thereby obtain the diester compound represented by the
general formula <201).
A polyimide of the present invention comprises a
repeating unit represented by the following general formula
(4} :
15 [Chem. 10]
13
NOPF15-514
N—R4-
[in the formula (4), A represents one selected from the
group consisting of optionally substituted divalent
aromatic groups in each of which the number of carbon atoms
5 forming an aromatic ring is S to 30, multiple R1s each
independently represent one selected from the group
consisting of a hydrogen atom and alkyl groups having 1
to 10 carbon atoms, andR4 represents an arylene group having
6 to 40 carbon atoms].
10 Note that, although it is not exactly clear why the
polyimide comprising a repeating unit represented by the
general formula (4) exhibits a sufficiently high heat
resistance, the present inventors speculate that the
sufficiently high heat resistance is achieved because the
15 repeating unit can improve the heat resistance of the
polyimide, and has a structure having a rigid aromatic ring,
and hence the polyimide has a chemically sufficiently
stable structure,
Meanwhile, a polyamic acid of the present invention
14
NOPF15-514
comprises a repeating unit represented by the following
general formula (5) :
[Chem. 11]
(5)
5 [in the formula (5) , A represents one selected from the
group consisting of optionally substituted divalent
aromatic groups in each of which the number of carbon atoms
forming an aromatic ring is S to 30, multiple R1s each
independently represent one selected from the group
10 consisting of a hydrogen atom and alkyl groups having 1
to 10 carbon atoms , and R4 represents anarylene group having
6 to 40 carbon atoms] . Note that the polyamic acid can
be obtained as a reaction intermediate when the
above-described polyimide of the present invention is
15 produced. In addition, the polyamic acid preferably has
an intrinsic viscosity [ri] of 0 . 05 to 3 . 0 dL/g, the intrinsic
viscosity [r|] being measured under a temperature condition
of 3Q°C with a kinematic viscometer by using a solution
of the polyamic acid at a concentration of 0 - 5 g/dL obtained
15
NOFF16-6U
10
by dissolving the polyamic acid in N,N- dime thy lace tamide .
Note that, when a varnish containing such a polyamic acid
is prepared, as appropriate, and used, a polyimide can be
produced efficiently in various shapes.
Meanwhile, in each of the above-described polyimide
of the present invention and the above-described polyamic
acid of the present invention, R4 (R4 in each of the general
formulae (4) and {5)) is preferably at least one selected
from groups represented by the following general formulae
(6) to (9) :
[Chem. 12]
(6) (7)
%J^~C?
(8) (9)
[each R5 in the formula (8) represents one selected from
the group consisting of a hydrogen atom, a fluorine atom,
15 a methyl group, an ethyl group, and a trif luoromethyl group,
and Q in the formula (9) represents one selected from the
group consisting of groups represented by the formulae:
-0-, -S-, -CO-, -CONH-, -SO2-, -C(CF3)2~, -C£CH3)2-, -CH2-,
-0-C6H4-C(CH3)2-C6H4-0-, -0-C6H4-S02-C6H4-0-,
16
NOPF15-514
"C(CH3)2-C6H4-C(CH3)2-/ -0-C6H^-C6H4-0-, and -0-C6H4-0-] .
Moreover, the above-described polyimide of the
present invention preferably comprises at least one
repeating unit selected from
5 repeating units represented by the general formula
(4) , wherein R4 in the formula (4) is a group represented
by the general formula (8) , and each R5 in the formula <8)
is a methyl group,
repeating units represented by the general formula
10 (4) , wherein R4 in the formula {4) is a group represented
by the general formula (9); and Q in the formula (9) is
the formula: -0- ,
repeating units represented by the general formula
(4) , wherein R4 in the formula (4) is a group represented
15 by the general formula (9), and Q in the formula {9) is
the formula: -O-CefU-C (CH3) 2-C6H4-0- ,
repeating units represented by the general formula
(4) , wherein R4 in the formula (4) is a group represented
by the general formula (9} , and Q in the formula (9) is
20 the formula : -O-C6H4-C (CF3) 2-C6H4-0- ,
repeating units represented by the general formula
(4}i wherein R4 in the formula (4) is a group represented
by the general formula (9), and Q in the formula (9) is
the formula: -0-C6H4-C6H4-0-, and
25 repeating units represented by the general formula
(4) , wherein R4 in the formula {4} is a group represented
17
NOPF15-514
by the general formula (9), and Q in the formula (9) is
the formula: -O-C&H4-Oat
a ratio of 40% by mole or more relative to all
repeating units. The polyimide comprising the repeating
5 unit represented by the formula {4 } , in which R4 isa specific
group, at a ratio of 40% by mole or more relative to all
repeating units can be dissolved more sufficiently in at
least one solvent used as a so-called casting solvent among
various solvents (more preferably one or both of CH2CI2
10 and CHCI3, which are lower-boiling point solvents
preferably used as casting solvents) according to the
composition, and hence can be provided with a higher
processability. In other words , the polyimide comprising
the repeating unit represented by the general formula (4) ,
15 in which R4 is a specific group, at a ratio of 40% by mole
or more relative to all repeating units can be a polyimide
(a polyimide soluble in a casting solvent) more
sufficiently soluble in a specific casting solvent, and
can be dissolved in such a casting solvent and processed
20 additionally after a long-term storage in the state of the
polyimide. For this reason, when the polyimide comprises
the repeating unit represented by the general formula (4) ,
in which R4 is a specific group, at a ratio of 40% by mole
or more relative to all repeating units, the polyimide can
25 be processed after a long-term storage in the form of the
polyimide stably, so that a higher long-term storability
18
NOPF15-514
and a higher processability can be obtained.
Moreover, the above-described polyamic acid of the
present invention preferably comprises at least one
repeating unit selected from
5 repeating units represented by the general formula
(5) , wherein R4 in the formula (5) is a group represented
by the general formula (8) , and each R5 in the formula (8}
is a methyl group,
repeating units represented by the general formula
10 (5), wherein R4 in the formula (5) is a group represented
by the general formula (9) , and Q in the formula (9) is
the formula: -O- ,
repeating units represented by the general formula
(5) , wherein R4 in the formula (5) is a group represented
15 by the general formula (9) , and Q in the formula (9) is
the formula: -0-C6H4-C (CH3) 2-C6H4-0- ,
repeating units represented by the general formula
(5) , wherein R4 in the formula (5) is a group represented
by the general formula (9) , and Q in the formula (9) is
20 the formula : -O-CetU-C (CF3) a-CelU-O- ,
repeating units represented by the general formula
(5), wherein R4 in the formula (5) is a group represented
by the general formula (9), and Q in the formula (9) is
the formula : -O-CeJU-C^ -0- , and
25 repeating units represented by the general formula
(5) , wherein R4 in the formula (5) is a group represented
19
NOPF15-514
10
by the general formula {9) , and Q in the formula (9) is
the formula: -0-C6H4-0-
at a ratio of 40% by mole or more relative to all
repeating units. Such a polyamic acid can be used
preferably as a material for producing a polyimide (a
polyimide soluble in a casting solvent} more sufficiently
soluble in at least one casting solvent.
In addition, a method for producing a polyamic acid
of the present invention comprises reacting a
tetracarboxylic dianhydride represented by the following
general formula (1) :
[Chem. 13]
(1)
[in the formula (1) , A represents one selected from the
15 group consisting of optionally substituted divalent
aromatic groups in each of which the number of carbon atoms
forming an aromatic ring is 6 to 30, and multiple R2s each
independently represent one selected from the group
20
NOPF15-514
consisting of a hydrogen atom and alkyl groups having 1
to 10 carbon atoms] with an aromatic diamine represented
by the following general formula {10):
fChem. 14]
10
H2N—R4-NH2
(i o)
[in the formula (10) , R4 represents an arylene group having
6 to 4 0 carbon atoms] in the presence of an organic solvent,
to thereby obtain a polyamic acid comprising a repeating
unit represented by the following general formula (5):
[Chem. IB]
UN/ J
F
R1
^ A \ V ^
^ T \ n)
0
JII L0H
HN—R4
R1
15
(5)
[in the formula (5), A represents one selected from the
group consisting of optionally substituted divalent
aromatic groups in each of which the number of carbon atoms
forming an aromatic ring is 6 to 30, multiple R1s each
independently represent one selected from the group
consisting of a hydrogen atom and alkyl groups having 1
21
NOPF15-514
to 10 carbon atoms, andR4 represents anarylene group having
6 to 40 carbon atoms].
A method for producing a polyimide of the present
invention comprises performing imidization of a polyamic
acid comprising a repeating unit represented by the
following general formula (5):
[Chem. 16]
,R1
IV \ \ /
F
^
^ A \ o x
?1
^^> n
0
|j
J-OH
T HN—R4
R1
(5)
[in the formula {5} , A represents one selected from the
10 group consisting of optionally substituted divalent
aromatic groups in each of which the number of carbon atoms
forming an aromatic ring is 6 to 30, multiple R2s each
independently represent one selected from the group
consisting of a hydrogen atom and alkyl groups having 1
15 to 10 carbon atoms, andR4 represents anarylene group having
6 to 40 carbon atoms] to thereby obtain a polyimide
comprising a repeating unit represented by the following
general formula (4):
[Chem. 17]
22
NOPF15-514
o
(4)
[in the formula (4), A represents one selected from the
group consisting of optionally substituted divalent
aromatic groups in each of which the number of carbon atoms
5 forming an aromatic ring is 6 to 30r multiple Rrs each
independently represent one selected from the group
consisting of a hydrogen atom and alkyl groups having 1
to 10 carbon atoms, and R4 represents an arylene group having
6 to 40 carbon atoms].
10 In addition, the method for producing a polyimide
of the present invention preferably comprises the step of
reacting a tetracarboxylic dianhydride represented by the
following general formula (1):
[Chem- IS]
23
NOPF15-514
10
(1)
[in the formula (1) , A represents one selected from the
group consisting of optionally substituted divalent
aromatic groups in each of which the number of carbon atoms
forming an aromatic ring is 6 to 30, and multiple R1s each
independently represent one selected from the group
consisting of a hydrogen atom and alkyl groups having 1
to 10 carbon atoms] with an aromatic diamine represented
by the following general formula (10):
[Chem. 19]
15
H2N—R4-NH2
d o)
[in the formula (10) , R4 represents an arylene group having
6 to 40 carbon atoms] in the presence of an organic solvent,
to thereby obtain a polyamic acid comprising a repeating
unit represented by the general formula (5) . In this case ,
the above-described method for producing a polyimide of
24
NOPF15-514
the present invention may be a method comprising the steps
of: reacting the tetracarboxylic dianhydride represented
by the general formula (1) with the aromatic diamine
represented by the general formula (10} in the presence
5 of the organic solvent, to thereby obtain the polyamic acid
comprising a repeating unit represented by the general
formula (5); and performing imidization of the polyamic
acid, to thereby obtain a polyimide comprising a repeating
unit represented by the general formula (4) , and hence the
10 it is also possible to efficiently produce the polyimide
by continuous steps -
In addition, a polyamic acid solution of the present
invention comprises : the above-described polyamic acid of
the present invention; and an organic solvent. The
15 polyamic acid solution {resin solution: varnish) makes it
possible to efficiently produce a polyimide in various
shapes.
In addition, a polyimide solution of the present
invention comprises : the above-described polyimide of the
20 present invention; and a solvent. Moreover, a film, a
transparent electrically conductive film, and a
transparent electrode substrate of the present invention
each comprise the above-described polyimide of the present
invention,
25 [Advantageous Effects of Invention]
According to the present invention, it is possible
25
NOPFI5-514
to provide a tetracarboxylic dianhydride which can be
produced by a simpler method and which is usable as a raw
material monomer for producing a polyimide having a high
light transmittance and a sufficiently high heat resistance ,
5 as well as a production method by which the tetracarboxylic
dianhydride can be produced efficiently and surely .
In addition, according to the present invention, it
is possible to provide a polyamic acid which can be
preferably used for producing a polyimide having a high
10 light transmittance and a sufficiently high heat resistance
and which can be produced efficiently by using the
above-described tetracarboxylic dianhydride, as well as
a method for producing the polyamic acid and a polyamic
acid solution comprising the polyamic acid. Moreover,
15 according to the present invention, it is possible to
provide a polyimide which can have a high light
transmittance and a sufficiently high heat resistance, and
a method for producing a polyimide by which the polyimide
can be produced efficiently and surely, and it is also
20 possible to provide a polyimide solution, a film, a
transparent electrically conductive film, and a
transparent electrode substrate using the polyimide.
[Brief Description of Drawings]
[Fig, 1] Fig, 1 is a graph showing an IR spectrum of a
25 tetracarboxylic dianhydride obtained in Example 1.
[Fig. 2] Fig- 2 is a graph showing a 1H-NMR (DMSO-de)
26
NOPF15-514
spectrum of the tetracarboxylic dianhydride obtained in
Example 1.
[Fig, 3] Fig. 3 is a graph showing an FD-MS spectrum of
the tetracarboxylic dianhydride obtained in Example 1.
5 [Fig. 4] Fig. 4 is a graph showing an IR spectrum of a
tetracarboxylic dianhydride obtained in Example 5.
[Fig. 5] Fig. 5 is a graph showing a LH-NMR (DMSO-d&)
spectrum of the tetracarboxylic dianhydride obtained in
Example 5 .
10 [Fig. 6] Fig. 6 is a graph showing an FD-MS spectrum of
the tetracarboxylic dianhydride obtained in Example 5,
[Fig. 7] Fig. 7 is a graph showing an IR spectrum of a
tetracarboxylic dianhydride obtained in Example 6.
[Fig. 8] Fig. 8 is a graph showing a iH-NMR (DMSO-de)
15 spectrum of the tetracarboxylic dianhydride obtained in
Example 6,
[Fig. 9] Fig. 9 is a graph showing an FD-MS spectrum of
.the tetracarboxylic dianhydride obtained in Example 6.
[Fig. 10] Fig. 10 is a graph showing an IR spectrum of
20 a tetracarboxylic dianhydride obtained in Example 9.
EFig. 11] Fig. 11 is a graph showing an FD-MS spectrum
of the tetracarboxylic dianhydride obtained in Example 9 .
[Fig. 12} Fig. 12 is a graph showing an IR spectrum of
a tetracarboxylic dianhydride obtained in Example 10.
25 [Fig, 13] Fig. 13 is a graph showing a iH-NMR (DMSO-de)
spectrum of the tetracarboxylic dianhydride obtained in
27
NOPF15-B14
Example 10.
[Fig. 14] Fig. 14 is a graph showing an FD-MS spectrum
of the tetracarboxylic dianhydride obtained in Example 10 .
[Fig. 15] Fig. 15 is a graph showing an IR spectrum of
5 a polyimide obtained in Example 11.
[Fig. 16] Fig. 16 is a graph showing an IR spectrum of
a polyimide obtained in Example 13.
[Fig. 17] Fig. 17 is a graph showing an IR spectrum of
a polyimide obtained in Example 14.
10 [Fig- IS] Fig. IS is a graph showing an IR spectrum of
a polyimide obtained in Example 15.
[Fig. 19] Fig, 19 is a graph showing an IR spectrum of
a polyimide obtained in Example 16.
[Fig. 20] Fig. 20 is a graph showing an IR spectrum of
15 a polyimide obtained in Example 17.
[Fig. 21] Fig. 21 is a graph showing an IR spectrum of
a polyimide obtained in Example 18.
[Fig. 22] Fig. 22 is a graph showing an IR spectrum of
a polyimide obtained in Example 19.
20 [Fig, 23] Fig. 23 is a graph showing a XH-NMR spectrum
of the polyimide obtained in Example 19.
[Description of Embodiments]
Hereinafter, the present invention will be described
in detail based on preferred embodiments thereof.
25 [Tetracarboxylic Dianhydride]
A tetracarboxylic dianhydride of the present
28
NOPF15-514
invention ia a compound represented by the following
general formula (1):
[Chem. 20]
(1)
5 [in the formula (1) , A represents one selected from the
group consisting of optionally substituted divalent
aromatic groups in each of which the number of carbon atoms
forming an aromatic ring is 6 to 30, and multiple Rxs each
independently represent one selected from the group
10 consisting of a hydrogen atom and alkyl groups having 1
to 10 carbon atoms].
A in the general formula (1) is an optionally
substituted divalent aromatic group as described above,
and the number of carbon atoms forming an aromatic ring
15 contained in the aromatic group is 6 to 30 (note that, in
a case where the aromatic group has a substituent (such
as a hydrocarbon group) containing a carbon atom(s), "the
number of carbon atoms forming an aromatic ring" herein
29
N0PF15-514
does not include the number of carbon atoms in the
substituent, but refers to only the number of carbon atoms
of the aromatic ring in the aromatic group. For example,
in the case of a 2-ethyl-l, 4 -phenylene group, the number
5 of carbon atoms forming the aromatic ring is 6) . As
described above, A in the general formula (1) is an
optionally substituted divalent group (divalent aromatic
group) having an aromatic ring having 6 to 3 0 carbon atoms .
If the number of carbon atoms forming an aromatic ring
10 exceeds the upper limit, a polyimide obtained by using the
aciddianhydride of the general formula (1) as a raw material
tends to be colored. In addition, from the viewpoints of
transparency and ease of purification, the number of carbon
atoms forming the aromatic ring of the divalent aromatic
15 group is more preferably 6 to 18, and further preferably
6 to 12 .
In addition, the divalent aromatic groups are not
particularly limited, as long as the above-described
condition of the number of carbon atoms is satisfied. For
20 example, it is possible to use, as appropriate, residues
formed when two hydrogen atoms are eliminated from aromatic
compounds such as benzene, naphthalene, terphenyl,
anthracene,phenanthrene, triphenylene,pyrene,chrysene,
biphenyl, terphenyl, quaterphenyl, and quinquephenyl
25 (note that, regarding these residues, the positions at
which the hydrogen atoms are eliminated are not
30
N0PF15-514
particularly limited, and examples thereof include a
1,4 -phenylene group, a 2,6-naphthylene group, a
2,7-naphthylene group, a 4,4' -biphenylene group, a
9, 10-anthracenylene group, and the like) ; and groups formed
5 when at least one hydrogen atom is replaced with a
substituent in the above-described residues (for example,
a 2,5-dimethyl-l,4-phenylene group and a
2,3,5,6-tetramethyl-l,4-phenylene group), and the like-
Note that, in these residues, the positions at which the
10 hydrogen atoms are eliminated are not particularly limited
as described above, and, for example, when the residue is
a phenylene group, the positions may be any of
ortho-positions, meta-positions, and para-positions.
The divalent aromatic groups are preferably
15 optionally substituted phenylene groups, optionally
substituted biphenylene groups, optionally substituted
naphthylene groups , optionally substituted anthracenylene
groups, and optionally substituted terphenylene groups,
from the viewpoint that when a polyimide is produced, the
20 polyimide has better solubility in solvent and offers a
higher processability. In other words, these divalent
aromatic groups are preferably phenylene groups,
biphenylene groups, naphthylene groups, anthracenylene
groups, and terphenylene groups, each of which is
25 optionally substituted. In addition, of these divalent
aromatic groups, phenylene groups, biphenylene groups , and
31
NOPF15514
naphthylene groups, each of which are optionally
substituted, are more preferable, phenylene groups and
biphenylene group, each of which are optionally
substituted, are further preferable, and optionally
5 substituted phenylene groups are the most preferable,
because a higher effect can be obtained from the
above-described viewpoint,
From the viewpoint that a better heat resistance can
be obtained, the divalent aromatic groups are preferably
10 optionally substituted phenylene groups, optionally
substituted biphenylene groups, optionally substituted
naphthylene groups, optionally substituted anthracenylene
groups, and optionally substituted terphenylene groups.
In addition, of these divalent aromatic groups, phenylene
15 groups, biphenylene groups, naphthylene groups, and
terphenylene groups, each of which is optionally
substituted, are more preferable, and phenylene groups,
biphenylene groups, and naphthylene groups, each of which
is optionally substituted, are further preferable, because
20 a higher effect can be obtained from the above-described
viewpoint.
In addition, in A in the general formula (1), the
substituents which may be present on the divalent aromatic
groups are not particularly limited, and examples thereof
25 include alkyl groups, alkoxy groups, halogen atoms, and
the like. Of these substituents which may be present on
32
NOPF15-514
the divalent aromatic groups, alkyl groups having 1 to 10
carbon atoms and alkoxy groups having 1 to 10 carbon atoms
are more pre f arable t from the viewpoint that, when a
polyimide is produced, the polyimide has better solubility
5 in solvent and offers a higher processability. If the
number of carbon atoms of each of the alkyl groups and the
alkoxy group preferable as the substituents exceeds 10,
the heat resistance of a polyimide obtained in the use as
a monomer for the polyimide tends to be lowered. In
10 addition, the number of carbon atoms of each of the alkyl
groups and the alkoxy groups preferable as the substituents
is preferably 1 to 6, more preferably 1 to 5, further
preferably 1 to 4 , and particularly preferably 1 to 3 , from
the viewpoint that a higher heat resistance can be obtained
15 when a polyimide is produced. In addition, each of the
alkyl groups and the alkoxy groups which may be selected
as the substituents may be linear or branched.
Meanwhile, the alkyl group which may be selected as
R1 in the general formula (1) is an alkyl group having 1
20 to 10 carbon atoms. If the number of carbon atoms exceeds
10, the heat resistance of a polyimide obtained in the use
as a monomer for the polyimide is lowered. In addition,
the number of carbon atoms of the alkyl group which may
be selected as R1 is preferably 1 to 6, more preferably
25 1 to 5, further preferably 1 to 4, and particularly
preferably 1 to 3, from the viewpoint that a higher heat
33
NOPF15-514
resistance can be obtained when a polyimide is produced.
In addition, the alkyl group which may be selected as R1
may be linear or branched-
Multiple H1s in the general formula {1) are each
5 independently more preferably a hydrogen atom, a methyl
group, an ethyl group, a n-propyl group, or an isopropyl
group, and particularly preferably a hydrogen atom or a
methyl group , for example , from the viewpoints that a higher
heat resistance can be obtained when a polyimide is
10 produced, that the raw material is readily available, and
that the purification is easier, in addition, multiple
Rls in the formula may be the same as one another or different
from one another, and are preferably the same from the
viewpoints of ease of purification and the like.
15 [First Method for Producing Tetracarboxylic Dianhydride
(First Production Method)]
A first method for producing a tetracarboxylic
dianhydride (first production method) of the present
invention comprises reacting an acid anhydride represented
20 by the following general formula (2):
[Chem. 21]
34
NOPF15-514
o
(2)
[in the formula {2) , multiple Rxs each independently
represent one selected from the group consisting of a
hydrogen atom and alkyl groups having 1 to 10 carbon atoms]
5 with an aromatic compound represented by the following
general formula (3):
[Chem. 22]
R3
(3)
[in the formula (3) , A represents one selected from the
10 group consisting of optionally substituted divalent
aromatic groups in each of which the number of carbon atoms
forming an aromatic ring is 6 to 30, and R2 and R3 each
independently represent a leaving group] in a mixture
liquid containing at least one reducing agent selected from
15 the group consisting of formic acid, 2-propanol and
hydrogen, abase, a palladium catalyst, the acid anhydride,
35
NOPF16-514
and the aromatic compound, to thereby obtain a
tetracarboxylic dianhydride represented by the
above-described general formula (1) .
In the acid anhydride represented by the general
5 formula (2), R1 in the formula is the same as that (R1 in
the general formula (1) ) described for the above-described
tetracarboxylic dianhydride of the present invention, and
preferred ones thereof are also the same. Accordingly,
examples of the acid anhydride represented by the general
10 formula (2) include nadic anhydride, 5-methylnadic
anhydride, 5,6-dimethylnadic anhydride,
5-ethyl-6-methylnadic anhydride, 5,6-diethylnadic
anhydride, 5-methyl-6 -isopropylnadic anhydride,
5-n-butylnadic anhydride, and the like . Note that a method
15 for producing the acid anhydride represented by the general
formula (2) is not particularly limited, and a known method
can be employed, as appropriate. Moreover, as the acid
anhydride represented by the general formula (2) ,
commercially available one may also be used, as
20 appropriate.
In the aromatic compound represented by the general
formula (3), A in the formula is the same as that (A in
the general formula (1) ) described for the above-described
tetracarboxylic dianhydride of the present invention, and
25 preferred ones thereof are also the same. In addition,
R2 and R3 in the general formula (3) each independently
36
NOPF15-514
represent a leaving group. The leaving group represented
by R2 or R3 is not particularly limited, as long as the
so-called reductive Heck reaction can be carried out.
Examples of the leaving group include halogen atoms such
5 as a fluorine atom, a chlorine atom, a bromine atom, and
an iodine atom, a trifluoromethanesulfonyl group, a
p-toluenesulfonyl group, a methanesulfonyl group, a
nonafluorobutanesulfonyl group, and the like. Of these
leaving groups represented by R2 and R3, halogen atoms are
10 more preferable, a chlorine atom, a bromine atom, or an
iodine atom is more preferable, and a bromine atom or an
iodine atom is particularly preferable . Examples of such
aromatic compounds include diiodobenzene, diiodobiphenyl,
dibromobenzene, 2,5-dibromo-p-xylene,
15 diethyldibromobenzene, dichlorobenzene,
dibromonaphthalene, and the like. Note that a method for
producing the aromatic compound is not particularly
limited, and a known method can be employed, as appropriate .
In addition, as the aromatic compound, commercially
20 available one may also be used, as appropriate.
In addition, in the present invention, the mixture
liquid containing the reducing agent, the base, and the
palladium catalyst together with the acid anhydride
represented by the general formula (2) and the aromatic
25 compound represented by the general formula (3) is used.
Since the mixture liquid contains the palladium catalyst
37
NOPF15-514
as described above, the reaction can. be caused to proceed
in the presence of the palladium catalyst.
The palladium catalyst is not particularly limited,
and a known palladium catalyst can be used, as appropriate .
5 For example, a palladium complex or a catalyst in which
palladium is supported on a support can be used preferably.
Examples of the palladium catalyst include palladium
acetate, palladium chloride, palladium nitrate, palladium
sulfate, palladium propionate, palladium on carbon,
10 palladium on alumina, palladium black, and the like. As
the palladium catalyst, it is more preferable to use
palladium acetate, palladium chloride, or a complex in
which another ligand (another complex ion or another
molecule: for example, in the case of palladium acetate,
15 a complex ion or molecule other than acetate ion) is further
bonded to palladium acetate or palladium chloride, and it
is particularly preferable to use palladium acetate or a
complex in which a ligand (another complex ion or another
molecule) is further bonded to palladium acetate, from the
20 viewpoint of the reaction yield. Note that one of these
palladium catalysts can be used alone , or two or more thereof
can be used in combination. In addition, examples of the
complex in which another ligand, another complex ion, or
another molecule is further bonded to palladium acetate
25 and which is preferable as the palladium catalyst include
complexes such as
38
NOPF15-514
[CLAIMS]
[ C l a im 1]
A t e t r a c a r b o x y l i c d i a n h y d r i d e , which is a compound
r e p r e s e n t e d by t h e f o l l o w i n g g e n e r a l formula ( 1 ):
[Chera. 1]
(1)
[in the formula (1} , A represents one selected from the
group consisting of optionally substituted divalent
aromatic groups in each of which the number of carbon atoms
10 forming an aromatic ring is 6 to 30, and multiple R1s each
independently represent one selected from the group
consisting of a hydrogen atom and alkyl groups having 1
to 10 carbon atoms] .
[Claim 2]
15 The tetracarboxylic dianhydride according to claim
1, wherein
A in the general formula (1) is one selected from
the group consisting of optionally substituted phenylene
204
NOPF15-514
groups t optionally substituted biphenylene groups,
optionally substituted naphthylene groups, optionally
substituted anthracenylene groups, and optionally
substituted terphenylene groups.
5 [Claim 3]
A method for producing a tetracarboxylic di anhydride ,
the method comprising
reacting an acid anhydride represented by the
following general formula (2):
10 [Chem. 2]
O
(2)
[in the formula (2) , multiple Ras each independently
represent one selected from the group consisting of a
hydrogen atom and alkyl groups having 1 to 10 carbon atoms]
15 with an aromatic compound represented by the following
general formula (3):
[Chem. 3]
205
NOPF15-514
10
3
(3)
[in the formula (3) , A represents one selected from the
group consisting of optionally substituted divalent
aromatic groups in each of which the number of carbon atoms
forming an aromatic ring is 6 to 30, and R3 and R3 each
independently represent a leaving group] in a mixture
liquid containing at least one reducing agent selected from
the group consisting of formic acid, 2-propanol and
hydrogen, abase, a palladium catalyst, the acid anhydride,
and the aromatic compound, to thereby obtain a
tetracarboxylic dianhydride represented by the following
general formula <1) :
[Chem. 4]
(1)
206
NOPF15-514
[in the formula (1), A represents one selected from the
group consisting of optionally substituted divalent
aromatic groups in each of which the number of carbon atoms
forming an aromatic ring is 6 to 30, and multiple R1s each
5 independently represent one selected from the group
consisting of a hydrogen atom and alkyl groups having l
to 10 carbon atoms].
[Claim 4]
A met hod for producing a tetracarboxylic dianhydride,
10 the method comprising the steps of:
reacting a diester compound represented by the
following general formula (201) :
[Chem. 5]
o
R1 ^ JL
RA 1XJ° R"
o
(201)
15 [in the formula (201), multiple R2s each independently
represent one selected from the group consisting of a
hydrogen atom and alkyl groups having 1 to 10 carbon atoms,
and multiple Raos each independently represent one selected
from the group consisting of alkyl groups having 1 to 5
20 carbon atoms] with an aromatic compound represented by the
following general formula (3):
207
NOPF15-514
[Chem. 6]
10
(3)
[in the formula (3), A represents one selected from the
group consisting of optionally substituted divalent
aromatic groups in each of which the number of carbon atoms
forming an aromatic ring is 6 to 30, and R2 and R3 each
independently represent a leaving group] in a mixture
liquid containing at least one reducing agent selected from
the group consisting of formic acid, 2-propanol and
hydrogen, a base, a palladium catalyst, the diester
compound, and the aromatic compound, to thereby obtain a
tetraester compound represented by the following general
formula {101):
[Chem, 7]
15
(1 01)
208
NOPF15-514
10
[in the formula (101) , A represents one selected from the
group consisting of optionally substituted divalent
aromatic groups in each of which the number of carbon atoms
forming an aromatic ring is 6 to 30, multiple R1s each
independently represent one selected from the group
consisting of a hydrogen atom and alkyl groups having l
to 10 carbon atoms, and multiple R10s each independently
represent one selected from the group consisting of alkyl
groups having 1 to 5 carbon atoms]; and
heating the tetraester compound in a carboxylic acid
having 1 to 5 carbon atoms with an acid catalyst being used,
to thereby obtain a tetracarboxylic dianhydride
represented by the following general formula (1):
[Chem. 8]
15
CD
[in the formula (1) , A represents one selected from the
group consisting of optionally substituted divalent
aromatic groups in each of which the number of carbon atoms
209
N0PF15-514
forming an aromatic ring is 6 to 30, and multiple R1s each
independently represent one selected from the group
consisting of a hydrogen atom and alkyl groups having 1
to 10 carbon atoms].
5 [Claim 5]
The method for producing a tetracarboxylic
dianhydride according to claim 4, further comprising the
step of
reacting an alcohol represented by a general formula :
10 R10-OH (in the formula, R10 represents one selected from
the group consisting of alkyl groups having 1 to 5 carbon
atoms) with an acid anhydride represented by the following
general formula (2):
[Chem. 9]
O
) P
0
(2)
15
[in the formula (2) , multiple Ras each independently
represent one selected from the group consisting of a
hydrogen atom and alkyl groups having 1 to 10 carbon atoms] ,
to thereby obtain the diester compound represented by the
20 general formula (201).
210
NOPF15-514
[Claim 6]
A polyimide comprising a repeating unit represented
by the following general formula {4):
[Chem. 10]
N—R4-
[in the formula {4), A represents one selected from the
group consisting of optionally substituted divalent
aromatic groups in each of which the number of carbon atoms
forming an aromatic ring is 6 to 30, multiple R^s each
10 independently represent one selected from the group
consisting of a hydrogen atom and alkyl groups having 1
to 10 carbon atoms , and R4 represents an arylene group having
6 to 40 carbon atoms].
[Claim 7]
15 The polyimide according to claim 6, wherein
R4 in the general formula (4) is at least one selected
from groups represented by the following general formulae
(6) to (9) :
[Chem. 11]
211
NOPF15-514
JiTV
( 6 ) (7)
t>-Q-<3>
(8) (9)
[each R5 in the formula (8) represents one selected from
the group consisting of a hydrogen atom, a fluorine atom,
a methyl group, an ethyl group, and a trif luoromethyl group ,
5 and Q in the formula (9) represents one selected from the
group consisting of groups represented by the formulae:
-0-, -S-, -CO-, -CONH-, -S0a-, -C(CF3)2-, -C(CH3)2-, -CHa- ,
-0-C6H4-C{CH3)2-C6H4-0-, -0-C6H4-S02-C6H4-0-,
-C(CH3)2-C6H4-C(CH3)2-, -0-C6H4-C6H4-0-, and -0-CeH4~0-].
10 [Claim 8]
The polyimide according to claim 7, comprising
at least one repeating unit selected from
repeating units represented by the general formula
(4) , wherein R4 in the formula (4) is a group represented
15 by the general formula (8) , and each R5 in the formula (Q)
is a methyl group,
repeating units represented by the general formula
(4) , wherein R4 in the formula {4) is a group represented
by the general formula (9), and Q in the formula (9) is
212
NOPF15-514
the formula: -0-,
repeating units represented by the general formula
(4), wherein R4 in the formula (4) is a group represented
by the general formula (9) , and Q in the formula (9) is
5 the formula : -O-CsH-j-C (CH3) 2-C6H4-0- ,
repeating units represented by the general formula
(4) , wherein R4 in the formula (4) is a group represented
by the general formula (9), and Q in the formula (9) is
the formula : -0-CsH4-C (CF3) 2-CsH4-0- ,
10 repeating units represented by the general formula
(4) , wherein R4 in the formula (4) is a group represented
by the general formula (9), and Q in the formula (9) is
the formula: -0-C6H4-CeH4-0-, and
repeating units represented by the general formula
15 (4) , wherein R4 in the formula (4) is a group represented
by the general formula (9) , and Q in the formula (9} is
the formula: -O-C6H4-Oat
a ratio of 40% by mole or more relative to all
repeating units,
20
[Claim 9]
A polyamic acid comprising a repeating unit
represented by the following general formula (5):
[Chem. 12]
213
NOPF15-514
10
15
(5)
[in the formula (5), A represents one selected from the
group consisting of optionally substituted divalent
aromatic groups in each of which the number of carbon atoms
forming an aromatic ring is 6 to 3 0, multiple R1s each
independently represent one selected from the group
consisting of a hydrogen atom and alkyl groups having 1
to 10 carbon atoms , and R4 represents an arylene group having
6 to 40 carbon atoms].
[Claim 10]
The polyamic acid according to claim 9, wherein
R4 in the general formula (5) is at least one selected
from groups represented by the following general formulae
(6) to (9) :
[Chem. 13]
214
NOPF15-514
(6) (7)
R5 R6
(8) (9)
[each R5 in the formula (8) represents one selected from
the group consisting of a hydrogen atom, a fluorine atom,
a methyl group, an ethyl group/ and a trif luoromethyl group,
5 and Q in the formula (9) represents one selected from the
group consisting of groups represented by the formulae:
-0-, -S-, -CO-, -CONH-, -S02~, -C(CF3)2-, -C(CH3)2-, -CHa-,
-Q-CsH4-C(CH3)2-CeH4-0- , -0-CGH4-S03-CsH4-0- ,
-C(CH3)a-CsH4-C(CH3)2-, -O-CelU-CeF^-O- , and -O-C6H4-O-] .
10 [Claim 11]
The polyamic acid according to claim 10, comprising
at least one repeating unit selected from
repeating units represented by the general formula
(5) , wherein R4 in the formula (5) is a group represented
15 by the general formula {8) , and each R5 in the formula (8)
is a methyl group,
repeating units represented by the general formula
(5) , wherein R4 in the formula (5) is a group represented
by the general formula (9), and Q in the formula (9) is
215
NOPF15-514
the formula: -O-,
repeating units represented by the general formula
(5) , wherein R4 in the formula (5) is a group represented
by the general formula (9) , and Q in the formula (9) is
5 the formula : -0-C6H4-C (CH3) 2-C6H4-O- ,
repeating units represented by the general formula
(5) , wherein R4 in the formula (5) is a group represented
by the general formula (9), and Q in the formula (9) is
the formula: -0-C6H4-C (CFn) 2-C6H4-0- ,
10 repeating units represented by the general formula
(5) t wherein R4 in the formula (5) is a group represented
by the general formula (9), and Q in the formula (9) is
the formula: -0-CsH4-C6H4-0- * and
repeating units represented by the general formula
15 (5) , wherein R4 in the formula {5) is a group represented
by the general formula (9) , and Q in the formula (9) is
the formula: -0-CeH4-0-
at a ratio of 40% by mole or more relative to all
repeating units.
20 [Claim 12]
The polyamic acid according to any one of claims 9
to 11, wherein
the polyamic acid has an intrinsic viscosity [ri] of
0 . 0 5 to 3 . 0 dL/g, the intrinsic viscosity [i]] being measured
25 under a temperature condition of 3 0 °C with a kinematic
viscometer by using a solution of the polyamic acid at a
21G
NOPF15-514
concentration of 0 . 5 g/dL obtained by dissolving the
polyamic acid in N,N-dimethylacetamide.
[Claim 13]
A method for producing a polyamic acid, comprising
reacting a tetracarboxylic dianhydride represented
by the following general formula (1):
[Chem. 14]
(1)
[in the formula (1), A represents one selected from the
10 group consisting of optionally substituted divalent
aromatic groups in each of which the number of carbon atoms
forming an aromatic ring is 6 to 30, and multiple R1s each
independently represent one selected from the group
consisting of a hydrogen atom and alkyl groups having 1
15 to 10 carbon atoms] with an aromatic diamine represented
by the following general formula (10):
[Chem. 15]
217
NOPF15-514
H2N—R4-NH2
(1 0)
[in the formula (10) , R4 represents an arylene group having
6 to 40 carbon atoms] in the presence of an organic solvent,
to thereby obtain a polyamic acid comprising a repeating
unit represented by the following general formula (5):
[Chem. 16]
(5)
[in the formula (5) , A represents one selected from the
group consisting of optionally substituted divalent
10 aromatic groups in each of which the number of carbon atoms
forming an aromatic ring is 6 to 3 0, multiple R1s each
independently represent one selected from the group
consisting of a hydrogen atom and alkyl groups having 1
to 10 carbon atoms , and R4 represents an arylene group having
15 6 to 40 carbon atoms].
[Claim 14]
A method for producing a polyimide, comprising
218
NOPF15-514
performing imidization of a polyamlc acid comprising
a repeating unit represented by the following general
formula (5) :
[Chem. 17]
[in the formula (5) , A represents one selected from the
group consisting of optionally substituted divalent
aromatic groups in each of which the number of carbon atoms
forming an aromatic ring is 6 to 30, multiple R1s each
10 independently represent one selected from the group
consisting of a hydrogen atom and alkyl groups having 1
to 10 carbon atoms , and R4 represents an arylene group having
6 to 40 carbon atoms], to thereby obtain a polyimide
comprising a repeating unit represented by the following
15 general formula (4} :
[Chem. 18]
219
NOPF15-514
o
(4)
[in the formula (4), A represents one selected from the
group consisting of optionally substituted divalent
aromatic groups in each of which the number of carbon atoms
5 forming an aromatic ring is 6 to 3 0, multiple R*s each
independently represent one selected from the group
consisting of a hydrogen atom and alkyl groups having 1
to 10 carbon atoms , and R4 represents an arylene group having
6 to 40 carbon atoms].
10 [Claim 15]
The method for producing a polyimide according to
claim 14, comprising the step of
reacting a tetracarboxylic dianhydride represented
by the following general formula (1):
16 [Chem. 19]
220
NOPF15-514
10
(1)
[in the formula (1)/ A represents one selected from the
group consisting of optionally substituted divalent
aromatic groups in each of which the number of carbon atoms
forming an aromatic ring is 6 to 30, and multiple Rxs each
independently represent one selected from the group
consisting of a hydrogen atom and alkyl groups having 1
to 10 carbon atoms] with an aromatic diamine represented
by the following general formula (10):
[Chem. 20]
15
H2N—R4-NH2
(1 0)
[in the formula (10), R4 represents an arylene group having
6 to 4 0 carbon atoms] in the presence of an organic solvent,
to thereby obtain a polyamic acid comprising a repeating
unit represented by the general formula (5).
[Claim 16]
221
NOPF15-614
A polyamic acid solution, comprising:
the polyamic acid according to any one of claims 9
to 12; and
an organic solvent.
5 [Claim 17]
A polyimide solution, comprising:
the polyimide according to any one of claims 6 to
8 ; and
a solvent.
10 [Claim 18]
A film, comprising the polyimide according to any
one of claims 6 to 8.
[Claim 19]
A transparent electrically conductive film,
15 comprising the polyimide according to any one of claims
6 to 8.
[Claim 20]
A transparent electrode substrate, comprising the
polyimide according to any one of claims 6 to 8.