U.S. patent application number 09/297203 was filed with the patent office on 2002-10-17 for resin composition and adhesive film.
Invention is credited to HONDA, YOSHIHIKO, IIOKA, SHINJI, KAGEYAMA, AKIRA, KAWAI, TOSHIYASU, NISHIMURA, SHIN, NOMURA, YOSHIHIRO, SUZUKI, MASAHIRO, SUZUKI, MASAO, TAKAHASHI, AKIO.
Application Number | 20020151659 09/297203 |
Document ID | / |
Family ID | 26429082 |
Filed Date | 2002-10-17 |
United States Patent
Application |
20020151659 |
Kind Code |
A1 |
SUZUKI, MASAHIRO ; et
al. |
October 17, 2002 |
RESIN COMPOSITION AND ADHESIVE FILM
Abstract
The present invention is to provide a resin composition
excellent in moisture absorption property, heat resistance,
adhesive property and electric characteristics, and excellent in
molding property, and suitable for an insulating material such as a
multilayer wiring substrate, electronic parts, etc., and an
adhesive film. There is disclosed a resin composition comprising
(A) a polymer containing a quinoline ring represented by the
formula (1) in the structure such as
6,6'-bis(2-(4-fluorophenyl)-4-phenylquinoline) and
4,4'-(1,1,1,3,3,3-hexafluoro-2,2-propylidene)bisphenol, etc., and
(B) a bismaleimide compound represented by the formula (2) such as
2,2-bis((4-male-imidophenoxy)phenyl)propane, etc.
Inventors: |
SUZUKI, MASAHIRO;
(HITACHI-SHI, IBARAKI, JP) ; NISHIMURA, SHIN;
(HITACHI-SHI, IBARAKI, JP) ; SUZUKI, MASAO;
(HITACHI-SHI, IBARAKI, JP) ; TAKAHASHI, AKIO;
(HITACHI-SHI, IBARAKI, JP) ; KAGEYAMA, AKIRA;
(SHINJUKU-KU, TOKYO, JP) ; HONDA, YOSHIHIKO;
(HITACHI-SHI, IBARAKI, JP) ; KAWAI, TOSHIYASU;
(ICHIHARA-SHI, CHIBA, JP) ; IIOKA, SHINJI;
(ICHIHARA-SHI, CHIBA, JP) ; NOMURA, YOSHIHIRO;
(ICHIHARA-SHI, CHIBA, JP) |
Correspondence
Address: |
ANTONELLI TERRY STOUT AND KRAUS
SUITE 1800
1300 NORTH SEVENTEENTH STREET
ARLINGTON
VA
22209
|
Family ID: |
26429082 |
Appl. No.: |
09/297203 |
Filed: |
October 7, 1999 |
PCT Filed: |
April 7, 1998 |
PCT NO: |
PCT/JP98/01587 |
Current U.S.
Class: |
525/529 |
Current CPC
Class: |
C08L 71/00 20130101;
C08G 75/23 20130101; C08G 65/4037 20130101; C08G 65/4006
20130101 |
Class at
Publication: |
525/529 |
International
Class: |
C08F 283/00 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 7, 1997 |
JP |
87838/1997 |
Apr 7, 1997 |
JP |
87839/1997 |
Claims
1. A resin composition which comprises, as essential components,
(A) a polymer containing a quinoline ring represented by the
following formula (1) in the structure, and (B) a bismaleimide
compound represented by the following formula (2): 6wherein Ar
represents a divalent organic group containing at least two carbon
atoms.
2. A composition which comprises a resin composition comprising, as
essential components, (A) a polymer containing a quinoline ring
represented by the following formula (1) in the structure and (B) a
bismaleimide compound represented by the following formula (2), and
(C) a polymeric compound selected from an aromatic diamine, an
epoxy compound and a polybutadiene compound, etc., being dissolved
in (D) an organic solvent; 7wherein Ar represents a divalent
organic group containing at least two carbon atoms.
3. A resin composition which is obtained by removing the organic
solvent from the composition according to claim 2.
4. A cured product which is obtained by heating and curing the
resin composition according to claim 3.
5. The resin composition according to claim 1, wherein the
composition has a temperature region showing the value of a storage
elastic modulus of from 107 dyn/cm.sup.2 to 10.sup.2 dyn/cm.sup.2
at the temperature of 250.degree. C. or lower, a saturation
moisture absorption ratio of 1% or less, and thermal resistance at
the atmosphere of 330.degree. C. for 10 minutes or longer and an
adhesive force with a material to be adhered of 0.6 kgf/cm or
more.
6. The resin composition according to claim 1, wherein a polymer
containing a quinoline ring represented by the following formula
(3) or (4): 8wherein R' each represents an alkyl group, an aryl
group, an alkoxy group, an aryloxy group, a formyl group, an ester
group, an amide group, a heteroaryl group, a cyano group or a
divalent hydrocarbon group which may contain an unsaturated bond
formed by binding two groups, where R represents a hydrogen atom,
an alkyl group or a heteroaryl group, n is an integer of 0 to 5, X
represents a single bond, --O--, --S--, --CO--, --SO--,
--SO.sub.2--, -A-, the following formula (7) or --Q--, where q is
an integer of 1 to 3, A represents --Ar--O--Ar--(where Ar is an
arylene group), --Hr-- (where Hr represents a heteroarylene group),
--CO--Ar--, --Ar--S--Ar--, --Ar--SO--Ar--, --Ar--or --Ar--Q--Ar--,
Q represents L1-C-L2, and L1 and L2 each represents a methyl group,
a trifluoromethyl group, or a divalent hydrocarbon group formed by
combining Li and L2 together with a carbon atoms to which they are
bound, which may contain an unsaturated bond(s) or may be
substituted by an unsaturated group(s), Z represents a single bond
or an arylene group, and Y represents --0--or --O--A--O--; 9is used
as the polymer containing a quinoline ring.
7. The resin composition according to claim 1, wherein the
bismaleimide compound has a structure represented by the formula
(5) or the formula (6) in the structure: 10wherein R.sub.1 to
R.sub.10 represents a hydrogen atom, CH.sub.3, C.sub.2H.sub.5,
CF.sub.3 or C.sub.2F.sub.5, which may be the same or different from
each other, and n is 0 or an integer of 1 to 4, which may be the
same or different from each other.
8. An adhesive film which comprises using the resin composition
according to claim 3.
9. The adhesive film according to claim 8, wherein at least one of
organic solvents selected from the group consisting of
N-methyl-2-pyrrolidone, quinoline, cyclopentanone and m-cresol is
used as an organic solvent. 10. The adhesive film according to
claim 8, wherein the film is dried with the final drying
temperature of 150.degree. C. to 220.degree. C. for removing the
organic solvent.
Description
TECHNICAL FIELD
[0001] This invention relates to a resin composition comprising a
polymer containing a quinoline ring and a thermosetting resin, an
insulating material constituted by said resin composition and an
adhesive film, particularly to a resin composition for an
interlayer insulation film excellent in electric characteristics,
molding property and adhesiveness with a material to be adhered,
and has a low moisture absorption ratio, an insulating material
constituted by said resin composition and an adhesive film.
BACKGROUND ART
[0002] As an interlayer insulating membrane for electronic parts, a
dehydration-condensation type polyimide resin polyimide resin has
heretofore been used (Japanese Provisional Patent Publication No.
222444/1988). Whereas the above-mentioned polyimide resin is
excellent in heat resistance, mechanical characteristics, etc., a
polyamic acid varnish which is a precursor thereof is required to
be stored in a refrigerator at -5.degree. C. or less whereby it is
insufficient in storage stability. Also, it requires curing at a
high temperature of 350.degree. C. or higher and the cured product
has the problem that it has a large moisture absorption ratio.
Moreover, when copper is used which is a representative conductive
material and inferior in adhesiveness with a material to be
adhered, it has a problem that it reacts during heating or the
like, and has a problem in the point of reliability.
[0003] As a measure of the above, an investigation of a polymer
containing a quinoline ring has been made in recent years, and
synthetic methods thereof have been described in U.S. Pat. No.
4,000,187, 5,247,050, 5,247,050, etc. Also, as the other
conventional example thereof, there may be mentioned Japanese
Provisional Patent Publication No. 25286/1987.
[0004] A polymer containing a quinoline ring has low specific
permittivity and dielectric dissipation factor, excellent in
electric characteristics, low moisture absorption ratio and good
stability at high temperatures, but it involves the problems that
adhesiveness with a material to be adhered is bad, molding property
is poor, and it dissolved in a solvent so that a multi-layered
structure can be hardly prepared or the like. In particular, when
it is used as an insulating material of a multi-layered wiring
board or an interlaminar insulating membrane of LSI, etc., for
preparing a multi-layered structure, an insulating layer is formed
by using a polymer containing a quinoline ring previously dissolved
in a solvent, and then, the next layer is similarly formed by using
a polymer containing a quinoline ring dissolved in a solvent
whereby an insulating layer is formed. However, the insulating
layer previously formed is dissolved in a solvent so that a
multi-layered structure can be difficultly formed. Moreover, in
order to solve the above-mentioned problems, it can be considered a
method in which a semi-cured film removing a solvent is formed, and
molding is carried out under heating and pressure. However, the
above film does not show flowability even when it is molded under
heating and pressure so that, at present, it is difficult to apply
the material to an insulating material for a multi-layered
structure.
[0005] When the polymer containing a quinoline ring as mentioned
above is used as an insulating material of a multi-layered wiring
board or an interlaminar insulating membrane of LSI, etc., a
multi-layered wiring board, etc. can be formed, for example, by
forming a varnish previously dissolving in a solvent, coating it
and drying to remove the solvent, and forming a conductive material
by sputtering or chemical plating, etc., and the procedure is
repeated. However, in this method, there are problems that a number
of steps is much, an adhesiveness to the conductive material is
poor, highly multi-layered structure can be difficultly prepared,
and peeling occurs in a soldering step of LSI, etc., whereby
reliability is insufficient, or the like.
[0006] An object of the present invention is to provide a resin
composition and an adhesive film each excellent in molding property
and has high adhesive force with a conductive material, resin,
ceramics, etc. without impairing electric characteristics, low
moisture absorption ratio and thermal stability at high
temperatures.
DISCLOSURE OF THE INVENTION
[0007] Summary of the present invention which solves the above
problems is as follows.
[0008] The first invention is a resin composition which comprises,
as essential components, (A) a polymer containing a quinoline ring
represented by the following formula (1) in the structure, and (B)
a bismaleimide compound represented by the following formula (2).
1
[0009] wherein Ar represents a divalent organic group containing at
least two carbon atoms.
[0010] The second invention is a composition obtained by dissolving
a resin composition comprising, as essential components, (A) a
polymer containing a quinoline ring represented by the following
formula (1) in the structure and (B) a bismaleimide compound
represented by the following formula (2), and (C) a polymeric
compound selected from an aromatic diamine, an epoxy compound and a
polybutadiene compound, etc. in (D) an organic solvent. 2
[0011] wherein Ar has the same meanings as defined above.
[0012] The third invention is a resin composition obtained by
removing the organic solvent from the composition according to the
second invention.
[0013] The fourth invention is a cured product obtained by heating
and curing the resin composition of the third invention.
[0014] The fifth invention is, in either of the first to the third
inventions, a resin composition which has a temperature region
showing the value of a storage elastic modulus of from 10.sup.7
dyn/cm.sup.2 to 10.sup.2 dyn/cm.sup.2 at the temperature of
250.degree. C. or lower, a saturation moisture absorption ratio of
1% or less, and thermal resistance at the atmosphere of 330.degree.
C. for 10 minutes or longer and an adhesive force with a material
to be adhered of 0.6 kgf/cm or more.
[0015] The sixth invention is, in either of the first to the fifth
inventions, a resin composition which comprises using, as the
polymer containing a quinoline ring, a polymer containing a
quinoline ring represented by the following formula (3) or (4).
3
[0016] Here, in the formula (3) or the formula (4), R' each
represents an alkyl group, an aryl group, an alkoxy group, an
aryloxy group, a formyl group (--COR), an ester group (--COR or
--OCOR), an amide group (--NRCOR or --CONRR), a heteroaryl group, a
cyano group or a divalent hydrocarbon group which may contain an
unsaturated bond formed by binding two groups (wherein R represents
a hydrogen atom, an alkyl group or a heteroaryl group.), n is each
independently an integer of 0 to 5, X represents a single bond,
--O--, --S--, --CO--, --SO--, --SO.sub.2--, --A--, the following
formula (7) or --Q--(wherein q is an integer of 1 to 3, A
represents --Ar--O--Ar--(where Ar represents an arylene group),
--Hr--(where Hr represents a heteroarylene group), --CO--Ar--,
--Ar--S--Ar--, --Ar--SO--Ar--, --Ar--or--Ar--Q--Ar--, Q represents
L.sub.1--C--L.sub.2, and L.sub.1 and L.sub.2 each represents a
methyl group, a trifluoromethyl group, or a divalent hydrocarbon
group formed by combining L.sub.1 and L.sub.2 together with a
carbon atoms to which they are bound, which may contain an
unsaturated bond(s) or may be substituted by an unsaturated
group(s).), Z represents a single bond or an arylene group, and Y
represents --O--or --O--A--O--. 4
[0017] The seventh invention is, in either of the first to the
sixth inventions, a resin composition represented by a bismaleimide
compound having the formula (5) or the formula (6) in the
structure. 5
[0018] wherein R.sub.1 to R.sub.10 represent a hydrogen atom,
CH.sub.3, C.sub.2H.sub.5, CF.sub.3 or C.sub.2F.sub.5, which may be
the same or different from each other, and n is 0 or an integer of
1 to 4, which may be the same or different from each other.
[0019] The eighth invention is an adhesive film which comprises
using the resin composition in the third, the fifth, the sixth or
the seventh invention.
[0020] The ninth invention is, in the eighth invention, an adhesive
film which comprises using at least one of the organic solvent
selected from the group consisting of N-methyl-2-pyrrolidone,
quinoline, cyclopentanone and m-cresol, as an organic solvent.
[0021] The tenth invention is, in the inventions of the eighth or
the ninth invention, an adhesive film which comprises drying the
film with the final drying temperature of 150.degree. C. to
220.degree. C. for removing the organic solvent.
BRIEF DESCRIPTION OF THE DRAWINGS
[0022] FIG. 1 shows a diagram showing the relationship between the
viscosity of varnishes of Examples and Comparative example and
lapsed days of the varnishes, and in the figure, the reference
numeral 1 shows the varnish viscosity of Example 1, 2 shows the
varnish viscosity of Example 3, 3 shows the varnish viscosity of
Example 5, 4 shows the varnish viscosity of Example 10, 5 shows the
varnish viscosity of Comparative example 1, and 9 shows the varnish
viscosity of Example 12, respectively.
[0023] FIG. 2 shows a diagram showing the relationship of storage
elastic modulus when heating films heated and dried of Examples and
Comparative example, and in the figure, the reference numeral 6
shows the storage elastic modulus of the film in Example 5 in which
it is dried at 100.degree. C. for 20 minutes and 200.degree. C. for
20 minutes, 7 shows the storage elastic modulus of the film in
Example 5 in which it is dried at 250.degree. C. for 60 minutes,
and 8 shows the storage elastic modulus of the film in Comparative
example 2 in which it is dried at 100.degree. C. for 20 minutes and
200.degree. C. for 20 minutes, respectively.
[0024] FIG. 3 is a diagram showing temperature dependency of the
storage elastic modulus of the respective resin cured compositions
of Example 17 and Comparative example 4, and in the figure, the
reference numeral 10 shows the resin cured composition of Example
17, and 11 shows the resin cured composition of Comparative example
4, respectively.
BEST MODE FOR CARRYING OUT THE INVENTION
[0025] In the following, the present invention is explained in
detail.
[0026] In the polymer containing a polyquinoline ring, for
obtaining an adhesive force, moldability and high multi-layered
constitution, it is indispensable to be melted during the molding
process under heating and pressure to adhere to a material to be
adhered, and further to be deformed. For obtaining such properties,
the polymer may be used through an adhesive which melts in the
molding process under heating and pressure, adheres to the material
to be adhered and deforms. However, when such a constitution is
employed, the resulting material is liable to receive an effect of
the adhesive and excellent characteristics obtained by the polymer
containing a polyquinoline ring such as a little water absorption
ratio, excellent in stability at high temperatures and excellent in
electric characteristics, etc. To solve the above problems, the
present inventors have investigated about fluidized phenomenon
during the curing process and have found that fluidity occurs by
dissolving the polymer containing a polyquinoline ring which is
caused by a fused thermosetting resin by heating.
[0027] From such a viewpoint, they have investigated about the
combination of the bismaleimide compound represented by the formula
(2) of the above-mentioned (B) and the polymer containing a
polyquinoline ring. As a result, whereas the polymer containing a
polyquinoline ring represented by the formula (1) of the
above-mentioned (A) has an elasticity at 250.degree. C. of 107
dyn/cm.sup.2 or more, it dissolves well in the fused bismaleimide
compound represented by the formula (2) of the above-mentioned (B)
whereby they have found that an elasticity is markedly lowered and
it has a processing window.
[0028] Here, the term "processing window" means a temperature and
time from softening the resin to curing the same in the curing
procedure of the bismaleimide compound represented by the formula
(2) in the above-mentioned (B). Those having a processing window is
a material excellent in adhesiveness or molding property, and a
resin having a processing window can be used as an insulating
material for various uses.
[0029] Also, by adding (C) a polymeric compound selected from an
aromatic diamine, an epoxy compound, a polybutadiene compound,
etc., depending on the purpose of uses, in addition to (A) the
polymer containing the polyquinoline ring represented by the
above-mentioned formula (1) and (B) the bismaleimide compound
represented by the above-mentioned formula (2), mechanical
characteristics of the resin composition, adhesive property with
the material to be adhered, moldability, etc. can be more improved.
Particularly, in these resin compositions, respective components
are previously dissolved in (D) an organic solvent, a resin
composition which is uniformly dissolved and excellent in
characteristics can be obtained.
[0030] Next, in addition to (A) the polymer containing the
polyquinoline ring represented by the above-mentioned formula (1)
and (B) the bismaleimide compound represented by the
above-mentioned formula (2), (C) the polymeric compound selected
from an aromatic diamine, an epoxy compound, a polybutadiene
compound, etc., depending on the purpose of uses is previously
dissolved in (D) the organic solvent uniformly, and then, the
organic solvent is removed to obtain a resin composition. The
above-mentioned resin composition becomes a non-solvent type, and,
for example, by making it in a film shape, it becomes a resin
composition suitable for an insulating material such as an organic
thin film multilayer wiring board for a multi-chip, a multilayer
print wiring board, etc.
[0031] A resin composition which comprises a resin composition, in
addition to (A) the polymer containing the polyquinoline ring
represented by the above-mentioned formula (1) and (B) the
bismaleimide compound represented by the above-mentioned formula
(2), (C) the polymeric compound selected from an aromatic diamine,
an epoxy compound, a polybutadiene compound, etc., depending on the
purpose of uses is previously dissolved in (D) the organic solvent
uniformly, and then, the organic solvent is removed has a
temperature region showing the storage elastic modulus at a
temperature of 250.degree. C. or less of 10.sup.7 dyn/cm.sup.2 to
10.sup.2 dyn/cm.sup.2 so that it is excellent in moldability.
[0032] Also, it has saturated moisture absorption of 1 % or less,
is less affected by the volatile component at heating, and peeling
and blister with the material to be adhered difficultly occur.
Moreover, it has heat resistance at heated atmosphere of
330.degree. C. of 10 minutes or more. For example, when it is used
as an insulating layer which is required to have heat resistance
such as a multi-chip module multilayer wiring board, etc., it can
be applied to a product having a process which is carried out a
heating step of a pin connecting temperature (330.degree. C./10
minutes) when electronic parts are connected (300.degree. C. to
330.degree. C./5 minutes). Furthermore, it has an adhesive forth to
the material to be adhered of 0.6 kgf/cm or more so that it is also
excellent in the point of reliability. From the above viewpoints,
the resin composition of the present invention is excellent in
moldability, low moisture absorption, heat resistance and
adhesiveness with the material to be adhered, whereby it becomes an
insulating material excellent in uniformity against the required
characteristics.
[0033] As a result of earnest studies on (A) the polymer containing
the quinoline ring represented by the above-formula (I), the
inventors have found that when (B) the polymer containing the
quinoline ring and a bismaleimide compound having a structure of
the above-mentioned formula (5) or (6), without mostly not impaired
the characteristic feature of the polymer having the quinoline
ring, (B) the bismaleimide compound having the structure of the
above-mentioned formula (2) uniformly dissolves and flown whereby
it is closely contacted with the material to be adhered so that
excellent adhesive property can be obtained and a resin composition
and an adhesive film both having excellent mechanical
characteristics can be provided.
[0034] As (A) the polymer containing the quinoline ring to be used
in the present invention, there may be mentioned, for example, a
polymer containing a 2-(2-fluorophenyl)-5-fluoro-4-phenylquinoline
unit, a polymer containing
2-(4-fluorophenyl)-5-fluoro-4-phenylquinoline unit, a polymer
containing 4-(2-fluorophenyl)-5-fluoro-4-phenylquinoline unit, a
polymer containing 2-(4-fluorophenyl)-7-fluoro-4-phenylquinoline
unit, a polymer containing 2,4-difluoroquinoline unit, a polymer
containing 1,5-difluoroquinoline unit, a polymer containing
2,7-difluoroquinoline unit, a polymer containing
2,7-difluoro-6-phenylquinoline unit, a polymer containing
4-(4-fluorophenyl)-7-fluoroquinoline unit, a polymer containing
6,6'-bis [2-(2-fluorophenyl)-4-phenylquinoline] unit, a polymer
containing 6,6'-bis[2-(4-fluorophenyl)-4-phenylquinoline] unit, a
polymer containing 6,6'-bis
[2-(4-fluorophenyl)-4-tert-butylquinoline] unit, a polymer
containing 6,6'-bis [4-(4-fluorophenyl)-2-phenyl -quinoline] unit,
a polymer containing 6,6'-bis-2-fluoroquinoline unit, a polymer
containing 6,6'-bis-4-fluoroquinoline unit, a polymer containing
6,6'-bis [4-(4-fluoro-phenyl)-2-(2-pyridyl)quinoline] unit, a
polymer containing 6,6'-bis
[4-(4-fluorophenyl)-2-(methyl)quinoline] unit, a polymer containing
6,6'-bis [2-fluoro-4-phenylquinoline unit, a polymer containing
oxy-6,6'-bis [2-(4-fluorophenyl)-4-phenylquinoline] unit, a polymer
containing 1,4-benzene-bis-2,2-[2-(4-fluorophenyl)quinoline] unit,
a polymer containing 1,4-benzene-bis-2,2-(4-fluoroquinoline) unit,
a polymer containing
1,4-benzene-bis-2,2-[4-(4-fluorophenyl)-quinoline unit, a polymer
containing 1,1,1,3,3,3-hexa-fluoroisopropylidene-bis-[(4--
phenoxy-4-phenyl)-2-(4-fluoroquinoline)] unit, and the like. These
polymers may be used singly or in combination of two or more
kinds.
[0035] As the (B) bismaleimide compound, there may be mentioned,
for example, a bifunctional bismaleimide compound represented by
N,N'-ethylenedimaleimide, N,N'-hexamethylenebismaleimide,
N,N'-dodecamethylenebismaleimide, N,N'-m-xylylenebismaleimide,
N,N'-p-xylylenebismaleimide,
N,N'-1,3-bismethylenecyclohexanebismaleimide- ,
N,N'-1,4-bismethylenecyclohexanebismaleimide,
N,N'-2,4-tolylenebismaleim- ide, N,N'-2,6-tolylenebismaleimide,
N,N'-3,3-diphenylmethanebismaleimide,
N,N'-4,4-diphenylmethanebismaleimide,
3,3-diphenylsulfonebismaleimide, 4,4-diphenylsulfonebismaleimide,
N,N'-4,4-diphenylsulfidebismaleimide,
N,N'-p-benzophenonebismaleimide, N,N'-diphenylethanebismaleimide,
N,N'-diphenyl ether bismaleimide,
N,N'-(methylene-ditetrahydrophenyl)bism- aleimide,
N,N'-(3-ethyl)-4,4-diphenylmethanebismaleimide,
N,N'-(3,3-dimethyl)-4,4-diphenylmethanebismaleimide,
N,N'-(3,3-diethyl)-4,4-diphenylmethanebismaleimide,
N,N'-(3,3-dichloro)-4,4-diphenylmethanebismaleimide,
N,N'-tolidinebismaleimide, N,N'-isophoronebismaleimide,
N,N'-p,p'-diphenyldimethylsilylbismaleimide,
N,N'-benzophenonebismaleimid- e, N,N'-diphenylpropanebismaleimide,
N,N'-naphthalenebismaleimide, N,N'-m-phenylenebismaleimide,
N,N'-4,4-(1,1-diphenyl-cyclohexane)-bismale- imide,
N,N'-3,5-(1,2,4-triazol)-bismaleimide,
N,N'-pyridine-2,6-diylbismal- eimide,
N,N'-5-methoxy-1,3-phenylenebismaleimide, 1,2-bis(2-maleimidoethox-
y)ethane, 1,3-bis(3-maleimidopropoxy)propane,
N,N'-4,4-diphenylmethane-bis- -dimethylmaleimide,
N,N'-hexamethylene-bis-dimethylmaleimide, N,N'-4,4'1-(diphenyl
ether)-bis-dimethylmaleimide,
N,N'-4,4'-(diphenylsulfone)-bis-dimethylmaleimide,
N,N'-bismaleimide of N,N'-4,4'-(diamino)-triphenylphosphate or the
like; a polyfunctional maleimide compound obtained by the reaction
of a reaction product (a polyamine compound) of aniline and
formalin, 3,4,4'-triaminodiphenylmetha- ne, triaminophenol, etc.,
with maleic anhydride; a maleimide compound obtained by the
reaction of tris-(4-aminophenyl)-phosphate,
tris(4-aminophenyl)-phosphate, tris(4-aminophenyl)-thiophosphate
with maleic anhydride; an aromatic bismaleimide compound such as
2,2-bis [4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis
[3-chloro-4-(4-maleimidoph- enoxy)phenyl]propane, 2,2-bis
[3-bromo-4-(4-maleimidophenoxy)phenyl]propan- e, 2,2-bis
[3-ethyl-4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis
[3-propyl-4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis
[3-isopropyl-4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis
[3-butyl-4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis
[3-sec-butyl-4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis
[3-methoxy-4-(4-maleimidophenoxy)phenyl]propane, 1,1-bis
[4-(4-maleimidophenoxy)phenyl]ethane, 1,1-bis
[3-methyl-4-(4-maleimidophe- noxy)phenyl]ethane, 1,1-bis
[3-chloro-4-(4-maleimidophenoxy)phenyl]ethane, 1,1-bis
[3-bromo-4-(4-maleimidophenoxy)phenyl]ethane, 1,1-bis
[4-(4-maleimidophenoxy)-phenyl]methane, 1,1-bis
[3-methyl-4-(4-maleimidop- henoxy)-phenyl]methane, 1,1-bis
[3-chloro-4-(4-maleimidophenoxy)-phenyl]me- thane, 1,1-bis
[3-bromo-4-(4-maleimidophenoxy)-phenyl]methane, 3,3-bis
[4-(4-maleimidophenoxy)phenyl]-pentane, 1,1-bis
[4-(4-maleimidophenoxy)ph- enyl]propane,
1,1,1,3,3,3-hexafluoro-2,2-bis [4-(4-maleimidophenoxy)-pheny-
l]propane, 1,1,1,3,3,3-hexafluoro-2,2-bis
[3,5-dimethyl-(4-maleimidophenox- y)phenyl]propane,
1,1,1,3,3,3-hexafluoro-2,2-bis [3,5-dibromo-(4-maleimido-
phenoxy)phenyl]-propane and 1,1,1,3,3,3-hexafluoro-2,2-bis-[3- or
5-methyl-(4-maleimidophenoxy)phenyl]propane, etc., and the
invention is not particularly limited by those as mentioned above.
Moreover, it is possible to use the component singly or two or more
kinds.
[0036] As an aromatic diamine among (C) the polymeric compound of
the present invention, there may be mentioned, for example,
m-phenylenediamine, p-phenylenediamine, 4,4-diaminediphenylmethane,
4,4-diaminodiphenylsulfide, 2,2-bis(4-amino-phenyl)propane,
4,4-diaminodiphenylsulfone, bis-(4-amino-phenyl)methylphosphine
oxide, bis-(4-aminophenyl)phosphine oxide,
bis-(4-aminophenyl)methylamine, 1,5-diaminonaphthalene,
m-xylylenediamine, 1,1-bis(p-aminophenyl)furan, p-xylylenediamine,
6,6-diamino-2,2-bipyridyl, 2,2-bis
[3-propyl-4-(4-aminophenoxy)phenyl]propane, 2,2-bis
[3-sec-butyl-4-(4-aminophenoxy)phenyl]propane, 2,2-bis
[3-methoxy-4-(4-aminophenoxy)phenyl]propane, 1,1-bis
[4-(4-aminophenoxy)phenyl]ethane, 1,1-bis
[3-methyl-4-(4-aminophenoxy)-ph- enyl]ethane, 1,1-bis
[3-chloro-4-(4-aminophenoxy)phenyl]-ethane, 1,1-bis
[3-bromo-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis
[4-(4-aminophenoxy)phen- yl]methane, 1,1-bis
[3-methyl-4-(4-aminophenoxy)phenyl]methane, 1,1-bis
[3-chloro-4-(4-aminophenoxy)phenyl]methane, 1,1-bis
[3-bromo-4-(4-amino-phenoxy)phenyl]methane, 3,3-bis
[4-(4-aminophenoxy)phenyl]-pentane, 1,1-bis
[4-(4-aminophenoxy)phenyl]pro- pane, 1,1,1,
3,3,3-hexafluoro-2,2-bis [4-(4-aminophenoxy)phenyl]propane,
1,1,1,3,3,3-hexafluoro-2,2-bis
[3,5-dimethyl-(4-aminophenoxy)phenyl]propa- ne, 1,1,1,3,3,
3-hexafluoro-2,2-bis [3,5-dibromo-(4-aminophenoxy)phenyl]pr- opane,
1,1,1,3,3,3-hexafluoro-2,2-bis [3- or
5-methyl-(4-aminophenoxy)phen- yl]-propane, and the like, and not
particularly limited to those as mentioned above. Incidentally, the
reason why an aromatic series compound is used is that they are
advantageous in the point of thermal resistance as compared with
those of an aliphatic series compound.
[0037] As an epoxy compound among (C) the polymeric compound, there
may be used, for example, at least one of a bifunctional epoxy
compound such as diglycidyl ether of bisphenol A,
3,4-epoxycyclohexylmethyl-3,4-epoxycyclo- hexanecarboxylate,
4,4'-(1,2-epoxyethyl)biphenyl, 4,4'-(1,2-epoxyethyl)-bi- phenyl
ether, resorcinglycidyl ether, bis(2,3-epoxycyclopentyl) ether,
N,N'-m-phenylenebis(4,5'-epoxy-1,2-cyclohexanedicarbodiimide),
etc., an epoxy compound of trifunctional or more such as a
triglycidyl compound of p-aminophenol,
1,3,5-tri(1,2-epoxyethyl)benzene, tetraglycidoxytetrapheny-
lethane, phenolformaldehyde novolac resin, an epoxy compound having
a hydrantoin skeleton, an epoxy compound containing a halogen atom
such as a brominated epoxy compound, and the like.
[0038] As a polybutadiene compound among (C) the compound, there
may be used, for example, at least one of 1,2-polybutadiene,
cyclized 1,2-polybutadiene, epoxy-modified 1,2-polybutadiene,
terminal epoxidized 1,2-polybutadiene, 1,2-polybutadiene glycol,
1,2-polybutadiene carboxylic acid, urethane-modified
1,2-polybutadiene, maleimidated 1,2-polybutadiene, terminal
acryl-modified 1,2-polybutadiene, terminal ester-modified
1,2-polybutadiene compound, and the like.
[0039] As (D) the organic solvent, there may be used at least one
selected from, for example, methyl cellosolve, methyl ethyl ketone,
N,N-dimethylformamide, N,N-dimethylacetamide,
N-methyl-2-pyrrolidone, quinoline, cyclopentanone, m-cresol,
chloroform, etc.
[0040] In the present invention, the formulation ratio of the
polymer containing the quinoline ring of Component (A) and the
bismaleimide compound of Component (B) is preferably 30% by weight
to 99.9% by weight of the polymer containing the quinoline ring of
Component (A) and 0.1% by weight to 70% by weight of the
bismaleimide compound of Component (B). If the amount of the
polymer containing the quinoline ring of Component (A) is made less
than 30% by weight, fluidity is excellent but mechanical
characteristics are poor so that desired film formation becomes
difficult and there cause the problem that crack occurs at the
insulating portion when making multilayer structure and the
like.
[0041] In the present invention, the formulation ratio of the
polymer containing the quinoline ring of Component (A) and the
bismaleimide compound of Component (B) is more preferably 30% by
weight to 70% by weight based on the total solid component which is
the sum of the both components when the preparation of an adhesive
film is intended by using the knife coating, the bar coating, etc.
On the other hand, when preparation of a multi-layered layer
insulation film with a low dielectric constant is intended by the
spin coating method, etc., the bismaleimide compound of Component
(B) is desirably contain 0.1 to 30% by weight, particularly
preferably 5 to 30% by weight based on the total solid component
which is the sum of the both components. If an amount of Component
(B) is made 5% by weight or less, mechanical characteristics are
excellent but solubility in a solvent becomes a large so that
cracks are sometimes generated at the insulating portion when a
multilayer structure is to be made.
[0042] Also, in the present invention, when the polymeric compound
of Component (C) is to be added, an amount thereof is desirably 40%
by weight or less based on the total resin component. When
Component (C) is added in an amount of 40% by weight or more,
whereas moldability and adhesiveness are excellent, it arises the
problem that heat resistance is poor.
[0043] In the present invention, as the method for obtaining the
resin composition comprising the polymer containing the quinoline
ring of Component (A) and the bismaleimide compound of Component
(B), or the resin composition comprising the polymer containing the
quinoline ring of Component (A), the bismaleimide compound of
Component (B) and the polymeric compound of Component (C), there
may be mentioned the method in which the bismaleimide compound of
Component (B) and the polymeric compound of Component (C) are
previously melted by heating, then, the polymer containing the
quinoline ring of Component (A) is added thereto to mix uniformly,
and thereafter the composition is cured to obtain the resin
composition. However, in general, suitable is the method in which
the polymer containing the quinoline ring of Component (A), the
bis-maleimide compound of Component (B) and the polymeric compound
of Component (C) are uniformly mixed in the organic solvent (D) to
obtain the composition as a varnish. Moreover, it is possible to
make a film by removing the solvent from the varnish.
[0044] The adhesive film in the present invention can be obtained,
for example, by flow casting or coating the above-mentioned varnish
on a substrate film such as a polyamide or a polyester, etc. with a
certain thickness, and after drying between 100.degree. C. and
250.degree. C., peeling from the substrate.
[0045] In the above-mentioned procedure, it is particularly
important to select the kind of the solvent to be used and the
final drying temperature at the time of removing the solvent. As
the above-mentioned solvent, there may be used a kind selected from
the group consisting of methyl cellosolve, methyl ethyl ketone,
N,N-dimethylformamide, N,N-dimethylacetamide,
N-methyl-2-pyrrolidone, quinoline, cyclopentanone, m-cresol and
chloroform, etc., or a mixed solvent of the above solvents. It is
preferred to use N-methyl-2-pyrrolidone, cyclopentanone and/or
m-cresol so that the resin composition is to be sufficiently
dissolved and sufficiently removed by drying, and by the same
reason, it is more preferred to use N-methyl-2-pyrrolidone and/or
cyclopentanone. Moreover, it is particularly preferred to use
cyclopentanone in the points that it is difficultly moisture
absorbed and the film is difficultly blushed.
[0046] The final drying temperature is preferably within the range
between 100.degree. C. and 250.degree. C.. If it is less than
100.degree. C., the solvent can hardly removed sufficiently while
if it exceeds 250.degree. C., Component (B) is thermoset whereby
fluidity at the time of adhesion is easily lowered. By the same
reason, the drying temperature is preferably 150.degree. C. to
220.degree. C., more preferably 160.degree. C. to 200.degree. C.,
particularly preferably 160.degree. C. to 180.degree. C.
[0047] According to the above solvent and the drying temperature,
an adhesive film having a sufficiently less amount of the residual
solvent and excellent in fluidity at the time of adhesion can be
obtained. After adhering the adhesive film to a material to be
adhered under heating and pressure, it is thermoset at 200.degree.
C. or more, preferably 250.degree. C. or more, more preferably
280.degree. C. or more, a cured layer having a less moisture
absorption ratio, excellent in mechanical characteristics,
adhesiveness with a material to be adhered, and heat resistance can
be formed. Also, at this time, adhesion under heating and pressure,
and thermosetting can be carried out simultaneously.
[0048] The thickness of the adhesive film is not particularly
limited, but to sufficiently heighten insulating property, the
thickness of the adhesive film is preferably 1 .mu.m or more, and
to make sufficiently thin the thickness of the layered material
when it is laminated, it is preferably 100 .mu.m or less. By the
same reason, the thickness of the adhesive film is preferably 5 to
50 .mu.m, particularly preferably 15 to 30 .mu.m.
[0049] Also, the thickness of the multi-layered layer insulation
film is not particularly limited, but by the reason to easily get a
smooth coating film, it is preferably 0.1 to 3 .mu.m, more
preferably 0.1 to 1 .mu.m.
[0050] In the resin composition of the present invention, it is
also possible to add an organic peroxide or a reaction promoter,
etc., if necessary, for the purpose of low temperature curing or
curing within a short period of time.
EXAMPLES
Example 1
Synthesis of polyquinoline
[0051] To a one-liter stainless flask were added 74.3 g (0.124
mole, 1.03 equivalents) of
6,6'-bis(2-(4-fluorophenyl)-4-phenylquinoline), 40.6 g (0.121 mole,
1.00 equivalent) of 4,4'-(1,1,1,3,3,3-hexafluoro-2,2-propyli-
den)bisphenol and 25 g (0.181 mole, 1.5 equivalents) of anhydrous
potassium carbonate, and 450 ml of N-methyl-2-pyrrolidone and 90 ml
of toluene were added as solvents. To the flask were provided a
water-cooling system cooling tube to which a calcium chloride tube
and a Dean-Stark tube for removing water had been attached, a dry
nitrogen inlet tube, a mechanical stirrer and a thermometer. By
using an oil bath, the mixture was refluxed under heating for 24
hours, and water in the system was removed by azeotropic
distillation with toluene for 24 hours. The solution was firstly
yellowish, then gradually changed to dark brown and became black at
this stage. The reaction temperature was further raised up to
200.degree. C. and the mixture was reacted for 6 hours. The
reaction solution changed from black to deep blue accompanying with
increase in viscosity. By adding 650 ml of N-methyl-2-pyrrolidone
to the mixture to dilute and cool the same, the reaction was
stopped. To purify the resulting polymer solution, the resulting
solution was thrown into water to form a precipitate. Further, the
precipitate was stirred in water at 50.degree. C. for 2 hours to
purify the same, and the procedure was repeated three times.
Thereafter, the polymer was collected by filtration and dried a day
and night by a vacuum drier at 60.degree. C. The yield of the
polymer: 101.1 g (89.0%).
[0052] Next, after setting a stirring rod, a cooling tube and a
thermometer to a 500 ml-volume three-necked flask, 60 g of the
above-mentioned polymer and 280 g of cyclopentanone were charged
therein, and the materials were dissolved by stirring at room
temperature for one hour. Moreover, 60 g of
2,2-bis((4-maleimidophenoxy)phenyl)propane was added to the mixture
and the resulting mixture was stirred for one hour to obtain the
desired varnish. Changes with a lapse of time of the resulting
varnish when it was stored at room temperature (20.degree. C. to
23.degree. C.) were measured by using an E-type viscometer VISCONIC
type (available from Tokyo Seimitsu Co.). The results are shown in
FIG. 1.
[0053] Next, a polyimide film (UPILEX 25S, trade name, available
from UBE INDUSTRIES, LTD.) having a thickness of 0.025 mm was
adhered to Pyrex glass plate with a size of 200 mm.times.200
mm.times.2 mm by using a heat-resistant tape. The resulting varnish
was uniformly coated by using a bar coater, and dried by heating at
100.degree. C. for 20 minutes and at 200.degree. C. for 20 minutes
to obtain two sheets of the films each having a thickness of about
0.030 mm from which cyclopentanone was removed. One of the
resulting films was cured by heating in a press to obtain a cured
resin composition. By using the above-mentioned cured resin
composition, a relative dielectric constant at 1 kHz, dielectric
loss factor (tan .delta.), breaking strain, and moisture absorption
amount when allowed to stand in a potassium iodide saturated
condition (humidity: about 70%) for 48 hours. By using the
above-mentioned cured resin composition and using a thermo-balance,
Type TA-2950 (trade name, available from TA Instrument Co.), a
decomposition initiating (kick-off) temperature was measured. The
results are shown in Table 1 and Table 2.
[0054] Also, copper foils each having a thickness of 0.012 mm were
attached up and down of a sheet of a dried film and the laminate
was cured by heating to obtain a both surface copper-clad cured
resin composition. At this time, the state of sticking out from the
adhered surface of the film was evaluated with eyes and it was made
an index of fluidity at the time of heat curing of the film.
Further, a sample with a size of 25 mm.times.25 mm was cut out from
the both surface copper-clad cured resin composition and allowed to
stand in a solder bath at 330.degree. C. for 10 minutes, and the
presence or absence of blister was confirmed. Moreover, peel
strength (adhesive force) of the copper and the cured resin
composition was confirmed. Curing conditions and measurement
conditions, etc. are shown in Table 1 and Table 2.
Example 2
[0055] By using 50 g of the varnish obtained in Example 1, 0.01 g
of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3 (perhexyne 2,5B,
trade name, available from Nippon Oil & Fats Co.) was added to
the varnish and uniformly dissolved.
[0056] Next, a polyimide film (UPILEX 25S, trade name, available
from UBE INDUSTRIES, LTD.) having a thickness of 0.025 mm was
adhered to Pyrex glass plate with a size of 200 mm.times.200
mm.times.2 mm by using a heat-resistant tape. Further, the
resulting varnish was uniformly coated by using a bar coater, and
dried by heating at 100.degree. C. for 20 minutes and at
200.degree. C. for 20 minutes to obtain two sheets of the films
each having a thickness of about 0.030 mm from which cyclopentanone
was removed. One of the resulting films was cured by heating in a
press to obtain a cured resin composition. By using the
above-mentioned cured resin composition, a relative dielectric
constant at 1 kHz, dielectric loss factor (tan .delta.), breaking
strain, and moisture absorption amount when allowed to stand in a
potassium iodide saturated condition (humidity: about 70%) for 48
hours. By using the above-mentioned cured resin composition and
using a thermobalance, Type TA-2950 (trade name, available from TA
Instrument Co.), a decomposition initiating (kick-off) temperature
was measured. The results are shown in Table 1 and Table 2.
[0057] Also, copper foils each having a thickness of 0.012 mm were
attached up and down of a sheet of a dried film and the laminate
was cured by heating to obtain a both surface copper-clad cured
resin composition. At this time, the state of sticking out from the
adhered surface of the film was evaluated with eyes and it was made
an index of fluidity at the time of heat curing of the film.
Further, a sample with a size of 25.times.25 (mm) was cut out from
the both surface copper-clad cured resin composition and allowed to
stand in a solder bath at 330.degree. C. for 10 minutes, and the
presence or absence of blister was confirmed. Moreover, peel
strength (adhesive force) of the copper and the cured resin
composition was confirmed. Curing conditions and measurement
conditions, etc. are shown in Table 1 and Table 2.
Example 3
[0058] By using 100 g of the varnish obtained in Example 1, 6 g of
epoxy-modified polybutadiene modified by diglycidyl ether bisphenol
A and 0.42 g of 4,4-diaminodiphenylmethane were added to the
varnish and uniformly dissolved to obtain a varnish. Changes of the
resulting varnish with a lapse of time when it was stored at room
temperature (20.degree. C. to 23.degree. C.) were measured by using
an E-type viscometer VISCONIC type (trade name, available from
Tokyo Seimitsu). The results are shown in FIG. 1.
[0059] Next, apolyimide film (UPILEX25S, trade name, available from
UBE INDUSTRIES, LTD.) having a thickness of 0.025 mm was adhered to
Pyrex glass plate with a size of 200 mm.times.200 mm.times.2 mm by
using a heat-resistant tape. Further, the resulting varnish was
uniformly coated by using a bar coater, and dried by heating at
100.degree. C. for 20 minutes and at 200.degree. C. for 20 minutes
to obtain two sheets of the films each having a thickness of about
0.030 mm from which cyclopentanone was removed. One of the
resulting films was cured by heating in a press to obtain a cured
resin composition. By using the above-mentioned cured resin
composition, a relative dielectric constant at 1 kHz, dielectric
loss factor (tan .delta.), breaking strain, and moisture absorption
amount when allowed to stand in a potassium iodide saturated
condition (humidity: about 70%) for 48 hours. By using the
above-mentioned cured resin composition and using a thermobalance,
Type TA-2950 (trade name, available from TA Instrument Co.), a
decomposition initiating (kick-off) temperature was measured. The
results are shown in Table 1 and Table 2.
[0060] Also, copper foils each having a thickness of 0.012 mm were
attached up and down of a sheet of a dried film and the laminate
was cured by heating to obtain a both surface copper-clad cured
resin composition. At this time, the state of sticking out from the
adhered surface of the film was evaluated with eyes and it was made
an index of fluidity at the time of heat curing of the film.
Further, a sample with a size of 25 mm.times.25 mm was cut out from
the both surface copper-clad cured resin composition and allowed to
stand in a solder bath at 330.degree. C. for 10 minutes, and the
presence or absence of blister was confirmed. Moreover, peel
strength (adhesive force) of the copper and the cured resin
composition was confirmed. Curing conditions and measurement
conditions, etc. are shown in Table 1 and Table 2.
Example 4
[0061] 15 g of the varnish obtained in Example 1 was charged in a
200 ml-volume three-necked flask equipped with a stirring rod, a
cooling tube and a thermometer, and 70 g of cyclopentanone was
added thereto and the mixture was dissolved by stirring at room
temperature for one hour. Next, 15 g of
2,2-bis(4-(2-trifluoromethyl-4-maleimidophenoxy)phenyl)-1,1,1,3,3-
,3-hexafluoropropane was added to the mixture and the resulting
mixture was stirred for one hour to obtain the desired varnish.
[0062] Next, a polyimide film (UPILEX 25S, trade name, available
from UBE INDUSTRIES, LTD.) having a thickness of 0.025 mm was
adhered to Pyrex glass plate with a size of 200 mm.times.200
mm.times.2 mm by using a heat-resistant tape. Further, the
resulting varnish was uniformly coated by using a bar coater, and
dried by heating at 100.degree. C. for 20 minutes and at
200.degree. C. for 20 minutes to obtain two sheets of the films
each having a thickness of about 0.030 mm from which cyclopentanone
was removed. One of the resulting films was cured by heating in a
press to obtain a cured resin composition. By using the
above-mentioned cured resin composition, a relative dielectric
constant at 1 kHz, dielectric loss factor (tan .delta.), breaking
strain, and moisture absorption amount when allowed to stand in a
potassium iodide saturated condition (humidity: about 70%) for 48
hours. By using the above-mentioned cured resin composition and
using a thermobalance, Type TA-2950 (trade name, available from TA
Instrument Co.), a decomposition initiating (kick-off) temperature
was measured. The results are shown in Table 1 and Table 2.
[0063] Also, copper foils each having a thickness of 0.012 mm were
attached up and down of a sheet of a dried film and the laminate
was cured by heating to obtain a both surface copper-clad cured
resin composition. At this time, the state of sticking out from the
adhered surface of the film was evaluated with eyes and it was made
an index of fluidity at the time of heat curing of the film.
Further, a sample with a size of 25 mm.times.25 mm was cut out from
the both surface copper-clad cured resin composition and allowed to
stand in a solder bath at 330.degree. C. for 10 minutes, and the
presence or absence of blister was confirmed. Moreover, peel
strength (adhesive force) of the copper and the cured resin
composition was confirmed. Curing conditions and measurement
conditions, etc. are shown in Table 1 and Table 2.
Example 5
[0064] In a two-liter round flask equipped with a mechanical
stirrer, a Dean-Stark tube having a condenser and a nitrogen inlet
tube, and a thermometer were charged 114.75 g (0.1925 mole, 1.03
equivalents) of 6,6-bis(2-(4-fluorophenyl)-4-phenylquinoline),
66.0472 g (0.18848 mole, 1.00 equivalent) of
9,9-bis(4-hydroxyphenyl)fluorene, 705 ml of N-methyl-2-pyrrolidone
and 421 ml of toluene. The reaction mixture was heated under
nitrogen atmosphere for 15 hours. Toluene was removed by the
Dean-Stark tube and the reaction mixture was further heated at
200.degree. C. for 12 hours. The reaction mixture was diluted by
N-methyl-2-pyrrolidone and cooled to room temperature. By gradually
pouring the resulting polymer solution to a 3-times volume of
acetone, the polymer material was condensed. The polymer material
was collected by filtration, dissolved in N-methyl-2-pyrrolidone
and diluted by a 3-times volume of water. The yield of the polymer
was 170 g (99%).
[0065] Next, after setting a stirring rod, a cooling tube and a
thermometer to a 500 ml-volume three-necked flask, 60 g of the
above-mentioned polymer and 280 g of m-cresol were charged therein,
and the materials were dissolved by stirring at room temperature
for one hour. Moreover, 60 g of bis(4-male-imidophenyl)methane was
added to the mixture and the resulting mixture was stirred for one
hour to obtain the desired varnish. Changes with a lapse of time of
the resulting varnish when it was stored at room temperature
(20.degree. C. to 23.degree. C.) were measured by using an E-type
viscometer VISCONIC type (trade name, available from Tokyo Seimitsu
Co.). The results are shown in FIG. 1.
[0066] Next, a polyimide film (UPILEX 25S, trade name, available
from UBE INDUSTRIES, LTD.) having a thickness of 0.025 mm was
adhered to Pyrex glass plate with a size of 200 mm.times.200
mm.times.2 mm by using a heat-resistant tape. The resulting varnish
was uniformly coated by using a bar coater, and dried by heating at
100.degree. C. for 20 minutes and at 200.degree. C. for 20 minutes
to obtain three sheets of the films each having a thickness of
about 0.030 mm from which m-cresol was removed. By using the
above-mentioned film, storage elastic modulus was measured with a
tensile mode by using a viscoelastic measurement device Type
DVA-200 (trade name, available from IT Keisoku Seigyo Co.). The
result is shown in FIG. 2. The storage elastic modulus of this film
gradually lowers as the temperature raises as shown in FIG. 2, but
it maintains a high value even when the temperature is raised over
300.degree. C.
[0067] Next, one of the resulting films was cured by heating in a
press to obtain a cured resin composition. By using the
above-mentioned cured resin composition, a relative dielectric
constant at 1 kHz, dielectric loss factor (tan .delta.), breaking
strain, and moisture absorption amount when allowed to stand in a
potassium iodide saturated condition (humidity: about 70%) for 48
hours. By using the above-mentioned cured resin composition and
using a thermobalance, Type TA-2950 (trade name, available from TA
Instrument Co.), a decomposition initiating (kick-off) temperature
was measured. The results are shown in Table 1 and Table 2.
[0068] Also, copper foils each having a thickness of 0.012 mm were
attached up and down of a sheet of a dried film and the laminate
was cured by heating to obtain a both surface copper-clad cured
resin composition. At this time, the state of sticking out from the
adhered surface of the film was evaluated with eyes and it was made
an index of fluidity at the time of heat curing of the film.
Further, a sample with a size of 25 mm.times.25 mm was cut out from
the both surface copper-clad cured resin composition and allowed to
stand in a solder bath at 330.degree. C. for 10 minutes, and the
presence or absence of blister was confirmed. Moreover, peel
strength (adhesive force) of the copper and the cured resin
composition was confirmed. Curing conditions and measurement
conditions, etc. are shown in Table 1 and Table 2.
Example 6
[0069] By using 50 g of the varnish obtained in Example 5, 0.01 g
of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3 (perhexyne 2,5B,
trade name, available from Nippon Oil & Fats Co.) was added to
the varnish and uniformly dissolved.
[0070] Next, a polyimide film (UPILEX 25S, trade name, available
from UBE INDUSTRIES, LTD.) having a thickness of 0.025 mm was
adhered to Pyrex glass plate with a size of 200 mm.times.200
mm.times.2 mm by using a heat-resistant tape. Further, the
resulting varnish was uniformly coated by using a bar coater, and
dried by heating at 100.degree. C. for 20 minutes and at
200.degree. C. for 20 minutes to obtain two sheets of the films
each having a thickness of about 0.030 mm from which m-cresol was
removed. One of the resulting films was cured by heating in a press
to obtain a cured resin composition. By using the above-mentioned
cured resin composition, a relative dielectric constant at 1 kHz,
dielectric loss factor (tan .delta.), breaking strain, and moisture
absorption amount when allowed to stand in a potassium iodide
saturated condition (humidity: about 70%) for 48 hours. By using
the above-mentioned cured resin composition and using a
thermobalance, Type TA-2950 (trade name, available from TA
Instrument Co.), a decomposition initiating (kick-off) temperature
was measured. The results are shown in Table 1 and Table 2.
[0071] Also, copper foils each having a thickness of 0.012 mm were
attached up and down of a sheet of a dried film and the laminate
was cured by heating to obtain a both surface copper-clad cured
resin composition. At this time, the state of sticking out from the
adhered surface of the film was evaluated with eyes and it was made
an index of fluidity at the time of heat curing of the film.
Further, a sample with a size of 25.times.25 (mm) was cut out from
the both surface copper-clad cured resin composition and allowed to
stand in a solder bath at 330.degree. C. for 10 minutes, and the
presence or absence of blister was confirmed. Moreover, peel
strength (adhesive force) of the copper and the cured resin
composition was confirmed. Curing conditions and measurement
conditions, etc. are shown in Table 1 and Table 2.
Example 7
[0072] By using 100 g of the varnish obtained in Example 5, 6 g of
epoxy-modified polybutadiene modified by diglycidyl ether bisphenol
A and 0.42 g of 4,4-diaminodiphenylmethane were added to the
varnish and uniformly dissolved to obtain a varnish.
[0073] Next, a polyimide film (UPILEX 25S, trade name, available
from UBE INDUSTRIES, LTD.) having a thickness of 0.025 mm was
adhered to Pyrex glass plate with a size of 200 mm.times.200
mm.times.2 mm by using a heat-resistant tape. Further, the
resulting varnish was uniformly coated by using a bar coater, and
dried by heating at 100.degree. C. for 20 minutes and at
200.degree. C. for 20 minutes to obtain two sheets of the films
each having a thickness of about 0.030 mm from which m-cresol was
removed. One of the resulting films was cured by heating in a press
to obtain a cured resin composition. By using the above-mentioned
cured resin composition, a relative dielectric constant at 1 kHz,
dielectric loss factor (tan .delta.), breaking strain, and moisture
absorption amount when allowed to stand in a potassium iodide
saturated condition (humidity: about 70%) for 48 hours. By using
the above-mentioned cured resin composition and using a
thermobalance, Type TA-2950 (trade name, available from TA
Instrument Co.), a decomposition initiating (kick-off) temperature
was measured. The results are shown in Table 1 and Table 2.
[0074] Also, copper foils each having a thickness of 0.012 mm were
attached up and down of a sheet of a dried film and the laminate
was cured by heating to obtain a both surface copper-clad cured
resin composition. At this time, the state of sticking out from the
adhered surface of the film was evaluated with eyes and it was made
an index of fluidity at the time of heat curing of the film.
Further, a sample with a size of 25 mm.times.25 mm was cut out from
the both surface copper-clad cured resin composition and allowed to
stand in a solder bath at 330.degree. C. for 10 minutes, and the
presence or absence of blister was confirmed. Moreover, peel
strength (adhesive force) of the copper and the cured resin
composition was confirmed. Curing conditions and measurement
conditions, etc. are shown in Table 1 and Table 2.
Example 8
[0075] 15 g of the varnish obtained in Example 5 was charged in a
200 ml-volume three-necked flask equipped with a stirring rod, a
cooling tube and a thermometer, and 70 g of cyclopentanone was
added thereto and the mixture was dissolved by stirring at room
temperature for one hour. Next, 15 g of
2,2-bis(4-(4-maleimidophenoxy)phenyl)propane was added to the
mixture and the resulting mixture was stirred for one hour to
obtain the desired varnish.
[0076] Next, apolyimide film (UPILEX25S, trade name, available from
UBE INDUSTRIES, LTD.) having a thickness of 0.025 mm was adhered to
Pyrex glass plate with a size of 200 mm.times.200 mm.times.2 mm by
using a heat-resistant tape. Further, the resulting varnish was
uniformly coated by using a bar coater, and dried by heating at
100.degree. C. for 20 minutes and at 200.degree. C. for 20 minutes
to obtain two sheets of the films each having a thickness of about
0.030 mm from which m-cresol was removed. One of the resulting
films was cured by heating in a press to obtain a cured resin
composition. By using the above-mentioned cured resin composition,
a relative dielectric constant at 1 kHz, dielectric loss factor
(tan .delta.), breaking strain, and moisture absorption amount when
allowed to stand in a potassium iodide saturated condition
(humidity: about 70%) for 48 hours. By using the above-mentioned
cured resin composition and using a thermobalance, Type TA-2950
(trade name, available from TA Instrument Co.), a decomposition
initiating (kick-off) temperature was measured. The results are
shown in Table 1 and Table 2.
[0077] Also, copper foils each having a thickness of 0.012 mm were
attached up and down of a sheet of a dried film and the laminate
was cured by heating to obtain a both surface copper-clad cured
resin composition. At this time, the state of sticking out from the
adhered surface of the film was evaluated with eyes and it was made
an index of fluidity at the time of heat curing of the film.
Further, a sample with a size of 25 mm.times.25 mm was cut out from
the both surface copper-clad cured resin composition and allowed to
stand in a solder bath at 330.degree. C. for 10 minutes, and the
presence or absence of blister was confirmed. Moreover, peel
strength (adhesive force) of the copper and the cured resin
composition was confirmed. Curing conditions and measurement
conditions, etc. are shown in Table 1 and Table 2.
Example 9
[0078] To a one-liter stainless flask were added 74.3 g (0.124
mole, 1.03 equivalents) of
6,6'-bis(2-(4-fluorophenyl)-4-phenylquinoline), 27.6 g (0.121 mole,
1.00 equivalent) of methyl-2,4-dihydroxybenzoate, isopropylidene
diphenol and 25 g (0.181 mole, 1.5 equivalents) of anhydrous
potassium carbonate, and 450 ml of N-methyl-2-pyrrolidone and 90 ml
of toluene were added as solvents. To the flask were provided a
water-cooling system cooling tube to which a calcium chloride tube
and a Dean-Stark tube for removing water had been attached, a dry
nitrogen inlet tube, a mechanical stirrer and a thermometer. By
using an oil bath, the mixture was refluxed under heating for 24
hours, and water in the system was removed by azeotropic
distillation with toluene for 24 hours. The solution was firstly
yellowish, then gradually changed to dark brown and became black at
this stage. The reaction temperature was further raised up to
200.degree. C. and the mixture was reacted for 6 hours. The
reaction solution changed from black to deep blue accompanying with
increase in viscosity. By adding 650 ml of N-methyl-2-pyrrolidone
to the mixture to dilute and cool the same, the reaction was
stopped. To purify the resulting polymer solution, the resulting
solution was thrown into water to form a precipitate. Further, the
precipitate was stirred in water at 50.degree. C. for 2 hours to
purify the same, and the procedure was repeated three times.
Thereafter, the polymer was collected by filtration and dried a day
and night by a vacuum drier at 60.degree. C. The yield of the
polymer was 84.0 g (87%).
[0079] 15 g of the resulting varnish was charged in a 200 ml-volume
three-necked flask equipped with a stirring rod, a cooling tube and
a thermometer, and 70 g of cyclopentanone was further added thereto
and the mixture was dissolved by stirring at room temperature for
one hour. Next, 15 g of
2,2-bis(4-(4-maleimidophenoxy)phenyl)-1,1,1,3,3,3-hexafluoropropa-
ne was added to the mixture and the resulting mixture was stirred
for one hour to obtain the desired varnish.
[0080] Next, apolyimide film (UPILEX25S, trade name, available from
UBE INDUSTRIES, LTD.) having a thickness of 0.025 mm was adhered to
Pyrex glass plate with a size of 200 mm x 200 mm.times.2 mm by
using a heat-resistant tape. The resulting varnish was uniformly
coated by using a bar coater, and dried by heating at 100.degree.
C. for 20 minutes and at 200.degree. C. for 20 minutes to obtain
two sheets of the films each having a thickness of about 0.030 mm
from which cyclopentanone was removed. One of the resulting films
was cured by heating in a press to obtain a cured resin
composition. By using the above-mentioned cured resin composition,
a relative dielectric constant at 1 kHz, dielectric loss factor
(tan .delta.8), breaking strain, and moisture absorption amount
when allowed to stand in a potassium iodide saturated condition
(humidity: about 70%) for 48 hours. By using the above-mentioned
cured resin composition and using a thermobalance, Type TA-2950
(trade name, available from TA Instrument Co.), a decomposition
initiating (kick-off) temperature was measured. The results are
shown in Table 1 and Table 2.
[0081] Also, copper foils each having a thickness of 0.012 mm were
attached up and down of a sheet of a dried film and the laminate
was cured by heating to obtain a both surface copper-clad cured
resin composition. At this time, the state of sticking out from the
adhered surface of the film was evaluated with eyes and it was made
an index of fluidity at the time of heat curing of the film.
Further, a sample with a size of 25 mm.times.25 mm was cut out from
the both surface copper-clad cured resin composition and allowed to
stand in a solder bath at 330.degree. C. for 10 minutes, and the
presence or absence of blister was confirmed. Moreover, peel
strength (adhesive force) of the copper and the cured resin
composition was confirmed. Curing conditions and measurement
conditions, etc. are shown in Table 1 and Table 2.
Example 10
[0082] To a one-liter stainless flask were provided a water-cooling
system cooling tube to which a calcium chloride tube and a
Dean-Stark tube for removing water had been attached, a dry
nitrogen inlet tube, a mechanical stirrer and a thermometer, and
400 ml of m-cresol as a solvent and 340 g of phosphorus pentoxide
as a catalyst were charged therein and the mixture was heated to
140.degree. C. under nitrogen stream while stirring and reacted for
3 hours to prepare a polymerization solvent. After cooling to room
temperature, 95.71 g (0.4 mole) of 5-acetyl-2-aminobenzophenone
recrystallized from ethanol was added to the solvent, and the
mixture was heated to 120.degree. C. under nitrogen stream while
stirring and the reaction was carried out for 48 hours. After
completion of the reaction, the reaction solvent was poured into a
large amount of a 10%-triethylamine ethanol solution to stop the
reaction whereby the polymer was isolated. The polymer was washed
with ethanol, and ethanol was removed by a Soxhlet's extractor and
dried at 100.degree. C. The yield of the polymer was 93.7 g
(98%).
[0083] 15 g of the resulting varnish was charged in a 200 ml-volume
three-necked flask equipped with a stirring rod, a cooling tube and
a thermometer, and 100 g of chloroform was further added thereto
and the mixture was dissolved by stirring at room temperature for
one hour. Next, 15 g of 2,2-bis-((4-maleimidophenoxy)phenyl)propane
was added to the mixture and the resulting mixture was stirred for
one hour to obtain the desired varnish. Changes with a lapse of
time of the resulting varnish when it was stored at room
temperature (20.degree. C. to 23.degree. C.) were measured by using
an E-type viscometer VISCONIC type (trade name, available from
Tokyo Seimitsu Co.). The results are shown in FIG. 1.
[0084] Next, apolyimide film (UPILEX-25S, tradename, available from
UBE INDUSTRIES, LTD.) having a thickness of 0.025 mm was adhered to
Pyrex glass plate with a size of 200 mm.times.200 mm.times.2 mm by
using a heat-resistant tape. Further, the resulting varnish was
uniformly coated by using a bar coater, and dried by heating at
100.degree. C. for 20 minutes and at 200.degree. C. for 20 minutes
to obtain two sheets of the films each having a thickness of about
0.030 mm from which chloroform was removed. One of the resulting
films was cured by heating in a press to obtain a cured resin
composition. By using the above-mentioned cured resin composition,
a relative dielectric constant at 1 kHz, dielectric loss factor
(tan .delta.), breaking strain, and moisture absorption amount when
allowed to stand in a potassium iodide saturated condition
(humidity: about 70%) for 48 hours. By using the above-mentioned
cured resin composition and using a thermobalance, Type TA-2950
(trade name, available from TA Instrument Co.), a decomposition
initiating (kick-off) temperature was measured. The results are
shown in Table 1 and Table 2.
[0085] Also, copper foils each having a thickness of 0.012 mm were
attached up and down of a sheet of a dried film and the laminate
was cured by heating to obtain a both surface copper-clad cured
resin composition. At this time, the state of sticking out from the
adhered surface of the film was evaluated with eyes and it was made
an index of fluidity at the time of heat curing of the film.
Further, a sample with a size of 25 mm.times.25 mm was cut out from
the both surface copper-clad cured resin composition and allowed to
stand in a solder bath at 330.degree. C. for 10 minutes, and the
presence or absence of blister was confirmed. Moreover, peel
strength (adhesive force) of the copper and the cured resin
composition was confirmed. Curing conditions and measurement
conditions, etc. are shown in Table 1 and Table 2.
Example 11
[0086] To a one-liter stainless flask were provided a water-cooling
system cooling tube to which a calcium chloride tube and a
Dean-Stark tube for removing water had been attached, a dry
nitrogen inlet tube, a mechanical stirrer and a thermometer, and
400 ml of m-cresol as a solvent and 340 g of phosphorus pentoxide
as a catalyst were charged therein and the mixture was heated to
140.degree. C. under nitrogen stream while stirring and reacted for
3 hours to prepare a polymerization solvent. After cooling to room
temperature, 95.71 g (0.4 mole) of 5-acetyl-2-aminobenzophenone
recrystallized from ethanol was added to the solvent, and the
mixture was heated to 120.degree. C. under nitrogen stream while
stirring and the reaction was carried out for 48 hours. After
completion of the reaction, the reaction solvent was poured into a
large amount of a triethylamine 10% ethanol solution to stop the
reaction whereby the polymer was isolated. The polymer was washed
with ethanol, and ethanol was removed by a Soxhlet's extractor and
dried at 100.degree. C. The yield of the polymer was 93.7 g
(98%).
[0087] 15 g of the resulting varnish was charged in a 200 ml-volume
three-necked flask equipped with a stirring rod, a cooling tube and
a thermometer, and 100 g of chloroform was further added thereto
and the mixture was dissolved by stirring at room temperature for
one hour. Next, 15 g of
2,2-bis(4-(4-maleimidophenoxy)phenyl)-1,1,1,3,3,3-hexafluoropropa-
ne was added to the mixture and the resulting mixture was stirred
for one hour to obtain the desired varnish.
[0088] Next, a polyimide film (UPILEX-25S, trade name, available
from UBE INDUSTRIES, LTD.) having a thickness of 0.025 mm was
adhered to Pyrex glass plate with a size of 200 mm.times.200
mm.times.2 mm by using a heat-resistant tape. Further, the
resulting varnish was uniformly coated by using a bar coater, and
dried by heating at 100.degree. C. for 20 minutes and at
200.degree. C. for 20 minutes to obtain two sheets of the films
each having a thickness of about 0.030 mm from which chloroform was
removed. One of the resulting films was cured by heating in a press
to obtain a cured resin composition. By using the above-mentioned
cured resin composition, a relative dielectric constant at 1 kHz,
dielectric loss factor (tan .delta.), breaking strain, and moisture
absorption amount when allowed to stand in a potassium iodide
saturated condition (humidity: about 70%) for 48 hours. By using
the above-mentioned cured resin composition and using a
thermobalance, Type TA-2950 (trade name, available from TA
Instrument Co.), a decomposition initiating (kick-off) temperature
was measured. The results are shown in Table 1 and Table 2.
[0089] Also, copper foils each having a thickness of 0.012 mm were
attached up and down of a sheet of a dried film and the laminate
was cured by heating to obtain a both surface copper-clad cured
resin composition. At this time, the state of sticking out from the
adhered surface of the film was evaluated with eyes and it was made
an index of fluidity at the time of heat curing of the film.
Further, a sample with a size of 25 mm.times.25 mm was cut out from
the both surface copper-clad cured resin composition and allowed to
stand in a solder bath at 330.degree. C. for 10 minutes, and the
presence or absence of blister was confirmed. Moreover, peel
strength (adhesive force) of the copper and the cured resin
composition was confirmed. Curing conditions and measurement
conditions, etc. are shown in Table 1 and Table 2.
Example 12
[0090] 18 g of the varnish obtained in Example 1 was charged in a
200 ml-volume three-necked flask equipped with a stirring rod, a
cooling tube and a thermometer, and 70 g of cyclopentanone was
added thereto and the mixture was dissolved by stirring at room
temperature for one hour. Next, 12 g of
2,2-bis(4-(2-trifluoromethyl-4-maleimidophenoxy)phenyl)-1,1,1,3,3-
,3-hexafluoropropane was added to the mixture and the resulting
mixture was stirred for one hour to obtain the desired varnish.
Changes with a lapse of time of the resulting varnish when it was
stored at room temperature (20.degree. C. to 23.degree. C.) were
measured by using an E-type viscometer VISCONIC type (trade name,
available from Tokyo Seimitsu Co.). The results are shown in FIG.
1.
[0091] Next, apolyimide film (UPILEX25S, trade name, available from
UBE INDUSTRIES, LTD.) having a thickness of 0.025 mm was adhered to
Pyrex glass plate with a size of 200 mm.times.200 mm.times.2 mm by
using a heat-resistant tape. Further, the resulting varnish was
uniformly coated by using a bar coater, and dried by heating at
100.degree. C. for 20 minutes and at 200.degree. C. for 20 minutes
to obtain two sheets of the films each having a thickness of about
0.030 mm from which chloroform was removed. One of the resulting
films was cured by heating in a press to obtain a cured resin
composition. By using the above-mentioned cured resin composition,
a relative dielectric constant at 1 kHz, dielectric loss factor
(tan .delta.5), breaking strain, and moisture absorption amount
when allowed to stand in a potassium iodide saturated condition
(humidity: about 70%) for 48 hours. By using the above-mentioned
cured resin composition and using a thermobalance, Type TA-2950
(trade name, available from TA Instrument Co.), a decomposition
initiating (kick-off) temperature was measured. The results are
shown in Table 1 and Table 2.
[0092] Also, copper foils each having a thickness of 0.012 mm were
attached up and down of a sheet of a dried film and the laminate
was cured by heating to obtain a both surface copper-clad cured
resin composition. At this time, the state of sticking out from the
adhered surface of the film was evaluated with eyes and it was made
an index of fluidity at the time of heat curing of the film.
Further, a sample with a size of 25 mm.times.25 mm was cut out from
the both surface copper-clad cured resin composition and allowed to
stand in a solder bath at 330.degree. C. for 10 minutes, and the
presence or absence of blister was confirmed. Moreover, peel
strength (adhesive force) of the copper and the cured resin
composition was confirmed. Curing conditions and measurement
conditions, etc. are shown in Table 1 and Table 2.
Comparative Example 1
[0093] After setting a stirring rod, a cooling tube and a
thermometer to a one-liter three-necked flask with a stirrer, 41.0
g of 2,2-bis((4-diaminophenoxy)phenyl)propane was charged therein
and dissolved by adding 415 ml of N-methyl-2-pyrrolidone. Next,
while cooling with ice water, 3,3,4,4-benzophenonetetracarboxylic
acid dianhydride was dissolved with a small amount and reacted for
4 hours to obtain a polyamic acid varnish. Further, after setting a
stirring rod, a cooling tube and a thermometer to a 200 ml-volume
three-necked flask, 100 g of the resulting varnish was charged
therein, 10 g of bis(4-maleimidophenyl)methane was added thereto
and the resulting mixture was stirred for 30 minutes to obtain the
desired varnish. Changes with a lapse of time of the resulting
varnish when it was stored at room temperature (20.degree. C. to
23.degree. C.) were measured by using an E-type viscometer VISCONIC
type (trade name, available from Tokyo Seimitsu Co.). The results
are shown in FIG. 1.
[0094] Next, apolyimide film (UPILEX25S, trade name, available from
UBE INDUSTRIES, LTD.) having a thickness of 0.025 mm was adhered to
Pyrex glass plate with a size of 200 mm.times.200 mm.times.2 mm by
using a heat-resistant tape. Further, the resulting varnish was
uniformly coated by using a bar coater, and dried by heating at
100.degree. C. for 20 minutes and at 200.degree. C. for 20 minutes
to obtain two sheets of the films each having a thickness of about
0.030 mm from which N-methyl-2-pyrrolidone was removed. One of the
resulting films was cured by heating in a press to obtain a cured
resin composition. By using the above-mentioned cured resin
composition, a relative dielectric constant at 1 kHz, dielectric
loss factor (tan .delta.), breaking strain, and moisture absorption
amount when allowed to stand in a potassium iodide saturated
condition (humidity: about 70%) for 48 hours. By using the
above-mentioned cured resin composition and using a thermobalance,
Type TA-2950 (trade name, available from TA Instrument Co.), a
decomposition initiating (kick-off) temperature was measured. The
results are shown in Table 1 and Table 2.
[0095] Also, copper foils each having a thickness of 0.012 mm were
attached up and down of a sheet of a dried film and the laminate
was cured by heating to obtain a both surface copper-clad cured
resin composition. At this time, the state of sticking out from the
adhered surface of the film was evaluated with eyes and it was made
an index of fluidity at the time of heat curing of the film.
Further, a sample with a size of 25 mm.times.25 mm was cut out from
the both surface copper-clad cured resin composition and allowed to
stand in a solder bath at 330.degree. C. for 10 minutes, and the
presence or absence of blister was confirmed. Moreover, peel
strength (adhesive force) of the copper and the cured resin
composition was confirmed. Curing conditions and measurement
conditions, etc. are shown in Table 1 and Table 2.
(Comparative example 2
[0096] After setting a stirring rod, a cooling tube and a
thermometer to a 200 ml-volume three-necked flask, 15 g of the
varnish obtained in Example 5 and 80 g of m-cresol were charged
therein and the mixture was dissolved by stirring at room
temperature for one hour to obtain the desired varnish. Changes
with a lapse of time of the resulting varnish when it was stored at
room temperature (20.degree. C. to 23.degree. C.) were measured by
using an E-type viscometer VISCONIC type (trade name, available
from Tokyo Seimitsu Co.). The results are shown in FIG. 2.
[0097] Next, a polyimide film (UPILEX 25S, trade name, available
from UBE INDUSTRIES, LTD.) having a thickness of 0.025 mm was
adhered to Pyrex glass plate with a size of 200 mm.times.200
mm.times.2 (mm) by using a heat-resistant tape. Further, the
resulting varnish was uniformly coated by using a bar coater, and
dried by heating at 100.degree. C. for 20 minutes and at
200.degree. C. for 20 minutes to obtain three sheets of the films
each having a thickness of about 0.030 mm from which m-cresol was
removed. By using the above-mentioned film, storage elastic modulus
was measured with a tensile mode by using a viscoelastic
measurement device Type DVA-200 (tradename, available from IT
Keisoku Seigyo Co.). The result is shown in FIG. 2.
[0098] Next, one of the resulting films was cured by heating in a
press to obtain a cured resin composition. By using the
above-mentioned cured resin composition, a relative dielectric
constant at 1 kHz, dielectric loss factor (tan .delta.), breaking
strain, and moisture absorption amount when allowed to stand in a
potassium iodide saturated condition (humidity: about 70%) for 48
hours. By using the above-mentioned cured resin composition and
using a thermobalance, Type TA-2950 (trade name, available from TA
Instrument Co.), a decomposition initiating (kick-off) temperature
was measured. The results are shown in Table 1 and Table 2.
[0099] Also, copper foils each having a thickness of 0.012 mm were
attached up and down of a sheet of a dried film and the laminate
was cured by heating to obtain a both surface copper-clad cured
resin composition. At this time, the state of sticking out from the
adhered surface of the film was evaluated with eyes and it was made
an index of fluidity at the time of heat curing of the film.
Further, a sample with a size of 25.times.25 (mm) was cut out from
the both surface copper-clad cured resin composition and allowed to
stand in a solder bath at 330.degree. C. for 10 minutes, and the
presence or absence of blister was confirmed. Moreover, peel
strength (adhesive force) of the copper and the cured resin
composition was confirmed. Curing conditions and measurement
conditions, etc. are shown in Table 1 and Table 2.
1TABLE 1 Dielec- relative tric loss Tensile Breaking Measure-
dielec- factor strength strain ment con- tric Room Room temperature
ditions Curing contstant temper- Rate: 5 mm/min Unit conditions 1
kHz ature kg/mm.sup.2 % Example 1 270.degree. C./90 min 2.8 0.0012
12 8 Example 2 250.degree. C./90 min 2.8 0.0013 11 7 Example 3
230.degree. C./60 min 2.9 0.0023 12 13 Example 4 270.degree. C./90
min 2.6 0.0010 10 9 Example 5 270.degree. C./90 min 3.0 0.0014 12 9
Example 6 250.degree. C./60 min 3.0 0.0013 13 11 Example 7
250.degree. C./60 min 3.0 0.0023 11 14 Example 8 270.degree. C./90
min 2.8 0.0013 10 10 Example 9 270.degree. C./90 min 2.9 0.0015 11
9 Example 10 270.degree. C./90 min 2.8 0.0012 12 10 Example 11
250.degree. C./90 min 2.9 0.0014 10 9 Example 12 300.degree. C./60
min 2.8 0.0012 12 8 Comparative 250.degree. C./90 min 3.5 0.0017 11
6 example 1 Comparative 270.degree. C./90 min 2.6 0.0012 12 13
example 2
[0100]
2TABLE 2 Thermal decomposition temperature Adhesion Temperature
Solder heat strength raising: resistance Adhesive Flow- 5.degree.
C./min: Presence or force with ability 100 ml/min absence of copper
at Flow- Measured 3% amount blister of the room temp- ability at
conditions decreased value value at 330.degree. C. erature curing
by Unit .degree. C. after 10 min kgf/cm heating*1 Example 1 480
None 1.2 .largecircle. Example 2 486 None 1.1 .largecircle. Example
3 385 None 1.6 .largecircle. Example 4 472 None 1.2 .largecircle.
Example 5 488 None 1.2 .largecircle. Example 6 482 None 1.1
.largecircle. Example 7 380 None 1.5 .largecircle. Example 8 475
None 1.2 .largecircle. Example 9 442 None 1.1 .largecircle. Example
10 434 None 1.2 .largecircle. Example 11 429 None 1.3 .largecircle.
Example 12 486 None 1.3 .circleincircle. Comparative 469 Present
0.9 .DELTA. example 1 Comparative 488 None 0.3 X example 2 *1
.circleincircle.: Flowability is extremely good .largecircle.:
Flowability is good .DELTA.: Flowability is bad X: Flowability is
significantly bad
Example 13
Synthesis of polyquinoline
[0101] To a one-liter stainless flask were added 74.3 g (0.124
mole, 1.03 equivalents) of
6,6'-bis(2-(4-fluorophenyl)-4-phenylquinoline), 40.6 g (0.121 mole,
1.00 equivalent) of 4,4'-(1,1,1,3,3,3-hexafluoro-2,2-propyli-
den)bisphenol and 25 g (0.181 mole, 1.5 equivalents) of anhydrous
potassium carbonate, and 450 ml of N-methyl-2-pyrrolidone and 90 ml
of toluene were added as solvents. To the flask were provided a
water-cooling system cooling tube to which a calcium chloride tube
and a Dean-Stark tube for removing water had been attached, a dry
nitrogen inlet tube, a mechanical stirrer and a thermometer. By
using an oil bath, the mixture was refluxed under heating for 24
hours, and water in the system was removed by azeotropic
distillation with toluene for 24 hours. The solution was firstly
yellowish, then gradually changed to dark brown and became black at
this stage. The reaction temperature was further raised up to
200.degree. C. and the mixture was reacted for 6 hours. The
reaction solution changed from black to deep blue accompanying with
increase in viscosity. By adding 650 ml of N-methyl-2-pyrrolidone
to the mixture to dilute and cool the same, the reaction was
stopped. To purify the resulting polymer solution, the resulting
solution was thrown into water to form a precipitate. Further, the
precipitate was stirred in water at 50.degree. C. for 2 hours to
purify the same, and the procedure was repeated three times.
Thereafter, the polymer was collected by filtration and dried a day
and night by a vacuum drier at 60.degree. C. The yield of the
polymer: 101.1 g (89.0%).
[0102] Next, after setting a stirring rod, a cooling tube and a
thermometer to a 500 ml-volume three-necked flask, 108 g of the
above-mentioned polymer and 280 g of cyclopentanone were charged
therein, and the materials were dissolved by stirring at room
temperature for one hour. Moreover, 12 g of
2,2-bis((4-maleimidophenoxy)phenyl)propane was added to the mixture
and the resulting mixture was stirred for one hour to obtain the
desired varnish. A polyimide film (UBILEX-25S, trade name,
available from UBE INDUSTRIES, LTD.) having a thickness of 0.025 mm
was adhered to Pyrex glass plate with a size of 200 mm.times.200
mm.times.2 mm by using a heat-resistant tape. The resulting varnish
was uniformly coated by using a bar coater, and dried by heating at
100.degree. C. for 20 minutes and at 200.degree. C. for 20 minutes
to obtain two sheets of the films each having a thickness of about
0.030 mm from which cyclopentanone was removed. One of the
resulting films was cured by heating in a press to obtain a cured
resin composition. By using the above-mentioned cured resin
composition, a relative dielectric constant at 1 kHz, dielectric
loss factor (tan .delta.), and moisture absorption amount when
allowed to stand in a potassium iodide saturated condition
(humidity: about 70%) for 48 hours. By using the above-mentioned
cured resin composition and using a thermobalance, Type TA-2950
(trade name, available from TA Instrument Co.), a decomposition
initiating (kick-off) temperature was measured.
[0103] Also, copper foils each having a thickness of 0.012 mm were
attached up and down of a sheet of a dried film and the laminate
was cured by heating to obtain a both surface copper-clad cured
resin composition. At this time, the state of sticking out from the
adhered surface of the film was evaluated with eyes and it was made
an index of fluidity at the time of heat curing of the film.
Further, a sample with a size of 25.times.25 (mm) was cut out from
the both surface copper-clad cured resin composition and allowed to
stand in a solder bath at 330.degree. C. for 10 minutes, and the
presence or absence of blister was confirmed. Moreover, peel
strength (adhesive force) of the copper and the cured resin
composition was confirmed. Curing conditions and measurement
conditions, etc. are shown in Table 3.
Example 14
[0104] By using 50 g of the varnish obtained in Example 13, 0.01 g
of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3 (perhexyne 2,5B,
trade name, available from Nippon Oil & Fats Co.) was added to
the varnish and uniformly dissolved. A polyimide film (UPILEX 25S,
trade name, available from UBE INDUSTRIES, LTD.) having a thickness
of 0.025 mm was adhered to Pyrex glass plate with a size of 200
mm.times.200 mm.times.2 mm by using a heat-resistant tape. Further,
the resulting varnish was uniformly coated by using a bar coater,
and dried by heating at 100.degree. C. for 20 minutes and at
200.degree. C. for 20 minutes to obtain two sheets of the films
each having a thickness of about 0.030 mm from which cyclopentanone
was removed. One of the resulting films was cured by heating in a
press to obtain a cured resin composition. By using the
above-mentioned cured resin composition, a relative dielectric
constant at 1 kHz, dielectric loss factor (tan .delta.), and
moisture absorption amount when allowed to stand in a potassium
iodide saturated condition (humidity: about 70%) for 48 hours. By
using the above-mentioned cured resin composition and using a
thermobalance, Type TA-2950 (trade name, available from TA
Instrument Co.), a decomposition initiating (kick-off) temperature
was measured.
[0105] Also, copper foils each having a thickness of 0.012 mm were
attached up and down of a sheet of a dried film and the laminate
was cured by heating to obtain a both surface copper-clad cured
resin composition. At this time, the state of sticking out from the
adhered surface of the film was evaluated with eyes and it was made
an index of fluidity at the time of heat curing of the film.
Further, a sample with a size of 25.times.25 (mm) was cut out from
the both surface copper-clad cured resin composition and allowed to
stand in a solder bath at 330.degree. C. for 10 minutes, and the
presence or absence of blister was confirmed. Moreover, peel
strength (adhesive force) of the copper and the cured resin
composition was confirmed. Curing conditions and measurement
conditions, etc. are shown in Table 3.
Example 15
[0106] By using 100 g of the varnish obtained in Example 13, 6 g of
epoxy-modified polybutadiene modified by diglycidyl ether bisphenol
A and 0.42 g of 4,4-diaminodiphenylmethane were added to the
varnish and uniformly dissolved. A polyimide film (UPILEX 25S,
trade name, available from UBE INDUSTRIES, LTD.) having a thickness
of 0.025 mm was adhered to Pyrex glass plate with a size of 200
mm.times.200 mm.times.2 mm by using a heat-resistant tape. Further,
the resulting varnish was uniformly coated by using a bar coater,
and dried by heating at 100.degree. C. for 20 minutes and at
200.degree. C. for 20 minutes to obtain two sheets of the films
each having a thickness of about 0.030 mm from which cyclopentanone
was removed. One of the resulting films was cured by heating in a
press to obtain a cured resin composition. By using the
above-mentioned cured resin composition, a relative dielectric
constant at 1 kHz, dielectric loss factor (tan .delta.), and
moisture absorption amount when allowed to stand in a potassium
iodide saturated condition (humidity: about 70%) for 48 hours. By
using the above-mentioned cured resin composition and using a
thermobalance, Type TA-2950 (trade name, available from TA
Instrument Co.), a decomposition initiating (kick-off) temperature
was measured.
[0107] Also, copper foils each having a thickness of 0.012 mm were
attached up and down of a sheet of a dried film and the laminate
was cured by heating to obtain a both surface copper-clad cured
resin composition. At this time, the state of sticking out from the
adhered surface of the film was evaluated with eyes and it was made
an index of fluidity at the time of heat curing of the film.
Further, a sample with a size of 25 mm.times.25 mm was cut out from
the both surface copper-clad cured resin composition and allowed to
stand in a solder bath at 330.degree. C. for 10 minutes, and the
presence or absence of blister was confirmed. Moreover, peel
strength (adhesive force) of the copper and the cured resin
composition was confirmed. Curing conditions and measurement
conditions, etc. are shown in Table 3.
Example 16
[0108] 45 g of the varnish obtained in Example 13 was charged in a
200 ml-volume three-necked flask equipped with a stirring rod, a
cooling tube and a thermometer, and 70 g of cyclopentanone was
added thereto and the mixture was dissolved by stirring at room
temperature for one hour. Next, 5 g of
2,2-bis(4-(2-trifluoromethyl-4-maleimidophenoxy)phenyl)-1,1,1,3,3,-
3-hexafluoropropane was added to the mixture and the resulting
mixture was stirred for one hour to obtain the desired varnish.
[0109] Next, a polyimide film (UPILEX 25S, trade name, available
from UBE INDUSTRIES, LTD.) having a thickness of 0.025 mm was
adhered to Pyrex glass plate with a size of 200 mm.times.200
mm.times.2 mm by using a heat-resistant tape. Further, the
resulting varnish was uniformly coated by using a bar coater, and
dried by heating at 100.degree. C. for 20 minutes and at
200.degree. C. for 20 minutes to obtain two sheets of the films
each having a thickness of about 0.030 mm from which cyclopentanone
was removed. One of the resulting films was cured by heating in a
press to obtain a cured resin composition. By using the
above-mentioned cured resin composition, a relative dielectric
constant at 1 kHz, dielectric loss factor (tan .delta.), and
moisture absorption amount when allowed to stand in a potassium
iodide saturated condition (humidity: about 70%) for 48 hours. By
using the above-mentioned cured resin composition and using a
thermobalance, Type TA-2950 (trade name, available from TA
Instrument Co.), a decomposition initiating (kick-off) temperature
was measured.
[0110] Also, copper foils each having a thickness of 0.012 mm were
attached up and down of a sheet of a dried film and the laminate
was cured by heating to obtain a both surface copper-clad cured
resin composition. At this time, the state of sticking out from the
adhered surface of the film was evaluated with eyes and it was made
an index of fluidity at the time of heat curing of the film.
Further, a sample with a size of 25 mm.times.25 mm was cut out from
the both surface copper-clad cured resin composition and allowed to
stand in a solder bath at 330.degree. C. for 10 minutes, and the
presence or absence of blister was confirmed. Moreover, peel
strength (adhesive force) of the copper and the cured resin
composition was confirmed. Curing conditions and measurement
conditions, etc. are shown in Table 3.
Example 17
[0111] In a two-liter round flask equipped with a mechanical
stirrer, a Dean-Stark tube having a condenser and a nitrogen inlet
tube, and a thermometer were charged 114.75 g (0.1925 mole, 1.03
equivalents) of 6,6-bis(2-(4-fluorophenyl)-4-phenylquinoline),
66.0472 g (0.18848 mole, 1.00 equivalent) of
9,9-bis(4-hydroxyphenyl)fluorene, 705 ml of N-methyl-2-pyrrolidone
and 421 ml of toluene. The reaction mixture was heated under
nitrogen atmosphere for 15 hours. Toluene was removed by the
Dean-Stark tube and the reaction mixture was further heated
at200.degree. C. for 12 hours. The reaction mixture was diluted by
N-methyl-2-pyrrolidone and cooled to room temperature. By gradually
pouring the resulting polymer solution to a 3-times volume of
acetone, the polymer material was condensed. The polymer material
was collected by filtration, dissolved in N-methyl-2-pyrrolidone
and diluted by a 3-times volume of water. The yield of the polymer
was 170 g (99%).
[0112] Next, after setting a stirring rod, a cooling tube and a
thermometer to a 500 ml-volume three-necked flask, 96 g of the
above-mentioned polymer and 280 g of cyclopentanone were charged
therein, and the materials were dissolved by stirring at room
temperature for one hour. Moreover, 24 g of
bis(4-maleimidophenyl)methane was added to the mixture and the
resulting mixture was stirred for one hour to obtain the desired
varnish.
[0113] Next, apolyimide film (UPILEX25S, trade name, available from
UBE INDUSTRIES, LTD.) having a thickness of 0.025 mm was adhered to
Pyrex glass plate with a size of 200 mm.times.200 mm.times.2 mm by
using a heat-resistant tape. The resulting varnish was uniformly
coated by using a bar coater, and dried by heating at 100.degree.
C. for 20 minutes and at 200.degree. C. for 20 minutes to obtain
three sheets of the films each having a thickness of about 0.030 mm
from which cyclopentanone was removed. By using the above-mentioned
film, storage elastic modulus was measured with a tensile mode by
using a viscoelastic measurement device Type DVA-200 (trade name,
available from IT Keisoku Seigyo Co.). The result is shown in FIG.
3. The storage elastic modulus of this film gradually lowers as the
temperature raises as shown in FIG. 3, but it maintains a high
value even when the temperature is raised over 300.degree. C.
[0114] Next, one of the resulting films was cured by heating in a
press to obtain a cured resin composition. By using the
above-mentioned cured resin composition, a relative dielectric
constant at 1 kHz, dielectric loss factor (tan .delta.), and
moisture absorption amount when allowed to stand in a potassium
iodide saturated condition (humidity: about 70%) for 48 hours. By
using the above-mentioned cured resin composition and using a
thermobalance, Type TA-2950 (trade name, available from TA
Instrument Co.), a decomposition initiating (kick-off) temperature
was measured.
[0115] Also, copper foils each having a thickness of 0.012 mm were
attached up and down of a sheet of a dried film and the laminate
was cured by heating to obtain a both surface copper-clad cured
resin composition. At this time, the state of sticking out from the
adhered surface of the film was evaluated with eyes and it was made
an index of fluidity at the time of heat curing of the film.
Further, a sample with a size of 25 mm.times.25 mm was cut out from
the both surface copper-clad cured resin composition and allowed to
stand in a solder bath at 330.degree. C. for 10 minutes, and the
presence or absence of blister was confirmed. Moreover, peel
strength (adhesive force) of the copper and the cured resin
composition was confirmed. Curing conditions and measurement
conditions, etc. are shown in Table 3.
Example 18
[0116] By using 50 g of the varnish obtained in Example 17, 0.01 g
of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3 (perhexyne 2,5B,
trade name, available from Nippon Oil & Fats Co.) was added to
the varnish and uniformly dissolved.
[0117] Next, a polyimide film (UPILEX 25S, trade name, available
from UBE INDUSTRIES, LTD.) having a thickness of 0.025 mm was
adhered to Pyrex glass plate with a size of 200.times.200.times.2
(mm) by using a heat-resistant tape. Further, the resulting varnish
was uniformly coated by using a bar coater, and dried by heating at
100.degree. C. for 20 minutes and at 200.degree. C. for 20 minutes
to obtain two sheets of the films each having a thickness of about
0.030 mm from which cyclopentanone was removed. One of the
resulting films was cured by heating in a press to obtain a cured
resin composition. By using the above-mentioned cured resin
composition, a relative dielectric constant at 1 kHz, dielectric
loss factor (tan .delta.), and moisture absorption amount when
allowed to stand in a potassium iodide saturated condition
(humidity: about 70%) for 48 hours. By using the above-mentioned
cured resin composition and using a thermobalance, Type TA-2950
(trade name, available from TA Instrument Co.), a decomposition
initiating (kick-off) temperature was measured.
[0118] Also, copper foils each having a thickness of 0.012 mm were
attached up and down of a sheet of a dried film and the laminate
was cured by heating to obtain a both surface copper-clad cured
resin composition. At this time, the state of sticking out from the
adhered surface of the film was evaluated with eyes and it was made
an index of fluidity at the time of heat curing of the film.
Further, a sample with a size of 25.times.25 (mm) was cut out from
the both surface copper-clad cured resin composition and allowed to
stand in a solder bath at 330.degree. C. for 10 minutes, and the
presence or absence of blister was confirmed. Moreover, peel
strength (adhesive force) of the copper and the cured resin
composition was confirmed. Curing conditions and measurement
conditions, etc. are shown in Table 3.
Example 19
[0119] By using 100 g of the varnish obtained in Example 17, 6 g of
epoxy-modified polybutadiene modified by diglycidyl ether bisphenol
A and 0.42 g of 4,4-diaminodiphenylmethane were added to the
varnish and uniformly dissolved to obtain a varnish.
[0120] Next, a polyimide film (UPILEX 25S, trade name, available
from UBE INDUSTRIES, LTD.) having a thickness of 0.025 mm was
adhered to Pyrex glass plate with a size of 200 mm.times.200
mm.times.2 mm by using a heat-resistant tape. Further, the
resulting varnish was uniformly coated by using a bar coater, and
dried by heating at 100.degree. C. for 20 minutes and at
200.degree. C. for 20 minutes to obtain two sheets of the films
each having a thickness of about 0.030 mm from which cyclopentanone
was removed. One of the resulting films was cured by heating in a
press to obtain a cured resin composition. By using the
above-mentioned cured resin composition, a relative dielectric
constant at 1 kHz, dielectric loss factor (tan .delta.), and
moisture absorption amount when allowed to stand in a potassium
iodide saturated condition (humidity: about 70%) for 48 hours. By
using the above-mentioned cured resin composition and using a
thermobalance, Type TA-2950 (trade name, available from TA
Instrument Co.), a decomposition initiating (kick-off) temperature
was measured.
[0121] Also, copper foils each having a thickness of 0.012 mm were
attached up and down of a sheet of a dried film and the laminate
was cured by heating to obtain a both surface copper-clad cured
resin composition. At this time, the state of sticking out from the
adhered surface of the film was evaluated with eyes and it was made
an index of fluidity at the time of heat curing of the film.
Further, a sample with a size of 25 mm.times.25 mm was cut out from
the both surface copper-clad cured resin composition and allowed to
stand in a solder bath at 330.degree. C. for 10 minutes, and the
presence or absence of blister was confirmed. Moreover, peel
strength (adhesive force) of the copper and the cured resin
composition was confirmed. Curing conditions and measurement
conditions, etc. are shown in Table 3.
Example 20
[0122] 24 g of the varnish obtained in Example 17 was charged in a
200 ml-volume three-necked flask equipped with a stirring rod, a
cooling tube and a thermometer, and 70 g of cyclopentanone was
added thereto and the mixture was dissolved by stirring at room
temperature for one hour. Next, 6 g of
2,2-bis(4-(4-maleimidophenoxy)phenyl)propane was added to the
mixture and the resulting mixture was stirred for one hour to
obtain the desired varnish.
[0123] Next, apolyimide film (UPILEX25S, tradename, available from
UBE INDUSTRIES, LTD.) having a thickness of 0.025 mm was adhered to
Pyrex glass plate with a size of 200 mm.times.200 mm.times.2 mm by
using a heat-resistant tape. Further, the resulting varnish was
uniformly coated by using a bar coater, and dried by heating at
100.degree. C. for 20 minutes and at 200.degree. C. for 20 minutes
to obtain two sheets of the films each having a thickness of about
0.030 mm from which cyclopentanone was removed. One of the
resulting films was cured by heating in a press to obtain a cured
resin composition. By using the above-mentioned cured resin
composition, a relative dielectric constant at 1 kHz, dielectric
loss factor (tan .delta.), and moisture absorption amount when
allowed to stand in a potassium iodide saturated condition
(humidity: about 70%) for 48 hours. By using the above-mentioned
cured resin composition and using a thermobalance, Type TA-2950
(trade name, available from TA Instrument Co.), a decomposition
initiating (kick-off) temperature was measured.
[0124] Also, copper foils each having a thickness of 0.012 mm were
attached up and down of a sheet of a dried film and the laminate
was cured by heating to obtain a both surface copper-clad cured
resin composition. At this time, the state of sticking out from the
adhered surface of the film was evaluated with eyes and it was made
an index of fluidity at the time of heat curing of the film.
Further, a sample with a size of 25 mm.times.25 mm was cut out from
the both surface copper-clad cured resin composition and allowed to
stand in a solder bath at 330.degree. C. for 10 minutes, and the
presence or absence of blister was confirmed. Moreover, peel
strength (adhesive force) of the copper and the cured resin
composition was confirmed. Curing conditions and measurement
conditions, etc. are shown in Table 3.
Example 21
[0125] To a one-liter stainless flask were added 74.3 g (0.124
mole, 1.03 equivalents) of
6,6'-bis(2-(4-fluorophenyl)-4-phenylquinoline), 27.6 g (0.121 mole,
1.00 equivalent) of methyl-2,4-dihydroxybenzoate, isopropylidene
diphenol and 25 g (0.181 mole, 1.5 equivalents) of anhydrous
potassium carbonate, and 450 ml of N-methyl-2-pyrrolidone and 90 ml
of toluene were added as solvents. To the flask were provided a
water-cooling system cooling tube to which a calcium chloride tube
and a Dean-Stark tube for removing water had been attached, a dry
nitrogen inlet tube, a mechanical stirrer and a thermometer. By
using an oil bath, the mixture was refluxed under heating for 24
hours, and water in the system was removed by azeotropic
distillation with toluene for 24 hours. The solution was firstly
yellowish, then gradually changed to dark brown and became black at
this stage. The reaction temperature was further raised up to
200.degree. C. and the mixture was reacted for 6 hours. The
reaction solution changed from black to deep blue accompanying with
increase in viscosity. By adding 650 ml of N-methyl-2-pyrrolidone
to the mixture to dilute and cool the same, the reaction was
stopped. To purify the resulting polymer solution, the resulting
solution was thrown into water to form a precipitate. Further, the
precipitate was stirred in water at 50.degree. C. for 2 hours to
purify the same, and the procedure was repeated three times.
Thereafter, the polymer was collected by filtration and dried a day
and night by a vacuum drier at 60.degree. C. The yield of the
polymer was 84.0 g (87%). 29.7 g of the resulting varnish was
charged in a 200 ml-volume three-necked flask equipped with a
stirring rod, a cooling tube and a thermometer, and 70 g of
cyclopentanone was further added thereto and the mixture was
dissolved by stirring at room temperature for one hour. Next, 0.3 g
of
2,2-bis-(4-(4-maleimidophenoxy)phenyl)-1,1,1,3,3,3-hexafluoro-propane
was added to the mixture and the resulting mixture was stirred for
one hour to obtain the desired varnish.
[0126] Next, a polyimide film (UPILEX25S, trade name, available
from UBE INDUSTRIES, LTD.) having a thickness of 0.025 mm was
adhered to Pyrex glass plate with a size of 200 mm.times.200
mm.times.2 mm by using a heat-resistant tape. The resulting varnish
was uniformly coated by using a bar coater, and dried by heating at
100.degree. C. for 20 minutes and at 200.degree. C. for 20 minutes
to obtain two sheets of the films each having a thickness of about
0.030 mm from which cyclopentanone was removed. One of the
resulting films was cured by heating in a press to obtain a cured
resin composition. By using the above-mentioned cured resin
composition, a relative dielectric constant at 1 kHz, dielectric
loss factor (tan .delta.), and moisture absorption amount when
allowed to stand in a potassium iodide saturated condition
(humidity: about 70%) for 48 hours. By using the above-mentioned
cured resin composition and using a thermobalance, Type TA-2950
(trade name, available from TA Instrument Co.), a decomposition
initiating (kick-off) temperature was measured.
[0127] Also, copper foils each having a thickness of 0.012 mm were
attached up and down of a sheet of a dried film and the laminate
was cured by heating to obtain a both surface copper-clad cured
resin composition. At this time, the state of sticking out from the
adhered surface of the film was evaluated with eyes and it was made
an index of fluidity at the time of heat curing of the film.
Further, a sample with a size of 25 mm.times.25 mm was cut out from
the both surface copper-clad cured resin composition and allowed to
stand in a solder bath at 330.degree. C. for 10 minutes, and the
presence or absence of blister was confirmed. Moreover, peel
strength (adhesive force) of the copper and the cured resin
composition was confirmed. Curing conditions and measurement
conditions, etc. are shown in Table 3.
Example 22
[0128] To a one-liter stainless flask were provided a water-cooling
system cooling tube to which a calcium chloride tube and a
Dean-Stark tube for removing water had been attached, a dry
nitrogen inlet tube, a mechanical stirrer and a thermometer, and
400 ml of m-cresol as a solvent and 340 g of phosphorus pentoxide
as a catalyst were charged therein and the mixture was heated to
140.degree. C. under nitrogen stream while stirring and reacted for
3 hours to prepare a polymerization solvent. After cooling to room
temperature, 95.71 g (0.4 mole) of 5-acetyl-2-aminobenzophenone
recrystallized from ethanol was added to the solvent, and the
mixture was heated to 120.degree. C. under nitrogen stream while
stirring and the reaction was carried out for 48 hours. After
completion of the reaction, the reaction solvent was poured into a
large amount of a 10%-triethylamine ethanol solution to stop the
reaction whereby the polymer was isolated. The polymer was washed
with ethanol, and ethanol was removed by a Soxhlet's extractor and
dried at 100.degree. C. The yield of the polymer was 93.7 g
(98%).
[0129] 24 g of the resulting varnish was charged in a 200 ml-volume
three-necked flask equipped with a stirring rod, a cooling tube and
a thermometer, and 100 g of chloroform was further added thereto
and the mixture was dissolved by stirring at room temperature for
one hour. Next, 6 g of 2,2-bis((4-maleimidophenoxy)phenyl)propane
was added to the mixture and the resulting mixture was stirred for
one hour to obtain the desired varnish.
[0130] Next, apolyimide film (UPILEX25S, trade name, available from
UBE INDUSTRIES, LTD.) having a thickness of 0.025 mm was adhered to
Pyrex glass plate with a size of 200 mm.times.200 mm.times.2 mm by
using a heat-resistant tape. Further, the resulting varnish was
uniformly coated by using a bar coater, and dried by heating at
100.degree. C. for 20 minutes and at 200.degree. C. for 20 minutes
to obtain two sheets of the films each having a thickness of about
0.030 mm from which cyclopentanone was removed. One of the
resulting films was cured by heating in a press to obtain a cured
resin composition. By using the above-mentioned cured resin
composition, a relative dielectric constant at 1 kHz, dielectric
loss factor (tan .delta.), and moisture absorption amount when
allowed to stand in a potassium iodide saturated condition
(humidity: about 70%) for 48 hours. By using the above-mentioned
cured resin composition and using a thermobalance, Type TA-2950
(trade name, available from TA Instrument Co.), a decomposition
initiating (kick-off) temperature was measured.
[0131] Also, copper foils each having a thickness of 0.012 mm were
attached up and down of a sheet of a dried film and the laminate
was cured by heating to obtain a both surface copper-clad cured
resin composition. At this time, the state of sticking out from the
adhered surface of the film was evaluated with eyes and it was made
an index of fluidity at the time of heat curing of the film.
Further, a sample with a size of 25 mm.times.25 mm was cut out from
the both surface copper-clad cured resin composition and allowed to
stand in a solder bath at 330.degree. C. for 10 minutes, and the
presence or absence of blister was confirmed. Moreover, peel
strength (adhesive force) of the copper and the cured resin
composition was confirmed. Curing conditions and measurement
conditions, etc. are shown in Table 3.
Example 23
[0132] 24 g of the varnish obtained in Example 22 was charged in a
200 ml-volume three-necked flask equipped with a stirring rod, a
cooling tube and a thermometer, and 100 g of chloroform was added
thereto and the mixture was dissolved by stirring at room
temperature for one hour. Next, 6 g of
2,2-bis(4-(4-maleimidophenoxy)phenyl)-1,1,1,3,3,3-hexafluoropropan-
e was added to the mixture and the resulting mixture was stirred
for one hour to obtain the desired varnish.
[0133] Next, a polyimide film (UPILEX 25S, trade name, available
from UBE INDUSTRIES, LTD.) having a thickness of 0.025 mm was
adhered to Pyrex glass plate with a size of 200 mm.times.200
mm.times.2 mm by using a heat-resistant tape. Further, the
resulting varnish was uniformly coated by using a bar coater, and
dried by heating at 100.degree. C. for 20 minutes and at
200.degree. C. for 20 minutes to obtain two sheets of the films
each having a thickness of about 0.030 mm from which chloroform was
removed. One of the resulting films was cured by heating in a press
to obtain a cured resin composition. By using the above-mentioned
cured resin composition, a relative dielectric constant at 1 kHz,
dielectric loss factor (tan .delta.), and moisture absorption
amount when allowed to stand in a potassium iodide saturated
condition (humidity: about 70%) for 48 hours. By using the
above-mentioned cured resin composition and using a thermobalance,
Type TA-2950 (trade name, available from TA Instrument Co.), a
decomposition initiating (kick-off) temperature was measured.
[0134] Also, copper foils each having a thickness of 0.012 mm were
attached up and down of a sheet of a dried film and the laminate
was cured by heating to obtain a both surface copper-clad cured
resin composition. At this time, the state of sticking out from the
adhered surface of the film was evaluated with eyes and it was made
an index of fluidity at the time of heat curing of the film.
Further, a sample with a size of 25 mm.times.25 mm was cut out from
the both surface copper-clad cured resin composition and allowed to
stand in a solder bath at 330.degree. C. for 10 minutes, and the
presence or absence of blister was confirmed. Moreover, peel
strength (adhesive force) of the copper and the cured resin
composition was confirmed. Curing conditions and measurement
conditions, etc. are shown in Table 3.
Comparative Example 3
[0135] After setting a stirring rod, a cooling tube and a
thermometer to a one-liter three-necked flask with a stirrer, 41.0
g of 2,2-bis((4-diaminophenoxy)phenyl)propane was charged therein
and dissolved by adding 415 ml of N-methyl-2-pyrrolidone. Next,
while cooling with ice water, 3,3,4,4-benzophenonetetracarboxylic
acid dianhydride was gradually dissolved with a small amount to
obtain a polyamic acid varnish. Further, after setting a stirring
rod, a cooling tube and a thermometer to a 200 ml-volume
three-necked flask, 100 g of the resulting varnish was charged
therein, 10 g of bis(4-maleimidophenyl)methane was added thereto
and the resulting mixture was stirred for 30 minutes to obtain a
varnish.
[0136] Next, a polyimide film (UPILEX 25S, trade name, available
from UBE INDUSTRIES, LTD.) having a thickness of 0.025 mm was
adhered to Pyrex glass plate with a size of 200 mm.times.200
mm.times.2 mm by using a heat-resistant tape. Further, the
resulting varnish was uniformly coated by using a bar coater, and
dried by heating at 100.degree. C. for 20 minutes and at
200.degree. C. for 20 minutes to obtain three sheets of the films
each having a thickness of about 0.030 mm from which
N-methyl-2-pyrrolidone was removed. By using the above-mentioned
film, storage elastic modulus was measured with a tensile mode by
using a viscoelastic measurement device Type DVA-200 (trade name,
available from IT Keisoku Seigyo Co.). Next, by using one of the
resulting films, it was cured by heating in a press to obtain a
cured resin composition. By using the above-mentioned cured resin
composition, a relative dielectric constant at 1 kHz, dielectric
loss factor (tan .delta.), and moisture absorption amount when
allowed to stand in a potassium iodide saturated condition
(humidity: about 70%) for 48 hours. By using the above-mentioned
cured resin composition and using a thermobalance, Type TA-2950
(trade name, available from TA Instrument Co.), a decomposition
initiating (kick-off) temperature was measured. The results are
shown in Table 1 and Table 2.
[0137] Also, copper foils each having a thickness of 0.012 mm were
attached up and down of a sheet of a dried film and the laminate
was cured by heating to obtain a both surface copper-clad cured
resin composition. At this time, the state of sticking out from the
adhered surface of the film was evaluated with eyes and it was made
an index of fluidity at the time of heat curing of the film.
Further, a sample with a size of 25 mm.times.25 mm was cut out from
the both surface copper-clad cured resin composition and allowed to
stand in a solder bath at 330.degree. C. for 10 minutes, and the
presence or absence of blister was confirmed. Moreover, peel
strength (adhesive force) of the copper and the cured resin
composition was confirmed. Curing conditions and measurement
conditions, etc. are shown in Table 3.
Comparative Example 4
[0138] After setting a stirring rod, a cooling tube and a
thermometer to a 200 ml-volume three-necked flask, 15 g of the
varnish obtained in Example 5 and 80 g of m-cresol were charged
therein and the mixture was dissolved by stirring at room
temperature for one hour.
[0139] Next, apolyimide film (UPILEX 25S, trade name, available
from UBE INDUSTRIES, LTD.) having a thickness of 0.025 mm was
adhered to Pyrex glass plate with a size of 200 mm.times.200
mm.times.2 (mm) by using a heat-resistant tape. Further, the
resulting varnish was uniformly coated by using a bar coater, and
dried by heating at 100.degree. C. for 20 minutes and at
200.degree. C. for 20 minutes to obtain three sheets of the films
each having a thickness of about 0.030 mm from which m-cresol was
removed. By using the above-mentioned film, storage elastic modulus
was measured with a tensile mode by using a viscoelastic
measurement device Type DVA-200 (trade name, available from IT
Keisoku Seigyo Co.). The storage elastic modulus of this film is,
as shown in FIG. 1, gradually lowered as the temperature becomes
high and showed an abrupt decrease at the neighbor of 300.degree.
C. Next, one of the resulting films was cured by heating in a press
to obtain a cured resin composition. By using the above-mentioned
cured resin composition, a relative dielectric constant at 1 kHz,
dielectric loss factor (tan .delta.), and moisture absorption
amount when allowed to stand in a potassium iodide saturated
condition (humidity: about 70%) for 48 hours. By using the
above-mentioned cured resin composition and using a thermobalance,
Type TA-2950 (trade name, available from TA Instrument Co.), a
decomposition initiating (kick-off) temperature was measured.
[0140] Also, copper foils each having a thickness of 0.012 mm were
attached up and down of a sheet of a dried film and the laminate
was cured by heating to obtain a both surface copper-clad cured
resin composition. At this time, the state of sticking out from the
adhered surface of the film was evaluated with eyes and it was made
an index of fluidity at the time of heat curing of the film.
Further, a sample with a size of 25.times.25 (mm) was cut out from
the both surface copper-clad cured resin composition and allowed to
stand in a solder bath at 330.degree. C. for 10 minutes, and the
presence or absence of blister was confirmed. Moreover, peel
strength (adhesive force) of the copper and the cured resin
composition was confirmed. Curing conditions and measurement
conditions, etc. are shown in Table 3.
3 TABLE 3 Moisture absorption tan .delta. ratio .epsilon. (%)
(.degree. C.) Td PS Blister Crack Example 13 2.8 0.0010 0.8 480 1.2
None None Example 14 2.8 0.0012 0.8 475 1.1 None None Example 15
3.0 0.0012 0.9 475 1.4 None None Example 16 2.8 0.0015 0.8 480 1.2
None None Example 17 2.8 0.0012 0.8 480 1.2 None None Example 18
2.8 0.0012 0.8 485 1.1 None None Example 19 3.0 0.0010 0.9 485 1.2
None None Example 20 2.8 0.0011 0.9 475 1.2 None None Example 21
3.0 0.0012 0.9 475 1.1 None None Example 22 3.1 0.0014 0.8 470 1.2
None None Example 23 3.2 0.0015 0.9 480 1.4 None None Comparative
3.5 0.0017 2.0 470 0.9 Present Present example 3 Comparative 2.6
0.0012 0.5 490 0.3 None Present example 4 .epsilon.: relative
dielectric constant (1 kHz) tan .delta.: dielectric loss factor (1
kHz) Td: 5% weight loss temperature PS: Peeling strength
(kgf/cm)
Utilizability in Industry
[0141] According to the present invention, a resin composition
excellent in electric characteristics, low moisture absorption
property, thermal stability at high temperature, and moldability,
and having high adhesive force, and an adhesive film can be
obtained.
* * * * *