Aromatic polycarbodiimide and film thereof

A polycarbodiimide having excellent heat resistance and humidity resistance, which comprises a structural unit represented by the following formula (A) ##STR1## wherein R represents a divalent organic group represented by any one of the following formulae (I) and (II), n is an integer of 2 to 400 ##STR2## wherein X.sub.1 to X.sub.4 independently represent a hydrogen or an alkyl group having 1 to 3 carbon atoms.

FIELD OF THE INVENTION 
The present invention relates to a novel aromatic polycarbodiimide. The 
aromatic polycarbodiimide of the present invention provides a film, an 
adhesive or a molded article, having various excellent properties, such as 
high heat resistance. 
BACKGROUND OF THE INVENTION 
Some aromatic polycarbodiimides have conventionally been obtained by 
polymerizing, for example, diphenylmethane diisocyanate (MDI) or tolylene 
diisocyanate (TDI) as a monomer. Such polycarbodiimides are used as a 
flame-retardant film or a heat-resistant adhesive because of its excellent 
heat resistance. 
However, the polycarbodiimide obtained from TDI or MDI has a poor 
solubility and, therefore, may cause gelation or may become solid to be 
precipitated, with increasing the molecular weight. Thus, a sufficiently 
high molecular weight polymer cannot be obtained. Further, although the 
polycarbodiimide film has a heat-resistance in the point that a volatile 
gas or a decomposed monomer is not generated even if it is exposed to high 
temperature of 400.degree. C. or more, if it is thermally treated at a 
temperature of 200.degree. C. or more, it will lose a self-supporting 
property and become brittle. As a result, the film cannot be practically 
used. Furthermore, the film has a low moisture resistance at high 
temperature and under high pressure and also has an insufficient adhesive 
force when thermally contact-bonded with an adherend, such as a copper 
foil. 
SUMMARY OF THE INVENTION 
As a result of various investigations on various aromatic polymers in order 
to solve such disadvantages of the conventional polycarbodiimides, it has 
been found that the disadvantages can be overcome by a novel polymer 
according to the present invention. 
Accordingly, an object of the present invention is to provide a novel 
aromatic polycarbodiimide which can provide various products having 
excellent properties. 
The aromatic polycarbodiimide according to the present invention comprises 
a structural unit represented by the following formula (A): 
##STR3## 
wherein R represents a divalent organic group represented by any one of 
the following formulae (I) and (II), n is an integer of 2 to 400; 
##STR4## 
In the above formula (II), X.sub.1 to X.sub.4 independently represent 
hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 
Regarding an embodiment wherein R in the above-described formula (A) is 
represented by the formula (II), U.S. Pat. No. 5,109,097, is disclosed an 
aromatic diisocyanate represented by the following formula (III) 
##STR5## 
However, it is not described at all in the U.S. patent that the aromatic 
diisocyanate compound is polymerized and polycarbodiimide can be obtained 
therefrom.

DETAILED DESCRIPTION OF THE INVENTION 
The polymer according to the present invention is represented by the 
formula (A) wherein n is an integer of 2 to 400. This novel polymer has an 
excellent solubility and also a considerably high heat resistance. 
Further, the polymer has excellent adhesive properties, low temperature 
workability and moisture resistance. The polycarbodiimide according to the 
present invention is obtained by polymerizing the diisocyanate 
corresponding to the following formulae (IV) and (V) as a monomer in the 
presence of a phosphorus catalyst by conventional process. 
##STR6## 
wherein X.sub.1 to X.sub.4 independently represent hydrogen atom or an 
alkyl group having 1 to 3 carbon atoms. 
Only the above-described monomer may be used as a monomer used for the 
polymerization. However, other organic diisocyanates (e.g., 
4,4'-diphenylmethane diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene 
diisocyanate, 1-methoxyphenyl-2,4-diisocyanate, 
3,3'-dimethoxy-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylether 
diisocyanate, 3,3'-dimethyl-4,4'-diphenylether diisocyanate, o-tolylene 
diisocyanate) can be copolymerized in an amount such that the properties 
of the above-described monomer are not impaired (about 30% by weight or 
less). 
Reaction temperature in the polymerization is preferably 40 to 150.degree. 
C., and more preferably 50 to 140.degree. C. When the reaction temperature 
is less than 40.degree. C., the reaction time is too prolonged. Thus, such 
a temperature is not practical. If the temperature exceeds 150.degree. C., 
it is difficult to select an appropriate solvent. 
Concentration of an isocyanate monomer in the synthesis of a 
polycarbodiimide is 2 to 70% by weight (hereinafter simply referred to as 
"%"), preferably 5 to 60%, and more preferably 15 to 50%. If the 
concentration is less than 2%, carbodiimidation may not proceed. On the 
other hand, if the concentration exceeds 70%, there is the possibility 
that it is difficult to control the reaction. 
The organic solvent used in the synthesis of a polycarbodiimide and in 
preparing a polycarbodiimide solution may be conventional organic 
solvents. Examples of the organic solvent include halogenated 
hydrocarbons, such as tetrachloroethane, 1,2-dichloroethane or chloroform; 
ketone solvents, such as acetone, methylethylketone, methylisobutylketone 
or cyclohexanone; ether solvents, such as tetrahydrofuran and dioxane; and 
aromatic hydrocarbon solvents, such as toluene, xylene or benzene. Those 
can be used alone or as mixtures thereof. 
Catalyst which can be used in carbodiimidation is phosphorene oxides (e.g., 
1-phenyl-2-phosphorene-1-oxide, 3-methyl-2-phosphorene-1-oxide, 
1-ethyl-2-phosphorene-1-oxide, 3-methyl-1-phosphorene-1-oxide, or 
3-phosphorene isomers thereof). 
In any one of the end stage, middle stage or initial stage of a 
polymerization reaction, or throughout the reaction, monoisocyanate may be 
added to the reaction system to perform an end-capping treatment. Such a 
monoisocyanate which can be used is aromatic monoisocyanates such as 
phenyl isocyanate, p-nitrophenyl isocyanate, p- or m-tolyl isocyanate or 
p-formylphenyl isocyanate. The polycarbodiimide solution thus obtained has 
excellent storage stability. 
After completion of the reaction, the reaction mixture may be poured into a 
poor solvent, such as methanol, ethanol or hexane, to precipitate a 
polycarbodiimide powder, thereby removing unreacted monomer or a catalyst. 
By conducting such an operation, the stability of the polycarbodiimide 
solution can be further improved. After precipitating the polycarbodiimide 
as a polymer powder, washing and drying thereof are effected according to 
a predetermined procedure, and the resulting polycarbodiimide is then 
dissolved again in an organic solvent. Thus, a polycarbodiimide solution 
can be obtained. 
By-products contained in the polymer solution may be adsorbed on an 
appropriate adsorbent to purify the solution. Examples of the adsorbent 
which can be used are alumina gel, silica gel, activated carbon, zeolite, 
activated magnesium oxide, activated bauxite, Fuller's earth, activated 
clay, molecular sieve carbon, and the like. Those can be used alone or in 
any combination thereof. 
The molecular weight of the polycarbodiimide of the present invention is 
1,000 to 200,000, and preferably 4,000 to 100,000, in terms of a number 
average molecular weight where R in the formula (A) is represented by the 
formula (I). Namely, in the formula (A), n is an integer of 2 to 400, and 
preferably 7 to 200. Further, the molecular weight of the polycarbodiimide 
of the present invention is 1,000 to 100,000, and preferably 4,000 to 
20,000, in terms of a number average molecular weight where R in the 
formula (A) is represented by the formula (II). Namely, in the formula 
(A), n is an integer of 2 to 280, and preferably 10 to 60. 
If the molecular weight of the polycarbodiimide is too large, gelation may 
readily occur within several minutes to several hours even if it is 
allowed to stand at an ordinary temperature. This phenomenon is not 
desirable in the practical use. On the other hand, if the molecular weight 
is too small, the resulting film undesirably lacks reliability. 
[Production of Film and Adhesive Sheet] 
A polycarbodiimide film (or sheet) of the present invention can be produced 
by forming a polycarbodiimide varnish into a film according to a 
conventional method (e.g., casting, spin coating, or roll coating). This 
film is desirably dried at a temperature which is usually required to 
remove a solvent and does not advance a hardening reaction considerably. 
The drying temperature is 30 to 350.degree. C., and preferably 50 to 
250.degree. C. If the drying temperature is too low, a solvent remains in 
a resulting film to undesirably decrease the reliability of the film. On 
the other hand, if the drying temperature is too high, crosslinking of the 
polycarbodiimide resin may advance to undesirably cause rupture or poor 
stretching in stretching the film. 
A polycarbodiimide composition of the present invention can be compounded 
with fine inorganic fillers in an amount which does not impair workability 
and heat resistance thereof. Further, in order to provide a surface 
smoothness, various additives such as a smoothing agent, a leveling agent, 
a deformer may be added depending upon a necessity. 
A molded article obtained by molding the polymer of the present invention 
in the form of a film can be used as a heat-resistant adhesive sheet. 
Thickness of the sheet which can be molded into a film or an adhesive 
sheet is generally 1 to 200 .mu.m. However, the thickness is not limited 
thereto and can be optionally selected depending upon an object for use. A 
shape or a size of the sheet can also be optionally selected depending 
upon an adherend, such as a lead frame or a semiconductor chip. 
In producing an adhesive sheet, in order to impart conductivity, improve 
heat transfer property, control elasticity modulus, and especially attain 
a high elasticity, for example, metals (e.g., aluminum, copper, silver, 
gold, nickel, chromium, lead, tin, zinc, palladium, or solder), or alloys 
thereof, ceramics (e.g., alumina, silica, magnesia, or silicon nitride), 
and other various inorganic powders comprising carbon can be compounded 
alone or as mixtures thereof. 
Alternatively, the film can be formed on a support to form an adhesive 
sheet. In order to produce the adhesive sheet having such a construction, 
a varnish may be coated on the support. Alternatively, the film is 
previously formed, and is then laminated on the support by means of a 
press. 
The support which can be used is a metal foil and an insulating film. 
Examples of the metal foil are metals (e.g., aluminum, copper, silver, 
gold, nickel, chromium, lead, tin, zinc, or palladium), and alloys 
thereof. Examples of the insulating film are heat-resistant or 
chemical-resistant films, such as polyimide, polyester or polyethylene 
terephthalate. 
The metal foil and the insulating film can be used alone or as a two or 
more layered product, for example, a two layered substrate of a metal 
foil/insulating film laminate. The two layered substrate is, for example, 
copper/polyimide two layered substrate. 
A sheet-like adhesive of the present invention is thermally cured by a 
thermal treatment to develop a strong adhesion and also form a cured 
product having a low hygroscopicity. In order to conduct the heat 
treatment, an optional method, for example, a heater, ultrasonic waves or 
ultraviolet rays, can be used. Accordingly, the adhesive sheet of the 
present invention is desirable for adhesion treatment of various 
materials. Particularly, it is desirable for sealing treatment of electric 
and electronic parts represented by a semiconductor chip and a lead frame, 
which are required to have a low hygroscopicity. The adhesive sheet of the 
present invention is excellent in the following points: it is low 
hygroscopic, it is highly flexible so that it can be readily handled, it 
has a good adhesion to a semiconductor element, and it has a desirable 
storage stability. Further, a metal foil having an adhesive applied 
thereon produced by coating a varnish of a resin composition of the 
present invention on one surface thereof, followed by drying is 
particularly useful for the production of a multilayered circuit board. 
A stretched film of the polycarbodiimide according to the present invention 
can have various shapes, such as a sheet or a tube. For example, a 
stretched film can be obtained by stretching the film obtained by the 
above-described method in one direction (main axial direction) at 1.2 to 
10 times, and preferably 2 to 6 times. If desired, stretching further can 
be effected in the direction perpendicular to the above-described 
stretching direction (main axial direction) at 1 to 5 times, and 
preferably 1.1 to 1.6 times. The order of the above-described stretching 
is optional. By stretching in the direction perpendicular to the main 
axial direction as described above, the impact property of the stretched 
film is improved and the property of readily tearing in one direction is 
relaxed. If the stretching in the direction perpendicular to the 
above-described stretching direction (main axial direction) exceeds 5 
times, the heat shrinkage in the direction perpendicular to the main axial 
direction becomes too large so that the finished appearance to which a 
heat shrinking treatment is applied is in waves. Thus, the appearance 
becomes undesirably ununiform. 
Stretching temperature is preferably 40 to 200.degree. C. so as to be dried 
before a curing reaction of a polycarbodiimide resin proceeds to a 
considerable extent. If the stretching temperature is less than 40.degree. 
C., a sufficient stretch ratio cannot be obtained and the resulting film 
tends to break. On the other hand, if it exceeds 200.degree. C., a curing 
reaction of the polycarbodiimide resin partially proceeds and, therefore, 
the heat recovery property thereof tends to be decrease. 
The stretching method is not particularly limited. For example, any 
conventional methods, such as a roll stretching method, a long gap 
stretching method, a tenter stretching method or a tubular stretching 
method, can be employed. 
[Object for Use] 
The polycarbodiimide film thus produced can be used as heat-resistant 
insulating materials and adhesive films of electric and electronic parts. 
Further, films which have been subjected to a stretching treatment are 
used as, for example, heat-resistant coating materials of various 
products. In coating a product with a stretched film, an adherend to be 
protected (product) is coated with a heat-shrinkable film made of a 
molding material comprising polycarbodiimide resin as a main component, 
and the coated product is then heat treated to cure the film. The curing 
reaction of the polycarbodiimide proceeds by this heat treatment, so that 
the polycarbodiimide resin flows into concave and convex portions formed 
on the surface of the adherend to produce anchor effects, and, at the same 
time, a chemical reaction between polar groups on the surface of the 
adherend and cumulative multiple bonds of the polycarbodiimide resin 
occurs. Thus, chemical and physical adhesion can be achieved. 
The adherend is not particularly limited, and examples thereof are glass, 
metals, resins, ceramic sheets or plates, and ring-shaped products. 
Specific products thereof are electrical wires of power cables, glass 
bottles and electronic parts. 
[Monomer] 
An isocyanate compound represented by the formula (IV), i.e., diisocyanate 
monomer which is a starting material of the aromatic polycarbodiimide of 
the present invention, is a novel aromatic diisocyanate. The production 
method thereof will be explained below. 
This diisocyanate can be produced by isocyanating an amino precursor of the 
diisocyanate compound by a conventional method. Conventional diamine 
compound represented by the following formula (VI) can be used as the 
precursor. 
##STR7## 
A method for isocyanating such a diamine compound is a method of reacting 
phosgene, diphenyl carbonate or carbonyl diimidazole. Alternatively, a 
diamine compound is converted to an urethane intermediate using a 
halogenated formate, and the urethane intermediate is then isocyanated in 
the presence of a catalyst, such as chlorosilane or catechol borane. Still 
another method which can be employed is a method of using a dicarboxylic 
acid represented by the following formula (VII) as a precursor of a 
diisocyanate, and isocyanating the same by Curtius decomposition. It 
should be noted that in view of ease in obtaining a starting material, a 
diamine is preferably used. 
##STR8## 
Of those production methods, a method wherein a diamine compound is 
converted to an urethane intermediate with a halogenated formate, and the 
intermediate is then isocyanated in the presence of chlorosilane as a 
catalyst (G. Greber, et al., Angew. Chem. Int. Ed. Vol. 17, No.12, 941 
(1968)) or a method of using catechol boran as a catalyst (V. L. K. Valli. 
et al., J. Org. Chem, Vol. 60, 257 (1995)) are preferable from the 
standpoints of yield and safety. Those methods will be described 
hereinafter. 
9,9-Bis(4-isocyanatophenyl)fluorene represented by the formula (V) which is 
the starting material of the polycarbodiimide of the present invention can 
be synthesized by isocyanating the amino precursor thereof, i.e., 
9,9-bis(4-aminophenyl)fluorene by various conventional methods. 
[Synthesis of Urethane Intermediate] 
An urethane intermediate is synthesized by reacting a halogenated alkyl 
formate, such as methylchloroformate, ethylchloroformate, 
phenylchloroformate or p-nitrophenylchloroformate, with a corresponding 
diamine compound. Of those halogenated formates, in order to proceed the 
isocyanation smoothly, phenylchloroformate or p-nitrophenylchloroformate 
is preferable. However, since p-nitrophenylchloroformate is highly active 
and has a possibility of causing a side reaction, phenylchloroformate is 
most preferable. 
A solvent used in the reaction can be any solvents so long as a diamine can 
be dissolved therein. Examples of the solvent are ether compounds (e.g., 
tetrahydrofuran (THF), dioxane or diethyl ether), aromatic hydrocarbon 
compounds (e.g., toluene, xylene or benzene), ketone compounds (e.g., 
acetone or methylethylketone), and ester compounds (e.g., ethyl acetate). 
Those solvents can be used alone or as mixtures thereof. 
The reaction temperature is -40 to 100.degree. C., preferably -20 to 
80.degree. C., and most preferably 0 to 60.degree. C. If the reaction 
temperature is less than -40.degree. C., the reaction is difficult to 
proceed. On the other hand, if the temperature exceeds 100.degree. C., a 
side reaction such as condensation may occur. 
A base for trapping hydrogen chloride generated by the reaction can be any 
so long as they can dissolve in a solvent used and do not inhibit the 
reaction. Examples of the base used are triethylamine, pyridine, sodium 
hydroxide and diazabicycloundecene (DBU). Such a base should be used in an 
amount of 1.5 to 4.0 moles, and preferably 1.8 to 3.5 moles, per mole of 
the diamine used. 
The resulting urethane intermediate can be purified by a conventional 
method, such as recrystallization or a column chromatography. Further, 
distillation may be conducted if necessary. 
(a) Isocyanation with Chlorosilane 
In order to convert the urethane intermediate to an isocyanate, thermal 
decomposition of the urethane is conducted using a chlorosilane in an 
amount of 1.5 to 4.6 moles, and preferably 1.8 to 3.5 moles, per mole of 
the urethane, as a catalyst. Examples of the chlorosilanes include 
trimethylchlorosilane, triethylchlorosilane, trimethoxychlorosilane and 
tetrachlorosilane. From the standpoint of ease in handling and cost, 
trimethylchlorosilane is preferable. 
The solvent can be any solvents so long as they can dissolve or suspend an 
urethane. Examples of the solvent include halogenated hydrocarbon 
compounds, such as dichloromethane, chloroform, dichloroethane or 
tetrachloroethane, in addition to the above-described ether compounds, 
aromatic hydrocarbon compounds, ketone compounds and ester compounds. 
Those solvents can be used alone or as mixtures thereof. Optionally, a part 
or all of the solvents can be replaced in the course of the reaction, 
thereby changing a reaction temperature. 
The reaction temperature is from 0.degree. C. to the boiling point of a 
solvent used, and preferably from room temperature to the boiling point. 
If the reaction temperature is too low, the reaction may not proceed at 
all. On the other hand, If the reaction temperature is too high or heating 
is applied too long, the resulting product may sometimes decompose. 
Therefore, it is desirable to proceed the reaction with gradually raising 
a temperature while tracing the reaction by IR. 
In order to trap hydrogen chloride generated in the reaction, a base, such 
as triethylamine, can be used as in the above. 
(b) Isocyanation using Halogenated Catecholborane 
For isocyanation of the urethane intermediate, a method can be used wherein 
instead of the above-described chlorosilane, halogenated catecholborane is 
used as a catalyst. The halogenated catecholborane which can be used 
includes chlorocatecholborane and bromocatecholborane. However, from the 
standpoint of cost and ease in handling, chlorocatecholborane is 
preferable. It should be noted that since catecholboranes have an activity 
to thermal decomposition higher than that of chlorosilanes, urethanes 
other than phenyl urethane can also be used as the urethane to be used in 
the present invention. 
A solvent used in the reaction can be the same solvents as used in the 
above-described isocyanation using chlorosilane. 
The reaction temperature is generally -50 to 80.degree. C., preferably 20 
to 60.degree. C., and more preferably 0 to 40.degree. C., when phenyl 
urethane is used. It is better to change the reaction temperature 
depending upon a kind of the urethane used. If the reaction temperature is 
fallen outside the range or an excessive heating is applied, a reaction 
may not proceed or a product may decompose as described in (a) above. 
Therefore, it is desirable to proceed the reaction with gradually raising 
a temperature while tracing the reaction by IR. 
A base used for trapping hydrogen chloride generated in the reaction can be 
the same bases as described above. 
After completion of the reaction, the solvent is removed, and the 
isocyanate monomer thus obtained can be purified with a flash column, 
recrystallization or distillation under reduced pressure. 
The above-described urethanation, isocyanation and carbodiimidation of a 
diamine can be proceeded stepwise by conducting isolation and purification 
in respective steps. Alternatively, these steps are continuously conducted 
in one reaction vessel as a series of reaction. 
The present invention will be described in more detail by reference to the 
following Examples, but it should be understood that the invention is not 
construed as being limited thereto. Properties of the resulting 
polycarbodiimide were measured as follows. 
IR 
Measured using FT/IR-230 (manufactured by Nippon Denshi K.K.). 
Heat Curing Temperature 
Measured using DSC-200(manufactured by Seiko Denshi Kogyo K.K.). Exothermic 
peak of a trimer was determined as a heat curing temperature. 
Glass Transition Temperature (Tg) 
Measured using SEIKO SSC/560M (manufactured by Seiko Denshi Kogyo K.K.) 
while raising a temperature from room temperature to 400.degree. C. at a 
rate of 10.degree. C./min. 
Thermal Decomposition Initiation Temperature (Td) 
Measured using TG/DTA300 (manufactured by Seiko Denshi Kogyo K.K.). 5% 
weight loss temperature was determined as Td. 
Number Average Molecular Weight 
Measured using HLC8120 (manufactured by Toso K.K.) as an apparatus, and 
GMH.sub.HR -H+GHR.sub.HR -H+G200H.sub.HR (manufactured by Toso K.K.) as a 
column. 
Adhesive Force 
180.degree. peeling strength was determined using Shimazu autograph 
AGS-100D (manufactured by Shimazu Seisakusho K.K.). 
EXAMPLE 1 
2 g (3.5 mmol) of 
1,1-bis[2'-methyl-4'-(p-aminophenoxy)-5'-tert-butylphenyl]butane, 20 ml of 
dichloromethane, and 0.72 g (7.1 mmol) of triethylamine were charged into 
a 50 ml eggplant-shape flask. The flask was ice-cooled, and 1.1 g (7.1 
mmol) of phenychloroformate was charged thereto. The resulting mixture was 
stirred as it is for several minutes, and then stirred at room temperature 
overnight. 0.65 g (6.4 mmol) of triethylamine and 0.69 g (6.4 mmol) of 
trimethylchlorosilane were successively charged into the flask at room 
temperature, and the resulting mixture was stirred for 5 minutes, and then 
further stirred at 50.degree. C. for 30 minutes. 
61 mg (0.32 mmol) of carbodiimidation catalyst 
(3-methyl-1-phenyl-2-phosphorene-1-oxide) was dissolved in 20 ml of 
toluene. The resulting mixture was charged into the flask and stirred at 
60.degree. C. for 1.5 hours. Stirring was further continued for 5.5 hours, 
while raising a temperature to 100.degree. C. During the stirring, 
dichloromethane was distilled off. Carbodiimidation was confirmed by IR 
absorption spectrum (see FIG. 1), and thereafter, triethylamine 
hydrochloride was filtered off to obtain a polycarbodiimide having a 
number average molecular weight of Mn=6,000 (yield 70%). 
This polymer was coated on a glass plate, followed by drying at 200.degree. 
C. for 10 minutes, thereby obtaining a film. This film had flexibility, 
heat curing temperature of 375.degree. C., Tg=172.degree. C. and 
Td=351.degree. C. Even after drying at 200.degree. C. for 60 minutes, this 
film still had flexibility. 
EXAMPLE 2 
Varnish prepared by dissolving the polycarbodiimide obtained in Example 1 
in tetrahydrofuran (THF) so as to have the polycarbodiimide concentration 
of 40% by weight was coated on a copper foil (thickness 35 .mu.m), and 
dried at 200.degree. C. for 10 minutes to obtain an adhesive sheet having 
a thickness of 20 .mu.m. The adhesive sheet thus obtained was adhered on 
42 alloy (Ni--Fe alloy) plate and bonded each other by pressing at 
350.degree. C. under a pressure of 50 kg/cm.sup.2 for 1 second. The 
measurement of the adhesive force showed 980 g/cm. This adhered product 
was placed in a 80.degree. C./90% RH constant temperature humidistat and 
maintained therein for 168 hours. Thereafter, the adhesive force was 
measured, and showed 810 g/cm. 
Comparative Example 1 
Example 1 was followed except for using tolylene diisocyanate (TDI) as an 
isocyanate monomer to obtain a polycarbodiimide having Mn=9,600. Varnish 
prepared by dissolving the polycarbodiimide thus obtained in THF so as to 
have the polycarbodiimide concentration of 40% by weight was coated on a 
glass plate, and dried at 90.degree. C. for 30 minutes to obtain a film 
having Tg of 78.degree. C. This film had a heat curing temperature of 
350.degree. C. When the film was heat treated at 200.degree. C. for 1 
hour, the film discolored and lost flexibility, resulting in losing 
self-supporting property. 
This varnish was treated in the same manner as in Example 2 to prepare an 
adhesive sheet, and the adhesive sheet was adhered to 42 alloy plate. As a 
result of measurement of the adhesive force, it showed 600 g/cm. This 
adhered product was placed in a 80.degree. C./90% RH constant temperature 
humidistat and maintained therein for 168 hours. As a result, adhesive 
sheet was peeled off from the 42 alloy plate. 
EXAMPLE 3 
10.0 g (28.7 mmol) of 9,9-bis(4-aminophenyl)fluorene, 240 ml of 
dichloromethane and 5.80 g (57.4 mmol) of triethylamine were charged into 
a 300 ml three-necked flask. 8.98 g (57.4 mmol) of phenylchloroformate was 
introduced into a dropping funnel, and a reaction vessel was cooled to 
0.degree. C. in an ice bath. The phenylchloroformate was added to the 
reaction vessel in several seconds, and then stirred overnight while 
returning the temperature to room temperature. 
7.53 g (74.6 mmol) of triethylamine and 8.09 g (74.6 mmol) of 
trimethylchlorosilane were successively charged in the flask, and the 
resulting mixture was refluxed therein for 2 hours. 100 ml of THF and 
0.441 g (2.30 mmol) of a carbodiimidation catalyst 
(3-methyl-1-phenyl-2-phosphorene-1-oxide) were added thereto, and stirring 
was conducted at 55.degree. C. for 2 hours, while distilling off 
dichloromethane, followed by refluxing for 5 hours. A salt formed was 
removed by filtration. Further, reprecipitation was conducted using 1.75 
liters of n-hexane. The resulting precipitate was dried at 30.degree. C. 
for 8 hours under reduced pressure to obtain 7.00 g (19.7 mmol, yield 69%) 
of white powdery polycarbodiimide. The polycarbodiimide had Mn=2,800. 
Carbodiimidation was confirmed by IR absorption spectrum (see FIG. 2). 
The white powder obtained above was soluble in organic solvents, such as 
THF, cyclohexanone or chloroform. Varnish prepared by dissolving 0.6 g of 
this white powder in 1.8 g of cyclohexanone was coated on a glass plate, 
followed by drying at 200.degree. C. for 20 minutes, thereby obtaining a 
film. This film had flexibility even after drying at 250.degree. C. for 20 
minutes and at 300.degree. C. for 20 minutes. Properties of the resulting 
film were measured. As a result, heat curing temperature was 390.degree. 
C., Td=505.degree. C. and Tg=185.degree. C. 
Comparative Example 2 
110 g (40 mmol) of diphenylmethane diisocyanate (MDI) was reacted in the 
presence of 60 mg (0.31 mmol) of the carbodiimidation catalyst 
(3-methyl-1-phenyl-2-phosphorene-1-oxide) in THF 50 ml at 60.degree. C. 
for 2 hours. The resulting reaction solution was casted on a glass plate 
to form a film. 
This film had a heat curing temperature of 350.degree. C. When the film was 
heat treated at 250.degree. C. for 1 hour, it was colored and lost 
flexibility, thereby losing the self-supporting property. White powdery 
polycarbodiimide obtained by reprecipitating the above reaction solution 
was not soluble in organic solvents, such as cyclohexanone, toluene or 
acetone. 
The polycarbodiimide according to the present invention is readily soluble 
in common organic solvents and also can be readily molded and processed. 
Further, since it has a glass transition temperature of about 200.degree. 
C., a low temperature processing can be readily effected. The film thereof 
has a good adhesion to an adherend such as a semiconductor element, has a 
low moisture absorption, has an excellent storage stability, and can be 
preserved for a long period of time at an ordinary temperature. Further, 
by curing this film by a heat treatment, the film shows excellent heat 
resistance and humidity resistance and, therefore, can be used as a 
heat-resistant coating material in soldering process in the production of 
electronic parts. 
While the invention has been described in detail and with reference to 
specific embodiments thereof, it will be apparent to one skilled in the 
art that various changes and modification can be made therein without 
departing from the spirit and scope thereof.