Note: Descriptions are shown in the official language in which they were submitted.
~297615
DISCLOSURE OF T~lE IN~ENTION
The present inventors have investigated extensively to achieve
the above object. Accordingly, they have found that a polyimide resin
composition comprising a novel polyimide and a specific amount of
fibrous reinforcing materials is effective in particular. Thus the
present invention has been completed.
Tha~ is, the present invention is a polyimide resin composition
which comprises 100 parts by weight of polyimide having recurring
units of the following formula (I):
O O
O ~Y~ O ~ ~
O O (I)
(where Y is a radical sélected from the group consisting of a bond,
divalent hydracarbon radical having from 1 to 10 carbons,
hexafluorinated isopropylidene radical, carbonyl radical, thio
radical, sulfinyl radical, sulfonyl radical or oxide, and R is a
tetra-valent radical selected from the group consisting of aliphatic
radical having 2 and more carbons, cycloaliphatic radical,
manoaromatic radical, condensed poIyaromatic radical, and
non-condensed polyaromatic radical wherein aromatic radicals are
mutually connected with a bond or a crosslinking function)
and from 5 to 100 parts by weight of a fibrous reinforcing material.
Polyimlde which is used in the present invention is prepared by
12976~S `
conducting a dehydrating ring-closure of polyamic acid obtained by
reacting an ether-diamine represented by the following formula (IV):
H2N~O~Y~--O~NH2
(where Y is a radical selected from the group consisting of a bond,
divalent hydrocarbon radical having from 1 to 10 carbons,
hexafluorinated isopropylidene radical, carbonyl radical, thio
radical, sulfinyl radical, sulfonyl radical or oxide)
with a tetracarboxylic acid dianhydride represented by the following
formula (V):
O O
Il 11
C C
O R O
C/ \C/
Il, 11
O O (V)
(where R is a tetra-valent radical selected from the group consisting
of aliphatic radical having 2 and more carbons, cycloaliphatic
radical, monoaromatic radical, condensed polyaromatic radical, and
non-condensed polyaromatic radical wherein aromatic radicals are
mutually connected with a bond or a crosslinking function).
Diamine in use for the method includes, for example, bis[4-(3-
aminophenoxy)phenyl]methane, l,l-bis[4-(3-aminophenoxy)phenyl]ethane,
1,2-bis[4-(3-aminophenoxy~phenyl]ethane, 2,2-bis[4-(3-aminophenoxy)-
phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]butane, 2,2-bis[4-
(3-am1nophe~oxy)pheny1~-1,1,1,3,3,3-hexaf1uoropropane, 4,4'-bf~(3-
129761S
aminophenoxy)biphenyl, bis[4-(3-aminophenoxy)phenyl] ketone,
bis[4-(3-aminophenoxy)phenyl] sulfide, bis[4-(3-aminophenoxy)phenyl~
sulfoxide, bis[4-(3-aminophenoxy)phenyl] sulfone and bis[4-(3-amino-
phenoxy)phenyl] ether These diamine can be used alone or in
mixtures of two or more.
Particularly preferred ether-diamine is 4,4'-bis-(3-amino-
phenoxy)biphenyl, 2,2-bis[4-(3-aminophenoxy)phenyl]-propane and
bis~4-(3-aminophenoxy)phenyl]sulfide
Tetracarboxylic acid dianhydride used in the method includes,
for example, ethylene tetracarboxylic dianhydride, cyclopentane
carboxylic dianhydride, pyromellitic dianhydride, 3,3',4,4'-
benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone
tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic
dianhydrlde, 2,2',3,3'-biphenyl tetracarboxylic dianhydride,
2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-
dicarboxyphenyl)propane dlanhydride, bis(3,4-dicarboxyphenyl) ether
dianhydride, bis(3,4-dicarboxyphenyl) sulfone dianhydride, l,l-bis-
(2,3-dicarboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl)-
methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride,
2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene
tetracarboxylic dianhydride, l,2,5,6-naphthalene tetracarboxylic
dianhydride, 1,2,3,4-benzene tetracarboxylic dianhydride,
3,4,9,10-perylene tetracarboxylic dianhydride, 2,3,6,7-anthracene
tetracarboxylic dianhydride and 1,2,7,3-phenanthrene tetracarboxylic
dianhydride. Tetracarboxylic acid dianhydride can be used alone or
in mixtures of two or more.
129761S
Particularly prefered tetracarboxylic acid dianhydride is
pyromellitic dianhydirde ana 3,3',4,4'-benzophenonetetracarboxylic
dianhydride.
The ether-diamine and tetracarboxylic acid dianhydride are
ordinarily reacted by known procedures to give a polyamic acid having
recurring units of the following formula (VI):
H O O H
~10 c / \ c oHJ
O O (VI)
(where R is the same as above)
and subsequently imidizing by a normal method to obtain polyimide
having recurring units of the following formula (I):
Il 11
O ~ Y ~ O ~ N f ~ ~
O O (I)
(where R is teh same as above).
In the practice of the present invention, particularly
preferred polyimide having recurring units of the above formula (I)
includes:
(a) A polyimide having the above formula (I) wherein Y is a bond
and R is represented by the following formula (II):
(II)
s
129'76~S
which is obtained by using 4,41-bis(3-aminophenoxy)biphenyl as the
diamine and pyromellitic dianhydride as the tetracarboxylic acid
dianhydride;
(b) A polyimide having the above f ormula (I) wherein Y is
isopropylidene radical and R is represented by the f ollowing f ormula
(III):
O
~C~ .
(III) ~
which is obtained by using 2,2-bis~4-(3-aminophenoxy)phenyl]propane as
the diamine and 3,3', 4,4'-benzophenone tetracarboxylic dianhydride as
the tetracarboxylic acid dianhydride;
(c) A polyimide having the above formula (I) wherein Y is thio
radical, R i8 represented by the following formula (II):
(II)
which is obtained by using bis~4-(3-aminophenoxy)phenyl]sulfide as the
diamine and pyromellitic dianhydride as the tetracarboxylic acid
dianhydride; and
(d) A polyimide having the above formula (I) wherein Y is thio
radical and R is represented by the following formula (III):
~29761S
o
~c,~
(III)
which is obtained using bis[4-(3-aminophenoxy)phenyl]sulfide as the
diamine and 3,3', 4,4'-benzophenone tetracarboxylic dianhydride as the
tetracarboxylic acid dianhydride.
A variety of the fibrous reinforcing materials is used for the
practice of this invention. The materials include, for example, glass
fibre, carbon fibre, potassium titanate fibre, aromatic polyamide
fibre, silicon~ carbide fibre, alumina fibre, boron fibre, and ceramic
fibre. Particularly preferred fibres are glass fibre, carbon fibre,
potasslum titanate fibre and aromatic polyamide fibre.
The glass fibre used in the practice of this invention i8 made
by various processes of quenching and drawing a molten glass to obtain
a fine fibre having a predetermined diameter. The term glass fibre
further includes strand prepared by bundling monofilaments with each
other by a bundling agent and roving prepared by uniformly making
parallel and bundling the strand. All of these materials can be used
in this invention. In order to obtain affinity with the base resin of
this invention, said glass fibre may be processed with
surface-treating agents which include silane coupling agents such as
aminosilane or epoxysilane, chromic chloride and other treating agents
for various objects.
The length of the glass fibre of this invention has a
remarkable effect on the properties of molded articles obtained and
the workability in manufacturing sùch molded articles. When fibre
129761S
length is increased, the properties of molded articles are generally
improved, and yet, on the contrary, the workability in manufacturing
becomes poor Therefore the length of the glass fibre in the practice
of this invention is preferably in the range of 0.1-6mm, more
preferably in the range of 0.3-4mm, because both the properties of the
molded articles and the workability in manufacturing are in a good
balance.
Besides the carbon fibre used in the practice of this invention
includes a high-modulus and high-strength fibre obtained by
carbonizing primarily polyacrylonitrile, petroleum pitch and the like.
Both acrylonitrile-based and petroIeum pitch-based materials are
suitable for this invention. The carbon fibre has a suitable diameter
and a proper aspect ratio (ratio of length/diameter) on the basis of
reinforcing effect and mixing ability. The diameter of carbon fibre
i~ normally in the range of from 5 to 20 microns and preferably in the
range of approximately from 8 to 15 microns in particular. The aspect
ratio ranges normally from 1 to 600, preferably from about 100 to
about 350 particularly according to the mixing ability and reinforcing
effect. Too small aspect ratio has no reinforcing effect and
excessive aspect ratio reduces mixing ability and inhibits to obtain
good molded articles. Besides the surface of said carbon fibre may
be processed with various treating agents which include, for example,
epoxy resin, polyamide resin, polycarbonate resin, polyacetal resin
and other known surface treating agents for a variety of objects.
In addition, the potassium titanate flbre of this invention is
a type of high strength fibre (whisker) and a needle crystal having a
chemical composition of fundamentally K20.6TiO2, K20.6TiO2.1/2 H20 and
1297615
a typical melting point of l,300-1,350C. The fibre is applied in an
average length of 5-50 microns and an average diameter of 0.05-1.0
micron, and preferably an average length of 20-30 microns and an
average diameter of 0.1-0.3 micron. Although said potassium titanate
fibre may normally be used in an untreated state, it may also be
surface treated in order to have the affinity with the base resin of
this invention. The silane coupling agents such as aminosilane and
epoxysilane, chromic chloride and other surface treating agents may be
used according to the objects.
Furthermore, the aromatic polyamide fibre used in the practice
of this invention is a relatively new organic fibre developed for
high-temperature stability and expected for use in a wide field by
applying its unique characteristics. Typical examples of the resin
include those having the following chemical structures. These resin
can be used alone or a combination of two and more,
(1)/ H H 0 0
N ~ N - C ~ C ~
~ xample: Trade Mark; Kevler, from E.I. du Pont de Nemours & Co.
(2) H H 0 0
l l 11 11
~ / N ~ N - C ~ C ~ n
Example: Trade Mark; Nomex, from E.I. du Pont de Nemours ~ Co.
- Trade Mark; Conex, from TEIJIN
. .
12976~5
(3) / H O
t~
~ here are many other aromatic polyamide fibres having various
polymer chains according to ortho-, meta-, or para-isomeric structure.
Among them, the type (1) resin having para-para located linkages
exhibits high softening point and melting point and is the most
preferable in this invention as the high-temperature stable organic
fibre.
The fibrous reinforcing material of this invention can be used
in an amount of 5-100 parts by weight, preferably 10-50 parts by
weight per 100 parts by weight of the polyimide. As to the glass
fibre and the carbon fibre, the amount of less than 5 parts by weight
can not afford the characteristic reinforcing effect of this invention
which is specific in the glas8 fibre or the carbon fibre. On the
other hand, the use of more than 100 parts by weight decreases
flowability of the composition during the molding and it becomes
difficult to obtain satisfactory articles.
The potassium titanate fibre can be used in an amount of 5-200
parts by weight, preferably 5-100 parts by weight per 100 parts by
weight of the polyimide. The amount of less than 5 parts by weight
can not sufficiently improve the mechanical properties in high-
temperatures which are characteristics of this invention. On the
contrary, the use of more than 200 parts by weight is undesirable
because insufficient dispersion occurs in the molten mixing, the
flowability decreases and the molding under normal conditions becomes
difficult.
.
12976i~
The aromatic polyamide fibre can be used in an amount of 5-100
parts by weight, preferably 10-50 parts by weight per 100 parts by
weight o~ the polyimide resin. The amount of less than 5 parts by
weight can not afford an excellent composition in the moldability and
mechanical strength which are characteristics of this invention. On
the other hand, the use of more than 100 parts by weight remarkably
improves the flowability of the composition in molding. Heat-
distortion temperature, however, drops and thus satisfactory high-
temperature stability can not be obtained.
The polyimide composition in the practice of this invention can
be prepared by the usually known methods and preferably by the
following methods in particular.
(1) The polyimide powder and the fibrous reinforcing material are
premixed by using a mortar, Henshel mixer, drum blender, tumbler
blender, ball mill, ribbon blender etc. The resultant mixture is
then kneaded with an ùsually known fusion mlxer or hot roll to form
pellets or powder.
(2) The polyimide powder is dissolved or suspended in organic
solvents in advance. The fibrous reinforcing material is dipped in
the resultant solution or suspension and then the solvents are removed
in a hot air oven. The residual mass is pelletized or powdered.
The organic solvents used in this method include, for example,
N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide,
N,N-dimethyl-methoxyacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-
2-imidazolidinone, N-methylcaprolactam, 1,2-dimethoxyethane, bis(2-
methoxyethyl) ether, 1,2-bis(2-methoxyethoxy)ethane, bis~2-(2-
methoxyethoxy)ethyl] ether, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane,
11
v,~.. ... . .
1 2976iS
pyridine, picoline, dimethyl sulfoxide, dimethyl sulfone,
tetramethylurea and hexamethylphosphoramide. These solvents can be
used alone or in mixtures of two or more.
(3) The polyamic acid precursor of polyimide of this invention
having recurring units of the formula (VI) is dissolved in the
afore-mentioned organic solvents. The fibrous reinforcing material
is impregnated in the resultant solution and followed by subjecting to
a heat treatment at a temperature of 100-400C or a chemical
imidization with an usually available imidizing agent. The solvents
are then removed and the residue is pelletized or powdered.
Besides at least one of antioxidants, heat stabilizers, ultra
violet absorbers, flame retardants, antistatic agents, lubricants,
colorants and other ordinary additives may be added to the composition
of this invention in a quantity of not rendering the object of this
invention lnvalid.
Other materials which may be blended in a proper amount
depending upon the object include thermoplastic resin (for exsmple,
polyethylene, pol~propylene, polyamide, polycarbonate, polysulfone,
polyethersulfone, polyetheretherketone, modified polyphenylene oxide,
polyphenylene sulfide and the like), thermosetting resin (for example,
phenolic resin, epoxy resin and the like) and fillers such as clay,
mica, silica, graphite, glass beads, alumina, calcium carbonate etc.
The polyimide resin of this invention may be molded by known
proceæsing methods such as injection molding, extruslon molding,
compression molding, rotation molding etc. and used for practical
application.
129~615
EXA~PLES
The present invention will be hereinafter illustrated with
respect to Synthetic examples, Specific examples and Comparative
examples.
Synthetic example 1
A 3 liter glass reaction vessel was charged with 186 grams (1.0
mol) of 4,4'-dihydroxybiphenyl, 438 grams (2.6 mols) of
m-dinitrobenzene, 363 grams of potassium carbonate and 2,000 ml of
N,N-dimethylformamide. The mixture was reacted at a temperature of
145-150C for 16 hours. After completing the reaction, the resultant
mixture was cooled and filtered to remove potassium nitrite. The
solvent was distilled off from the filtrate under reduced pressure.
-The residue was cooled to 65C, added with 2,000 ml of methanol and
stirred for an hour. The resulted cystals were filtered, washed
with water, washed with methanol and dried to obtain 426 grams (99.5%
yield) of 4,4'-bis(3-nitrophenoxy)biphenyl as brown crystals.
In the next step, a 1 1 glass reaction vessel was charged with
100 grams (0.23 mol) of crude 4,4'-bis(3-nitrophenoxy)biphenyl, 10
grams of active carbon, 1 grams of ferric chloride hexahydrate and 500
ml of 2-methoxyethanol. The mixture was stirred for 30 minutes under
reflux and then added dropwise with 46 grams (0.92 mol) of hydrazine
hydrate during 3 hours at 70-80C. The reaction was terminated by
stirring for 5 hours at 70-80C after ending the dropwise addition.
The reaction mixture was cooled, filtered to remove the catalyst and
poured into 500 ml of water. The separated crystals were filtered,
added with 48 grams of 35% hydrochloric acid and 540 ml of 50%
1297615
isopropyl alcohol and warmed. The solution thus obtained was allowed
to cool. The separated 4,4'-bis(3-aminophenoxy)biphenyl hydrochloride
was filtered, added with 540 ml of 50% isopropyl alcohol and warmed.
The solution thus obtained was added with 5 grams of active carbon,
filtered and neutralized with aqueous ammonia. The separated crystals
were filtered, washed with water and dried to give 72.0 grams (85%
yield) of 4,41-bis(3-aminophenoxy)biphenyl as colorless crystals
having a melting point of 144-146C. The purity was 99.6% according
to high-speed liquid chromatography.
Elementary analysis : C24 H20N2 2
. .
C H N
. ._
Calculated (%)78.26 5.43 7.61
Found (%) 78,56 5.21 7.66
MS : 368 (M ): 340, 184
IR (KBr.cm 1) : 3400 and 3310 tamino group),
1240 (ether linkage)
Synthetic example 2
A 1 liter glass reaction vessel was charged with 85.6 grams
(0.375 mol) of 2,2-bis(4-hydroxyphenyl)propane, 151.2 grams (0.9 mol)
of m-dinitrobenzene, 124.6 grams of potassium carbonate and 660 ml of
N,N-dimethylformamide. The mixture was reacted for 10 hours at a
temperature of 145-150C. After completing the reaction, the
resultant mixture was cooled and filtered to remove potassium nitrite.
The solvent was distilled off from the filtrate under reduced
pressure. The resldue was cooled to 65C, added with 450 ml of
14
,. . . .
129761S
methanol and stirred for an hour. The resulted crystals were
filtered, washed with water, washed with methanol, and dried to obtain
164.8 grams (93.5% yield) of 2,2-bis[4-(3-nitrophenoxy)phenyllpropane
as yellow brown crystals.
In the next step, a 500 ml glass reaction vessel was charged
with 100 grams (0.21 mol) of 2,2-bis[4-(3-nitrophenoxy)phenyl]propane,
10 grams of active carbon, 1 gram of ferric chloride hexahydrate and
300 ml of 2-methoxyethanol. The mixture was stirred for 30 minutes
under reflux and then added dropwise with 42 grams (0.84 mol) of
hydrazine hydrate during 2 hours at 70-80C. The reaction mixture
was further stirred for 5 hours at 70-80~C, cooled, filtered to remove
the catalyst, and 150 ml of 2-methoxyethanol was distilled off. The
residue thus obtained was added with 270 grams of 20% aqueous
hydrochloric acid solution and further 30 grams of sodium chloride,
and cooled to 20-25C with stirring. The separated crystals were
filtered and neutralized in 30% isopropyl alcohol with aqueous
ammonia. Thus separated cystals were filtered, washed with water,
dried and recrystallized from a solvent mixture of benzene and
n-hexane.
2,2-Bis[4-(3-aminophenoxy)phenyl]propane thus obtained was 69.2
grams (75% yield) and was colorless crystals having a melting point of
106-108C. The purity was 99.5% according to high-speed liquid
chromatography.
`- ~2976~S
Elementary analysis : C27 H26 N2 2
-
C H N
Calculated (%) 79.02 6.34 6.83
Found (%) 79.21 6.40 6.71
MS : 470 (M ): 455 (M-Ch3)+
IR (KBr.cm ) : 3460 and 3370 (amino group),
1220 (ether linkage)
Synthetic example 3
A 3 liter glass reaction vessel was charged with 218 grams (1
mol) of bis(4-hydroxyphenyl)sulfide, 403 grams (2.4 mols) of
m-dinitrobenzene, 331 grams (2.4 mols) of potassium carbonate and
2.5 1 of N,N-dimethylformamide. The mixture was reacted for 20
minutes at a temperature of 145-150C. After completlng the reaction,
the resultant mixture was cooled, filtered and the solvent was
distilled from the filtrate under reduced pressure. The residue thus
obtained was cooled to 65C, added with 800 ml of methanol and stirred
for an hour. The crystals obtained was filtered, washed with
methanol and dried to give 429 grams (92.3% yield) of bis[4-(3-nitro-
phenoxy)phenyl]sulfide as crystals.
In the next step, 428 grams (0.93 mol) of the crude
intermediate was charged in a 3 1 glass reaction vessel and added with
22.6 grams of active carbon, 0.9 gram of ferric chloride hexahydrate
and 1.5 1 of 2-methoxyethanol. The mixture was stirred for 30 minutes
under reflux, and then 115.2 grams (3.1 mols) of hydrazine hydrate was
added dropwise during 2 hours at 110-115C. The resultant mixture
16
129'7615
was further stirred for 3.5 hours under reflux, cooled and filtered to
remove the catalyst. The filtrate was concentrated under reduced
pressure and added with 205 ml of 35% hydrochloric acid, 1,120 ml of
water and 480 ml of isopropyl alcohol The mixture was warmed to
obtain a solution, added with 20 grams of active carbon and hot
filtered. The filtrate was then added with 112 grams of sodium
chloride, cooled and separated hydrochloride crystals were filtered.
The hydrochloride crystals were neutralized with aqueous ammonia by a
normal procedure to obtain 265 grams (66% yield) of desired
bis[4-(3-aminophenoxy)phenyl]sulfide as colorless crystals having a
melting point of 112-113C (corr.). The purity was higher than 99.9%.
Elementary analysis : C24 H20 N2 2 S
C H N S
Calculated (%) 71.97 5,03 7,00 8.01
Found (%) 71.90 4.54 6.92 7.72
MS (PD) : 400 (M )
IR (KBr.cm 1) : 3390 and 3300 (amino group),
1220 (ether linkage)
Examples 1-6
A reaction vessel equipped with a stirrer, reflux condenser and
nitrogen inlet tube was charged with 36.8 kilograms (100 mols) of
4,4'-(3-aminophenoxy)biphenyl and 175.8 kilograms of
N,N-dimethylacetamide. The mixture was added by portions with 21.8
kilograms (100 mols) of pyromellitic dianhydride at room temperature
17
129761S
under nitrogen atmosphere with care to prevent temperature rise of the
mixture, and stirred for about 20 hours at room temperature. The
polyamic acid thus obtained had an inherent viscosity of 2.47 dl/g.
The inherent viscosity is a value measured at 35C in a concentration
of 0.5 gram of sample/100 ml of solvent by use of N,N-dimethylacetamide
as the solvent.
In the next step 150 kilograms of above polyamic acid solution
was added with 337.5 kilograms of N,N-dimethylacetamide, warmed to
70C with stlrring under nitrogen atmosphere, and added dropwise with
26.1 kilograms (26 mols) of acetic anhydride and 9.05 kilograms (9
mols) of triethylamine. Yellow polyimide powder was started to
separate about 10 minutes after ending the dropwise addition, further
stirred for 2 hours under warming, and then hot filtered. The
polyimlde powder thus obtained was washed with methanol and dried at
150C for 5 hours under reduced pres~ure to afford 34,5 kilograms (98%
yield~ of polyimide powder.
To 100 parts by weight of the polyimide powder above obtained,
a silane treated glass fibre having 3mm in length and 13 microns in
diameter (Trade Mark; CS-3PE-476S, from Nitto Boseki) was added in an
amount illustrated in Table 1 and mixed in a drum blender (from Kawata
Seisakusho). The resultant mixture was kneaded in a molten state
at a temperature of 390C in a single screw extruder having 30mm in
apperture. The strand thus formed was air cooled and cut into
pellets.
The pellets obtained were injection molded with an Arburg
injection molding machine having a maximum mold clamping force of 35
tons under conditions; injection pressure of 500 kg/cm2, cylinder
' ~ '" ,~'
~2976~S
temperature of 400C and mold temperature of 180C. Specimens for
various tests were thus prepared and measured. The results are
illustrated in Table 1. The following physical properties were
measured in accordance with ASTM Testing methods.
Tensile strength ASTM D-638
Flexural modulus ASTM D-790
Flexural strength ASTM D-790
Notched Izod impact strength ASTM D-256
Heat distortion temperature ASTM D-648
Molding shrinkage ASTM D-955
Example 7
To 100 parts by weight of the polyimide powder obtained by the
same procedure as in Example 1, 150 parts by weight of
N,N~dimethylacetamide were added to make a suspension. The
suspension was further added and uniformely dispersed with 30 parts by
weight of a silane treated glass fibre having a length of 3mm and
diameter of 13 microns (Trade Mark; CS-3PE-476S, from Nitto Boseki).
After preliminary drying the resultant mixture in a hot air oven at
200C for 20 hours, it was dried in a vacuum desiccatar at 150C for 5
hours under reduced pressure in order to completely remove the
solvent. The polyimide impregnated glass fibre powder thus obtained
was pelletized and in;ection molded by the same procedure as in
Examples 1-6 to obtain specimens for testing the physical properties.
The physical properties were tested by the same procedure as in
Examples 1-6 and the results are illustrated in Table 2,
1297615
Examples 8
To 400 parts by weight of the polyamic acid solution obtained
by the same procedure as in Example 1, 30 parts by weight of the same
glass fibre as used in Examples 1-6 were dipped. Then the procedure
of Example 7 was repeated to obtain a polyimide impregnated glass
fibre powder. The powder was processed by the same procedure as in
Example 7 and the results are illustrated in Table 2.
Examples 9-11 and Comparative examples 1-3
To 100 parts by weight of the polyimide powder derived from the
diamine and tetracarboxylic dianhydride which are illustrated in Table
2, the same glass fibre as used in Examples 1-6 was added in an amount
illustrated in Table 2. The same procedures as in Examples 1-6 were
carried out to obtain results in Table 2.
In addition, the results obtained by using the glass fibre in
an amount outside the scope of this invention are also illustrated in
Table 3 as Comparative examples,
12976~S
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23
1297615
Examples 12-17
To 100 parts by weight of the polyimide powder obtained by the
same procedure as in Example 1, the carbon fibre having an average
diameter of 12 microns, length of 3 mm and aspect ratio of 250 (Trade
Mark; Torayca, from Toray Industries) was added in an amount
illustrated in Table 4. After mixing in a drum blender (from Kawata
Seisakusho), the resultant mixture was kneaded in a molten state at a
temperature of 390C in a single screw extruder having an aperture of
30mm. The strand thus formed was air cooled and cut into pellets.
The pellets obtained were injection molded with an Arburg
injection molding machine having a maximum mold clamping force of 35
tons under conditions; injection pressure of 500 kg/cm2, cylinder
temperature of 400C and mold temperature of 180C. Specimens for
various tests were prepared and measured. The results illustrated in
Table 4 are tensile strength, flexural modulus~ flexural strength,
notched Izod impact strength, heat distortion temperature and molding
shrinkage.
Example 18
To 100 parts by weight of the polyimide powder obtained by the
same procedure as in Example 1, 150 parts by weight of
N,N-dimethylacetamide were added to make a suspension. The suspension
was further added and uniformly dispersed with 30 parts by weight of a
carbon fibre having an average diameter of 12 microns, length of 3mm
and aspect ratio of 250 (Trade Mark; Torayca from Toray Industries).
After preliminary drying in a hot air oven at 200C for 20 hours, the
resultant mixture was dried in a vacuum desiccator at 150C for 5
hours under reduced pressure in order to completely remove the
24
12976~S
solvent. The polyimide impregnated carbon fibre powder thus obtained
was pelletized and injection molded by the same procedure as in
Examples 12-17 to obtain specimens for testing the physical
properties. The physical properties were tested by the same procedure
as in Examples 12-17 and the results are illustrated in Table 5.
Example 19
To 400 parts by weight of the polyamic acid solution obtained
by the same procedure as in Example 1, 30 parts by weight of the same
carbon fibre as used in Examples 12-17 were dipped. Then the
procedure of ~xample 18 was repeated to obtain a polyimide impregnated
carbon fibre powder. The powder was processed by the same procedure
as in Example 18 and the results are illustrated in Table 5.
In addition, the results obtained by using the carbon fibre in
an amount outside the scope of this invention are also illustrated in
Table 6 as Comparative examples,
12976i5
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26
129761S
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Examples 23-27
To 100 parts by weight of the polyimide powder obtained by the
same procedure as in Example 1, a potassium titanate fibre having a
sectional diameter of 0.2 micron and average length of 20 microns
(Trade Mark; Tismo-D from Ohtsuka Chemicals) was added in an amount
illustrated in Table 7 and mixed in a drum blender (from Kawata
Seisakusho). The resultant mixture was kneaded in a molten state at
a temperature of 390C in a single screw extruder having an apperture
of 30mm. The strand thus formed was air cooled and cut into pellets.
The pellets thus obtained were injection molded with an Arburg
injection molding machine having a maximum mold clamping force of 35
tons under conditions; injec~ion pressure of 500 kg/cm2, cylinder
temperature of 400C and mold temperature of 180C. Specimens for
various tests were prepared and measured. The specimen to measure
the molding shrinkage is a plate having dimensions of 50 x 50 x 3 mm.
A film gate having a thickness of 1 mm is provided in a side of 50mm.
The flow direction of the molten material is indicated by MD
(machine-direction) and the rectangular direction to that is indicated
by TD (transverse-direction). Table 7 shows tensile strength,
flexural modulus, flexural strength, notched Izod impact strength,
heat distortion temperature and molding shrinkage.
Example 28
.
To 100 parts by weight of the polyimide powder obtained by the
same procedure as in Example 1, 150 parts by weight of
N,N-dimethylacetamide were added to make a suspension. The suspension
is further added and uniformly dispersed with 30 parts by weight of a
potassium titanate fibre having a sectional diameter of 0.2 micron and
29
~297615
average length of 20 microns (Trade Mark; Tismo-D, from Ohtsuka
Chemcials). After preliminary drying in a hot air oven at 200C for
20 hours, the resultant mixture was dried in a vacuum desiccator at
150C for 5 hours under reduced pressure in order to completely remove
the solvent. The polyimide impregnated potassium titanate fibre thus
obtained was pelletized and injection molded by the same procedure as
in Examples 23-27 to obtain specimens for testing the physical
properties. The physical properties were examined by using these
specimens and the results obtained are illustrated in Table 8.
Example 29
To 400 parts by weight of the polyamic acid solution obtained
by the same procedure as in Example 1, 30 parts by weight of the same
potassium titanate fibre as used in Example 28 were dipped. Then the
procedure of Example 28 was repeated to obtain a polyimide impregnated
potassium titanate fibre. The fibre was processed by the same
procedure as in Example 28 and the results are illustrated in Table 8.
Examples 30-32 and Comparative examples 7-9
To 100 parts by weight of the polyimide powder derived from the
diamine and tetracarboxylic acid dianhydride which are illustrated in
Table 8, the same potassium titanate fibre as used in Examples 23-27
was added in an amount shown in Table 8. The same procedures as in
Examples 23-27 were carried out to obtain the results illustrated in
Table 8.
In addition, similar Comparative examples are illustrated in
Table 9.
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1297615
Examples 33-38
To 100 parts by weight of the polyimide powder obtained by the
same procedure as in Example 1, an aromatic polyamide fibre having an
average length of 3mm (Trade Mark; Kevlar, from E.I. du Pont de
Nemours & Co.) was added in an amount illustrated in Table 10 and
mixed in a drum blender (from Kawata Seisakusho). The resultant
mixture was kneaded in a molten state at a temperature of 390C in a
single screw extruder having an apperture of 30mm. The strand thus
formed was air cooled and cut into pellets.
The pellets thus obtained were injection molded with an Arburg
injection molding machine having a maximum mold clamping force of 35
tons under conditions; injection pressure of 500 kg/cm2, cylinder
temperature of 400C and mold temperature of 180C. Specimens for
various tests were prepared and measured. Table 10 shows tensile
Mtrength, flexural modulus, flexural strength, notched Izod impact
strength, heat distortion temperature and flowability.
Besides the test result on the flowability in molding is
demonstrated by the spiral flow length having a width of 10 mm and
thickness of 2.0mm under the aforesaid injection molding conditions,
that is, injection pressure of 500 kg/cm2, cylinder temperature of
400C and mold temperature of 180C.
Example 39
To 100 parts by weight of the polyimide powder obtained by the
same procedure as in Example 1, 150 parts by weight of
N,N-dimethylacetamide were added to make a suspension. The
su~pension is further added and uniformly dispersed with 30 parts by
weight of an aromatic polyamide fibre having an average length of 3mm
34
~ " .
129761S
(Trade Mark; Kevlar, from E.I, du Pont de Nemours & Co.). After
preliminary drying in a hot air oven at 200C for 20 hoursl the
resultant mixture was dried in a vacuum desiccator at 150C for 5
hours under reduced pressure in order to completely remove the
solvent. The polyimide impregnated aromatic polyamide fibre powder
thus obtained was pelletized and injection molded by the same
procedure as in Examples 33-38 to obtain specimens for testing the
physical properties, The physical properties were examined by using
these specimens and the results obtained are illustrated in Table 11.
Example 40
To 400 parts by weight of the polyamic acid solution obtained
by the same procedure as in Example 1, 30 parts by weight of the same
aromatic polyamide fibre as used in Examples 33-38 were impregnated.
The procedure of 39 was repeated to obtain the results
illustrated in Table 11.
Examples 41-43 and Comparative examples 10-12
To 100 parts by weight of the polyimide power derived from the
diamine and tetracarboxylic acid dianhydride which are illustrated in
Table 11, the same aromatic polyamide fibre as used in Examples 33-38
was added in an amount ~hown in Table 11. The same procedures as in
Examples 33-38 were carried out to obtain the results illustrated in
Table 11.
In addition, slmilar Comparative exampes are illustrated in
Table 12.
12976iS
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1297615
POSSIBILITY FOR USE I~ INDUSTRY
The polyimide resin composition of this invention has a high
heat distortion temperature and further holds a high-temperature
stability, dimensional stability and mechanical strength. Thus the
composition is a useful material for electric and elctronic devices,
automotive parts and articles for precision instruments. Therefore
the polyimide resin composition of this invention is very valuable in
industry.
39
