U.S. patent application number 11/667384 was filed with the patent office on 2007-12-27 for biaxially oriented polyarylene sulfide film and laminated polyarylene sulfide sheets comprising the same.
Invention is credited to Takuji Higashioji, Yasuyuki Imanishi, Atsushi Ishio, Tetsuya Machida, Masatoshi Ohkura, Megumi Yamada.
Application Number | 20070299219 11/667384 |
Document ID | / |
Family ID | 36336341 |
Filed Date | 2007-12-27 |
United States Patent
Application |
20070299219 |
Kind Code |
A1 |
Higashioji; Takuji ; et
al. |
December 27, 2007 |
Biaxially Oriented Polyarylene Sulfide Film and Laminated
Polyarylene Sulfide Sheets Comprising the Same
Abstract
A biaxially oriented polyarylene sulfide film and laminated
polyarylene sulfide sheets of the film contain polyarylene sulfide
and other thermoplastic resin A different from the polyarylene
sulfide, wherein the contents of the polyarylene sulfide and the
thermoplastic resin A are 70 to 99 parts by weight and 1 to 30
parts by weight respectively when the total amount of the
polyarylene sulfide and the thermoplastic resin A is taken as 100
parts by weight and the resin thermoplastic A forms a dispersed
phase with an average particle diameter of 10 to 500 nm and the
biaxially oriented polyarylene sulfide film exhibits a tensile
elongation at break of 110 to 250% in at least one of the
longitudinal direction and width direction and a tensile fracture
elongation of 80 to 250% in the other direction.
Inventors: |
Higashioji; Takuji; (Kyoto,
JP) ; Machida; Tetsuya; (Osaka, JP) ; Ohkura;
Masatoshi; (Shiga, JP) ; Imanishi; Yasuyuki;
(Shiga, JP) ; Ishio; Atsushi; (Aichi, JP) ;
Yamada; Megumi; (Shiga, JP) |
Correspondence
Address: |
KUBOVCIK & KUBOVCIK
SUITE 710
900 17TH STREET NW
WASHINGTON
DC
20006
US
|
Family ID: |
36336341 |
Appl. No.: |
11/667384 |
Filed: |
October 4, 2005 |
PCT Filed: |
October 4, 2005 |
PCT NO: |
PCT/JP05/18311 |
371 Date: |
July 6, 2007 |
Current U.S.
Class: |
525/535 |
Current CPC
Class: |
B32B 27/281 20130101;
B32B 2307/206 20130101; C08J 5/18 20130101; C08L 81/02 20130101;
B32B 27/28 20130101; B32B 27/34 20130101; B32B 2270/00 20130101;
C08J 2381/04 20130101; B32B 27/08 20130101; C08L 2666/02 20130101;
B32B 27/285 20130101; B32B 2307/734 20130101; B32B 2307/518
20130101; C08L 81/02 20130101; B32B 27/286 20130101 |
Class at
Publication: |
525/535 |
International
Class: |
C08L 81/02 20060101
C08L081/02; C08J 5/18 20060101 C08J005/18; C08L 101/00 20060101
C08L101/00 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 12, 2004 |
JP |
2004-328716 |
Jan 18, 2005 |
JP |
2005-010140 |
Claims
1. A biaxially oriented polyarylene sulfide film comprising
polyarylene sulfide and other thermoplastic resin A different from
the polyarylene sulfide, wherein the contents of the polyarylene
sulfide and the thermoplastic resin A are 70 to 99 parts by weight
and 1 to 30 parts by weight respectively when the total amount of
the polyarylene sulfide and the thermoplastic resin A is taken as
100 parts by weight and the resin thermoplastic A forms a dispersed
phase with an average particle diameter of 10 to 500 nm and the
biaxially oriented polyarylene sulfide film exhibits a tensile
elongation at break of 110 to 250% in at least one of the
longitudinal direction and width direction and a tensile elongation
at break of 80 to 250% in the other direction.
2. The biaxially oriented polyarylene sulfide film according to
claim 1, wherein the polyarylene sulfide is polyphenylene
sulfide.
3. The biaxially oriented polyarylene sulfide film according to
claim 1, wherein the thermoplastic resin A is at least one kind of
polymer selected from polyamide, polyether imide, polyether sulfone
and polysulfone.
4. The biaxially oriented polyarylene sulfide film according to
claim 1, wherein the crystal melting heat quantity of the
polyarylene sulfide is 20 to 45 (J/g).
5. The biaxially oriented polyarylene sulfide film according to
claim 1, wherein the primary dispersion peak temperature at loss
tangent of dynamic viscoelasticity at a frequency of 1 Hz is 100 to
135.degree. C.
6. A laminated polyarylene sulfide sheet wherein at least one of
the outermost layers is a laminated polyarylene sulfide sheet, and
the outermost layer is a biaxially oriented polyarylene sulfide
film layer (layer a) containing polyarylene sulfide and other
thermoplastic resin A different from the polyarylene sulfide, and
the contents of the polyarylene sulfide and the thermoplastic resin
A in the layer a are 70 to 99 parts by weight and 1 to 30 parts by
weight respectively when the total amount of the polyarylene
sulfide and the thermoplastic resin A is taken as 100 parts by
weight in the layer a and the resin A forms a dispersed phase with
an average particle diameter of 10 to 500 nm and the laminated
polyarylene sulfide sheet exhibits a tensile elongation at break of
80 to 250% in both the longitudinal direction and width
direction.
7. The laminated polyarylene sulfide sheet according to claim 6,
wherein the polyarylene sulfide is polyphenylene sulfide.
8. The laminated polyarylene sulfide sheet according to claim 6,
wherein the thermoplastic resin A is at least one kind of polymer
selected from the group consisting of polyamide, polyether imide,
polyether sulfone and polysulfone.
9. The laminated polyarylene sulfide sheet according to claim 6,
wherein the tensile elongation at break in at least one of the
longitudinal direction and width direction is 110 to 250%.
10. The laminated polyarylene sulfide sheet according to claim 6,
wherein the thickness of a layer other than the outermost layer is
2% to 30% based on the total thickness of the sheet.
11. The laminated polyarylene sulfide sheet according to claim 6,
which comprises a non-oriented polyarylene sulfide film layer
(layer b) as a layer other than the outermost layer.
12. The laminated polyarylene sulfide sheet according to claim 6,
which comprises a copolymerized polyphenylene sulfide film layer
(layer c) as a layer other than the outermost layer.
Description
TECHNICAL FIELD
[0001] The present invention relates to a biaxially oriented
polyarylene sulfide film and a laminated polyarylene sulfide sheet,
which have excellent heat resistance, dimensional stability,
electrical properties and chemical resistance. The film or sheet of
the present invention can be used in an electrical insulating
material for a motor, a transformer, an insulated cable etc., a
molding material, a circuit board material, a step/release film
such as circuit/optical element etc., a protective film, a lithium
ion battery material, a fuel battery material, a speaker diaphragm,
etc. More specifically, the present invention relates to a
biaxially oriented polyarylene sulfide film which can be preferably
used in an electrical insulating material for a hot-water supplier
motor, a motor for car air conditioner and a driving motor used in
a hybrid car, and a speaker diaphragm for cell-phone.
BACKGROUND ART
[0002] In electrical insulating materials for motors, it has
recently demanded to have heat resistance at high temperature and
hydrolysis resistance. For example, new alternatives for cooling
medium have been proposed as electrical insulating materials for
motors used in refrigerators and air conditioners, in connection
with abolition of specific chlorofluorocarbons from an
environmental problem. Such cooling medium and its compatible
lubricant easily absorb water, so in the above-mentioned insulating
materials, there is a demand for hydrolysis resistance in addition
to heat resistance. In electrical insulating materials for motors
used in hybrid cars, water is infiltrated into the materials under
usage environment, so there is a demand for hydrolysis resistance
in addition to heat resistance.
[0003] A polyarylene sulfide film has excellent features such as
heat resistance, flame retardancy, rigidity, chemical resistance,
electrical insulating properties and low hygroscopicity and is used
particularly preferably in electrical instruments, electronics,
machine parts and automobile parts.
[0004] In recent years, application of a polyphenylene sulfide
(hereinafter abbreviated sometimes as PPS) film to electrical
insulating materials proceeds to make use of its electrical
insulating properties and excellent low hygroscopicity. For
example, (1) use of a biaxially oriented film as an electrical
insulating material is known (see Patent Document 1). Further, (2)
a non-oriented PPS sheet is also known (see Patent Documents 2 and
3). In addition, (3) a laminate comprising a biaxially oriented PPS
layer laminated on a non-oriented PPS layer without an adhesive is
known (see Patent Documents 4 and 5).
[0005] However, the conventional film, sheet, laminated film and
laminate described above have the following problems. That is, the
film in the item (1) above may be unsatisfactory in tensile
elongation at break, impact resistance and tear propagation
strength, and when used for example as a motor slot liner or as a
wedge, causes film breakage or delamination in some cases. The
non-oriented PPS sheet in the item (2) above is excellent in tear
propagation strength, but is extremely poor in tensile elongation
at break and lowers its strength rapidly at a temperature near to
the melting point, thus significantly deteriorating shape retention
in some cases. The laminate in the item (3) above is laminated
without an adhesive to increase the film thickness thereby
increasing the stiffness of the film, but the adhesive strength of
laminate interface is insufficient so the tensile elongation at
break is low thus causing a problem in processability in some
cases.
[0006] As described above, the polyphenylene sulfide film is poor
in ductility and tensile elongation at break, thus making its
applications limited at present, and its improvement is strongly
desired. For a method of improving its ductility, a resin
composition or a film having other thermoplastic resin mixed in
polyphenylene sulfide is proposed. For example, a composition
comprising nylon 11 and nylon 12 dispersed as particles having an
average diameter of 1 .mu.m or less (see Patent Document 6), a
composition comprising PPS, polyamide and epoxy resin (see Patent
Document 7), a composition comprising PPS and polyamide (see Patent
Documents 8 and 9), a film comprising PPS and polyether imide (see
Patent Document 10), a film comprising PPS and polysulfone (see
Patent Document 11) etc. are disclosed, but a resin composition or
a film having thermoplastic resin such as polyamide or polysulfone
dispersed ultra-finely in the range of 10 to 500 nm in PPS is not
described. On the other hand, a resin composition having
thermoplastic resin such as polyamide dispersed ultra-finely in a
characteristically dispersed state is proposed (see Patent Document
12). However, this resin composition has formed a structure by
shear field-dependent phase solubilization/phase separation wherein
the resin is destabilized again in a non-shear state to cause phase
separation after it is once compatibilized in a shear field at the
time of melt-kneading, and when a sheet or film is formed, its
structural stability is not sufficient in some cases, and the
appropriate method for forming a biaxially oriented film is not
described.
[0007] Patent Document 1: Japanese Unexamined Patent Publication
No. 1980-35456
[0008] Patent Document 2: Japanese Unexamined Patent Publication
No. 1981-34426
[0009] Patent Document 3: Japanese Unexamined Patent Publication
No. 1982-121052
[0010] Patent Document 4: Japanese Unexamined Patent Publication
No. 1990-45144
[0011] Patent Document 5: Japanese Unexamined Patent Publication
No. 1992-319436
[0012] Patent Document 6: Japanese Unexamined Patent Publication
No. 1991-81367
[0013] Patent Document 7: Japanese Unexamined Patent Publication
No. 1984-155462
[0014] Patent Document 8: Japanese Unexamined Patent Publication
No. 1988-189458
[0015] Patent Document 9: Japanese Unexamined Patent Publication
No. 2001-302918
[0016] Patent Document 10: Japanese Unexamined Patent Publication
No. 1992-146935
[0017] Patent Document 11: Japanese Unexamined Patent Publication
No. 1987-121761
[0018] Patent Document 12: Japanese Unexamined Patent Publication
No. 2003-113307
DISCLOSURE OF INVENTION
Problem to be Solved by the Invention
[0019] The object of the present invention is to provide a
biaxially oriented polyarylene sulfide film excellent in molding
processability by improving the tensile elongation at break of a
biaxially oriented polyarylene sulfide film having excellent heat
resistance, dimensional stability, electrical properties, and
chemical resistance. The film or sheet of the present invention can
be used in an electrical insulating material for a motor, a
transformer, an insulated cable etc., a molding material, a circuit
board material, a step/release film for circuit/optical element
etc., a protective film, a lithium ion battery material, a fuel
battery material, a speaker diaphragm etc. and more specifically,
it can be used in an electrical insulating material for a hot-water
supplier motor, a motor for car air conditioner and a driving motor
used in a hybrid car, and a speaker diaphragm for cell-phone.
[0020] The object of the laminated polyarylene sulfide sheet of the
present invention is to improve molding processability by improving
tensile elongation at break. Particularly, the object of the
laminated polyarylene sulfide sheet of the present invention is to
prevent an electrical insulating material for a hot-water supplier
motor and a motor for car air conditioner and a driving motor used
in a hybrid car from generating film cracking upon bending
processing, thus making it usable preferably as a slot or
wedge.
Means for Solving the Problem
[0021] To achieve the object, the present invention has the
following constitution:
[0022] (1) a biaxially oriented polyarylene sulfide film comprising
polyarylene sulfide and other thermoplastic resin A different from
the polyarylene sulfide, wherein the contents of the polyarylene
sulfide and the thermoplastic resin A are 70 to 99 parts by weight
and 1 to 30 parts by weight respectively when the total amount of
the polyarylene sulfide and the thermoplastic resin A is taken as
100 parts by weight and the resin thermoplastic A forms a dispersed
phase with an average particle diameter of 10 to 500 nm and the
biaxially oriented polyarylene sulfide film exhibits a tensile
elongation at break of 110 to 250% in at least one of the
longitudinal direction and width direction and a tensile elongation
at break of 80 to 250% in the other direction;
[0023] (2) the biaxially oriented polyarylene sulfide film
according to the above-mentioned (1), wherein the polyarylene
sulfide is polyphenylene sulfide;
[0024] (3) the biaxially oriented polyarylene sulfide film
according to the above-mentioned (1) or (2), wherein the
thermoplastic resin A is at least one kind of polymer selected from
polyamide, polyether imide, polyether sulfone and polysulfone;
[0025] (4) the biaxially oriented polyarylene sulfide film
according to any of the above-mentioned (1) to (3), wherein the
crystal melting heat quantity of the polyarylene sulfide is 20 to
45 (J/g);
[0026] (5) the biaxially oriented polyarylene sulfide film
according to any of the above-mentioned (1) to (4), wherein the
primary dispersion peak temperature at loss tangent of dynamic
viscoelasticity at a frequency of 1 Hz is 100 to 135.degree.
C.;
[0027] (6) a laminated polyarylene sulfide sheet wherein at least
one of the outermost layers is a laminated polyarylene sulfide
sheet, and the outermost layer is a biaxially oriented polyarylene
sulfide film layer (layer a) containing polyarylene sulfide and
other thermoplastic resin A different from the polyarylene sulfide,
and the contents of the polyarylene sulfide and the thermoplastic
resin A in the layer a are 70 to 99 parts by weight and 1 to 30
parts by weight respectively when the total amount of the
polyarylene sulfide and the thermoplastic resin A is taken as 100
parts by weight in the layer a and the resin A forms a dispersed
phase with an average particle diameter of 10 to 500 nm and the
laminated polyarylene sulfide sheet exhibits a tensile elongation
at break of 80 to 250% in both the longitudinal direction and width
direction;
[0028] (7) the laminated polyarylene sulfide sheet according to the
above-mentioned (6), wherein the polyarylene sulfide is
polyphenylene sulfide;
[0029] (8) the laminated polyarylene sulfide sheet according to the
above-mentioned (6) or (7), wherein the thermoplastic resin A is at
least one kind of polymer selected from the group consisting of
polyamide, polyether imide, polyether sulfone and polysulfone;
[0030] (9) the laminated polyarylene sulfide sheet according to any
of the above-mentioned (6) to (8), wherein the elongation at break
in at least one of the longitudinal direction and width direction
is 110 to 250%;
[0031] (10) the laminated polyarylene sulfide sheet according to
any of the above-mentioned (6) to (9), wherein the thickness of a
layer other than the outermost layer is 2% to 30% based on the
total thickness of the sheet;
[0032] (11) the laminated polyarylene sulfide sheet according to
any of the above-mentioned (6) to (10), which comprises a
non-oriented polyarylene sulfide film layer (layer b) as a layer
other than the outermost layer; and
[0033] (12) the laminated polyarylene sulfide sheet according to
any of the above-mentioned (6) to (10), which comprises a
copolymerized polyphenylene sulfide film layer (layer c) as a layer
other than the outermost layer.
Effects of the Invention
[0034] According to the present invention, a high-quality biaxially
oriented polyarylene sulfide film and laminated polyarylene sulfide
sheet excellent in molding processability can be provided by
improving the tensile elongation at break of a biaxially oriented
polyarylene sulfide film having excellent heat resistance,
dimensional stability, electrical properties and chemical
resistance, as described above. Particularly, there can be obtained
a biaxially oriented polyarylene sulfide film and a laminated
polyarylene sulfide sheet which can be used preferably in an
electrical insulating material for a hot-water supplier motor, a
motor for car air conditioner and a driving motor used in a hybrid
car, and a speaker diaphragm for cell-phone.
BEST MODE FOR CARRYING OUT THE INVENTION
[0035] Hereinafter, the biaxially oriented polyarylene sulfide film
of the present invention is described. The biaxially oriented
polyarylene sulfide film of the present invention is a biaxially
oriented polyarylene sulfide film comprising polyarylene sulfide
and other thermoplastic resin A different from the polyarylene
sulfide, wherein the contents of the polyarylene sulfide and the
thermoplastic resin A are 70 to 99 parts by weight and 1 to 30
parts by weight respectively when the total amount of the
polyarylene sulfide and the other thermoplastic resin A is taken as
100 parts by weight. The resin thermoplastic A forms a dispersed
phase with an average particle diameter of 10 to 500 nm. The
obtained film can thereby be endowed with improved tensile
elongation at break.
[0036] In the biaxially polyarylene sulfide film wherein the total
amount of the polyarylene sulfide and the other thermoplastic resin
A is taken as 100 parts by weight, preferably the content of the
polyarylene sulfide is 70 to 95 parts by weight and the content of
the thermoplastic resin A is 5 to 30 parts by weight, more
preferably the content of the polyarylene sulfide is 80 to 95 parts
by weight and the content of the thermoplastic resin A is 5 to 20
parts by weight, still more preferably the content of the
polyarylene sulfide is 80 to 93 parts by weight and the content of
the thermoplastic resin A is 7 to 20 parts by weight. When the
thermoplastic resin A is greater than 30 parts by weight, the heat
resistance and chemical resistance of the biaxially oriented
polyarylene sulfide may be deteriorated. When the thermoplastic
resin A is less than 1 part by weight, the tensile elongation at
break is hardly improved to confer ductility.
[0037] The biaxially oriented polyarylene sulfide film of the
present invention has excellent tensile elongation and ductility in
addition to excellent heat resistance, chemical resistance and
electrical properties inherent in the polyarylene sulfide film. To
exhibit such characteristics, it is important that the polyarylene
sulfide forms a sea phase (continuous phase or matrix), while the
other thermoplastic resin A forms an island phase (dispersed
phase). As used herein, the dispersed phase consists of a phase of
2 or more components which can be measured with an optical
microscope or an electron microscope, and refers to a phase
dispersed as an island phase in a sea phase that is a continuous
phase, wherein the sea phase and island phase are contacted with
each other via an interface. The shape of the dispersed phase is
for example roughly spherical, thin island-shaped, roughly
elliptical, or fibrous. The shape may be approximately in the above
form, and the interface between the sea phase and island phase may
be in a concavo-convex form or multileaf form. The adjacent
dispersed phases may be bound to one another. The dispersed phase
of the present invention can be confirmed with a transmission
electron microscope. It is important that the average particle
diameter of dispersed thermoplastic resin A is in the range of 10
to 500 nm, preferably 20 to 300 nm, more preferably 30 to 200 nm,
most preferably 30 to 120 nm. The polyarylene sulfide forms a
continuous phase by which the film can greatly reflect the
excellent heat resistance, chemical resistance and electrical
properties of the polyarylene sulfide. By regulating the average
particle diameter of the dispersed phase in the above range, a
biaxially oriented polyarylene sulfide film excellent in balance
between heat resistance and tensile elongation at break can be
obtained. When the average particle diameter of the dispersed phase
is less than 10 nm, the effect of improvement of tensile elongation
in the present invention cannot be sufficiently conferred on the
film in some cases. On the other hand, when the average particle
diameter of the dispersed phase is greater than 500 nm, the heat
resistance may be deteriorated and the film may be broken upon
stretching. When the adjacent dispersed phases are bound to one
another, the average particle diameter in the form of dispersed,
spherical, thin island-shaped, elliptical or fibrous phases is
determined.
[0038] As used herein, the average particle diameter of the
dispersed phase refers to the average diameter in the longitudinal
direction, the width direction and the thickness direction of the
film. The average particle diameter of the dispersed phase can be
measured with a transmission electron microscope. For example, the
average particle diameter of the dispersed phase is determined by
preparing a sample by ultramicrotomy, then observing it with a
transmission electron microscope under the condition of an applied
voltage of 100 kV, taking a photograph thereof at 20,000-fold
magnification, scanning the obtained photograph as an image with an
image analyzer and selecting arbitrary 100 dispersed phases,
followed by image processing (measurement method will be described
in detail later).
[0039] The aspect ratio of the dispersed phase is not particularly
limited, and is preferably in the range of 1 to 20. The aspect
ratio of the dispersed phase is more preferably in the range of 2
to 15, still more preferably in the range of 2 to 10. Preferably,
the aspect ratio of these island components is regulated in the
above range so that the biaxially oriented polyarylene sulfide film
with improvement in tensile elongation can be easily obtained. The
aspect ratio refers to the average major axis/average minor axis
ratio of the dispersed phase. The aspect ratio can be measured with
a transmission electron microscope. For example, the aspect ratio
is determined by preparing a sample by ultramicrotomy, then
observing it with a transmission electron microscope under the
condition of an applied voltage of 100 kV, taking a photograph
thereof at 20,000-fold magnification, scanning the obtained
photograph as an image with an image analyzer and selecting
arbitrary 100 dispersed phases, followed by image processing
(measurement method will be described in detail later).
[0040] As used herein, the polyarylene sulfide is a homopolymer or
copolymer having a repeating unit --(Ar--S)--. Ar includes
structural units represented by the following formula (A) to (K):
##STR1## wherein R1 and R2 each represent a substituent group
selected from hydrogen, an alkyl group, an alkoxy group and a
halogen group, and R1 and R2 may be the same or different.
[0041] The repeating unit of the polyarylene sulfide used in the
present invention is preferably a structural formula represented by
the above formula (A), and typical examples include polyphenylene
sulfide, polyphenylene sulfide sulfone, polyphenylene sulfide
ketone, random copolymers and block copolymers thereof and mixtures
thereof. From the standpoint of film physical properties and from
an economical viewpoint, the polyarylene sulfide is particularly
preferably polyphenylene sulfide (PPS) that is a resin containing,
as a major constituent unit of the polymer, preferably at least 80
mol %, more preferably at least 90 mol %, p-phenylene sulfide unit
represented by the structural formula below. When such p-phenylene
sulfide component is less than 80 mol %, the crystallinity and heat
transfer temperature of the polymer are low, and properties of PPS,
that is, heat resistance, dimensional stability, mechanical
characteristics and dielectric characteristics may be deteriorated.
##STR2##
[0042] In the above-mentioned PPS resin, other copolymerizable
sulfide linkage-containing units may be contained in an amount of
less than 20 mol %, preferably less than 10 mol %, based on the
total repeating units. Repeating units contained in an amount of
less than 20 mol %, preferably less than 10 mol %, based on the
total repeating units include, for example, a trifunctional unit,
an ether unit, a sulfone unit, a ketone unit, a meta-linkage unit,
an aryl unit having a substituent group such as an alkyl group, a
biphenyl unit, a terphenylene unit, a vinylene unit and a carbonate
unit, and specific examples include the following structural units.
Among these units, one or more units can be coexistent to
constitute the resin. In this case, the structural units may be
copolymerized to form a random or block copolymer. ##STR3##
[0043] Insofar as the PPS resin and PPS resin composition can be
melted and kneaded, the melt viscosity thereof is not particularly
limited, and is preferably in the range of 100 to 2,000 Pas, more
preferably 200 to 1,000 Pas, at a shear rate of 1,000 (1/sec) at a
temperature of 315.degree. C.
[0044] PPS mentioned in the present invention can be produced by
various methods, for example, by a method of obtaining a polymer
having a relatively small molecular weight as described in Japanese
Examined Patent Publication No. 1970-3368 or a method of obtaining
a polymer having a relatively large molecular weight as described
in Japanese Examined Patent Publication No. 1977-12240 or Japanese
Unexamined Patent Publication 1986-7332.
[0045] In the present invention, the resulting PPS resin can also
be used after various treatments such as
crosslinkage/polymerization by heating in air, heat treatment under
an inert gas atmosphere such as nitrogen or under reduced pressure,
washing with an organic solvent, hot water and an aqueous acid
solution, and activation with a functional group-containing
compound such as an acid anhydride, amine, isocyanate and
functional disulfide compound.
[0046] Now, the method of producing PPS resin is illustrated, but
is not particularly limited in the present invention. For example,
sodium sulfide and p-dichlorobenzene are reacted at high
temperature at high pressure in an amide-based polar solvent such
as N-methyl-2-pyrrolidone (NMP). If necessary, a copolymerization
component such as trihalobenzene can be contained therein. As an
agent for regulating the degree of polymerization, potassium
hydroxide or an alkali metal carboxylate can be added for
polymerization reaction at 230 to 280.degree. C. After
polymerization, the polymer is cooled and filtered as water slurry
through a filter to give a granular polymer. This product is
stirred in an aqueous solution such as acetate at 30 to 100.degree.
C. for 10 to 60 minutes, then washed several times with deionized
water at 30 to 80.degree. C. and dried to give PPS powder. This
powdery polymer is washed with NMP at an oxygen partial pressure of
10 Torr or less, preferably 5 Torr or less, then washed several
times with deionized water at 30 to 80.degree. C. and dried under
reduced pressure at 5 Torr or less. The polymer thus obtained is a
substantially linear PPS polymer and can thus be stably stretched
to produce a film. As a matter of course, other polymer compounds
and organic or inorganic compounds such as silicon oxides,
magnesium oxide, calcium carbonate, titanium oxide, aluminum oxide,
crosslinked polyester, crosslinked polystyrene, mica, talc and
kaolin, pyrolysis inhibitors, heat stabilizers and antioxidants may
be added if necessary.
[0047] The method of crosslinkage/polymerization of PPS resin by
heating can be exemplified specifically by a method which involves
heating until desired melt viscosity is obtained at a predetermined
temperature in a heated container, in an oxidizing gas atmosphere
such as air or oxygen or in a mixed-gas atmosphere consisting of
the oxidizing gas and an inert gas such as nitrogen and argon. The
heat treatment temperature is usually selected in the range of 170
to 280.degree. C., more preferably 200 to 270.degree. C., and the
heat treatment time is usually selected in the range of 0.5 to 100
hours, more preferably 2 to 50 hours, and both the heat treatment
temperature and time can be regulated to attain the intended
viscosity level. The device for heat treatment may be a usual hot
air drying machine or a rotary heating device or a heating device
equipped with a stirring blade, and for efficient and uniform
treatment, a rotary heating device or a heating device equipped
with a stirring blade is preferably used.
[0048] The method of heat treatment of PPS resin in an inert gas
atmosphere such as nitrogen or under reduced pressure can be
exemplified specifically by a method of heat treatment at a heat
treatment temperature of 150 to 280.degree. C., preferably 200 to
270.degree. C., for a heating time of 0.5 to 100 hours, preferably
2 to 50 hours, in an inert gas atmosphere such as nitrogen or under
reduced pressure. The device for heat treatment may be a usual hot
air drying machine or a rotary heating device or a heating device
equipped with a stirring blade, and for efficient and uniform
treatment, a rotary heating device or a heating device equipped
with a stirring blade is preferably used. The PPS resin used in the
present invention is preferably substantially linear PPS which is
not subjected to polymerization by thermal oxidation crosslinking
treatment in order to achieve the aim of improvement of tensile
elongation at break.
[0049] The PPS resin used in the present invention is preferably
PPS resin subjected to deionization treatment. The method of
deionization treatment can be exemplified specifically by washing
treatment with an aqueous acid solution, washing treatment with hot
water and washing treatment with an organic solvent, and these
treatments may be a combination of two or more methods.
[0050] The method of washing treatment of PPS resin with an organic
solvent can be exemplified by the following method. That is, the
organic solvent is not particularly limited insofar as it does not
have an action of decomposing PPS resin, and examples include
nitrogen-containing polar solvents such as N-methyl pyrrolidone,
dimethyl formamide, dimethyl acetamide etc., sulfoxide sulfone
solvents such as dimethyl sulfoxide, dimethyl sulfone etc., ketone
solvents such as acetone, methyl ethyl ketone, diethyl ketone,
acetophenone etc., ether solvents such as dimethyl ether, dipropyl
ether, tetrahydrofuran etc., halogen-based solvents such as
chloroform, methylene chloride, trichloroethylene, ethylene
dichloride, dichloroethane, tetrachloroethane, chlorobenzene etc.,
alcohol phenol solvents suchasmethanol, ethanol, propanol, butanol,
pentanol, ethylene glycol, propylene glycol, phenol, cresol,
polyethylene glycol etc., and aromatic hydrocarbon solvents such as
benzene, toluene and xylene. Among these organic solvents, N-methyl
pyrrolidone, acetone, dimethyl formamide and chloroform can be
particularly preferably used. These organic solvents can be used
alone or as a mixture of two or more thereof.
[0051] The method of washing with an organic solvent includes a
method of dipping PPS resin in an organic solvent, wherein the
resin can be suitably stirred or heated if necessary. When PPS
resin is washed with an organic solvent, the washing temperature is
not particularly limited and can be selected arbitrarily in the
range of ordinary temperature to 300.degree. C. As the washing
temperature is increased, the efficiency of washing tends to
increase, and usually a sufficient effect can be obtained at
ordinary temperature to a temperature of 150.degree. C. The PPS
resin washed with an organic solvent is preferably washed several
times with water or heated water to remove the residual organic
solvent.
[0052] The specific method of washing PPS resin with heated water
can be exemplified by the following method. That is, the water used
is preferably distilled water or deionized water to exhibit the
effect of preferable chemical modification of PPS resin by washing
with heated water. The operation of treatment with heated water is
carried out usually by introducing a predetermined amount of PPS
resin into a predetermined amount of water and heating it under
stirring at ordinary pressures or in a pressurized container. The
ratio of PPS resin to water is established preferably such that
water is greater than PPS resin, and usually a bath ratio of 200 g
or less of PPS resin to 1 L of water is selected.
[0053] The specific method of washing PPS resin with an aqueous
acid solution can be exemplified by the following method. That is,
there is a method of dipping PPS resin in an acid or in an aqueous
acid solution, if necessary under suitable stirring or heating. The
used acid is not particularly limited insofar as it does not have
an action of decomposing PPS resin, and examples of such acid
include aliphatic saturated monocarboxylic acids such as formic
acid, acetic acid, propionic acid and butyric acid,
halogen-substituted aliphatic saturated carboxylic acids such as
chloroacetic acid, dichloroacetic acid etc., aliphatic unsaturated
monocarboxylic acids such as acrylic acid, crotonic acid etc.,
aromatic carboxylic acids such as benzoic acid, salicylic acid
etc., dicarboxylic acids such as oxalic acid, malonic acid,
succinic acid, phthalic acid, fumaric acid etc., and inorganic acid
compounds such as sulfuric acid, phosphoric acid, hydrochloric
acid, carbonic acid and silicic acid. Among these compounds, acetic
acid and hydrochloric acid are preferably used. Acid-treated PPS
resin is preferably washed several times with water or heated water
to remove a residual acid, salt etc. The water used in washing is
preferably distilled water or deionized water in the sense that the
effect of preferable chemical modification of PPS resin is not
deteriorated by acid treatment. By washing with an aqueous acid
solution, the acid terminal component of PPS resin is preferably
increased to increase dispersibility and mixing performance with
other thermoplastic resin A thereby easily attaining an effect of
reducing the average particle diameter of the dispersed phase.
[0054] As the other thermoplastic resin A different from the
polyarylene sulfide contained in the biaxially oriented polyarylene
sulfide film of the present invention, it is possible to employ,
for example, various polymers such as polyamide, polyether imide,
polyether sulfone, polysulfone, polyphenylene ether, polyester,
polyarylate, polyamide imide, polycarbonate, polyolefin and
polyether ether ketone, and blends containing at least one of these
polymers. From the viewpoint of mixing with the polyarylene sulfide
and exhibiting the effect of the present invention, the
thermoplastic resin A in the present invention is preferably at
least one member selected from polyamide, polyether imide,
polyether sulfone and polysulfone. Particularly, the polyamide
itself can be preferably used because it is a polymer having
excellent ductility.
[0055] As the thermoplastic resin A contained in the biaxially
oriented polyarylene sulfide of the present invention, a polyamide
is preferably used. The polyamide is not particularly limited
insofar as it is a known polyamide, and the polyamide is usually a
polyamide based on main constituents such as amino acid, lactam or
diamine and dicarboxylic acid. Typical examples of its main
constituents include amino acids such as 6-aminocaproic acid,
11-aminoundecanoic acid, 12-aminododecanoic acid,
para-aminomethylbenzoic acid etc., lactams such as
.epsilon.-aminocaprolactam, .omega.-laurolactam etc., aliphatic,
alicyclic and aromatic diamines such as tetramethylenediamine,
hexamethylenediamine, undecamethylene diamine, dodecamethylene
diamine, 2,2,4-/2,4,4-trimethylhexamethylene diamine,
5-methylnonamethylene diamine, meta-xylene diamine, para-xylylene
diamine, 1,3-bis(aminomethyl)cyclohexane,
1,4-bis(aminomethyl)cyclohexane,
1-amino-3-aminomethyl-3,5,5-trimethyl cyclohexane,
bis(4-aminocyclohexyl)methane,
bis(3-methyl-4-aminocyclohexyl)methane,
2,2-bis(4-aminocyclohexyl)propane, bis(aminopropyl)piperazine,
aminoethyl piperazine, 2-methylpentamethylene diamine etc.,
aliphatic, alicyclic and aromatic dicarboxylic acids such as adipic
acid, suberic acid, azelaic acid, sebacic acid, dodecane diacid,
terephthalic acid, isophthalic acid, 2-chloroterephthalic acid,
2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium
sulfoisophthalic acid, hexahydroterephthalic acid,
hexahydroisophthalic acid etc., and in the present invention,
polyamide homopolymers or copolymers derived from these materials
can be used alone or as a mixture thereof.
[0056] The polyamide useful in the present invention includes
homopolyamide resins such as polycaproamide (nylon 6),
polyhexamethylene adipamide (nylon 66), polytetramethylene
adipamide (nylon 46), polyhexamethylene cebacamide (nylon 610),
polyhexamethylene dodecamide (nylon 612), polydodecane amide (nylon
12), polyundecane amide (nylon 11), polyhexamethylene
terephthalamide (nylon 6T), polyxylylene adipamide (nylon XD6) etc.
or copolymers thereof, that is, copolymer polyamide (nylon 6/66,
nylon 6/10, nylon 6/66/610, 66/6T) etc. These polyamide resins can
also be used as a mixture thereof ("/" indicates copolymerization;
this hereinafter applies).
[0057] As the homopolyamide resin described above, nylon 6, nylon
610 or nylon 46 is more preferably used. Particularly, nylon 610
can be preferably used because it has high heat resistance in
co-extrusion with polyarylene sulfide and has an effect of
improving tensile elongation to exhibit ductility at high level. As
the copolymer polyamide, a copolymer comprising nylon 6
copolymerized with another polyamide component can be used more
preferably for improving tensile elongation to exhibit ductility,
and particularly nylon 6/66 copolymer has a significant effect of
improving tensile elongation to exhibit ductility, so the nylon
6/66 copolymer containing nylon 6 copolymer in a higher amount than
nylon 66 can be particularly preferably used.
[0058] Other examples of the other thermoplastic resin A contained
in the biaxially oriented polyarylene sulfide film of the present
invention include polyether imide. The polyether imide is not
particularly limited, and preferable examples can include a polymer
that is a structural unit containing an ether linkage in a
polyimide constituent, as shown in the following general formula:
##STR4## wherein R1 is a divalent organic group selected from the
group consisting of divalent aromatic, aliphatic and alicyclic
groups each having 2 to 30 carbon atoms, and R2 is the divalent
organic group similar to that of the above-mentioned R.
[0059] The above-mentioned R1 and R2 can include, for example, the
following aromatic groups: ##STR5##
[0060] When polyether imide having a glass transition temperature
of 350.degree. C. or less, more preferably 250.degree. C. or less,
is used in the present invention, the effect of the present
invention can be easily attained, and from the viewpoint of
compatibility with polyarylene sulfide, melt-moldability etc., a
condensate of 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane
dianhydride and m-phenylene diamine or p-phenylene diamine, having
a structural unit shown in the following formula, is preferable:
##STR6##
[0061] The polyether imide having this structural unit is available
under the registered trademark "Ultem" from GE Plastics. For
example, the polyether imide having the structural unit (the former
formula) containing a unit derived from m-phenylene diamine
includes "Ultem 1000" and "Ultem 1010". The polyether imide having
the structural unit (the latter formula) containing a unit derived
from m-phenylene diamine includes "Ultem CRS5000".
[0062] Other examples of the other thermoplastic resin A contained
in the biaxially oriented polyarylene sulfide film of the present
invention include polysulfone and polyether sulfone containing, in
the molecular skeleton thereof, the same sulfur atom as in the
polyarylene sulfide. The polysulfone and polyether sulfone used can
be the various sulfones known in the art. From the viewpoint of
mixing with polyarylene sulfide, the terminal group of the
polyether sulfone includes a chlorine atom, an alkoxy group and a
phenolic hydroxyl group. The thermoplastic resin A can also be
exemplified by polyphenylene ether having a similar molecular
structure to that of the polyarylene sulfide.
[0063] For further improving tensile elongation to exhibit more
excellent ductility in the present invention, a compound having one
or more groups selected from an epoxy group, an amino group and an
isocyanate group is added as a compatibilizing agent in an amount
of 0.1 to 10 parts by weight based on 100 parts by weight of the
polyarylene sulfide and thermoplastic resin A in total.
[0064] Specific examples of such compatibilizing agent include
bisphenol glycidyl ethers such as bisphenol A, resorcinol,
hydroquinone, pyrocatechol, bisphenol F, saligenin,
1,3,5-trihydroxybenzene, bisphenol S, trihydroxy-diphenyl dimethyl
methane, 4,4'-dihydroxybiphenyl, 1,5-dihydroxynaphthalene, cashew
phenol, 2.2.5.5-tetrakis(4-hydroxyphenyl)hexane etc., the same
compounds as above except that halogenated bisphenol was used in
place of bisphenol, glycidyl ether epoxy compounds such as butane
diol diglycidyl ether, glycidyl ester compounds such as phthalic
glycidyl ester, glycidyl epoxy resin such as glycidyl amine
compounds of N-glycidyl aniline etc., linear epoxy compounds such
as epoxidized polyolefin, epoxidized soybean oil etc., and cyclic,
non-glycidyl epoxy resin such as vinylcyclohexene dioxide,
dicyclopentadiene dioxide etc. Other novolac-type epoxy resin can
also be mentioned. The novolac-type epoxy resin has 2 or more epoxy
groups and is obtained usually by reacting epichlorohydrin with
novolac-type phenol resin. The novolac-type phenol resin is
obtained by condensation reaction of phenols with formaldehyde. The
starting phenols are not particularly limited, and examples thereof
include phenol, o-cresol, m-cresol, p-cresol, bisphenol A,
resorcinol, p-tertiary butyl phenol, bisphenol F, bisphenol S and
condensates thereof.
[0065] Other olefin copolymers having an epoxy group can also be
mentioned. The olefin copolymer shaving an epoxy group (epoxy
group-containing olefin copolymers) include olefin copolymers
obtained by introducing a monomer component having an epoxy group
into an olefin (co)polymer. A copolymer comprising an olefin
polymer having a double bond in its main chain wherein the double
bond moiety was epoxidized can also be used.
[0066] Examples of functional group-containing components for
introducing a monomer component having an epoxy group into an
olefin (co)polymer include monomers having an epoxy group, such as
glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate,
glycidyl itaconate and glycidyl citraconate.
[0067] The method of introducing the epoxy group-containing
component is not particularly limited, and a method of
copolymerizing it with .alpha.-olefin or a method of grafting it
onto an olefin (co)polymer with a radical initiator can be
used.
[0068] The amount of the epoxy group-containing monomer component
introduced is suitably in the range of 0.001 to 40 mol %,
preferably 0.01 to 35 mol %, based on the whole of the monomer
serving as the starting material of the epoxy group-containing
olefin copolymer.
[0069] The epoxy group-containing olefin copolymer which is
particularly useful in the invention is preferably an olefin
copolymer having an .alpha.-olefin and an
.alpha.,.beta.-unsaturated carboxylic glycidyl ester as copolymer
components. The .alpha.-olefin is preferably ethylene. The
copolymer may be further copolymerized with
.alpha.,.beta.-unsaturated carboxylic acids and alkyl esters
thereof, such as acrylic acid, methyl acrylate, ethyl acrylate,
butyl acrylate, methacrylic acid, methyl methacrylate, ethyl
methacrylate, butyl methacrylate etc., styrene, acrylonitrile
etc.
[0070] Such olefin copolymers may be in any modes of random,
alternating, block and graft copolymers.
[0071] The olefin copolymer having an .alpha.-olefin and an
.alpha.,.beta.-unsaturated carboxylic glycidyl ester copolymerized
therein is particularly preferably an olefin copolymer having 60 to
99 wt % .alpha.-olefin and 1 to 40 wt % .alpha.,.beta.-unsaturated
carboxylic glycidyl ester copolymerized therein.
[0072] Specific examples of the .alpha.,.beta.-unsaturated
carboxylic glycidyl ester include glycidyl acrylate, glycidyl
methacrylate and glycidyl ethacrylate, among which glycidyl
methacrylate is preferably used.
[0073] Specific examples of the olefin copolymer having an
.alpha.-olefin and an .alpha.,.beta.-unsaturated carboxylic
glycidyl ester essentially copolymerized therein include an
ethylene/propylene-g-glycidyl methacrylate copolymer ("g" indicates
graft; this hereinafter applies), an ethylene/butene-1-g-glycidyl
methacrylate copolymer, an ethylene-glycidyl methacrylate
copolymer-g-polystyrene, an ethylene-glycidyl methacrylate
copolymer-g-acrylonitrile-styrene copolymer, an ethylene-glycidyl
methacrylate copolymer-g-PMMA, an ethylene/glycidyl acrylate
copolymer, an ethylene/glycidyl methacrylate copolymer, an
ethylene/methyl acrylate/glycidyl methacrylate copolymer, and an
ethylene/methyl methacrylate/glycidyl methacrylate copolymer.
[0074] Specific examples of the compatibilizing agent include
alkoxysilane having one or more functional groups selected from an
epoxy group, an amino group and an isocyanate group. Specific
examples of such compounds include epoxy group-containing
alkoxysilane compounds such as .gamma.-glycidoxypropyltrimethoxy
silane, .gamma.-glycidoxypropyltriethoxy silane,
.beta.-(3,4-epoxycyclohexyl)ethyltrimethoxy silane etc., ureido
group-containing alkoxysilane compounds such as
.gamma.-ureidopropyltriethoxy silane,
.gamma.-ureidopropyltrimethoxy silane, .gamma.-(2-ureidoethyl)
aminopropyltrimethoxy silane etc., isocyanato group-containing
alkoxysilane compounds such as .gamma.-isocyanatopropyltriethoxy
silane, .gamma.-isocyanatopropyltrimethoxy silane,
.gamma.-isocyanatopropylmethyldimethoxy silane,
.gamma.-isocyanatopropylmethyldiethoxy silane,
.gamma.-isocyanatopropylethyldimethoxy silane,
.gamma.-isocyanatopropylethyldiethoxy silane,
.gamma.-isocyanatopropyl trichlorosilane etc., and amino
group-containing alkoxysilane compounds such as
.gamma.-(2-aminoethyl)aminopropylmethyldimethoxy silane,
.gamma.-(2-aminoethyl)aminopropyltrimethoxy silane,
.gamma.-aminopropyltrimethoxy silane etc.
[0075] The alkoxysilane having one or more functional groups
selected from an epoxy group, an amino group and an isocyanate
group can be mentioned as the most preferable example of the
compatibilizing agent in the present invention and can be used to
easily reduce a coarse dispersion attributable to insufficient
dispersion of the dispersed phase of the biaxially oriented
polyarylene sulfide film containing the thermoplastic resin A and
easily regulate the average particle diameter in the preferable
range of the present invention thereby easily attaining the effect
of the present invention.
[0076] The tensile elongation at break of the biaxially oriented
polyarylene sulfide film of the present invention in both of the
longitudinal direction (MD) and width direction (TD) is 80 to
250(%), and the tensile elongation at break thereof in least one of
the longitudinal direction and width direction is 110 to 250%. The
tensile elongation at break thereof in both of the longitudinal
direction and width direction is preferably 110 to 230(%), most
preferably 120 to 200(%). For attaining the preferable range of
tensile elongation at break, the content of the thermoplastic resin
A and the average particle diameter of the dispersed phase are
preferably controlled in the preferable range of the present
invention. When the tensile elongation at break of the film in both
the longitudinal direction and width direction is less than 80(%),
the film is poor in ductility for processing for use as a motor
slot liner or wedge and is thus broken or practically not usable in
some cases. For obtaining a film having a tensile elongation at
break of greater than 250(%) in both the longitudinal direction and
width direction of the film, the draw ratio should be decreased in
the drawing process, but the planarity of the film may be
deteriorated or the mechanical strength may be decreased to lower
the stiffness of the film.
[0077] The tensile elongation at break is determined with an
Instron-type tensile testing machine by cutting a sample out in the
tensile direction as measurement direction, putting the sample
between upper and lower mounted parts, and measuring the elongation
of the sample at breakage in a tensile test as the tensile
elongation at break. That is, a sample film width 10 mm.times.chuck
distance 100 mm was measured with an Instron-type tensile testing
machine at a stress rate of 100 mm/min. in an atmosphere at a
temperature of 23.degree. C. and 65% relative humidity according to
a method prescribed in ASTM D-882. The number of samples was 10,
and the samples were measured respectively to determine the average
tensile at break elongation.
[0078] The tensile strength at break of the biaxially oriented
polyarylene sulfide film of the present invention in the
longitudinal direction (MD) and width direction (TD) is preferably
100 to 400 (MPa), more preferably 150 to 350 (MPa), still more
preferably 180 to 320 (MPa). For attaining the preferable range of
tensile strength at break, the average particle diameter of the
dispersed phase of the thermoplastic resin A is preferably
controlled in the preferable range of the present invention. When
the rupture strength at break in both the longitudinal and width
directions is less than 100 (MPa), for example, the film is poor in
mechanical strength and is thus broken during processing or at use
or is practically not usable in some cases. For obtaining a film
having a tensile strength at break of greater than 400 (MPa) in
both the longitudinal and width directions of the film, the draw
ratio should be increased in the drawing process, but the film may
be broken upon stretching or may be poor in tensile elongation.
[0079] The primary dispersion peak temperature at loss tangent of
dynamic viscoelasticity of the biaxially oriented polyarylene
sulfide film of the present invention at a frequency of 1 Hz is
preferably 100 to 135.degree. C. Such film can be easily endowed
with improved features such as improved tensile elongation at break
and molding processability. The primary dispersion peak temperature
is more preferably in the range of 105 to 130.degree. C., further
more preferably in the range of 110 to 125.degree. C. When the
primary dispersion peak temperature at loss tangent of dynamic
viscoelasticity is less than 100.degree. C., the molecular-chain
orientation of polyarylene sulfide is insufficient so that the
tensile elongation at break is too low and the ductility is
insufficient, and the film is broken during processing or at use or
is practically not usable in some cases. On the other hand, when
the primary dispersion peak temperature is higher than 135.degree.
C., the molecular-chain orientation is progressed extremely and the
tensile elongation at break is too low, so the film is broken
during processing or at use or is practically not usable in some
cases, and heat shrinkage may become high. The primary dispersion
peak temperature at loss tangent of dynamic viscoelasticity of the
polyarylene sulfide film can be controlled for example by allowing
the draw temperature and draw ratio in longitudinal drawing and the
draw temperature and draw ratio in lateral drawing to be in the
preferable range of the present invention. As used herein, the
primary dispersion peak temperature at loss tangent of dynamic
viscoelasticity refers to the temperature of a dispersion peak
having the largest value in temperature dispersion at loss
tangent.
[0080] For the primary dispersion peak temperature of dynamic
viscoelasticity, a sample having a width of 10 mm and a length
(chuck distance) of 20 mm (provided that the longitudinal direction
of the film is the sample length) is heated at a temperature of
30.degree. C. to 200.degree. C. at a temperature increasing rate of
2.degree. C./min. and measured at a vibrational frequency of 1 Hz.
A graph wherein loss tangent (tan.delta.) obtained from data is
plotted against temperature (30 to 200.degree. C.) on the abscissa
is prepared, and the temperature at which tan.delta. becomes the
highest is read as the primary dispersion peak temperature of
dynamic viscoelasticity.
[0081] The crystal melting heat quantity of polyarylene sulfide in
the biaxially oriented polyarylene sulfide film of the present
invention is preferably 20 to 45 (J/g). The crystal melting heat
quantity is more preferably in the range of 23 to 40 (J/g), more
preferably in the range of 25 to 37 (J/g). The crystal melting heat
quantity of polyarylene sulfide reflects the amount of polyarylene
sulfide crystals. When the melting heat quantity is higher than 45
(J/g), the film is easily made brittle, and for example, the film
is broken during processing or at use or is practically not usable
in some cases. When the melting heat quantity is less than 20
(J/g), heat shrinkage may be increased and heat resistance may be
insufficient. For example, when the preliminary heating temperature
before lateral stretching, the stretching temperature in lateral
stretching and the heat fixation temperature after stretching are
in the preferable range of the present invention, the crystal
melting heat quantity of the polyarylene sulfide film can be in the
range of the present invention. The crystal melting heat quantity
refers to the heat quantity in an endothermic peak of melting point
measured with a differential scanning calorimeter (DSC).
[0082] Although the time when the polyarylene sulfide is mixed with
the other thermoplastic resin A is not particularly limited in the
present invention, there is a method wherein before melt-extrusion,
a mixture of polyarylene sulfide and other thermoplastic resin A is
preliminarily melt-kneaded (pelletized) into master chips and a
method wherein the materials are mixed at the time of
melt-extrusion and melt-kneaded. The method is particularly
preferably a method wherein the materials are preliminarily kneaded
into master chips with a high-shear mixer such as a twin-screw
extruder capable of applying shear stress. In this case, a master
chip material consisting of the mixture may be introduced into a
usual single-screw extruder and then melted to form a film or
subjected directly to sheeting under high shearing without forming
master chips. For mixing in a twin-screw extruder, a 3- or 2-thread
twin-screw extruder is equipped preferably with a kneading zone in
the temperature range of preferably the polyarylene sulfide resin
melting point +5 to 55.degree. C. for reducing insufficient
dispersing. The temperature range is more preferably the
polyarylene sulfide resin melting point +10 to 45.degree. C., still
more preferably the polyarylene sulfide resin melting point +10 to
35.degree. C.
[0083] By regulating the temperature in the kneading zone in the
preferable range, the shear stress can be increased, insufficient
dispersing can be reduced, and the particle diameter of the
dispersed phase can be controlled in the preferable range of the
present invention. At that time, the retention time is preferably
in the range of 1 to 5 minutes. The number of revolutions of the
screw is preferably in the range of 100 to 500 rpm, more preferably
200 to 400 rpm. By setting the number of revolutions of the screw
in the preferable range, high shear stress can be easily applied,
and the particle diameter of the dispersed phase can be controlled
in the preferable range of the present invention. The ratio (screw
length/screw diameter ratio) of the twin-screw extruder is
preferably in the range of 20 to 60, more preferably in the range
of 30 to 50.
[0084] The twin-screw extruder is provided with kneading zones with
a kneading paddle for increasing kneading force wherein the number
of the kneading zones is 2 or more, still more preferably 3 or
more. In this case, the order of mixing the materials is not
particularly limited, and it is possible to use a method wherein
all the materials are compounded and then melt-kneaded by the above
method, a method wherein a part of the materials is compounded,
then melt-kneaded by the above method, compounded with the rest of
the materials and melt-kneaded, or a method wherein a part of the
materials is compounded and then melt-kneaded by a single- or
twin-screw extruder and simultaneously mixed with the rest of the
materials sent via a side feeder. A method of utilizing a
supercritical fluid, as described in "Seikei Kakou (Molding
Processing)", Journal of Japan Society of Polymer Processing
(JSPP), Vol. 15, No. 6, pp. 382-385 (2003), can also be preferably
used.
[0085] The biaxially oriented polyarylene sulfide film of the
present invention may contain other components such as a heat
stabilizer, an antioxidant, an ultraviolet absorber, an antistatic
agent, a flame retardant, pigment, dye, and an organic lubricant
such as fatty ester and wax insofar as the advantages of the
present invention are not reduced. In order to impart slipability,
wear resistance, and/or scratch resistance to surface of the film,
the biaxially oriented polyarylene sulfide film may contain
inorganic or organic particles. Such additives may contain
inorganic particles such as those of clay, mica, titanium oxide,
calcium carbonate, kaolin, talc, wet- or dry-process silica,
colloidal silica, calcium phosphate, barium sulfate, alumina and
zirconia, organic particles composed of acrylates, styrene etc.,
internal particles to be precipitated by a catalyst etc. added at
the time of polymerization reaction of polyarylene sulfide, and a
surfactant.
[0086] The thickness of the biaxially oriented polyarylene sulfide
film of the present invention varies depending on applications
etc., and is preferably 500 .mu.m or less, and from the viewpoint
of application to thin film and workability, is more preferably in
the range of 10 to 300 .mu.m, still more preferably in the range of
20 to 200 .mu.m.
[0087] The biaxially oriented polyarylene sulfide film of the
present invention may further be laminated, directly or via a layer
such as an adhesive layer, with a layer consisting of polyarylene
sulfide or another polymer, for example a layer consisting of
polyester, polyolefin, polyamide, polyimide, polyvinylidene
chloride or an acrylic polymer.
[0088] The biaxially oriented polyarylene sulfide film of the
present invention may be subjected if necessary to arbitrary
processing such as heat treatment, molding, surface treatment,
lamination, coating, printing, embossing or etching.
[0089] Although applications of the biaxially oriented polyarylene
sulfide film of the present invention are not particularly limited,
the biaxially oriented polyarylene sulfide film can be used in
various industrial materials, for example an electrical insulating
material for a motor, a transformer, an insulated cable etc.,
molding material, a circuit board material, a step/release film for
circuit/optical element etc., a protective film, a lithium ion
battery material, a fuel battery material, a speaker diaphragm,
etc. More specifically, it can be preferably used in an electrical
insulating material for a hot-water supplier motor, a motor for car
air conditioner and a driving motor used in a hybrid car, and a
speaker diaphragm for cell-phone.
[0090] The laminated polyarylene sulfide sheet of the present
invention comprises the biaxially oriented polyarylene sulfide
layer (layer a) arranged in at least one of the outermost layers.
As the biaxially oriented polyarylene sulfide layer, a biaxially
oriented polyarylene sulfide film is used which comprises
polyarylene sulfide and other thermoplastic resin A different from
the polyarylene sulfide, wherein the contents of the polyarylene
sulfide and the thermoplastic resin A are 70 to 99 parts by weight
and 1 to 30 parts by weight respectively when the total amount of
the polyarylene sulfide and the thermoplastic resin A is taken as
100 parts by weight and the resin thermoplastic A forms a dispersed
phase with an average particle diameter of 10 to 500 nm.
[0091] The layer a contains polyarylene sulfide and other
thermoplastic resin A, wherein the contents of the polyarylene
sulfide and the thermoplastic resin A are preferably 70 to 95 parts
by weight and 5 to 30 parts by weight respectively when the total
amount of both is taken as 100 parts by weight. The contents of the
polyarylene sulfide and the thermoplastic resin A are more
preferably 80 to 95 parts by weight and 5 to 20 parts by weight
respectively, and still more preferably, the contents of the
polyarylene sulfide and the thermoplastic resin A are 80 to 93
parts by weight and 7 to 20 parts by weight respectively. The
average particle diameter of the dispersed phase of the
thermoplastic resin A is preferably in the range of 20 to 300 nm,
more preferably 30 to 200 nm, most preferably 30 to 120 nm.
[0092] It is important that the laminated polyarylene sulfide sheet
has a non-oriented polyarylene sulfide layer (layer b) as an
intermediate layer in order to improve the impact resistance of the
laminated polyarylene sulfide sheet. The number of laminated layers
is preferably 2 to 10, more preferably 3 to 5. Particularly, a
3-layer sheet is the most preferable.
[0093] In the laminated polyarylene sulfide sheet of the present
invention, at least one of the outermost layers is a biaxially
oriented polyarylene sulfide layer (layer a), or each of the
outermost layers in the front-back both sides may be a biaxially
oriented polyarylene sulfide layer. From the viewpoint of tear
resistance, the laminated polyarylene sulfide sheet preferably has
a non-oriented polyarylene sulfide layer (layer b) as a layer
(intermediate layer) other than the outermost layers. In the
present invention, it is important that the laminated polyarylene
sulfide sheet has the biaxially oriented polyarylene sulfide layer
in the outermost layer so that the tensile elongation at break of
the sheet can be in the range of the present invention.
[0094] The non-oriented polyarylene sulfide layer (layer b) used
preferably in the present invention refers generally to a
substantially non-oriented film, sheet or plate formed by
melt-molding. In biaxial orientation, molecular chains in film
plane in the longitudinal direction and width direction of the film
are more oriented than in the thickness direction of the film,
while in non-orientation, molecular-chain orientation is almost
isotropic in film plane such as in the longitudinal and width
directions of the film and in the thickness direction. The
thickness of the layer b is preferably 1 mm or less. Particularly,
the laminated polyarylene sulfide sheet can be exemplified
preferably by a laminated sheet having a 3-layer structure (a/b/a)
consisting of biaxially oriented polyarylene sulfide films (layers
a) as the outermost layers and a non-oriented polyarylene sulfide
layer (layer b) as an intermediate layer.
[0095] Although the method of laminating the laminated polyarylene
sulfide sheet of the present invention is not particularly limited,
a heat lamination method of fixation by heat melting without an
adhesive can be used preferably for improving interlayer
adhesion.
[0096] In the laminated polyarylene sulfide sheet of the present
invention, the non-oriented polyarylene sulfide layer may be
subjected to heat treatment or oxidation crosslinking treatment
before lamination. The surfaces of the non-oriented polyarylene
sulfide layer (layer b) and the biaxially oriented polyarylene
sulfide layer (layer a) are preferably subjected to corona
discharge treatment or plasma treatment.
[0097] In the laminated polyarylene sulfide sheet comprising the
non-oriented polyarylene sulfide layer (layer b) and the biaxially
oriented polyarylene sulfide layer (layer a), the orientation of
each layer can be determined for example by preparing a section of
the laminated sheet by ultramicrotomy and then measuring the sheet
section by techniques such as laser raman spectroscopy and infrared
spectroscopy. When the thickness of each layer is not sufficient, a
sample section can be prepared by crosswise cutting etc. For
example, when the orientation of the polyphenylene sulfide is
measured by laser raman spectroscopy, the ratio of raman intensity
(I.sub.740) at 740 cm.sup.-1 to raman intensity at 1570 cm.sup.-1
(I.sub.1570), that is, I.sub.1570/I.sub.740, can be an indicator of
molecular-chain orientation, and by polarized light parallel to
each of the longitudinal direction, width direction and thickness
direction of the film, the orientation of molecular chains in each
direction can be obtained as an indicator. When the indicator is
almost equal regardless of the longitudinal direction, the width
direction and the thickness direction, it can be judged that the
film is non-oriented. On the other hand, when the indicator in the
longitudinal and width directions is greater than the indicator in
the thickness direction, it can be judged that the film is
biaxially oriented. The method of producing the non-oriented
polyphenylene sulfide film involves drying the PPS resin
composition and copolymerized PPS sufficiently and then feeding
them to different extruders or mixing copolymerized PPS in an
amount of 10 to 100 wt % with the PPS resin composition and then
feeding the mixture to a melting extruder heated to a temperature
not lower than the melting point of the resin composition in a
nitrogen stream or under reduced pressure so as not to reduce the
inherent viscosity, then extruding it through a die, and cooled and
solidified by intimate contact, by a contacting means such as
electrostatic charging or by an air chamber method, an air knife
method or a press rolling method, with a cast drum having a surface
temperature not higher than the glass transition point of the resin
composition, whereby the non-oriented polyphenylene sulfide film is
prepared. A filter made of sintered metal, porous ceramic, sand or
gauze is preferably used to remove contaminants, foreign matters
and/or deteriorated polymer matters in the melting extruder.
[0098] In the present invention, the copolymerized polyphenylene
sulfide layer (layer c) is preferably contained between the
biaxially oriented polyarylene sulfide film layers (layers a) as
the outermost layers in order that the tensile elongation at break
of the laminated sheet of the present invention is in the
preferable range of the present invention. Particularly, the
laminated polyarylene sulfide sheet can be exemplified preferably
by a laminated sheet having a 3-layer structure (a/c/a) consisting
of biaxially oriented polyarylene sulfide films (layers a) as the
outermost layers and the copolymerized polyphenylene sulfide layer
(layer c) as an intermediate layer.
[0099] The copolymerized polyphenylene sulfide used in the present
invention is composed of p-phenylene sulfide units in an amount of
50 to less than 95 mol %, preferably 70 to less than 92 mol %,
still more preferably 80 to less than 92 mol %, based on the total
repeating units. When such component is less than 50 mol %, the
heat resistance of the film may be significantly lowered, while in
an amount of 95% or more, interlayer adhesion cannot be
sufficiently increased, so the laminated sheet cannot be highly
elongated.
[0100] The copolymerized unit includes the following m-phenylene
sulfide units: ##STR7## wherein X represents an alkylene, CO or
SO.sub.2 unit. ##STR8## wherein R represents an alkyl, nitro,
phenylene or alkoxy group, and a combination of these units may be
present. The copolymer unit is preferably m-phenylene sulfide unit.
The amount of these units copolymerized is preferably 3 to 50 mol
%, more preferably 5 to 30 mol %, still more preferably 8 to 20 mol
%. When the amount of such copolymerized component is less than 3
mol %, interlayer adhesion cannot be sufficiently increased, so the
laminated sheet may not be highly elongated, and as a result, the
tensile elongation at break of the film is lowered, and the effect
of improving impact resistance may be insufficient. When the amount
of the copolymerized component is higher than 50 mol %, heat
resistance may be significantly lowered. The copolymerization
composition of such copolymer can be measured by NMR.
[0101] Although the mode of copolymerization of the above component
with the copolymerized component in the copolymerized polyphenylene
sulfide used in the present invention is not particularly limited,
the copolymerized polyphenylene sulfide is preferably a random
copolymer.
[0102] In the present invention, the rest of the copolymer
repeating units constituting the copolymerized polyphenylene
sulfide may be composed of other copolymerizable units which in a
trifunctional phenyl sulfide represented by formula (7), for
example, are preferably not higher than 1 mol % based on the whole
of the copolymer. ##STR9##
[0103] The method of polymerizing copolymerized PPS includes for
example the following method: Sodium sulfide and p-dichlorobenzene
and minor monomer are compounded at the ratio defined in the
present invention and reacted at high temperature at high pressure
in the presence of a polymerization assistant in an amide polar
solvent such as N-methyl-2-pyrrolidone (NMP). The minor monomer
includes: ##STR10## wherein X represents an alkylene, CO or
SO.sub.2 unit. ##STR11## ##STR12## wherein R represents an alkyl,
nitro, phenylene or alkoxy group, and a plurality of these minor
monomers may be present. Preferably, the minor monomer is:
##STR13##
[0104] The melting point of the copolymerized polyphenylene sulfide
used in the present invention is preferably 180 to 260.degree. C.,
more preferably 200 to 250.degree. C., still more preferably 220 to
240.degree. C. When the melting point is less than 180.degree. C.,
heat resistance may be significantly lowered, while when the
melting point is higher than 260.degree. C., interlayer adhesion
cannot be sufficiently increased, so the laminated sheet may not be
highly elongated.
[0105] In respect of the balance among the tensile elongation at
break, impact resistance and reduced cracking in slot processing of
the laminated sheet, the thickness of the layer other than the
outermost layer in the laminated polyarylene sulfide sheet of the
present invention is preferably 2 to 30% based on the total
thickness of the laminated sheet. The thickness is more preferably
5 to 30%, more preferably 10 to 20%. When the thickness of the
layer other than the outermost layer is less than 2% based on the
total thickness, the impact resistance of the laminated film is
lowered and film cracking may be generated, while when the
thickness is greater than 30%, the tensile elongation at break of
the laminated film is reduced and film cracking may be generated
increasingly in slot processing.
[0106] The thickness of the layer in the laminated polyarylene
sulfide sheet of the present invention can be measured for example
by preparing a section of the laminated sheet by ultramicrotomy
etc. and examining the sheet section with an optical microscope or
a scanning electron microscope.
[0107] The tensile elongation at break of the laminated polyarylene
sulfide sheet of the present invention both in the longitudinal
direction (MD) and in the width direction (TD) is preferably 80 to
250(%). The tensile elongation at break thereof in least one of the
longitudinal and width directions is more preferably 110 to 250%.
The tensile elongation at break thereof in both of the longitudinal
and width directions is still more preferably 110 to 230(%), most
preferably 120 to 200(%). For attaining the preferable range of
tensile elongation at break, the content of the thermoplastic resin
A, the average particle diameter of the dispersed phase and the
laminate structure or thickness of the laminated sheet are
preferably controlled in the preferable range of the present
invention. When the tensile elongation at break in both the
longitudinal and width directions is less than 80(%), the film is
poor in ductility for processing for use as a motor slot liner or
wedge and is thus broken or practically not usable in some cases.
For obtaining a film having a tensile elongation at break of
greater than 250(%) in both the longitudinal and width directions
of the film, the draw ratio should be decreased in the drawing
process, but the planarity of the film may be deteriorated or the
mechanical strength maybe decreased to lower the nerve of the film
in some cases.
[0108] The impact strength of the laminated polyarylene sulfide
sheet of the present invention is preferably 3 to 10 N/.mu.m, more
preferably 4 to 10 N/.mu.m, still more preferably 5 to 10 N/.mu.m,
in order to suppress cracking of the film in a step of processing a
slot and wedge. When the impact resistance is less than 3 N/.mu.m,
film cracking may be generated in a step of processing a slot and
wedge, while when the impact strength is higher than 10 N/.mu.m,
the content of the non-oriented polyarylene sulfide layer in the
laminated polyarylene sulfide sheet may be high, and thus the heat
resistance of the laminated sheet maybe lowered. The tensile
elongation at break of the laminated sheet may be lowered, and film
cracking may be generated in a step of processing a slot and
wedge.
[0109] The impact strength is determined by cutting a test sample
of width 1 mm.times.length 70 mm and measuring it at a test
temperature of 23.degree. C. with a Charpy impact tester (capacity,
10 kgcm; hammer weight, 1.019 kg; lifting angle of a hammer without
a sample, 127.degree.; distance from shaft center to gravity
center, 6.12 cm). The impact strength is expressed in the unit
N/.mu.m after dividing the measured value by the sectional area of
the sample (sample thickness.times.sample width). 7 samples were
measured to determine their average.
[0110] The laminated polyarylene sulfide sheet of the present
invention may contain other components such as a heat stabilizer,
an antioxidant, an ultraviolet absorber, an antistatic agent, a
flame retardant, pigment, dye, and an organic lubricant such as
fatty ester and wax insofar as the advantages of the present
invention are not reduced. In order to impart slipability, wear
resistance, and/or scratch resistance to surface of the film, the
film may contain inorganic or organic particles. Such additives may
contain inorganic particles such as those of clay, mica, titanium
oxide, calcium carbonate, kaolin, talc, wet- or dry-process silica,
colloidal silica, calcium phosphate, barium sulfate, alumina and
zirconia, organic particles composed of acrylates, styrene etc.,
internal particles to be precipitated by a catalyst etc. added at
the time of polymerization reaction of polyarylene sulfide, and a
surfactant.
[0111] The laminated polyarylene sulfide sheet of the present
invention can be used in various industrial materials, for example
an electrical insulating material for a motor, a transformer etc.,
a circuit board material, a step/release material for
circuit/optical element etc., a protective film, a lithium ion
battery material and a fuel battery material. More specifically, it
can be used in an electrical insulating material for a hot-water
supplier motor, a motor for car air conditioner and a driving motor
used in a hybrid car.
[0112] The method of producing the biaxially oriented polyphenylene
sulfide film of the present invention wherein nylon 6 that is
polyamide is used as thermoplastic resin A and mixed with
poly-p-phenylene sulfide is described by reference to production of
the biaxially oriented polyphenylene sulfide film, but the present
invention is naturally not limited to the following
description.
[0113] When the polyphenylene sulfide is mixed with nylon 6, a
method of preliminarily melt-kneading (pelletizing) a mixture of
the respective resins into master chips before melt-extrusion is
preferably used.
[0114] In the present invention, the above PPS and nylon 6 are
introduced preferably into a twin-screw extruder to produce a blend
material having a weight ratio of PPS to nylon 6 in the range of
99/1 to 60/40. The method of mixing and kneading the resin
composition as blend material is not particularly limited, and
various mixing and kneading means are used. For example, the PPS
and nylon 6 may be separately fed to different melt extruders and
then mixed, or alternatively, powdery raw materials may be
subjected to the preliminary dry blending utilizing a mixing unit
such as a Henschel mixer, a ball mixer, a blender, or a tumbler in
advance and then melt-kneaded with a melt-kneader. Thereafter, the
blend material, if necessary together with PPS and their recycled
material, is introduced into an extruder to produce an intended
composition which is preferably used as the raw material from the
viewpoint of film quality and film formability. When the raw
material is prepared, the resin can be subjected preferably to
filtration in the melt-extrusion step in order to reduce
contamination of the films with foreign matters to the minimum
degree. Various filters for removing foreign matters and/or
deteriorated polymer matters in the extruder are preferably those
made of materials such as sintered metal, porous ceramic, sand or
gauze. In order to improve quantitative feeding, a gear pump may be
arranged, if necessary. When the laminated film is produced, two or
more extruders and a manifold or a confluent block are used to
laminate the polyphenylene sulfide with the resin composition of
thermoplastic resin A in a molten state. The molten sheet is
extruded from a slit of a die and cooled on a casting roll to
produce an unstretched film.
[0115] More specific conditions for the preferable method of
producing the biaxially oriented polyphenylene sulfide film are as
follows:
[0116] First, polyphenylene sulfide pellets or granules and
polyamide pellets are mixed in a predetermined ratio, fed to a
vented twin-screw extruder and melt-kneaded to give blend chips. A
high-shear mixer giving shear stress, such as a twin-screw
extruder, is preferably used, and from the viewpoint of reducing
insufficient dispersing, the mixer is preferably a 3- or 2-thread
twin-screw extruder wherein the retention time is preferably in the
range of 1 to 5 minutes. The kneading zone is preferably in the
temperature range of 290 to 340.degree. C., more preferably 295 to
330.degree. C., still more preferably 300 to 320.degree. C. When
the kneading zone is set in the preferable temperature range, the
shear stress can be easily increased, insufficient dispersing can
be reduced, and the particle diameter of the dispersed phase can be
controlled in the preferable range of the present invention. The
number of revolutions of the screw is preferably in the range of
100 to 500 rpm, more preferably 200 to 400 rpm. By setting the
number of revolutions of the screw in the preferably range, high
shear stress can be easily applied, and the particle diameter of
the dispersed phase can be controlled in the preferable range of
the present invention. The ratio (screw length/screw diameter
ratio) of the twin-screw extruder is preferably in the range of 20
to 60, more preferably in the range of 30 to 50. The twin-screw
extruder is provided preferably with a kneading zone with a
kneading paddle for increasing kneading power, more preferably with
two or more kneading zones having a usual feed screw
therebetween.
[0117] When a composition having polyphenylene sulfide mixed with
nylon 6, or a compatibilizing agent, is added in mixing
polyphenylene sulfide with nylon 6, insufficient dispersing can be
reduced to increase compatibilizability in some cases.
[0118] Thereafter, blend chips consisting of PPS and nylon 6,
obtained by the pelletizing operation described above, is mixed if
necessary with a predetermined amount of PPS or a recycled material
after film making and then dried at 180.degree. C. for 3 hours or
more under vacuum and then introduced into an extruder having a
melting zone heated at a temperature of 300 to 350.degree. C.,
preferably 320 to 340.degree. C. Thereafter, the melted polymer
from the extruder is passed through a filter and discharged through
a slit of a T-die to give a sheet-shaped polymer. The temperature
of the filter and die is set higher preferably by 3 to 20.degree.
C., more preferably by 5 to 15.degree. C., than the melting zone of
the extruder. By setting the temperature of the filter and die
higher than the temperature of the melting zone in the extruder,
abnormal retention can be suppressed and the sheet can have the
preferable particle diameter of the dispersed phase in the present
invention. The sheet-shaped polymer is cooled and solidified by
allowing it to be in contact with a cooling drum having a surface
temperature of 20 to 70.degree. C., whereby an unstretched film
that is not substantially oriented is obtained.
[0119] Then, this unstretched film is biaxially stretched and
thereby biaxially oriented. As the stretching method, it is
possible to use a sequential biaxial stretching process (stretching
process including a step of performing longitudinal stretching and
then performing transverse stretching) and a simultaneous biaxial
stretching process (stretching process including a step of
simultaneously performing longitudinal stretching and transverse
stretching), which may be used alone or in combination.
[0120] The sequential biaxial stretching process (stretching
process including a step of performing longitudinal stretching and
then performing transverse stretching) is used herein. The
stretching temperature varies depending on constituents in PPS and
other thermoplastic resin A, and the process is described below by
reference to a resin composition consisting of 90 parts by weight
of PPS and 10 parts by weight of nylon 6, for example.
[0121] An unstretched polyphenylene sulfide film is heated with a
group of heating rolls and then stretched at a draw ratio of 2 to
4, preferably 2.5 to 4, more preferably 3 to 4 in one step or
multiple steps in the longitudinal direction (MD stretching). The
stretching temperature is in the range of Tg (glass transition
temperature of PPS) to (Tg+50).degree. C., preferably (Tg+5) to
(Tg+50).degree. C., more preferably (Tg+5) to (Tg+40).degree. C.,
still more preferably (Tg+10) to (Tg+30).degree. C., most
preferably (Tg+15) to (Tg+30).degree. C. Thereafter, the film is
cooled with a group of cooling rolls at 20 to 50.degree. C.
[0122] After MD stretching, a method of stretching the film in the
width direction with at enter is generally used, for example. By
retaining both ends of the resulting film with clips, the film is
introduced into a tenter and stretched in the width direction (TD
stretching). The stretching temperature is preferably in the range
of Tg to (Tg+60).degree. C., more preferably (Tg+5) to
(Tg+50).degree. C., still more preferably (Tg+10) to
(Tg+40).degree. C. Particularly, the film is stretched in TD
stretching, preferably at a temperature lower by 3 to 15.degree.
C., more preferably by 5 to 10.degree. C., than the stretching
temperature in MD stretching. By setting the stretching temperature
in TD stretching in the preferable range, crystallization of
polyarylene sulfide is not progressed excessively, whereby the
molecular-chain orientation can be controlled in the range of the
present invention and the effect of the invention, that is,
improvement of tensile elongation at break and improvement of
molding processability, can be easily attained. In a preheating
zone before the stretching zone in TD stretching, the film is
stretched preferably at a preheating temperature lower by 3 to
10.degree. C., more preferably by 5 to 7.degree. C., than the
stretching temperature in TD stretching. By setting the preheating
temperature in the preferable range before TD stretching,
crystallization of polyarylene sulfide is not progressed
excessively, whereby the molecular-chain orientation can be
controlled in the range of the present invention and the effect of
the invention, that is, improvement of fracture elongation and
improvement of molding processability, can be easily attained. The
draw ratio is preferably in the range of 2 to 4, more preferably
2.5 to 4, still more preferably 3 to 4.
[0123] Then, the stretched film is heat-set under strain or under
relaxation in the width direction. The heat treatment temperature
is preferably in the range of 200 to 270.degree. C., more
preferably 210 to 260.degree. C., still more preferably 220 to
255.degree. C. Heat treatment is carried out preferably in 2 stages
at different temperatures. In this case, the heat treatment
temperature in the second stage is preferably set higher by 5 to
20.degree. C. than in the first stage. The heat treatment is
carried out preferably for 0.2 to 30 seconds, more preferably for 5
to 20 seconds. The film is cooled under relaxation in the width
direction at a temperature zone of 40 to 180.degree. C. The degree
of relaxation is preferably in the range of 1 to 10%, more
preferably 2 to 8%, still more preferably 3 to 7%, from the
viewpoint of reducing the degree of thermal shrinkage in the width
direction.
[0124] Then, the film is cooled to room temperature, if necessary
under relaxation treatment in the longitudinal and width
directions, and then wounded to give the objective biaxially
oriented polyphenylene sulfide film.
[0125] The method of laminating the non-oriented polyphenylene
sulfide layer (layer b) with the biaxially oriented polyphenylene
sulfide layer (layer a) includes a method of using an adhesive
resin such as an adhesive or a method of thermocompression bonding
at high temperature at high pressure, and a method of
thermocompression bonding of the two at high temperature at high
pressure without using an adhesive can be particularly used. The
method of thermocompression bonding is carried out with heating
rolls or by hot plate pressing, preferably by heating rolls from
the viewpoint of production process. Thermocompression bonding
conditions are preferably a temperature of 180 to 270.degree. C.
and a pressure of 1 to 20 kg/cm.sup.2. When the temperature is
lower than 180.degree. C., adhesion cannot be sufficiently
increased, and when the temperature is higher than 270.degree. C.,
the planarity of the laminated sheet may be rapidly deteriorated
and the mechanical characteristics may be deteriorated. On the
other hand, when the pressure is less than 1 kg/cm.sup.2, adhesion
is insufficient even if the thermocompression bonding temperature
is increased, while when the pressure is higher than 20
kg/cm.sup.2, the planarity of the laminated sheet may be
deteriorated, and the non-oriented polyphenylene sulfide layer may
be broken. From the viewpoint of adhesion and mechanical
characteristics, the thermocompression bonding temperature is more
preferably in the range of 200 to 250.degree. C., still more
preferably in the range of 220 to 240.degree. C. The
thermocompression bonding pressure is more preferably in the range
of 3 to 15 kg/cm.sup.2, still more preferably in the range of 5 to
10 kg/cm.sup.2, but these ranges are not intended to be
limitative.
[0126] The method of laminating the copolymerized polyphenylene
sulfide layer (layer c) with the biaxially oriented polyphenylene
sulfide layer (layer a) includes a method of using an adhesive
resin such as an adhesive or a method of thermocompression bonding
at high temperature at high pressure, and a method of
thermocompression bonding of the two at high temperature at high
pressure without using an adhesive can be particularly used. The
method of thermocompression bonding is carried out with heating
rolls or by hot plate pressing, preferably by heating rolls from
the viewpoint of production process. A biaxially stretched
laminated film consisting of 2 layers (a/c) or 3 layers (c/a/c),
obtained by biaxially stretching a co-extruded sheet having the
copolymerized polyphenylene sulfide layer laminated on at least one
side of the polyphenylene sulfide layer (layer a) is subjected
particularly preferably to thermocompression bonding.
[0127] The method of producing the biaxially stretched laminated
film having a copolymerized polyphenylene sulfide layer laminated
therein is described. The polyphenylene sulfide material and the
copolymerized polyphenylene sulfide material are fed to different
melting extruders and heated to a temperature not lower than the
melting point of each material. The respective materials melted by
heating are laminated to give a 2- or 3-layer laminate in melted
state in a converging device arranged between the melting extruder
and the outlet of a die and then extruded through a slit of the
die. The melted laminate is cooled to a temperature not higher than
the glass transition point of the polyphenylene sulfide on a
cooling drum, to give a substantially amorphous unstretched sheet
having 2 or 3 layers laminated therein. The unstretched sheet can
be biaxially stretched by the same method as for the polyphenylene
sulfide sheet described above.
[0128] The 2-layer laminated films each having the polyphenylene
sulfide layer (layer a)/copolymerized polyphenylene sulfide layer
(layer c) laminated therein are introduced into a heat-fusion
device composed of a group of heated rolls and heat-fused such that
the biaxially stretched film composed of a/c layer and the
biaxially stretched film composed of c/a layer are attached to each
other at the side of the copolymerized polyphenylene sulfide layer
(layer c) to give a 3-layer laminated sheet of the polyphenylene
sulfide layer (layer a)/copolymerized polyphenylene sulfide layer
(layer c)/polyphenylene sulfide layer (layer a). When the films are
attached to each other at the side of the copolymerized
polyphenylene sulfide, the whole of their fused copolymerized
polyphenylene sulfide layer is regarded as one layer.
[0129] The copolymerized polyphenylene sulfide layer (layer c) in
the above 2-layer laminated film (a/c) can be heat-fused with a
biaxially oriented polyphenylene sulfide film layer (layer a) to
give a laminated sheet of the polyphenylene sulfide layer (layer
a)/copolymerized polyphenylene sulfide layer (layer
c)/polyphenylene sulfide layer (layer a).
[0130] When a 3-layer laminated film consisting of the
copolymerized polyphenylene sulfide layer (layer c)/polyphenylene
sulfide layer (layer a)/copolymerized polyphenylene sulfide layer
(layer c) is used, single, biaxially oriented sulfide film can be
heat-fused with both sides of the 3-layer laminated film
respectively to give a 5-layer laminated sheet of the polyphenylene
sulfide layer (layer a)/copolymerized polyphenylene sulfide layer
(layer c)/polyphenylene sulfide layer (layer a)/copolymerized
polyphenylene sulfide layer (layer c)/polyphenylene sulfide layer
(layer a).
[0131] The temperature condition for thermocompression bonding is
preferably in the range of (the melting point of copolymerized
polyphenylene sulfide) to 280.degree. C., more preferably in the
range of (the melting point of copolymerized polyphenylene sulfide
+10).degree. C. to 280.degree. C. from the viewpoint of adhesion
and mechanical characteristics. It is considered that a part of
polymer chains constituting the biaxially oriented copolymerized
polyolefin sulfide layer is thereby non-oriented. When the
thermocompression bonding temperature is lower than the melting
point of copolymerized polyphenylene sulfide, adhesion cannot be
sufficiently increased in some cases, while when the temperature is
higher than 280.degree. C., the planarity of the laminated sheet
may be rapidly deteriorated and the mechanical characteristics may
be deteriorated. The pressure for thermocompression bonding is
preferably 1 to 20 kg/cm.sup.2. When the pressure is less than 1
kg/cm.sup.2, adhesion is insufficient even if the thermocompression
bonding temperature is increased, while when the pressure is higher
than 20 kg/cm.sup.2, the planarity of the laminated sheet may be
deteriorated. The thermocompression bonding pressure is more
preferably in the range of 3 to 15 kg/cm.sup.2, still more
preferably in the range of 5 to 10 kg/cm.sup.2, but these ranges
are not intended to be limitative.
[0132] In a preferable mode of the present invention, the
copolymerized polyphenylene sulfide layer and the polyphenylene
sulfide layer used in the present invention may be subjected to
corona discharge treatment or plasma treatment in order to confer
stronger adhesion. In the present invention, another sheet layer
may be laminated, if necessary, insofar as the effect of the
present invention is not hindered.
[0133] The method of measuring characteristic values and the method
of evaluating the effect in the present invention are as
follows:
(1) Average Particle Diameter and Aspect Ratio of the Dispersed
Phase
[0134] The film was cut by ultramicrotomy in a direction (A)
parallel to the longitudinal direction and perpendicular to the
surface of the film, in a direction (B) parallel to the width
direction and perpendicular to the surface of the film and in a
direction (C) parallel to the surface of the film, to prepare a
sample. For clarifying the contrast of the dispersed phase, the
sample may be stained with osmic acid, ruthenium acid or
phosphotungstic acid. When the thermoplastic resin A is polyamide,
staining with phosphotungstic acid was preferably used. Its section
was observed under a transmission electron microscope (H-7100FA
model manufactured by Hitachi Ltd.) under the condition of an
applied voltage of 100 kV, and its photograph was taken at
20,000-fold magnification. The resulting photograph was scan as an
image with an image analyzer and arbitrary 100 dispersed phases
were selected, and subjected to image processing where appropriate,
thereby determining the sizes of the dispersed phases in the
following manner. When the number of dispersed phases in one
photograph is less than 100, another section in the same direction
is observed whereby 100 dispersed phases can be selected. The
maximum length (1a) of the individual dispersed phases in the
thickness direction of the film and the maximum length (1b) thereof
in the longitudinal direction in the section (A), the maximum
length (1c) of the individual dispersed phases in the thickness
direction of the film and the maximum length (1d) thereof in the
width direction in the section (B), and the maximum length (1e) of
the individual dispersed phases in the longitudinal direction of
the film and the maximum length (1f) thereof in the width direction
in the section (C) were determined. Then, when the dispersed phase
form index I=(number-average value of 1b+number-average value of
1e)/2, form index J=(number-average value of 1d+number-average
value of 1f)/2, and form index K=(number-average value of
1a+number-average value of 1c)/2, the average particle diameter of
the dispersed phases was expressed as (I+J+K)/3. Further, the
maximum value was determined as the average major axis L and the
minimum value as the average minor axis D, from I, J and K, and the
aspect ratio of the dispersed phases was expressed as L/D.
(2) Glass Transition Temperature (Tg), Melting Temperature (Tm),
Crystal Melting Heat Quantity
[0135] Samples were measured for specific heat according to JIS K
7121 in a quasi-isothermal mode under the following conditions
using the following instrument. The number of the measured samples
was three and obtained measurements were averaged. [0136]
Instrument: Temperature-modulated DSC manufactured by TA
Instruments, Inc. [0137] Measurement conditions: [0138] Heating
temperature: 270 to 570 K (RCS Cooling) [0139] Temperature
calibration: Melting point of high-purity indium and melting point
of high-purity tin [0140] Temperature modulation amplitude: .+-.1 K
[0141] Temperature modulation cycle: 60 seconds [0142] Heating
step: 5 K [0143] Sample weight: 5 mg [0144] Sample container:
Aluminum open container (22 mg) [0145] Reference container:
Aluminum open container (18 mg)
[0146] The glass transition points (Tg) of the three samples were
calculated using the following equation: Tg=(Extrapolated Initial
Glass Transition Temperature+Extrapolated Final Glass Transition
Temperature)/2
[0147] A differential scanning calorimeter, DSC (RDC 220)
manufactured by Seiko Instruments Inc. and a data analyzer, Disk
Station (SSC/5200), manufactured by Seiko Instruments Inc. were
used. Each 5 mg sample was placed on an aluminum pan, heated from
room temperature to 340.degree. C. at a rate of 20.degree. C./min.,
and the heat quantity of an endothermic peak, observed in this
step, was defined as crystal melting heat quantity. Thereafter, the
sample was kept molten at 340.degree. C. for 5 minutes, then
solidified by quenching, and heated from room temperature at a rate
of 20.degree. C./min. The peak temperature of an endothermic peak
in melting observed was defined as the melting temperature
(Tm).
(3) Tensile Strength at Break, Tensile Elongation at Break
[0148] Measurement was performed according to ASTM D-882 with an
Instron-type tensile testing machine. Measurement conditions
described below were used. Ten samples were measured and obtained
measurements were averaged. [0149] Measurement device: Automatic
film tensile tester, Tensilon AMF/RTA-100, manufactured by Orientec
Co., Ltd. [0150] Sample size: Width of 10 mm and chuck distance of
100 mm [0151] Strain rate: 10 mm/min. [0152] Measurement
environment: Temperature of 23.degree. C. and a relative humidity
of 65% (4) Impact Strength
[0153] The impact strength is determined by cutting a test sample
of width 1 mm.times.length 70 mm and measuring it at a test
temperature of 23.degree. C. with a Charpy impact tester
manufactured by Toyo Seiki (capacity, 10 kgcm; hammer weight, 1.019
kg; lifting angle of a hammer without a sample, 127.degree.;
distance from shaft center to gravity center, 6.12 cm). The impact
strength is expressed in the unit N/.mu.m after dividing the
measured value by the sectional area of the sample (sample
thickness.times.sample width). Seven samples were measured and
obtained measurements were averaged.
(5) Peak Temperature at Loss Tangent of Dynamic Viscoelasticity
[0154] Using DMS6100 (manufactured by Seiko Instruments Inc.), a
sample having a width of 10 mm and a length (chuck distance) of 20
mm (provided that the longitudinal direction of the film is the
sample length) was measured under the following conditions. [0155]
Measurement temperature range: 30 to 200.degree. C. [0156]
Vibrational frequency: 1 Hz [0157] Vibration displacement (strain):
10 (.mu.m) [0158] Temperature increasing rate: 2 (.degree.
C./min)
[0159] A graph wherein loss tangent (tan.delta.) from data obtained
under the above conditions was plotted against temperature (30 to
200.degree. C.) on the abscissa was prepared, and the temperature
at which tan.delta. became the highest was read as the peak
temperature.
(6) Molding Processability
[0160] Using a motor processing machine (manufactured by Odawara
Engineering Co., Ltd.), a film with a size of 12.times.80 mm (80 mm
in the longitudinal direction of the film) is punched out and
creased at a total processing rate of 2 samples/sec., and 1,000
samples were thus prepared and the number of cracks was counted and
judged as follows: [0161] Excellent: less than 50 cracks. [0162]
Good: 50 to 100 cracks. [0163] Acceptable: 100 to 200 cracks.
[0164] Not acceptable: Over 200 cracks. (7) Melt Viscosity
[0165] Using Flow Tester CFT-500 (manufactured by Shimadzu
Corporation), measurement was carried out with a die of 10 mm in
length, a die diameter of 1.0 mm, for a preheating time of 5
minutes.
EXAMPLES
Reference Example 1
Polymerization of PPS (PPS-1)
[0166] A 70-L autoclave equipped with a stirrer was charged with
8,267.37 g (70.00 moles) of 47.5% sodium hydrosulfide, 2,957.21 g
(70.97 moles) of 96% sodium hydroxide, 11,434.50 g (115.50 moles)
of N-methyl-2-pyrrolidone (NMP), 2,583.00 g (31.50 moles) of sodium
acetate and 10,500 g deionized water, and the mixture was gradually
heated to 245.degree. C. over about 3 hours at normal pressures
with nitrogen passing into it, and after 14,780.1 g water and 280 g
NMP were distilled away, the reaction container was cooled to
160.degree. C. The amount of water remaining in the system,
including water consumed in hydrolysis of NMP, was 1.06 moles per
mole of the alkali metal sulfide charged. The amount of hydrogen
sulfide scattered was 0.02 mol per mol of the alkali metal sulfide
charged.
[0167] Then, 10,235.46 g (69.63 moles) of p-dichlorobenzene and
9,009.00 g (91.00 moles) of NMP were added, and the reaction
container was sealed under a nitrogen gas and heated to 238.degree.
C. at a rate of 0.6.degree. C./min. under stirring at 240 rpm.
After reaction at 238.degree. C. for 95 minutes, the reaction
mixture was heated to 270.degree. C. at a rate of 0.8.degree.
C./min. After reaction at 270.degree. C. for 100 minutes, 1,260 g
(70 moles) of water was pressed over 15 minutes into the reaction
container which was then cooled to 250.degree. C. at a rate of
1.3.degree. C./min. Thereafter, the reaction mixture was cooled to
200.degree. C. at a rate of 1.0.degree. C./min. and then rapidly
cooled to a temperature in the vicinity of room temperature.
[0168] The reaction mixture was removed, diluted with 26,300 g NMP
and then separated into the solvent and solids through a screen (80
mesh), and the resulting particles were washed with 31,900 g NMP
and separated by filtration. These particles were washed several
times with 56,000 g deionized water, separated by filtration and
washed with 70,000 g of 0.05 wt % aqueous acetic acid and separated
by filtration. The particles were washed with 70,000 g deionized
water and then separated by filtration, and the resulting
water-containing PPS particles were dried with hot air at
80.degree. C. and then dried under reduced pressure at 120.degree.
C. The resulting PPS has a melt viscosity of 200 Pas (310.degree.
C., 1,000/s shear rate), a glass transition temperature of
90.degree. C. and a melting point of 285.degree. C.
Reference Example 2
Preparation of Copolymerized PPS Composition (PPS-2)
[0169] An autoclave was charged with 100 moles of sodium
sulfide.9H.sub.2O, 45 moles of sodium hydroxide and 25-L
N-methyl-2-pyrrolidone (referred to hereinafter as NMP), and the
mixture was gradually heated to 220.degree. C. under stirring to
remove the contained water by distillation.
[0170] The system after conclusion of dehydration was charged with
86 moles of p-dichlorobenzene as a main monomer, 15 moles of
m-dichlorobenzene as a minor monomer and 0.2 mole of
1,2,4-trichlorobenzene, together with 5-L NMP, then filled at
170.degree. C. with 3 kg/cm.sup.2 nitrogen under pressurization,
and heated to polymerize the mixture at 260.degree. C. for 4 hours.
After the polymerization was finished, the reaction mixture was
cooled to precipitate the polymer in distilled water, which was
then passed thorough a gauze having 150-mesh openings to recover a
small massive polymer.
[0171] This polymer was washed 5 times with distilled water at
90.degree. C. and dried at 120.degree. C. under reduced pressure to
give a white particulate copolymerized PPS composition having a
melting point of 240.degree. C.
Reference Example 3
Preparation of Copolymerized PPS Composition (PPS-3)
[0172] An autoclave was charged with 100 moles of sodium
sulfide.9H.sub.2O, 45 moles of sodium hydroxide and 25-L NMP, and
the mixture was gradually heated to 220.degree. C. under stirring
to remove the contained water by distillation.
[0173] The system after conclusion of dehydration was charged with
94.8 moles of p-dichlorobenzene as a main monomer, 5 moles of
m-dichlorobenzene as a minor monomer and 0.2 mole of
1,2,4-trichlorobenzene, together with 5-L NMP, then filled at
170.degree. C. with 3 kg/cm.sup.2 nitrogen under pressurization,
and heated to polymerize the mixture at 260.degree. C. for 4 hours.
After the polymerization was finished, the reaction mixture was
cooled to precipitate the polymer in distilled water, which was
then passed thorough a gauze having 150-mesh openings to recover a
small massive polymer.
[0174] This polymer was washed 5 times with distilled water at
90.degree. C. and dried at 120.degree. C. under reduced pressure to
give a white particulate copolymerized PPS composition having a
melting point of 260.degree. C.
Reference Example 4
Polyamide-1 (PA-1), Nylon 6/66 Copolymer
[0175] 50 wt % aqueous adipic acid/hexamethylene diamine salt (AH
salt) solution, and .epsilon.-caprolactam (CL), were mixed to give
a mixture of 20 parts by weight of the AH salt and 80 parts by
weight of CL and then charged into a 30-L autoclave. The mixture
was heated to 270.degree. C. at an internal pressure of 10
kg/cm.sup.2 and then gradually depressurized to 0.5 kg/cm.sup.2
under stirring while the internal temperature was kept at
245.degree. C., and then stirring was terminated. After the
reaction system was allowed to reach normal pressures with
nitrogen, the reaction mixture was extruded into strands to form
pellets which were then subjected to extraction with boiling water
to remove unreacted materials, and then dried. The copolymer
polyamide 6/66 resin thus obtained had a relative viscosity of 4.20
and a melting point of 193.degree. C.
Reference Example 5
Non-oriented Polyphenylene Sulfide Film (Sheet)
[0176] The PPS composition obtained as described above (Reference
Example 1) was dried at 180.degree. C. for 3 hours under reduced
pressure at 1 mmHg, fed to an extruder, melted at 310.degree. C.,
filtered with a 95%-cutting filter of pore diameter of 10 .mu.m
using a metal fiber, and then the discharge rate was regulated with
a device in an upper part of a die so as to form the PPS
composition (50 .mu.m), and was discharged via a T-die slit of 400
mm in width having linear lips with a distance of 1.0 mm. The
molten sheet thus extruded was cooled and solidified by intimate
contact with a metallic drum with a surface kept at 25.degree. C.
in such a manner that the sheet was statically charged, whereby a
non-oriented polyphenylene sulfide sheet of 50 .mu.m in thickness
was obtained.
Reference Example 6
Non-oriented Polyphenylene Sulfide Film (Sheet)
[0177] A non-oriented polyphenylene sulfide sheet was obtained in
the same manner as in Reference Example 5 except that its thickness
was made 70 .mu.m.
Reference Example 7
Non-oriented Polyphenylene Sulfide Film (Sheet)
[0178] A non-oriented polyphenylene sulfide sheet was obtained in
the same manner as in Reference Example 5 except that its thickness
was made 80 .mu.m.
Reference Example 8
Non-oriented Polyphenylene Sulfide Film (Sheet)
[0179] A non-oriented polyphenylene sulfide sheet was obtained in
the same manner as in Reference Example 5 except that its thickness
was made 120 .mu.m.
Example 1
[0180] 90 parts by weight of the PPS resin prepared in Reference
Example 1 were dried at 180.degree. C. for 3 hours under reduced
pressure, and as thermoplastic resin A, 10 parts by weight of nylon
6/66 copolymer (PA-1) prepared in Reference Example 4 were dried at
120.degree. C. for 3 hours under reduced pressure. Then, 2 parts by
weight of bisphenol A type epoxy resin (Epikote 1004, manufactured
by Yuka Shell Epoxy Co., Ltd.) were incorporated as a
compatibilizing agent into 100 parts by weight of the PPS resin and
the nylon 6/66 copolymer in total. Thereafter, the mixture was fed
to a vented co-rotating twin-screw extruder (a screw diameter of 30
mm and a screw length/screw diameter ratio of 45.5, manufactured by
Japan Steel Works, Ltd.) including 3 kneading paddling zones heated
to 310.degree. C. The mixture was melt-extruded into strands at a
screw speed of 300 rpm and a residence time of 90 seconds, then
cooled with water at a temperature of 25.degree. C. and immediately
cut into blend chips. 0.3 wt % calcium carbonate powder having an
average particle diameter of 1.2 .mu.m and 0.05 wt % calcium
stearate were added to, and uniformly mixed with, the blend chips
of PPS/PA-1 (90/10 wt %), and the resulting blended material,
designated resin X, was dried at 180.degree. C. for 3 hours under
reduced pressure and then fed to a full-flight single-screw
extruder having a melting zone heated at 320.degree. C. The polymer
melted in the extruder was filtered through a filter set at a
temperature of 330.degree. C., melt-extruded through a slit of a
T-die set at a temperature of 330.degree. C. and cooled and
solidified by intimate contact with a cast drum having a surface
temperature of 25.degree. C. in such a manner that the extrudate
was statically charged, whereby an unstretched film was
prepared.
[0181] The unstretched film was stretched at a temperature of
103.degree. C. and a draw ratio of 3.5 in the longitudinal
direction of the film by using a difference in rotation speed
between rolls in a stretching machine including a plurality of
groups of heated rolls. Thereafter, both ends of the resulting film
were retained with clips and the film was stretched at a stretching
temperature of 105.degree. C. and a draw ratio of 3.5 with a tenter
in the width direction of the film and then heat-treated at a
temperature of 260.degree. C. for 2 seconds. Thereafter, the
resulting film was relaxed by 4% in the transverse direction in a
cooling zone maintained at 150.degree. C. and then cooled to room
temperature, followed by removing film edges, whereby a biaxially
oriented PPS film of 125 .mu.m was prepared.
[0182] As shown in the results of measurement and evaluation of the
structure and properties of the resulting biaxially oriented PPS
film in Table 1, this biaxially oriented polyphenylene sulfide film
was excellent in tensile elongation and molding processability.
Examples 2 and 3
[0183] A biaxially oriented polyphenylene sulfide film was obtained
in the same manner as in Example 1 except that the amount of PA-1
added as thermoplastic resin A was changed as shown in Table 1. As
shown in the results of measurement and evaluation of the structure
and properties of the resulting biaxially oriented PPS film in
Table 1, this biaxially oriented polyphenylene sulfide film was
excellent in tensile elongation and molding processability.
Example 4
[0184] A biaxially oriented polyphenylene sulfide film was obtained
in the same manner as in Example 1 except that nylon 6 (CM1001
manufactured by Toray Industries, Inc.) (polyamide-2 (PA-2)) was
used as thermoplastic resin A. As shown in the results of
measurement and evaluation of the structure and properties of the
resulting biaxially oriented PPS film in Table 1, this biaxially
oriented polyphenylene sulfide film was excellent in tensile
elongation and molding processability.
Example 5
[0185] A biaxially oriented polyphenylene sulfide film was obtained
in the same manner as in Example 1 except that nylon 12 (CM5051F
manufactured by Toray Industries, Inc.) (polyamide-3 (PA-3)) was
used as thermoplastic resin A. As shown in the results of
measurement and evaluation of the structure and properties of the
resulting biaxially oriented PPS film in Table 1, this biaxially
oriented polyphenylene sulfide film was excellent in tensile
elongation and molding processability.
Example 6
[0186] 90 parts by weight of the PPS resin prepared in Reference
Example 1 were dried at 180.degree. C. for 3 hours under reduced
pressure, and as thermoplastic resin A, 10 parts by weight of nylon
6/66 copolymer (PA-1) prepared in Reference Example 4 were dried at
120.degree. C. for 3 hours under reduced pressure. Then, 2 parts by
weight of bisphenol A type epoxy resin (Epikote 1004, manufactured
by Yuka Shell Epoxy Co., Ltd.) were incorporated as a
compatibilizing agent into 100 parts by weight of the PPS resin and
the nylon 6/66 copolymer in total. Thereafter, the mixture was fed
to a vented co-rotating twin-screw extruder (a screw diameter of 30
mm and a screw length/screw diameter ratio of 45.5, manufactured by
Japan Steel Works, Ltd.) including 3 kneading paddling zones heated
to 325.degree. C. The mixture was melt-extruded into strands at a
screw speed of 300 rpm and a residence time of 90 seconds, then
cooled with water at a temperature of 25.degree. C. and immediately
cut into blend chips. Thereinafter, an unstretched film was
obtained in the same manner as in Example 1, and a biaxially
oriented PPS film of 125 .mu.m in thickness was prepared.
[0187] As shown in the results of measurement and evaluation of the
structure and properties of the resulting biaxially oriented PPS
film in Table 1, this biaxially oriented polyphenylene sulfide film
was excellent in tensile elongation and molding processability.
Example 7
[0188] The PPS resin X obtained in Example 1 was dried at
180.degree. C. for 3 hours under reduced pressure and then fed to
an extruder having a melting zone heated at 320.degree. C., and the
polymer melted in the extruder was filtered through a filter set at
a temperature of 330.degree. C., melt-extruded through a slit of a
T-die set at a temperature of 320.degree. C. and cooled and
solidified by intimate contact with a cast drum having a surface
temperature of 25.degree. C. in such a manner that the extrudate
was statically charged, whereby an unstretched film was
prepared.
[0189] This unstretched film was formed into a biaxially oriented
PPS film of 125 .mu.m in thickness by the same method as in Example
1.
[0190] As shown in the results of measurement and evaluation of the
structure and properties of the resulting biaxially oriented PPS
film in Table 1, this biaxially oriented polyphenylene sulfide film
was excellent in tensile elongation and molding processability.
Example 8
[0191] 90 parts by weight of the PPS resin prepared in Reference
Example 1 were dried at 180.degree. C. for 3 hours under reduced
pressure, and as thermoplastic resin A, 10 parts by weight of nylon
6/66 copolymer (PA-1) prepared in Reference Example 4 were dried at
120.degree. C. for 3 hours under reduced pressure. Further, 0.5
part by weight of .gamma.-isocyanate propyltriethoxysilane
(KBE9007, manufactured by Shin-Etsu Chemical Co., Ltd.) was
incorporated as a compatibilizing agent into 100 parts by weight of
the PPS resin and the nylon 6/66 copolymer in total. Thereafter,
the mixture was fed to a vented co-rotating twin-screw extruder (a
screw diameter of 30 mm and a screw length/screw diameter ratio of
45.5, manufactured by Japan Steel Works, Ltd.) including 3 kneading
paddling zones heated to 310.degree. C. The mixture was
melt-extruded into strands at a screw speed of 300 rpm and a
residence time of 90 seconds, then cooled with water at a
temperature of 25.degree. C. and immediately cut into blend chips
Y. 0.3 wt % calcium carbonate powder having an average particle
diameter of 1.2 .mu.m and 0.05 wt % calcium stearate were added to
and were uniformly dispersed in and blended with the blend chips Y
of PPS/PA-1 (90/10 wt %), and the resulting blended material was
dried at 180.degree. C. for 3 hours under reduced pressure and then
fed to a full-flight single-screw extruder having a melting zone
heated at 320.degree. C. The polymer melted in the extruder was
filtered through a filter set at a temperature of 330.degree. C.,
melt-extruded through a slit of a T-die set at a temperature of
330.degree. C. and cooled and solidified by intimate contact with a
cast drum having a surface temperature of 25.degree. C. in such a
manner that the extrudate was statically charged, whereby an
unstretched film was prepared.
[0192] This unstretched film was formed into a biaxially oriented
PPS film of 125 .mu.m in thickness by the same method as in Example
1.
[0193] As shown in the results of measurement and evaluation of the
structure and properties of the resulting biaxially oriented PPS
film in Table 1, this biaxially oriented polyphenylene sulfide film
was excellent in tensile elongation and molding processability.
Example 9
[0194] 90 parts by weight of the PPS resin prepared in Reference
Example 1 were dried at 180.degree. C. for 3 hours under reduced
pressure, and as thermoplastic resin A, 10 parts by weight of nylon
610 (Amilan CM2001, manufactured by Toray Industries, Inc.)
(polyamide-4 (PA-4)) were dried at 120.degree. C. for 3 hours under
reduced pressure. Further, 0.5 part by weight of .gamma.-isocyanate
propyltriethoxysilane (KBE9007, manufactured by Shin-Etsu Chemical
Co., Ltd.) was incorporated as a compatibilizing agent into 100
parts by weight of the PPS resin and the nylon 610 in total.
Thereafter, the mixture was fed to a vented co-rotating twin-screw
extruder (a screw diameter of 30 mm and a screw length/screw
diameter ratio of 45.5, manufactured by Japan Steel Works, Ltd.)
including 3 kneading paddling zones heated to 310.degree. C. The
mixture was melt-extruded into strands at a screw speed of 300 rpm
and a residence time of 90 seconds, then cooled with water at a
temperature of 25.degree. C. and immediately cut into blend chip
resin Z. 0.3 wt % calcium carbonate powder having an average
particle diameter of 1.2 .mu.m and 0.05 wt % calcium stearate were
added to and were uniformly dispersed in and blended with the blend
chip resin Z of PPS/PA-1 (90/10 wt %), and the resulting blended
material was dried at 180.degree. C. for 3 hours under reduced
pressure and then fed to a full-flight single-screw extruder having
a melting zone heated at 320.degree. C. The polymer melted in the
extruder was filtered through a filter set at a temperature of
330.degree. C., melt-extruded through a slit of a T-die set at a
temperature of 330.degree. C. and cooled and solidified by intimate
contact with a cast drum having a surface temperature of 25.degree.
C. in such a manner that the extrudate was statically charged,
whereby an unstretched film was prepared.
[0195] This unstretched film was formed into a biaxially oriented
PPS film of 125 .mu.m in thickness by the same method as in Example
1.
[0196] As shown in the results of measurement and evaluation of the
structure and properties of the resulting biaxially oriented PPS
film in Table 1, this biaxially oriented polyphenylene sulfide film
was excellent in tensile elongation and molding processability.
Example 10
[0197] An unstretched film obtained in the same manner as in
Example 9 was stretched at a temperature of 107.degree. C. and a
draw ratio of 3.0 in the longitudinal direction of the film by
using a difference in rotation speed between rolls in a stretching
machine including a plurality of groups of heated rolls.
Thereafter, both ends of the resulting film were retained with
clips and the film was stretched at a stretching temperature of
105.degree. C. and a draw ratio of 3.5 with a tenter in the width
direction of the film and then heat-treated at a temperature of
260.degree. C. for 10 seconds. Thereafter, the resulting film was
relaxed by 4% in the transverse direction in a cooling zone
maintained at 150.degree. C. and then cooled to room temperature,
followed by removing film edges, whereby a biaxially oriented PPS
film of 125 .mu.m in thickness was prepared.
[0198] As shown in the results of measurement and evaluation of the
structure and properties of the resulting biaxially oriented PPS
film in Table 1, this biaxially oriented polyphenylene sulfide film
was excellent in tensile elongation and molding processability.
Example 11
[0199] An unstretched film obtained in the same manner as in
Example 9 was stretched at a temperature of 107.degree. C. and a
draw ratio of 3.0 in the longitudinal direction of the film by
using a difference in rotation speed between rolls in a stretching
machine including a plurality of groups of heated rolls.
Thereafter, both ends of the resulting film were retained with
clips and the film was stretched at a stretching temperature of
100.degree. C. and a draw ratio of 3.0 with a tenter in the width
direction of the film and then heat-treated at a temperature of
260.degree. C. for 10 seconds. Thereafter, the resulting film was
relaxed by 4% in the transverse direction in a cooling zone
maintained at 150.degree. C. and then cooled to room temperature,
followed by removing film edges, whereby a biaxially oriented PPS
film of 125 .mu.m in thickness was prepared.
[0200] As shown in the results of measurement and evaluation of the
structure and properties of the resulting biaxially oriented PPS
film in Table 1, this biaxially oriented polyphenylene sulfide film
was excellent in tensile elongation and molding processability.
Example 12
[0201] An unstretched film obtained in the same manner as in
Example 9 was stretched at a temperature of 107.degree. C. and a
draw ratio of 3.0 in the longitudinal direction of the film by
using a difference in rotation speed between rolls in a stretching
machine including a plurality of groups of heated rolls.
Thereafter, both ends of the resulting film were retained with
clips and the film was stretched at a stretching temperature of
100.degree. C. and a draw ratio of 3.0 with a tenter in the width
direction of the film and then heat-treated at a temperature of
250.degree. C. for 10 seconds. Thereafter, the resulting film was
relaxed by 4% in the transverse direction in a cooling zone
maintained at 150.degree. C. and then cooled to room temperature,
followed by removing film edges, whereby a biaxially oriented PPS
film of 125 .mu.m in thickness was prepared.
[0202] As shown in the results of measurement and evaluation of the
structure and properties of the resulting biaxially oriented PPS
film in Table 1, this biaxially oriented polyphenylene sulfide film
was excellent in tensile elongation and molding processability.
Example 13
[0203] A biaxially oriented polyphenylene sulfide film was obtained
in the same manner as in Example 12 except that the amount of PA-4
added as thermoplastic resin A was changed to 5 parts by weight as
shown in Table 1.
[0204] As shown in the results of measurement and evaluation of the
structure and properties of the resulting biaxially oriented PPS
film in Table 1, this biaxially oriented polyphenylene sulfide film
was excellent in tensile elongation and molding processability.
Example 14
[0205] A biaxially oriented polyphenylene sulfide film was obtained
in the same manner as in Example 1 except that polyether imide
(PEI) (Ultem 1010, produced by GE Plastics) (glass transition
temperature 215.degree. C.) was used as thermoplastic resin A. As
shown in the results of measurement and evaluation of the structure
and properties of the resulting biaxially oriented PPS film in
Table 1, this biaxially oriented polyphenylene sulfide film was
excellent in tensile elongation and molding processability.
Example 15
[0206] A biaxially oriented polyphenylene sulfide film was obtained
in the same manner as in Example 1 except that polysulfone (PSF)
(UDEL, produced by Amoco) (glass transition temperature 190.degree.
C.) was used as thermoplastic resin A. As shown in the results of
measurement and evaluation of the structure and properties of the
resulting biaxially oriented PPS film in Table 1, this biaxially
oriented polyphenylene sulfide film was excellent in tensile
elongation and molding processability.
Example 16
[0207] A biaxially oriented polyphenylene sulfide film was obtained
in the same manner as in Example 1 except that polyether sulfone
(PES) (RADEL, produced by Amoco) (glass transition temperature
225.degree. C.) was used as thermoplastic resin A. As shown in the
results of measurement and evaluation of the structure and
properties of the resulting biaxially oriented PPS film in Table 1,
this biaxially oriented polyphenylene sulfide film was excellent in
tensile elongation and molding processability.
Example 17
[0208] A biaxially oriented polyphenylene sulfide film was obtained
in the same manner as in Example 12 except that polyether imide
(PEI) (Ultem 1010, produced by GE Plastics) (glass transition
temperature 215.degree. C.) was used as thermoplastic resin A. As
shown in the results of measurement and evaluation of the structure
and properties of the resulting biaxially oriented PPS film in
Table 1, this biaxially oriented polyphenylene sulfide film was
excellent in tensile elongation and molding processability.
Example 18
[0209] A biaxially oriented polyphenylene sulfide film was obtained
in the same manner as in Example 12 except that polysulfone (PSF)
(UDEL, produced by Amoco) (glass transition temperature 190.degree.
C.) was used as thermoplastic resin A. As shown in the results of
measurement and evaluation of the structure and properties of the
resulting biaxially oriented PPS film in Table 1, this biaxially
oriented polyphenylene sulfide film was excellent in tensile
elongation and molding processability.
Example 19
[0210] A biaxially oriented polyphenylene sulfide film was obtained
in the same manner as in Example 12 except that polyether sulfone
(PES) (RADEL, produced by Amoco) (glass transition temperature
225.degree. C.) was used as thermoplastic resin A. As shown in the
results of measurement and evaluation of the structure and
properties of the resulting biaxially oriented PPS film in Table 1,
this biaxially oriented polyphenylene sulfide film was excellent in
tensile elongation and molding processability.
Comparative Example 1
[0211] A biaxially oriented film was obtained in the same manner as
in Example 1 except that only the polyphenylene sulfide resin
obtained in Reference Example 1 was used. The resulting biaxially
oriented polyphenylene sulfide film, as shown in the results of
measurement and evaluation of the structure and properties thereof
in Table 1, was a film poor in tensile elongation and molding
processability.
Comparative Example 2
[0212] A biaxially oriented polyphenylene sulfide film was obtained
in the same manner as in Example 1 except that the compatibilizing
agent was not added. The resulting biaxially oriented polyphenylene
sulfide film, as shown in the results of measurement and evaluation
of the structure and properties thereof in Table 1, was a film poor
in tensile elongation and molding processability.
Comparative Example 3
[0213] 90 parts by weight of the PPS resin prepared in Reference
Example 1 were dried at 180.degree. C. for 3 hours under reduced
pressure, and as thermoplastic resin A, 10 parts by weight of nylon
6/66 copolymer (PA-1) prepared in Reference Example 4 were dried at
120.degree. C. for 3 hours under reduced pressure. Then, 2 parts by
weight of bisphenol A type epoxy resin (Epikote 1004, manufactured
by Yuka Shell Epoxy Co., Ltd.) were incorporated as a
compatibilizing agent into 100 parts by weight of the PPS resin and
the nylon 6/66 copolymer in total. Thereafter, the mixture was fed
to a vented co-rotating twin-screw extruder (a screw diameter of 30
mm and a screw length/screw diameter ratio of 45.5, manufactured by
Japan Steel Works, Ltd.) including 3 kneading paddling zones heated
to 310.degree. C. The mixture was melt-extruded into strands at a
screw speed of 80 rpm and a residence time of 90 seconds, then
cooled with water at a temperature of 25.degree. C. and immediately
cut into blend chips. Thereinafter, a biaxially oriented
polyphenylene sulfide film was obtained in the same manner as in
Example 1.
[0214] The resulting biaxially oriented polyphenylene sulfide film,
as shown in the results of measurement and evaluation of the
structure and properties thereof in Table 1, was a film poor in
tensile elongation and molding processability.
Comparative Example 4
[0215] 90 parts by weight of the PPS resin prepared in Reference
Example 1 were dried at 180.degree. C. for 3 hours under reduced
pressure, and as thermoplastic resin A, 10 parts by weight of nylon
6/66 copolymer (PA-1) prepared in Reference Example 4 were dried at
120.degree. C. for 3 hours under reduced pressure. Then, 2 parts by
weight of bisphenol A type epoxy resin (Epikote 1004, manufactured
by Yuka Shell Epoxy Co., Ltd.) were incorporated as a
compatibilizing agent into 100 parts by weight of the PPS resin and
the nylon 6/66 copolymer in total. Thereafter, the mixture was fed
to a vented co-rotating twin-screw extruder (a screw diameter of 30
mm and a screw length/screw diameter ratio of 45.5, manufactured by
Japan Steel Works, Ltd.) including 3 kneading paddling zones heated
to 350.degree. C. The mixture was melt-extruded into strands at a
screw speed of 300 rpm and a residence time of 90 seconds, then
cooled with water at a temperature of 25.degree. C. and immediately
cut into blend chips. Thereinafter, an unstretched film was
obtained in the same manner as in Example 1, and a biaxially
oriented PPS film of 125 .mu.m in thickness was prepared.
[0216] The resulting biaxially oriented PPS film, as shown in the
results of measurement and evaluation of the structure and
properties thereof in Table 1, was a film poor in molding
processability.
Comparative Example 5
[0217] 90 parts by weight of the PPS resin prepared in Reference
Example 1 were dried at 180.degree. C. for 3 hours under reduced
pressure, and as thermoplastic resin A, 10 parts by weight of nylon
6/66 copolymer (PA-1) prepared in Reference Example 4 were dried at
120.degree. C. for 3 hours under reduced pressure. Then, 2 parts by
weight of bisphenol A type epoxy resin (Epikote 1004, manufactured
by Yuka Shell Epoxy Co., Ltd.) were incorporated as a
compatibilizing agent into 100 parts by weight of the PPS resin and
the nylon 6/66 copolymer in total. Thereafter, the mixture was fed
to a full-flight single-screw extruder heated at 310.degree. C.
(screw diameter 40 mm, manufactured by Tanabe Plastics Machinery
Co., Ltd) and melt-extruded into strands at a screw speed of 80 rpm
and a residence time of 90 seconds, then cooled with water at a
temperature of 25.degree. C. and immediately cut into blend chips.
Thereinafter, a biaxially oriented polyphenylene sulfide film was
obtained in the same manner as in Example 1.
[0218] The resulting biaxially oriented polyphenylene sulfide film,
as shown in the results of measurement and evaluation of the
structure and properties thereof in Table 1, was a film poor in
tensile elongation and molding processability.
Comparative Example 6
[0219] 90 parts by weight of the PPS resin prepared in Reference
Example 1 were dried at 180.degree. C. for 3 hours under reduced
pressure, and as thermoplastic resin A, 10 parts by weight of nylon
6/66 copolymer (PA-1) prepared in Reference Example 4 were dried at
120.degree. C. for 3 hours under reduced pressure. 100 parts by
weight of the PPS resin and the nylon 6/66 copolymer in total were
blended with 2 parts by weight of bisphenol A type epoxy resin
(Epikote 1004, manufactured by Yuka Shell Epoxy Co., Ltd.), 0.3 wt
% calcium carbonate powder having an average particle diameter of
1.2 .mu.m and 0.05 wt % calcium stearate, and the resulting blended
material was fed to a full-flight single-screw extruder having a
melting zone heated at 320.degree. C. The polymer melted in the
extruder was filtered through a filter set at a temperature of
330.degree. C., melt-extruded through a slit of a T-die set at a
temperature of 330.degree. C. and cooled and solidified by intimate
contact with a cast drum having a surface temperature of 25.degree.
C. in such a manner that the extrudate was statically charged,
whereby an unstretched film was prepared. The resulting unstretched
film was formed into a biaxially oriented polyphenylene sulfide
film in the same manner as in Example 1.
[0220] The resulting biaxially oriented polyphenylene sulfide film,
as shown in the results of measurement and evaluation of the
structure and properties thereof in Table 1, was a film poor in
tensile elongation and molding processability.
Comparative Examples 7 to 9
[0221] A biaxially oriented polyphenylene sulfide film was obtained
in the same manner as in Example 1 except that the amount of PA-1
added as thermoplastic resin A was changed as shown in Table 1. As
shown in the results of measurement and evaluation of the structure
and properties of the resulting biaxially oriented PPS film in
Table 1, this biaxially oriented polyphenylene sulfide film was a
film poor in tensile elongation and molding processability.
Comparative Example 10
[0222] An unstretched film obtained in the same manner as in
Example 9 was stretched at a temperature of 107.degree. C. and a
draw ratio of 3.0 in the longitudinal direction of the film by
using a difference in rotation speed between rolls in a stretching
machine including a plurality of groups of heated rolls.
Thereafter, both ends of the resulting film were retained with
clips and the film was stretched at a stretching temperature of
100.degree. C. and a draw ratio of 3.0 with a tenter in the width
direction of the film and then heat-treated at a temperature of
285.degree. C. for 10 seconds. Thereafter, the resulting film was
relaxed by 4% in the transverse direction in a cooling zone
maintained at 150.degree. C. and then cooled to room temperature,
followed by removing film edges, whereby a biaxially oriented PPS
film of 125 .mu.m in thickness was prepared. As shown in the
results of measurement and evaluation of the structure and
properties of the resulting biaxially oriented PPS film in Table 1,
this biaxially oriented polyphenylenesulfide film was a film poor
in tensile elongation and molding processability.
Comparative Example 11
[0223] An unstretched film obtained in the same manner as in
Example 9 was stretched at a temperature of 103.degree. C. and a
draw ratio of 4.2 in the longitudinal direction of the film by
using a difference in rotation speed between rolls in a stretching
machine including a plurality of groups of heated rolls.
Thereafter, both ends of the resulting film were retained with
clips and the film was stretched at a stretching temperature of
100.degree. C. and a draw ratio of 3.0 with a tenter in the width
direction of the film and then heat-treated at a temperature of
260.degree. C. for 10 seconds. Thereafter, the resulting film was
relaxed by 4% in the transverse direction in a cooling zone
maintained at 150.degree. C. and then cooled to room temperature,
followed by removing film edges, whereby a biaxially oriented PPS
film of 125 .mu.m in thickness was prepared. As shown in the
results of measurement and evaluation of the structure and
properties of the resulting biaxially oriented PPS film in Table 1,
this biaxially oriented polyphenylene sulfide film was a film poor
in tensile elongation and molding processability.
Comparative Example 12
[0224] An unstretched film obtained in the same manner as in
Example 9 was stretched at a temperature of 107.degree. C. and a
draw ratio of 3.0 in the longitudinal direction of the film by
using a difference in rotation speed between rolls in a stretching
machine including a plurality of groups of heated rolls.
Thereafter, both ends of the resulting film were retained with
clips and the film was stretched at a stretching temperature of
105.degree. C. and a draw ratio of 4.2 with a tenter in the width
direction of the film and then heat-treated at a temperature of
260.degree. C. for 10 seconds. Thereafter, the resulting film was
relaxed by 4% in the transverse direction in a cooling zone
maintained at 150.degree. C. and then cooled to room temperature,
followed by removing film edges, whereby a biaxially oriented PPS
film of 125 .mu.m in thickness was prepared. As shown in the
results of measurement and evaluation of the structure and
properties of the resulting biaxially oriented PPS film in Table 1,
this biaxially oriented polyphenylene sulfide film was a film poor
in tensile elongation and molding processability. TABLE-US-00001
TABLE 1 Peak Content of Average temperature at Crystal Content of
thermoplastic particle Tensile Tensile loss tangent of melting
polyarylene resin A diameter elongation strength dynamic heat
sulfide (parts Thermoplastic (parts by (dispersed at break at break
viscoelasticity quantity Molding by weight) resin A weight) phase)
(nm) MD/TD (%) MD/TD (MPa) (.degree. C.) (J/g) processability
Example 1 90 PA-1 10 80 160/180 280/230 124 32 Excellent Example 2
75 PA-1 25 250 110/125 210/170 118 25 Good Example 3 95 PA-1 5 80
120/135 280/240 126 34 Good Example 4 90 PA-2 10 120 135/150
270/220 127 32 Excellent Example 5 90 PA-3 10 220 90/115 250/220
132 33 Good Example 6 90 PA-1 10 280 110/125 250/215 128 33 Good
Example 7 90 PA-1 10 330 95/130 240/210 137 34 Acceptable Example 8
90 PA-1 10 70 170/180 250/220 120 32 Good Example 9 90 PA-4 10 60
170/180 220/200 124 32 Good Example 10 90 PA-4 10 60 180/180
200/200 120 35 Good Example 11 90 PA-4 10 60 180/190 190/170 118 35
Excellent Example 12 90 PA-4 10 60 185/195 200/180 116 33 Excellent
Example 13 95 PA-4 5 60 165/175 220/200 123 38 Good Example 14 90
PEI 10 170 130/140 260/230 131 31 Good Example 15 90 PSF 10 270
115/135 240/220 133 31 Good Example 16 90 PES 10 280 110/125
230/210 133 30 Good Example 17 90 PEI 10 150 140/150 240/220 127 33
Good Example 18 90 PSF 10 230 125/145 230/220 128 32 Good Example
19 90 PES 10 230 130/135 230/215 128 32 Good Comparative 100 -- 0
-- 70/90 300/250 137 38 Not acceptable Example 1 Comparative 90
PA-1 10 650 65/85 150/130 136 32 Not acceptable Example 2
Comparative 90 PA-1 10 570 75/90 160/130 136 33 Not acceptable
Example 3 Comparative 90 PA-1 10 530 65/80 180/135 138 33 Not
acceptable Example 4 Comparative 90 PA-1 10 720 50/75 130/120 139
34 Not acceptable Example 5 Comparative 90 PA-1 10 1200 30/50
115/90 140 35 Not acceptable Example 6 Comparative 65 PA-1 35 400
85/95 170/140 115 22 Not acceptable Example 7 Comparative 55 PA-1
45 510 65/80 165/125 128 33 Not acceptable Example 8 Comparative
99.5 PA-1 0.5 50 65/90 280/235 136 38 Not acceptable Example 9
Comparative 90 PA-4 10 60 70/75 280/260 120 55 Not acceptable
Example 10 Comparative 90 PA-4 10 60 60/90 280/250 137 37 Not
acceptable Example 11 Comparative 90 PA-4 10 60 80/60 290/240 136
40 Not acceptable Example 12 (Note) MD (longitudinal direction of
film) TD (width direction of film)
Example 20
[0225] An unstretched film obtained in the same manner as in
Example 1 was stretched at a temperature of 103.degree. C. and a
draw ratio of 3.0 in the longitudinal direction of the film by
using a difference in rotation speed between rolls in a stretching
machine including a plurality of groups of heated rolls.
Thereafter, both ends of the resulting film were retained with
clips and the film was stretched at a stretching temperature of
105.degree. C. and a draw ratio of 3.5 with a tenter in the width
direction of the film and subjected to heat treatment at the first
stage at a temperature of 240.degree. C. for 2 seconds and then to
heat treatment at the second stage at a temperature of 260.degree.
C. for 2 seconds. Thereafter, the resulting film was relaxed by 4%
in the transverse direction in a cooling zone maintained at
150.degree. C. and then cooled to room temperature, followed by
removing film edges, whereby a biaxially oriented PPS sheet of 100
.mu.m in thickness was prepared.
[0226] This biaxially oriented PPS film and the non-oriented PPS
sheet obtained in Reference Example 5 were laminated by a press
roll at a temperature of 240.degree. C. at a pressure of 10
kg/cm.sup.2, to constitute a 3-layer laminate composed of the
biaxially oriented polyphenylene sulfide (layer a)/non-oriented
polyphenylene sulfide (layer b)/biaxially oriented polyphenylene
sulfide (layer a) (100/50/100 (.mu.m)).
[0227] As shown in the results of measurement and evaluation of the
structure and properties of the resulting laminated PPS sheet in
Table 2, this sheet was excellent in tensile elongation and molding
processability.
Examples 21 and 22
[0228] A laminated polyphenylene sulfide sheet was obtained in the
same manner as in Example 20 except that the amount of PA-1 added
as thermoplastic resin A was changed as shown in Table 1 to give a
biaxially oriented polyphenylene sulfide sheet. As shown in the
results of measurement and evaluation of the structure and
properties of the resulting laminated polyphenylene sulfide sheet
in Table 2, this laminated polyphenylene sulfide film was excellent
in tensile elongation and molding processability.
Example 23
[0229] A laminated polyphenylene sulfide film was obtained in the
same manner as in Example 20 except that nylon 6 (CM1001
manufactured by Toray Industries, Inc.) (polyamide-2 (PA-2)) was
used as thermoplastic resin A to give a biaxially oriented
polyphenylene sulfide sheet. As shown in the results of measurement
and evaluation of the structure and properties of the resulting
laminated polyphenylene sulfide sheet in Table 2, this laminated
polyphenylene sulfide sheet was excellent in tensile elongation and
molding processability.
Example 24
[0230] A laminated polyphenylene sulfide sheet was obtained in the
same manner as in Example 20 except that nylon 12 (CM5051
manufactured by Toray Industries, Inc.) (polyamide-3 (PA-3)) was
used as thermoplastic resin A to give a biaxially oriented
polyphenylene sulfide sheet. As shown in the results of measurement
and evaluation of the structure and properties of the resulting
laminated polyphenylene sulfide sheet in Table 2, this laminated
polyphenylene sulfide sheet was excellent in tensile elongation and
molding processability.
Example 25
[0231] 90 parts by weight of the PPS resin prepared in Reference
Example 1 were dried at 180.degree. C. for 3 hours under reduced
pressure, and as thermoplastic resin A, 10 parts by weight of nylon
6/66 copolymer (PA-1) prepared in Reference Example 4 were dried at
120.degree. C. for 3 hours under reduced pressure. Then, 2 parts by
weight of bisphenol A type epoxy resin (Epikote 1004, manufactured
by Yuka Shell Epoxy Co., Ltd.) were incorporated as a
compatibilizing agent into 100 parts by weight of the PPS resin and
the nylon 6/66 copolymer in total. Thereafter, the mixture was fed
to a vented co-rotating twin-screw extruder (a screw diameter of 30
mm and a screw length/screw diameter ratio of 45.5, manufactured by
Japan Steel Works, Ltd.) including 3 kneading paddling zones heated
to 325.degree. C. The mixture was melt-extruded into strands at a
screw speed of 300 rpm and a residence time of 90 seconds, then
cooled with water at a temperature of 25.degree. C. and immediately
cut into blend chips. Thereafter, an unstretched film was prepared
in the same manner as in Example 20. This unstretched film was
formed into a biaxially oriented polyphenylene sulfide sheet in the
same method as in Example 20, and a laminated polyphenylene sulfide
sheet was obtained in the same manner as in Example 20.
[0232] As shown in the results of measurement and evaluation of the
structure and properties of the resulting laminated polyphenylene
sulfide sheet in Table 2, this laminated polyphenylene sulfide
sheet was satisfactory in molding processability.
Example 26
[0233] An unstretched film was obtained in the same manner as in
Example 9 was obtained in the same manner as in Example 9 except
that nylon 610 (Amilan CM2001, manufactured by Toray Industries,
Inc.) (polyamide-4 (PA-4)) was used as thermoplastic resin A.
Thereafter, a laminated polyphenylene sulfide sheet was obtained in
the same manner as in Example 20. As shown in the results of
measurement and evaluation of the structure and properties of the
resulting laminated polyphenylene sulfide sheet in Table 2, this
laminated polyphenylene sulfide sheet was excellent in tensile
elongation and molding processability.
Example 27
[0234] The biaxially oriented PPS film containing 10 wt % nylon 610
obtained in Example 12 and the non-oriented PPS sheet obtained in
Reference Example 5 were laminated by a press roll at a temperature
of 240.degree. C. at a pressure of 10 kg/cm.sup.2, to constitute a
3-layer laminate composed of the biaxially oriented polyphenylene
sulfide (layer a)/non-oriented polyphenylene sulfide (layer
b)/biaxially oriented polyphenylene sulfide (layer a).
[0235] As shown in the results of measurement and evaluation of the
structure and properties of the resulting laminated PPS sheet in
Table 2, this sheet was excellent in tensile elongation and molding
processability.
Example 28
[0236] A laminated polyphenylene sulfide sheet was obtained in the
same manner as in Example 20 except that polyether imide (PEI)
(Ultem 1001, produced by GE Plastics) (glass transition temperature
215.degree. C.) was used as thermoplastic resin A. As shown in the
results of measurement and evaluation of the structure and
properties of the resulting laminated polyphenylene sulfide sheet
in Table 2, this biaxially oriented polyphenylene sulfide film was
excellent in tensile elongation and molding processability.
Example 29
[0237] A laminated polyphenylene sulfide sheet was obtained in the
same manner as in Example 20 except that polysulfone (PSF) (UDEL,
produced by Amoco) (glass transition temperature 190.degree. C.)
was used as thermoplastic resin A. As shown in the results of
measurement and evaluation of the structure and properties of the
resulting laminated polyphenylene sulfide sheet in Table 2, this
laminated polyphenylene sulfide sheet was excellent in tensile
elongation and molding processability.
Example 30
[0238] A laminated polyphenylene sulfide sheet was obtained in the
same manner as in Example 20 except that polyether sulfone (PES)
(RADEL, produced by Amoco) (glass transition temperature
225.degree. C.) was used as thermoplastic resin A. As shown in the
results of measurement and evaluation of the structure and
properties of the resulting laminated polyphenylene sulfide sheet
in Table 2, this biaxially oriented polyphenylene sulfide film was
excellent in tensile elongation and molding processability.
Example 31
[0239] The copolymerized PPS composition obtained in Reference
Example 2 and resin X obtained in Example 1 were dried respectively
at 180.degree. C. for 3 hours under reduced pressure at 1 mmHg, and
0.3 wt % calcium carbonate powder having an average particle
diameter of 1.2 .mu.m and 0.05 wt % calcium stearate were uniformly
dispersed in and blended with resin X. Thereafter, the
copolymerized PPS composition and the blend resin X were fed to
different extruders respectively, melted at 310.degree. C.,
filtered with a 95%-cutting filter of pore diameter of 100 .mu.m
using a metal fiber, and then the discharge rate was regulated with
a lamination device in an upper part of a die so as to form a
2-layer laminate of resin X/copolymerized PPS (1,210 .mu.m/110
.mu.m), from which a non-oriented PPS sheet of 1,320 .mu.m in
thickness was then obtained in the same manner as in production of
the non-oriented polyphenylene sulfide sheet in Reference Example
4. This non-oriented PPS sheet was stretched in the same manner as
in Example 20 to produce a biaxially oriented polyphenylene sulfide
film of 125 .mu.m in thickness consisting of resin X/copolymerized
PPS (PPS-2) (115 .mu.m/10 .mu.m) The biaxially oriented
polyphenylene sulfide films were laminated with each other at the
side of the copolymerized PPS film in the same manner as in Example
20, to give a laminated polyphenylene sulfide sheet consisting of
the polyphenylene sulfide layer (layer a)/copolymerized PPS (layer
c)/polyphenylene sulfide layer (layer a) (115/20/115 (.mu.m)).
[0240] As shown in the results of measurement and evaluation of the
structure and properties of the resulting laminated polyphenylene
sulfide sheet in Table 2, this sheet was excellent in tensile
elongation and molding processability.
Example 32
[0241] A laminated polyphenylene sulfide sheet (polyphenylene
sulfide layer (layer a)/copolymerized PPS (layer
c)/polyphenylenesulfide layer (layer a) (105/40/105 (.mu.m))) was
obtained in the same manner as in Example 31 except that the
non-oriented polyphenylene sulfide sheet was made of a 2-layer
laminate of resin X/copolymerized PPS (PPS-2) (1,100 .mu.m/210
.mu.m), and a biaxially oriented polyphenylene sulfide film
consisting of resin X/copolymerized PPS (105 .mu.m/20 .mu.m) was
used.
[0242] As shown in the results of measurement and evaluation of the
structure and properties of the resulting laminated polyphenylene
sulfide sheet in Table 2, this sheet was excellent in tensile
elongation and molding processability.
Example 33
[0243] The copolymerized PPS composition obtained in Reference
Example 2 and resin Z obtained in Example 9 were dried respectively
at 180.degree. C. for 3 hours under reduced pressure at 1 mmHg, and
0.3 wt % calcium carbonate powder having an average particle
diameter of 1.2 .mu.m and 0.05 wt % calcium stearate were uniformly
dispersed in and blended with resin Z. Thereafter, the
copolymerized PPS composition and the blend resin Z were fed to
different extruders respectively, melted at 310.degree. C.,
filtered with a 95%-cutting filter of pore diameter of 100 .mu.m
using a metal fiber, and then the discharge rate was regulated with
a lamination device in an upper part of a die so as to form a
2-layer laminate of resin Z/copolymerized PPS (PPS-2) (1,110
.mu.m/210 .mu.m), from which a non-oriented PPS sheet of 1,320
.mu.m in thickness was then obtained in the same manner as in
production of the non-oriented polyphenylene sulfide sheet in
Reference Example 4. This non-oriented PPS sheet was stretched in
the same manner as in Example 20 to produce a biaxially oriented
polyphenylene sulfide film of 125 .mu.m in thickness consisting of
resin Z (layer a)/copolymerized PPS (layer c) (105 .mu.m/20
.mu.m).
[0244] The biaxially oriented polyphenylene sulfide films were
laminated with each other at the side of the copolymerized PPS film
in the same manner as in Example 20, to give a laminated
polyphenylene sulfide sheet (polyphenylene sulfide layer (layer
a)/copolymerized PPS (layer c)/polyphenylene sulfide layer (layer
a) (105/40/105 (.mu.m)).
[0245] As shown in the results of measurement and evaluation of the
structure and properties of the resulting laminated polyphenylene
sulfide sheet in Table 2, this sheet was excellent in tensile
elongation and molding processability.
Example 34
[0246] An unstretched sheet obtained in the same manner as in
Example 33 was subjected to biaxial stretching in the same manner
as in Example 12 to produce a biaxially oriented polyphenylene
sulfide film of 125 .mu.m in thickness consisting of resin Z (layer
a)/copolymerized PPS (PPS-2) (layer c) (105 .mu.m/20 .mu.m). The
biaxially oriented polyphenylene sulfide films were laminated with
each other at the side of the copolymerized PPS film in the same
manner as in Example 20, to give a laminated polyphenylene sulfide
sheet (polyphenylene sulfide layer (layer a)/copolymerized PPS
(layer c)/polyphenylene sulfide layer (layer a) (105/40/105
(.mu.m)).
[0247] As shown in the results of measurement and evaluation of the
structure and properties of the resulting laminated polyphenylene
sulfide sheet in Table 2, this sheet was excellent in tensile
elongation and molding processability.
Example 35
[0248] An unstretched sheet obtained in the same manner as in
Example 33 was subjected to biaxial stretching in the same manner
as in Example 12 to produce a biaxially oriented polyphenylene
sulfide film of 125 .mu.m in thickness consisting of resin Z (layer
a)/copolymerized PPS (PPS-2) (layer c) (100 .mu.m/25 .mu.m). The
copolymerized PPS layer (layer c) of this laminated biaxially
oriented polyphenylene sulfide film was laminated in the same
manner as in Example 20 with a biaxially stretched PPS film (layer
a) of 100 .mu.m in thickness obtained in the same manner as in
Example 12, to give a laminated polyphenylene sulfide sheet
(polyphenylene sulfide layer (layer a)/copolymerized PPS (layer
c)/polyphenylene sulfide layer (layer a) (100/25/100 (.mu.m))).
[0249] As shown in the results of measurement and evaluation of the
structure and properties of the resulting laminated polyphenylene
sulfide sheet in Table 2, this sheet was excellent in tensile
elongation and molding processability.
Example 36
[0250] A laminated polyphenylene sulfide sheet (polyphenylene
sulfide layer (layer a)/copolymerized PPS (PPS-2) (layer
c)/polyphenylenesulfide layer (layer a) (100/25/100 (.mu.m))) was
obtained in the same manner as in Example 35 except that the
thermocompression bonding temperature was 255.degree. C.
[0251] As shown in the results of measurement and evaluation of the
structure and properties of the resulting laminated polyphenylene
sulfide sheet in Table 2, this sheet was excellent in tensile
elongation and molding processability.
Example 37
[0252] A laminated polyphenylene sulfide sheet (polyphenylene
sulfide layer (layer a)/copolymerized PPS (PPS-2) (layer
c)/polyphenylene sulfide layer (layer a) (100/25/100 (.mu.m))) was
obtained in the same manner as in Example 35 except that nylon 610
(PA-4) was used as thermoplastic resin A and added in an amount of
5 parts by weight.
[0253] As shown in the results of measurement and evaluation of the
structure and properties of the resulting laminated polyphenylene
sulfide sheet in Table 2, this sheet was excellent in tensile
elongation and molding processability.
Example 38
[0254] A laminated polyphenylene sulfide sheet (polyphenylene
sulfide layer (layer a)/copolymerized PPS (layer c)/polyphenylene
sulfide layer (layer a) (100/2.5/100 (.mu.m))) was obtained in the
same manner as in Example 35 except that the copolymerized PPS
(PPS-3) obtained in Reference Example 3 was used as the
copolymerized PPS layer, and the thermocompression bonding
temperature was 270.degree. C. As shown in the results of
measurement and evaluation of the structure and properties of the
resulting laminated polyphenylene sulfide sheet in Table 2, this
sheet was excellent in tensile elongation and molding
processability.
Example 39
[0255] A biaxially oriented PPS film of 85 .mu.m in thickness was
obtained in the same manner as in Example 20. The resulting
biaxially oriented PPS film and the non-oriented PPS sheet of 70
.mu.m in thickness obtained in Reference Example 6 were laminated
by a press roll at a temperature of 240.degree. C. at a pressure of
10 kg/cm.sup.2, to constitute a 3-layer laminate composed of the
biaxially oriented polyphenylene sulfide (layer a)/non-oriented
polyphenylene sulfide (layer b)/biaxially oriented polyphenylene
sulfide (layer a) (a/b/a=90/70/90 (.mu.m)).
[0256] As shown in the results of measurement and evaluation of the
structure and properties of the resulting laminated PPS sheet in
Table 2, this sheet was satisfactory in respect of molding
processability.
Comparative Example 13
[0257] A biaxially oriented PPS film was prepared in the same
manner as in Example 20 and a laminated polyphenylene sulfide sheet
was obtained in the same manner as in Example 20, except that only
the PPS resin prepared in Reference Example 1 was used and this
resin was used as the outermost layer.
[0258] As shown in the results of measurement and evaluation of the
structure and properties of the resulting laminated polyphenylene
sulfide sheet in Table 2, this laminated polyphenylene sulfide
sheet was a sheet poor in tensile elongation and molding
processability.
Comparative Example 14
[0259] A biaxially oriented PPS film was prepared in the same
manner as in Example 20 and a laminated polyphenylene sulfide sheet
was obtained in the same manner as in Example 20, except that the
compatibilizing agent was not added to the raw material of the
biaxially oriented polyphenylene sulfide sheet.
[0260] As shown in the results of measurement and evaluation of the
structure and properties of the resulting laminated polyphenylene
sulfide sheet in Table 2, this laminated polyphenylene sulfide
sheet was a sheet poor in tensile elongation and molding
processability.
Comparative Example 15
[0261] 90 parts by weight of the PPS resin prepared in Reference
Example 1 were dried at 180.degree. C. for 3 hours under reduced
pressure, and as thermoplastic resin A, 10 parts by weight of nylon
6/66 copolymer (PA-1) prepared in Reference Example 4 were dried at
120.degree. C. for 3 hours under reduced pressure. Then, 2 parts by
weight of bisphenol A type epoxy resin (Epikote 1004, manufactured
by Yuka Shell Epoxy Co., Ltd.) were incorporated as a
compatibilizing agent into 100 parts by weight of the PPS resin and
the nylon 6/66 copolymer in total. Thereafter, the mixture was fed
to a vented co-rotating twin-screw extruder (a screw diameter of 30
mm and a screw length/screw diameter ratio of 45.5, manufactured by
Japan Steel Works, Ltd.) including 3 kneading paddling zones heated
to 310.degree. C. The mixture was melt-extruded into strands at a
screw speed of 80 rpm and a residence time of 90 seconds, then
cooled with water at a temperature of 25.degree. C. and immediately
cut into blend chips. Thereinafter, a biaxially oriented PPS film
of 125 .mu.m in thickness was obtained in the same manner as in
Example 20, and a laminated polyphenylene sulfide sheet was
obtained in the same manner as in Example 20.
[0262] The resulting laminated polyphenylene sulfide sheet, as
shown in the results of measurement and evaluation of the
properties thereof in Table 2, was a film poor in tensile
elongation and molding processability.
Comparative Example 16
[0263] 90 parts by weight of the PPS resin prepared in Reference
Example 1 were dried at 180.degree. C. for 3 hours under reduced
pressure, and as thermoplastic resin A, 10 parts by weight of nylon
6/66 copolymer (PA-1) prepared in Reference Example 4 were dried at
120.degree. C. for 3 hours under reduced pressure. Then, 2 parts by
weight of bisphenol A type epoxy resin (Epikote 1004, manufactured
by Yuka Shell Epoxy Co., Ltd.) were incorporated as a
compatibilizing agent into 100 parts by weight of the PPS resin and
the nylon 6/66 copolymer in total. Thereafter, the mixture was fed
to a full-flight single-screw extruder heated at 310.degree. C.
(screw diameter 40 mm, manufactured by Tanabe Plastics Machinery
Co., Ltd) and melt-extruded into strands at a screw speed of 80 rpm
and a residence time of 90 seconds, then cooled with water at a
temperature of 25.degree. C. and immediately cut into blend chips.
Thereinafter, a biaxially oriented PPS film of 125 .mu.m in
thickness was obtained in the same manner as in Example 20, and a
laminated polyphenylene sulfide sheet was obtained in the same
manner as in Example 20.
[0264] The resulting biaxially oriented polyphenylene sulfide film,
as shown in the results of measurement and evaluation of the
properties thereof sheet in Table 2, was a film poor in tensile
elongation and molding processability.
Comparative Examples 17 to 19
[0265] A laminated polyphenylene sulfide sheet was obtained in the
same manner as in Example 20 except that the amount of PA-1 added
as thermoplastic resin A was changed as shown in Table 2. As shown
in the results of measurement and evaluation of the structure and
properties of the resulting laminated polyphenylene sulfide sheet
in Table 2, this biaxially oriented polyphenylene sulfide sheet was
a film poor in tensile elongation and molding processability.
Comparative Example 20
[0266] A biaxially oriented PPS film of 85 .mu.m in thickness was
obtained in the same manner as in Example 20. The resulting
biaxially oriented PPS film and the non-oriented PPS sheet obtained
in Reference Example 7 were laminated by a press roll at a
temperature of 240.degree. C. at a pressure of 10 kg/cm.sup.2, to
constitute a 3-layer laminate composed of the biaxially oriented
polyphenylene sulfide (layer a)/non-oriented polyphenylene sulfide
(layer b)/biaxially oriented polyphenylene sulfide (layer a)
(a/b/a=85/80/85 (.mu.m)).
[0267] The results of measurement and evaluation of the structure
and properties of the resulting laminated PPS sheet are shown in
Table 2.
Comparative Example 21
[0268] A biaxially oriented PPS film of 65 .mu.m in thickness was
obtained in the same manner as in Example 20. The resulting
biaxially oriented PPS film and the non-oriented PPS sheet of 120
.mu.m in thickness obtained in Reference Example 8 were laminated
by a press roll at a temperature of 240.degree. C. at a pressure of
10 kg/cm.sup.2, to constitute a 3-layer laminate composed of the
biaxially oriented polyphenylene sulfide (layer a)/non-oriented
polyphenylene sulfide (layer b)/biaxially oriented polyphenylene
sulfide (layer a) (65/120/65 (.mu.m)).
[0269] The results of measurement and evaluation of the structure
and properties of the resulting laminated PPS sheet are shown in
Table 2. This sheet was poor in tensile elongation and molding
processability. TABLE-US-00002 TABLE 2 Outermost layer Content of
Average Thickness of Laminated sheet thermoplastic particle layer
other Tensile Content of resin A diameter than outermost elongation
Impact polyarylene sulfide Thermoplastic (parts by (dispersed
layer/all at break strength Molding (parts by weight) resin A
weight) phase) (nm) layers (%) MD/TD (%) (N/.mu.m) processability
Example 20 90 PA-1 10 80 20 160/180 5 Excellent Example 21 75 PA-1
25 250 20 110/125 4 Good Example 22 95 PA-1 5 80 20 120/130 4 Good
Example 23 90 PA-2 10 120 20 135/150 5 Excellent Example 24 90 PA-3
10 220 20 90/115 3 Good Example 25 90 PA-1 10 280 20 110/125 4 Good
Example 26 90 PA-4 10 60 20 145/155 4 Good Example 27 90 PA-4 10 60
20 170/180 5 Excellent Example 28 90 PEI 10 170 20 130/140 4 Good
Example 29 90 PSF 10 270 20 115/135 5 Good Example 30 90 PES 10 280
20 110/125 4 Good Example 31 90 PA-1 10 80 8 105/115 4 Good Example
32 90 PA-1 10 80 16 110/115 4 Excellent Example 33 90 PA-4 10 60 16
150/160 4 Excellent Example 34 90 PA-4 10 60 16 170/175 5 Excellent
Example 35 90 PA-4 10 60 11 170/170 4 Excellent Example 36 90 PA-4
10 60 11 180/190 6 Excellent Example 37 95 PA-4 5 60 11 155/160 5
Excellent Example 38 90 PA-4 10 60 11 145/160 4 Good Example 39 90
PA-1 10 80 28 105/110 3 Acceptable Comparative 100 -- 0 -- 20 60/70
2 Not acceptable Example 13 Comparative 90 PA-1 10 650 20 65/90 2
Not acceptable Example 14 Comparative 90 PA-1 10 570 20 75/90 1 Not
acceptable Example 15 Comparative 90 PA-1 10 720 20 50/75 2 Not
acceptable Example 16 Comparative 65 PA-1 35 400 20 85/95 3 Not
acceptable Example 17 Comparative 55 PA-1 45 510 20 65/80 2 Not
acceptable Example 18 Comparative 99.5 PA-1 0.5 50 20 65/90 1 Not
acceptable Example 19 Comparative 90 PA-1 10 80 32 70/75 3 Not
acceptable Example 20 Comparative 90 PA-1 10 80 48 50/55 1 Not
acceptable Example 21 (Note) MD (longitudinal direction of film) TD
(width direction of film)
INDUSTRIAL APPLICABILITY
[0270] The biaxially oriented polyarylene sulfide film of the
present invention or the laminated polyarylene sulfide sheet
comprising the same can be preferably used in applications to
various industrial materials, for example an electrical insulating
material for a motor, a transformer, an insulated cable etc., a
molding material, a circuit board material, a step/release film for
circuit/optical element etc., a lithium ion battery material, a
fuel battery material, a speaker diaphragm, etc. More specifically,
it can be preferably used in an electrical insulating material for
a hot-water supplier motor, a motor for car air conditioner and a
driving motor used in a hybrid car, and a speaker diaphragm for
cell-phone.
* * * * *