U.S. patent application number 14/300911 was filed with the patent office on 2014-11-27 for method for preparing microporous polyolefin film with improved productivity and easy control of physical properties.
The applicant listed for this patent is SK INNOVATION CO., LTD.. Invention is credited to In Hwa Jung, Gwi Gwon KANG, Jang-Weon Rhee.
Application Number | 20140349193 14/300911 |
Document ID | / |
Family ID | 44834632 |
Filed Date | 2014-11-27 |
United States Patent
Application |
20140349193 |
Kind Code |
A1 |
KANG; Gwi Gwon ; et
al. |
November 27, 2014 |
METHOD FOR PREPARING MICROPOROUS POLYOLEFIN FILM WITH IMPROVED
PRODUCTIVITY AND EASY CONTROL OF PHYSICAL PROPERTIES
Abstract
Provided is a method of manufacturing a microporous polyolefin
film useable as a battery separator, which is easy to control
strength, permeability and shrinking properties of the microporous
film and embodies excellent quality uniformity and production
stability in fabricating the microporous film.
Inventors: |
KANG; Gwi Gwon; (Daejeon,
KR) ; Rhee; Jang-Weon; (Daejeon, KR) ; Jung;
In Hwa; (Cheonan, KR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SK INNOVATION CO., LTD. |
Seoul |
|
KR |
|
|
Family ID: |
44834632 |
Appl. No.: |
14/300911 |
Filed: |
June 10, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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13642072 |
Dec 26, 2012 |
8790559 |
|
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PCT/KR2011/002808 |
Apr 20, 2011 |
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14300911 |
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Current U.S.
Class: |
429/249 ;
264/41 |
Current CPC
Class: |
B29K 2023/065 20130101;
B29C 48/0012 20190201; H01M 2/145 20130101; C08K 3/26 20130101;
B29K 2995/0088 20130101; H01M 2220/20 20130101; B29C 67/202
20130101; C08L 91/00 20130101; C08L 23/06 20130101; C08K 3/26
20130101; B29C 48/914 20190201; B29C 48/08 20190201; C08L 91/00
20130101; H01M 2/1653 20130101; B29L 2031/3468 20130101; H01M
10/0525 20130101; B29K 2105/0005 20130101; B29C 48/0018 20190201;
B29C 48/91 20190201; B29K 2105/0088 20130101; H01M 2220/30
20130101; B29C 55/143 20130101; C08L 23/06 20130101; H01M 2/166
20130101 |
Class at
Publication: |
429/249 ;
264/41 |
International
Class: |
B29C 67/20 20060101
B29C067/20; H01M 2/16 20060101 H01M002/16; B29C 55/14 20060101
B29C055/14; H01M 2/14 20060101 H01M002/14; B29C 47/00 20060101
B29C047/00; B29C 47/88 20060101 B29C047/88 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 20, 2010 |
KR |
10-2010-0036339 |
Claims
1-11. (canceled)
12. A microporous polyolefin film manufactured by a method by using
a roll type stretching machine, the method at least including: (a)
melting/mixing/extruding a sheet composition containing a
polyolefin composition having a weight-average molecular weight of
not less than 1.times.10.sup.5 to less than 1.times.10.sup.6
(component I) and a diluent (component II) in a ratio by weight of
15.about.50:85.about.50 and shaping these compositions into a sheet
form through a T-die; (b) using the stretching machine of roll type
consisting of at least three rolls to stretch the sheet to the
machine direction, and then, stretch the film stretched uni-axially
to the machine direction into the transverse direction by a
stretching machine of tenter type, in order to form a film by
sequential biaxial stretching; and (c) extracting the diluent from
the film stretched to the machine and transverse direction and
drying the film, wherein the stretching machine to the machine
direction includes at least one preheating roll, at least one
stretching roll and at least one cooling roll or air-cooled device,
a total roll contact time at the preheating rolls ranges from 1 to
500 seconds, the stretching is executed in at least one section
between rolls, a stretching ratio in one section between two rolls
ranges from 1.05 to 6 times, a roll contact coefficient of the
sheet on the stretching roll ranges from 1.5 to 54 degree (of
angle).times.m, and a coefficient of non-contact section between
rolls ranges from 0.1.times.10.sup.-3 to 200.times.10.sup.-3
min.
13. A microporous polyolefin film manufactured by a method by using
a roll type stretching machine, the method at least including: (a)
melting/mixing/extruding a sheet composition containing a
polyolefin composition having a weight-average molecular weight of
not less than 1.times.10.sup.5 to less than 1.times.10.sup.6
(component I) and a diluent (component IS) in a ratio by weight of
15.about.50:85.about.50 and shaping these compositions into a sheet
form through a T-die; (b) using the stretching machine of roll type
consisting of at least three rolls to stretch the sheet to the
machine direction, and then, stretch the film stretched uni-axially
to the machine direction into the transverse direction by a
stretching machine of tenter type, in order to form a film by
sequential biaxial stretching; and (c) extracting the diluent from
the film stretched to the machine and transverse direction and
drying the film, wherein the stretching machine to the machine
direction includes at least one preheating roll, at least one
stretching roll and at least one cooling roll or air-cooled device,
a total roll contact time at the preheating rolls ranges from 1 to
500 seconds, the stretching is executed in at least one section
between rolls, a stretching ratio in one section between two rolls
ranges from 1.05 to 8 times, a roll contact coefficient of the
sheet on the stretching roll ranges from 1.5 to 54 degree (of
angle).times.m, and a coefficient of non-contact section between
rolls ranges from 0.1.times.10.sup.-3 to 200.times.10.sup.-3 min,
and wherein the polyolefin composition in (a) includes at least one
polyolefin resin component, or 80 to 99.9 wt % of at least one
polyolefin resin and 0.1 to 20 wt % of a component selected from an
inorganic material or other resins except for the polyolefin
resin.
14. A microporous polyolefin film manufactured by a method by using
a roll type stretching machine, the method at least including: (a)
melting/mixing/extruding a sheet composition containing a
polyolefin composition having a weight-average molecular weight of
not less than 1.times.10.sup.5 to less than 1.times.10.sup.6
(component I) and a diluent (component II) in a ratio by weight of
15.about.50:85.about.50 and shaping these compositions into a sheet
form through a T-die; (b) using the stretching machine of roll type
consisting of at least three rolls to stretch the sheet to the
machine direction, and then, stretch the film stretched uni-axially
to the machine direction into the transverse direction by a
stretching machine of tenter type, in order to form a film by
sequential biaxial stretching; and (c) extracting the diluent from
the film stretched to the machine and transverse direction and
drying the film, wherein the stretching machine to the machine
direction includes at least one preheating roll, at least one
stretching roll and at least one cooling roll or air-cooled device,
a total roll contact time at the preheating rolls ranges from 1 to
500 seconds, the stretching is executed in at least one section
between rolls, a stretching ratio in one section between two rolls
ranges from 1.05 to 6 times, a roll contact coefficient of the
sheet on the stretching roll ranges from 1.5 to 54 degree (of
angle).times.m, and a coefficient of non-contact section between
rolls ranges from 0.1.times.10.sup.-3 to 200.times.10.sup.-3 min,
wherein the stretching to the machine direction is performed by
stretching the sheet introduced info the stretching machine while
applying a tensile strength of 550N/cm.sup.2 in the machine
direction for 4.about.12 times, and the stretching to the
transverse direction is performed by stretching the film introduced
into the stretching machine while applying a tensile strength of
100.about.700N/cm.sup.2 in the machine direction for 4.about.9
times, wherein the method further includes a heat setting process
that uses heat setting equipment of tenter type, after the
extracting in (c), to stretch the film for 20.about.100% to the
transverse direction, and then, shrink the film to have a width of
5.about.50%, compared to the film after stretching, with conducting
thermal relaxation in a range of temperatures in which crystals of
5.about.50% in the film are molten, wherein the stretching
includes: stretching to the machine direction wherein the
temperature of the preheating roll ranges from a melting
temperature of the resin in the sheet -50.degree. C. to a
temperature at which 70% of crystals contained in the resin of the
sheet are molten, the temperature of the stretching roll ranges
from the melting temperature of the resin in the sheet -50.degree.
C. to a temperature at which 90% of crystals contained in the resin
of the sheet are molten, the temperature of the cooling roll is a
temperature of the stretching roll -5.degree. C., or less, or
air-cooling is conducted, so that a sheet width holding ratio
between rolls in the stretching roll after stretching ranges from
70 to 99% and an overall sheet width holding ratio after stretching
to the machine direction ranges from 50 to 95%; and stretching to
the transverse direction wherein the stretching machine to the
machine direction includes a preheating part, a stretching part,
and a heat setting part, and the temperature of the preheating part
is a melting temperature of the resin in the sheet +20.degree. C.,
or less, the temperature of the stretching part ranges from a
melting temperature of the resin in the sheet -20.degree. C. to the
melting temperature of the resin in the sheet +10.degree. C., and
the temperature of the heat setting part is the melting temperature
of the resin in the sheet, or less.
Description
CROSS-REFERENCE TO BELATED APPLICATIONS
[0001] This is a division of application Ser. No. 13/642,072
(allowed), which is a national phase application of International
Application No. PCT/KR2011/002808, filed on Apr. 20, 2011, which
claims the benefit of Korean Patent Application No, 10-2010-0036339
filed Apr. 20, 2010, the content of all of which are incorporated
herein by reference.
TECHNICAL FIELD
[0002] The present invention relates to a method for preparing a
microporous polyolefin film capable of being used as a separator
for a battery, with beneficial characteristics such as ease of
controlling mechanical strength, permeability and thermal-shrinking
properties of the microporous film, and excellent uniform quality,
production stability, productivity, or the like, compared to
existing production methods. More particularly, a stretching
process involved in the method for preparing a microporous
polyolefin film, which significantly influences determination of
shrinkable properties as well physical properties of the
microporous film and to provide quality uniformity and production
stability of the same.
BACKGROUND ART
[0003] A microporous film having excellent chemical stability and
superior physical properties is broadly used as a battery
separator, a separation filter, a micro-filtration film, or the
like.
[0004] A method for preparing a microporous film based on
polyolefin may be generally classified into four (4) groups; first,
formation of a microporous film in a non-woven fabric form by
preparing a thin polyolefin fiber; second, a dry process that
includes preparing a polyolefin film, stretching the film at a low
temperature and causing micro-cracks between lamella, which are a
crystal part of the polyolefin, to form micro-pores; third, a
process of forming pores at an interface between polyolefin and a
filler during stretching by introducing the filler, for example, an
inorganic material, an organic material non-compatible with
polyolefin, or the like, into a polyolefin resin. Three of the
methods have favorable features such as formation of pores, which
proposes desired permeability and reduced production costs to
achieve economical benefits, but also have disadvantages such as
low mechanical strength, irregular and large pore size, and
difficulties in securing quality uniformity. Alternatively, a
fourth method is a wet process that includes mixing a polyolefin
resin with a diluent (a low molecular weight organic material
having a molecular structure similar to polyolefin) at a high
temperature at which the polyolefin resin melts as a single phase,
occurring phase separation into the polyolefin and the diluent
during cooling, and then, extracting the diluent part, to thereby
form pores in a resultant film. The wet process generally provides
desired mechanical strength and permeability through
stretching/extraction after phase separation, has advantageous
features such as providing a film having a small and uniform
thickness, compared to previously described methods, formation of
pores having a uniform size, securing excellent physical
properties, or the like, therefore, is widely used in fabricating a
separator for a secondary battery such as a lithium ion
battery.
[0005] With continuous development of high performance secondary
batteries since they began to be used in earnest, a battery
separator fabricated by a wet process is also increasingly used. In
addition, efforts to improve productivity of a microporous film and
characteristics of a film by the wet process have been continuously
conducted. A representative method may include using ultra-high
molecular weight, polyolefin (UHMWPO) having a weight-average
molecular weight of about 1,000,000 or adding the same to a raw
material to increase a molecular weight of a composition to be
prepared and using a stretching process to increase a strength of a
porous film.
[0006] Regarding this, U.S. Pat. Nos. 5,051,183, 5,830,554,
6,245,272 and 6,566,012 describe a method of fabricating a
microporous film by using a composition that contains polyolefin
having a weight-average molecular weight of not less than 500,000
and a diluent dissolving the polyolefin at a high temperature to
prepare a sheet, and then, sequentially conducting a stretching
process and a diluent extraction process. In these patents, the
stretching process is conducted by uniaxial or biaxial stretching
and using a typical tenter, roll, calendar, or the like, or a
combination thereof. In relation to the biaxial stretching, the
foregoing patents generally describe that both of simultaneous
biaxial stretching and sequential biaxial stretching may be used.
However, overall examples recited, in the above patents are
particularly restricted to the simultaneous biaxial stretching or
simply describe a biaxial stretching, however, have not
specifically defined about stretching temperature in each of the
machine and transverse directions. In other words, features of a
sequentially biaxial stretching process by using a roll to stretch
to the machine direction, and then, to stretch to a transverse
direction by using a tenter, features of a simultaneously biaxial
stretching process, and differences therebetween were not disclosed
in the foregoing patents.
[0007] In recent years, among microporous polyolefin films
commercially available in the market, products manufactured by a
wet process, which are recognized to have excellent performance,
may include one stretched after extracting the diluent and the
other stretched before extracting diluent. The former has pores
formed while extracting the diluent, which are prone to be deformed
during stretching, therefore, the stretching process could hardly
improve physical properties. Further, since flexibility of the
polyolefin free from the diluent is not proper, the stretching
process is not easily conducted. On the other hand, the latter
allows the polyolefin to become flexible by the diluents, thus
allowing the stretching process to be much more easily conducted
and securing excellent production stability. Moreover, since a
thickness of a film is reduced by stretching, the diluent may be
easily removed from the film while extracting after stretching.
However, most of the commercialized products formed via the above
stretching process before extracting are currently well known in
the art as products manufactured by a simultaneously biaxial
stretching process.
[0008] A simultaneously biaxial stretching process is a stretching
method that uses a chuck (an biting device) to grip and fix the top
and bottom sides of a sheet prepared by mixing polyolefin and a
diluent, similar to thumbs and index fingers of hands of a human,
and broadens the gap between chucks in both a machine direction and
a transverse direction, simultaneously. In case of the
simultaneously biaxial stretching process, a gap between chucks is
narrow before stretching, however, broadened by a specific draw
ratio after stretching, thus increasing an area not gripped by the
chucks (see FIG. 1). Such a non-gripped area has a lower actual
stretching ratio than that of a gripped area, to cause
non-uniformity in qualities between the gripped area and the
non-gripped area. The above tendency is more serious in the case
where a stretching ratio is increased, a stretching temperature is
decreased for enhancing a mechanical strength, and a sheet before
stretching has a relatively large thickness, or the like. For this
reason, when a thick film, having a high strength is fabricated by
the simultaneously biaxial stretching process, a problem of
deteriorated uniformity in quality may be encountered. As the
application of lithium ion secondary batteries is increased from
small electronics to laptop computers, electronic tools, hybrid
cars, or the like, a battery separator having high strength and a
high thickness is required. Therefore, when a microporous film is
fabricated, a stretching ratio and/or a thickness of a sheet before
stretching must be increased. However, the simultaneous biaxial
drawing process has disadvantages in that quality uniformity is
reduced when the sheet is thick and rigid, which can be easily
disengaged from the grip chuck, thus causing a decrease in
productivity stability.
[0009] Further, as for the simultaneously biaxial stretching
process, due to difficulties in designing a machine and limitation
in equipment costs, it is difficult to design the machine having a
variable stretching ratio and apply tints in commercial production
lines. That is, it is not easy to manufacture commercial products
having different characteristics by controlling the stretching
ratio.
[0010] Korean Patent No. 10-0599893, Japanese Patent No.
2002-088138, Japanese Patent No. 2010-00705, and Japanese Patent
No, 2009-226736, respectively, disclose a sequentially biaxial
stretching process to sequentially conduct stretching to the
machine direction and to the transverse direction. A method of
fabricating a battery separator through the sequentially biaxial
stretching process disclosed in Korean Patent No. 10-0599898,
Japanese Patent No, 2002-086188 and Japanese Patent No. 2010-00705
includes melting/mixing polyolefin, a diluent, and inorganic
particles to prepare a sheet, extracting the diluent and the
inorganic particles with a solvent to form pores and sequentially
stretching the sheet to the machine and transverse directions to
enhance a mechanical strength and permeability of the film.
However, this method has a limitation in improving the mechanical
strength via stretching. Accordingly, the separator with high
strength cannot be fabricated via this method. Compared to a
mechanical strength improved by orientation of a polyolefin resin
during stretching, the deformation of pores easily occurs to
enlarge pores. That is, since a size of the pore and permeability
of the film tend to excessively increase whereas the mechanical
strength is slightly enhanced, an increase in a stretching ratio
above a critical level is restricted. In other words, it is
difficult to manufacture products having a wide range of mechanical
strengths (in particular, a product having puncture strength of not
less than 0.25N/.mu.m); and, when a pore size is excessively
increased, quality uniformity is seldom secured. The method
disclosed in Japanese Patent No. 2009-226736 includes preparing a
polyolefin sheet, forming micro-cracks inside crystals by a dry
process during stretching to the transverse direction and enlarging
the micro-cracks during stretching to the transverse direction,
thus providing desired permeability. Compared to formation of pores
by using inorganic particles as above described in the foregoing
patents, a size of the pore is reduced and a stretching ratio may
be increased. However, it is difficult to overcome limitations of a
battery separator fabricated by the dry process such as low
mechanical strength and reduced quality uniformity.
[0011] In view of such circumstances, the present invention,
proposes application of a sequentially biaxial stretching process
to fabricate microporous polyolefin films so that quality
uniformity and production stability daring manufacturing may be
secured, a variety of properties may be provided by controlling
physical properties, permeability, shrinking property, or the like,
and, in particular, provides a method of fabricating a high
strength battery separator.
DISCLOSURE OF INVENTION
Technical Problem
[0012] As described above, in order to fabricate a microporous
polyolefin film for a lithium ion secondary battery, a process of
forming pores to offer permeability to the film and a drawing
process for improving a mechanical strength of the film are
necessarily conducted.
[0013] Fore formation may be performed by a dry process that forms
micro-cracks in a resin or induces cracks at an interface between
the resin and inorganic particles by adding the inorganic particles
to the resin, or a wet process that uses a polyolefin resin and a
material to occur phase separation, causes the phase separation,
and then, extracts the phase separated material to form pores. As
described above, with respect to quality uniformity and quality
level, the wet process is superior to the dry process.
[0014] When a stretching process to enhance mechanical strength
carries out at dry process, the mechanical strength is not much
improved since the stretching process at dry process offers
improving mechanical properties and forming/enlarging pores. On the
other hand, the wet process (limited to a process of stretching
before extraction) may conduct stretching while maintaining
flexibility of a resin with a diluent; to thereby considerably
increase orientation of the resin and easily control orientation.
As a result; a variety of microporous films having high and
different mechanical strengths may be produced.
[0015] Meanwhile, although a method of fabricating a separator via
a wet process like a simultaneously biaxial stretching process is
well known and commercialized (a separator for a lithium ion
secondary battery fabricated by a commercial wet process is
generally manufactured by a simultaneously biaxial stretching
process, there is a difference in actual stretching ratios, between
a gripped area by a chuck (a sheet biting device) and a non-gripped
area, to deteriorate quality uniformity of a final product. Also,
when manufacturing a product having a high strength/a high film
thickness, the sheet is prone to be disengaged from the chuck, thus
causing difficulty in securing production stability. Furthermore,
since a difference in actual stretching ratios between the gripped
area and the non-gripped area is relatively higher than a low
strength/a low film thickness product, quality uniformity is
further deteriorated.
[0016] A method of fabricating a separator through sequential
biaxial stretching reported in the art is generally classified into
three kinds of processes. First, a separator has a mechanical
strength as pores induced by a dry process through sequential
biaxial stretching. Since The pores are easily deformed during
stretching in the dry process, it is difficult to control or
improve mechanical strength, and quality uniformity significantly
decreases due to enlarged pores, and the increase of stretching
ratio is not allowed; as a result, deteriorating productivity.
Second, after phase separation is executed by a wet process and a
diluent is extracted to form a thick film having pores formed
thereon, sequential biaxial stretching is conducted. Similar to the
dry process, pores are easily deformed and enlarged during
stretching. As a result, problems existing in the dry process, such
as low mechanical strength, low quality uniformity, and low
productivity due to a low stretching ratio, may not be overcome by
the second method, too. Although this method has advantages in
that, a diluent used herein may allow extruding process to be
easily executed and relatively high permeability may be embodied,
compared to the dry process, it entails a limitation in that a high
mechanical strength cannot be obtained. As a third method,
sequential biaxial stretching is executed before a sheet (obtained
after phase separation) prepared by a wet process is subjected to
extraction. The foregoing methods disclosed in the art include, in
general, stretching at the same temperature without separated
temperatures control for machine direction stretching and for
transverse direction stretching or adopt a method to conduct
drawing only when a resin contained in a sheet is substantially
molten, thus having a limited range of physical properties to be
controlled. In addition, although there are various conditions for
stretching process to the machine direction to machine that
significantly influence quality uniformity, production stability
and productivity during sequential biaxial stretching, only a
stretching ratio and a drawing temperature are mentioned in the
above methods, therefore, quality uniformity, production stability,
productivity, or the like are not determined. Since the stretching
was conducted without considering the foregoing conditions, drawing
quality was not excellent.
[0017] Accordingly, the present invention is directed to provision
of a method for manufacturing a microporous polyolefin film by a
wet process securing quality uniformity and excellent quality and a
sequential stretching process before extraction, which easily
controls physical properties and shrinking properties and secures
excellent production stability and productivity.
Solution to Problem
[0018] With regard to fabrication of a microporous polyolefin film
to solve problems described above, the present, inventors developed
a novel fabricating method, which includes forming gores by a wet
process, conducting a stretching process while maintaining a wet
state to improve mechanical strength via stretching, and conducting
a sequentially biaxial stretching process, to thereby control
physical properties and thermal shrinking property and secure
quality uniformity and production stability.
[0019] According to the present invention, it was surprisingly
found that a film having high quality uniformity as well as
excellent quality capable of easily controlling physical properties
and shrinking property and exhibiting superior production stability
and productivity may be fabricated by conducting a stretching
process before extracting a diluent, and combining the stretching
process with a sequentially biaxial stretching process under
specific conditions.
[0020] That is, an important feature of the sequentially biaxial
stretching process according to the present invention is to use a
roll for stretching a sheet to the machine direction, and then, a
stretcher of tenter type to conduct stretching to the transverse
direction. That is, it was found that, by adopting a combination of
the foregoing specific stretching processes and stretching the
sheet under individual specific stretching conditions, quality
uniformity and production stability may be remarkably enhanced.
More particularly, it was found that an area not gripped is almost
not present even during stretching to the transverse direction,
thus producing a product having noticeably enhanced quality
uniformity (FIG. 2).
[0021] Moreover, after stretching to the machine direction with a
roll, the resultant thin film enters into a stretcher of tenter
type to the transverse direction to thereby considerably reduce
possibility of disengaging the film out of the stretcher to the
transverse direction, therefore, securing unexpected process
stability.
[0022] According to the present invention, the foregoing object may
be accomplished by a method of fabricating a microporous polyolefin
film according to the present invention and, more particularly, a
fabricating method that at least includes:
[0023] (a) melting/mixing/extruding a sheet composition containing
a polyolefin composition having a weight-average molecular weight
of not less than 1.times.10.sup.5 to less than 1.times.10.sup.6
(component I) and a diluent (component II) in a ratio by weight of
15-50:85-50 through a T-die, into a sheet form;
[0024] (b) using a stretching machine of roll type consisting of at
least three rolls to stretch the sheet to the machine direction,
and then, stretch the film drawn uni-axially to the machine
direction into a transverse direction by stretcher of tenter type,
in order to form a film by sequentially biaxial stretching; and
[0025] (c) extracting the diluent from the stretched film and
drying the film.
[0026] Before, during or after steps (a) to (c), alternative
processes may be added. However, such stretching to the machine and
transverse direction must be executed before the extraction/drying
process.
[0027] According to another embodiment of the present invention, a
heat setting process may be further added after the foregoing
process, that is, step (c).
[0028] The following description will be given to concretely
explain preferred embodiments of the present invention. However,
the present invention is not particularly limited the embodiments
described below, instead being variously modified within, the
spirit of the present invention.
[0029] A process of preparing a sheet by mixing a polyolefin resin
and a diluent is described as follows.
[0030] A sheet composition may include a polyolefin resin
composition: a diluent in a ratio by weight of
15.about.50:85.about.50 during melting/mixing/extruding the
polyolefin resin and the diluent. If a content of the polyolefin
resin is less than 15 wt %, a uniform sheet is not readily formed
and, due to a relatively high content of oil in the sheet, slips or
appearance faults may occur during stretching to the machine
direction by using a stretching machine of roll type. Moreover,
since orientation of polymer during stretching is insufficient, a
sufficient mechanical strength is not easily achieved. On the other
hand, if a content of the polyolefin resin exceeds 50 wt %,
extrusion load is increased which deteriorates extrusion
performance and considerably reduce permeability of a battery
separator. Furthermore, since load applied to a stretching machine
during stretching to the machine direction is too high, production
stability is rarely secured.
[0031] According to the present invention, the polyolefin resin
composition may include at least one polyolefin resin alone or a
combined material containing at least one polyolefin resin and an
inorganic material or any other resin except for the foregoing
polyolefin resin.
[0032] The polyolefin resin used in the foregoing polyolefin resin
composition may include at least one polyolefin resin selected from
polyethylene, polypropylene, poly-4-methyl-1-pentene, or the like,
which use ethylene, propylene, .alpha.-olefin, 4-methyl-1-penten,
or the like, no a monomer and a co-monomer, respectively. That is,
the polyolefin resin described above may be used alone or as a
copolymer or a mixture thereof.
[0033] In view of strength, mixing/extruding performance,
stretching performance, heat resistance of a final resultant
separator, or the like, an example of appropriate polyolefin resins
is preferably a high density polyethylene having a co-monomer
content of less than 2 wt % or a mixture thereof. The polyethylene
resin used herein may have a weight-average molecular weight,
ranging from 1.times.10.sup.5 to 1.times.10.sup.6, preferably,
2.times.10.sup.5 to 5.times.10.sup.5. If the molecular weight is
less than 1.times.10.sup.5, the strength of the separator may be
poor. When the molecular weight exceeds 1.times.10.sup.6,
mixing/extruding performance and stretching performance are
deteriorated, in turn providing poor appearance and uniformity of
the separator and causing a problem in implementing high
permeability thereof.
[0034] In order to improve thermal resistance and permeability of
the separator, the resin composition may optionally include an
inorganic material or any other kinds of resin except for the
polyolefin resin (resins other than the polyolefin resin). Such, an
additive may be added in an amount of not more than 20 wt %,
compared to the polyolefin resin, More particularly, the amount: of
additive may range from 0.1 to 20 wt %. If the amount exceeds 20 wt
%, the mechanical strength of the separator may be rapidly
decreased and, film rupture may occur stretching to the machine
direction.
[0035] Examples of the inorganic material may include calcium
carbonate, silica, barium sulfate, talc, mixtures thereof, or the
like.
[0036] Resins other than polyolefin may include, for example, a
polyamide resin (a nylon based resin), polybutylene terephthalate
(PET), polyethylene terephthalate (PET),
polychlorotrifluoroethylene (PCTFE), polyoxymethylene (POM),
polyvinylfluoride (PVF), poly vinyl idene fluoride (PVdf),
polycarbonate, polyarylate, polysulfone, polyetherimide, mixtures
thereof, or the like.
[0037] If required, the resin composition may include any general
additives to enhance specific characteristics, such as an oxidation
stabilizer, a UV stabilizer, an anti-static agent, or the like,
within a range in which characteristics of the separator are not
inhibited.
[0038] The diluents used in the present invention may include any
organic compound combined, with the polyolefin resin used in the
resin composition to form a single phase at a predetermined
extrusion temperature. Examples thereof may include: an aliphatic
or cyclic hydrocarbon such as nonane, decane, decalin, a paraffin
oil, a paraffin wax, or the like; a phthalic acid ester such as
dibutyl phthalate, dioctyl phthalate, or the like; a fatty acid
having 10 to 20 carbon atoms, such as palmitic acid, stearic acid,
oleic acid, linoleic acid, linolenic acid, or the like; a fatty
acid alcohol having 10 to 20 carbon atoms such as palmitic alcohol,
stearic alcohol, oleic alcohol, or the like; and mixtures thereof.
The paraffin oil, which is non-toxic to the human body and has a
higher boiling point and contains a relatively small, amount of
volatile ingredients, may be suitable. More preferably, the
paraffin oil having a kinetic viscosity of 20 cSt to 200 cSt at
40.degree. C. is used. When the kinetic viscosity of the paraffin
oil exceeds 200 cSt, the kinetic viscosity during extruding may be
high, to cause problems such as an increase in extruding load,
surface failures of a sheet and/or a film, or the like.
Furthermore, it causes difficulties in extraction, leading to
problems such as decreasing productivity and reducing permeability
of film due to oil residue. If the kinetic viscosity of the
paraffin oil is less than 20 cSt, a difference in viscosities
between the paraffin oil and the molten polyethylene is so nigh to
cause difficulties in mixing during extruding processing.
[0039] The sheet composition may be produced by using a biaxial
compounder, a mixer, a Banbury mixer, or the like, which are
designed to mix the polyolefin resin used for the resin composition
with the diluent, to melt/mix the same, thus obtaining a single
phase mixture. The extruding temperature may be a temperature at
which the used resin is present in a complete liquid phase (not
less than 30.degree. C., compared to a resin melting temperature)
and, preferably, ranges from 160 to 300.degree. C., more
preferably, 180 to 250.degree. C. By extruding the mixture through
a T-die while cooling the same, a sheet type product is formed.
Then, through casting or calendaring in water-cooling or
air-cooling, a solid phase sheet is obtained. Polyolefin and the
diluent used herein may be preliminarily blended and then
introduced into the compounder or, otherwise, introduced therein
from separated feeders of the polyolefin and the diluent,
respectively.
[0040] The sheet prepared according to the foregoing processes is
subjected to stretching to the machine direction in a range of 4 to
12 times, preferably, 5 no 10 times, by using a stretcher to the
machine direction consisting of at least three rolls. If a
stretching ratio is less than 4 times, the mechanical strength of
the separator is low. When a stretching ratio exceeds 12 times,
slips may occur between the roll and the sheet daring drawing due
to a high degree of orientation of the resin constituting the
sheet, thus deteriorating quality uniformity. Moreover, since the
film shows significant shrinkage in the machine direction after
stretching to the machine direction, deflection of the film at an
inlet of the stretcher to the machine direction may occur, in turn
causing a difficulty in securing production stability.
[0041] The stretcher to the machine direction may have at least one
preheating roll, at least one stretching roll, at least one cooling
roll, or air-cooled device.
[0042] The preheating roll, means a rear roll among rolls having a
relative speed ratio of less than 1.05 (a draw ratio between rolls,
a rear roll speed/a front roll speed), and a first roll at the
inlet of the stretcher to the machine direction may also be the
preheating roll. The preheating rolls may be defined as a section,
to which preheating is applied to increase a temperature of the
sheet before stretching to reach around a stretching temperature,
and a size of the preheat roll and the number of the preheating
rolls may depend on a heating time of the sheet before stretching
by the roll (a contact time of the sheet to the roll; `a preheating
roll contact time`). In consideration of quality uniformity and
production stability, the preheat roll contact time may range from
1 to 500 seconds, preferably 10 to 200 seconds, more preferably 20
to 100 seconds. If the preheating roll contact time exceeds 500
seconds, the sheet is present at a temperature of not less than
room temperature for a long time, which in turn causes the diluents
to significantly emit from a surface of the sheet, thus causing
slips of the sheet on a surface of the roll and consequently
inhibiting quality uniformity and production stability. A
temperature of the preheating roll may range from [a melting
temperature of the resin in the sheet -50.degree. C.] to [a
temperature at which 70% of the crystals contained in the resin in
the sheet are molten]. Here, in the case where different kinds of
resins are mixed and the resin mixture is used in the sheet
composition, (the melting temperature of the resin in the sheet)
means a melting temperature of one of the plural resins, which is
the highest content by weight among all of the resins, in a
prepared sheet, likewise, crystals of the resin in the sheet refer
to crystals of the resin, which is contained in the highest content
by weight, among all of the resins. The (melting temperature of the
resin in the sheet -50.degree. C.) indicates a temperature at which
a polymer chain forming a resin crystal begins to exhibit mobility
against external stress and, if a temperature is less than the
above temperature, the resin has less mobility during stretching,
thus causing an internal fracture of sheet in the stretching
process or roll slips and consequently inhibiting quality
uniformity. Also, if a temperature exceeds the [temperature at
which 70% of the crystals contained in the resin in the sheet are
molten], the sheet adheres to a surface of the preheating roll due
to the high temperature, in turn damaging the sheet, surface and
causing significant emitting of the diluent due to the high
temperature, causing slips of the sheet. As a result, quality
uniformity may be inhibited.
[0043] The stretching roll means a rear roll among rolls having a
speed ratio of 1.05 to 6 (a draw ratio between rolls, a rear roll
speed/a front roll speed). The stretching to be conducted by a
stretcher to the machine direction is mostly executed by using a
stretching roll. If the speed ratio between rolls exceeds 6 in a
section defined by one stretching roll, the stretching is
excessively performed in a single draw section, in turn applying a
strong tensile strength to the sheet. Therefore, slips of the sheet
occur on a surface of the roll, thus inhibiting quality uniformity.
A size of the drawing roll and the number of drawing rolls may
depend on the basis of a total draw ratio to be achieved. For the
stretching roll, since a strong tensile strength is applied in a
machine direction to the sheet by stretching, slips on the roll
surf-ace must be prevented and the sheet on the roll surface must
be sufficiently heated. Therefore, a contact length of the sheet to
a roll (`a roll contact length`) on a roll surface is very
important. A roll contact coefficient (Equation 1) means a numeral
value to measure and estimate a roll contact length and may
suitably range from 1.5 to 54 (degree of angle.times.m).
Preferably, the roll contact coefficient ranges from 3 to 27
(degree of angle.times.m). If the roll contact coefficient is less
than 1.5, a friction force between the sheet and the roll surface
is insufficient to allow occurrence of slips caused by tensile
strength. In addition, thermal conductivity of the sheet on the
roll surface is insufficient, thus inhibiting quality uniformity.
On the other hand, when the roll contact coefficient exceeds 54,
the orientation of the resin induced by stretching is relaxed due
to a long roll contact time and oil is emitted, in turn causing
slips and deteriorating drawing effects. As a result, the
mechanical strength is decreased.
Roll contact coefficient (degree of angle.times.m)=[a contact angle
(degree) of a sheet to a roll].times.[a radius of a roll (m)]
[Equation 1]
[0044] On stretching in the stretching rolls, neck-in occurs in a
transverse direction. A neck-in is increased when a speed ratio
between rolls is high and a section, in which a sheet between,
rolls does not come into contact with the rolls, is increased. On
the other hand, when a stretching speed is high, the time taken to
generate transverse shrinkage is relatively short and thus a degree
of neck-in is reduced. If the neck-in is great, a product may have
a narrow width in the transverse direction, leading to a decrease
in productivity. In addition, since a degree of orientation of the
resin is decreased, a mechanical strength may be reduced. Further,
in a non-contact section between rolls, the sheet does not contact
the roll but is subjected to stretching while being exposed to air
at room temperature. As a length of the non-contact section is
increased, drawing stability is inhibited, in turn deteriorating
quality uniformity. Accordingly, a gap between stretching rolls, a
location of each of the rolls and a stretching speed must be
determined, in consideration of all of production stability,
productivity, quality uniformity, or the like. As an indication
parameter that briefly summarizes and compares a coefficient of
non-contact section between rolls (Equation 2) may range from
0.1.times.10.sup.-3 to 200.times.10.sup.-3 minutes (`min`),
preferably, ranges from 0.1.times.10.sup.-3 to 100.times.10.sup.-3
min and, more preferably, ranges from 0.1.times.10.sup.-3 to
50.times.10.sup.-3 min. If the coefficient of non-contact section
between rolls is less than 0.1.times.10.sup.-3 min, drawing is
conducted at a high drawing speed and a high draw ratio in a short
non-contact section and a high tensile strength is instantaneously
applied to the sheet, thus causing roll slips and inconvenience to
working efficiency due to a narrow working space. On the other
hand, when the coefficient of non-contact section between rolls
exceeds 200.times.10.sup.-3 rain, since the non-contact section has
a long length between stretching roll, neck-in (shrinkage) of the
sheet may be increased, thus reducing productivity and a mechanical
strength, and deteriorating quality uniformity.
Coefficient of non-contact section between rolls (min)=[length of
non-contact section (m)].times.[1/speed of a rear roll
(m/min)].times.[speed of a rear roll (m/min)/speed of a front roll
(m/min)] [Equation 2]
[0045] Most preferably, in consideration of productivity and
physical properties, a stretcher to the machine direction designed
while satisfying the foregoing conditions may have a sheet width
holding ratio after drawing between respective rolls in the
stretching rolls (a sheet width on a surface of the rear roll/a
sheet width on a surface of the front roll) of 70 to 90%, and a
sheet width holding ratio after overall machine direction drawing
(a sheet width at an inlet of the stretcher to the machine
direction/a sheer width at an outlet of the stretcher to the
machine direction) of 50 to 95%. A suitable temperature of the
stretching roll may range from [a melting temperature of the resin
in the sheet -50.degree. C.] to [a temperature at which 90% of the
crystals contained in the resin in the sheet are molten]. The
[melting temperature of the resin in the sheet -50.degree. C.]
indicates a temperature at which, polymer chains constituting the
resin have mobility and, if a temperature is less than this
temperature, the mobility of polymer chain in the resin may be
decreased, causing ruptures or slips caused by tensile strength
during drawing. At a higher temperature than the [temperature at
which 90% of the crystals contained in the resin in the sheet are
molten], the sheet is jammed on the roll surface which may
contaminate the roll surface or the strength of the sheet is
decreased due to a high temperature, in turn causing rupture or the
sheet during drawing, therefore, reducing production stability and
improving the mechanical strength insufficiently. The reason for
setting a maximum temperature of the stretching roll at a higher
temperature than the [temperature at which 70% of the crystals
contained in the resin in the sheet are molten] as a maximum
temperature of the preheating roll, is that, in order to reach the
[temperature at which 90% of the crystals contained in the resin in
the sheet are molten], the resin in the sheet is oriented during
stretching, thus increasing a melting temperature. As a result,
even the melting temperature becomes the temperature at which 90%
of the crystals of the resin in the sheet are molten, preventing
the sheet from jamming on the roll surface. Among the stretching
rolls (a roll having a speed ratio between rolls of not less than
1.05), the last stretching roll may have a lower temperature than
the others. Since a roll provided after the last stretching roll is
not used for stretching, it may be set to a lower temperature than
the stretching temperature, enabling the resin in the sheet to be
frozen while being drawn. The above temperature may be set to the
same temperature as that of a cooling roll described below.
[0046] Each of the preheating roll and the stretching roll may
comprise at least one roll and have a group of rolls or, if
required, the preheating roll and the stretching roll may be
arranged alternately,
[0047] A film stretched by the preheating roll and the stretching
roll is subjected to cooling at a lower temperature than the
temperature of the stretching roll, in order to maintain an
orientation of the film to be frozen. Such a cooling process may be
conducted by using a cooling roll or be air-cooled, or may adopt a
combination of the cooling roll and the air-cooling method. The
cooling roll may function to allow the oriented resin during
stretching to be frozen at a lower temperature than the temperature
of the stretching roll and to maintain, the orientation of the
resin. The temperature of the cooling roll is set to a temperature
5.degree. C. lower than the temperature of the stretching roll.
Since a specific period of time is required to cool the sheet so
that the cooling roll may implement its function, a size of the
roll and the number of rolls may depend on a roll contact time. A
cooling roll contact time may range from 1 to 120 seconds. If the
sheet contacts the cooling roll for less than 1 second, the film
after drawing is not sufficiently cooled. Therefore, after
stretching to the machine direction, a diluent emits due to
continuous relaxation, and production stability may be inhibited.
On the other hand, if the cooling time exceeds 120 seconds, the
cooling is sufficiently executed and favorable, however, equipment
costs are high and the number of cooling rolls is excessively
increased, in turn causing problems in maintenance of rolls. In
addition, the temperature of the cooling roll is preferably a
[temperature of the stretching roll -5.degree. C.] or less and,
more preferably, ranges from 10.degree. C. to a [temperature of the
stretching roll -10.degree. C.]. If the temperature of the cooling
roll is higher than the [temperature of the stretching roll
-5.degree. C.], a diluent emits from the sheet oriented via
stretching, through relaxation of the resin, causing slips or the
like, in turn inhibiting production stability, increasing the
relaxation of the resin, consequently deteriorating a mechanical
strength. When the temperature of the cooling roll is not more than
10.degree. C., the oriented resin is preferably frozen. But
moisture in air may be condensed on the roll surface and cause a
problem, in tarn inhibiting production stability. However, this may
be insignificant if an industrial plant has a drying apparatus.
After stretching in an air-cooling manner, a drawn film may be
cooled by exposing the same to air or by injecting air at a
temperature set to the [temperature of the stretching roll
-5.degree. C.] to the film. It is preferable to enable the
temperature of the film to rapidly reach the [temperature of the
stretching -5.degree. C.] or lower as soon as possible. If an
air-cooling time is extended, the oriented resin may undergo
relaxation, causing oil to be discharged from the film, thus
inhibiting production stability. During cooling, a predetermined
level of tensile strength must be applied to the resin to minimise
the relaxation of the resin, thereby securing production stability.
The tensile strength will be more concretely described below.
[0048] The stretching ratio of the stretcher to the machine
direction may be defined by [a speed of the last stretching
roll]/[a speed of the first preheating roll]. The overall
stretching ratio of the stretcher to the machine direction may be
achieved by a single stretching roll or, otherwise, by several
separated stretching rolls. For accomplishment of stretching
stability, stretching may be conducted in parts by using several
rolls. The rolls used in the stretcher to the machine direction may
be made of a metal or ceramic material without particular
limitation thereof but must enable temperature control. A roughness
of a surface of the roll used in the stretcher to the machine
direction may be freely selected in a range on which the sheet
closely contacts the roll surface to easily transfer heat while not
damaging a surface of the sheet. For a metal material, the
roughness may range from 0.1 s to 10 s,
[0049] The stretching to the transverse direction is performed by
using she stretcher of the tenter type in order to stretch the film
for 1 to 9 times in a transverse direction. If the stretching ratio
is less than 4 times, a degree of orientation of the resin in the
transverse direction is reduced, thus decreasing the mechanical
strength of the film. In addition, since the stretching ratio in
the transverse direction is low, quality uniformity in the
transverse direction may be deteriorated. On the other hand, when
the stretching ratio exceeds 9 times, the stretching ratio in the
transverse direction is nigh, which enhances quality uniformity.
However, since the tensile strength applied to the film in the
transverse direction is increased, the film may disengage out of a
chuck or ruptures or the like may occur during stretching to the
transverse direction, in turn inhibiting production stability. The
stretching ratio of the transverse direction stretching means a
ratio of a distance between chucks (a distance between cuter ends
of the chucks) at: the inlet of the stretcher to a distance between
chucks (a distance between outer ends of the chucks) at the outlet
of the stretcher. The stretching to the transverse direction may be
performed by any suitable methods, for example, by stretching the
film to a level more than the stretching ratio and then relaxing
the same, stretching the film to the stretching ratio, or the like.
The stretcher to the transverse direction, may comprise three
divisional parts including a preheating part, a stretching part and
a heat setting part. The preheating part, is a section to heat the
film cooled after stretching to the machine direction, in order to
be easily stretched in the stretching part, and may optionally
stretch the film a little in the transverse direction in order to
apply tensile strength to the film. The stretching part is a
section in which the film reaches the maximum draw ratio, while the
heat setting part is a section in which the stretching ratio may be
relaxed or maintained in the range of the maximum draw ratio to a
final draw ratio. Each of the sections may have different drawing
temperatures. The temperature of the preheating part, may be freely
selected from the [melting temperature of the resin in the sheet
+20.degree. C.] or less. If the temperature is set in a range of
temperatures more than the [melting temperature of the resin in the
sheet +20.degree. C.], a surface of the film may melt to inhibit
quality uniformity and production stability. The stretching part is
an important section to determine physical properties of a
separator and the temperature in this section significantly
influences physical properties and quality stability of the
separator. A temperature of the stretching part may be freely
determined in a range from the [melting temperature of the resin,
in the sheet -20.degree. C.] to the [melting temperature of the
resin in the sheet +10.degree. C.], depending on required physical
properties of the separator, the stretching ratio and the thickness
of the separator. When the temperature is set in a range of
temperatures of less than the [melting temperature of the resin in
the sheet -20.degree. C.], the film, may disengage out of the chuck
or have a rupture during stretching, in turn inhibiting production
stability. On the other hand, if the temperature is set in a range
of temperatures of more than the [melting temperature of the resin
in the sheet +10.degree. C.], a film during stretching is partially
overheated which inhibits quality uniformity and lacks tensile
strength at a high temperature, causing film vibration, thus
inhibiting production stability and quality uniformity. The heat
setting part is a section in which the resin in the film shows
relaxation behavior and a tensile strength of the film is
decreased, and may be freely selected in a range of temperatures of
not more than the [melting temperature of the resin in the sheet].
If the temperature exceeds the [melting temperature of the resin in
the sheet], a polyolefin resin in the film is present in a molten
state, which rapidly incurs relaxation of the resin, rapidly
decreases tensile strength of the film and causes vibration inside
the stretcher, thus inhibiting production stability.
[0050] As described above, when the stretching to the machine and
transverse direction are conducted, the tensile strength applied to
a sheet introduced into the stretcher to the machine direction may
range from 5 to 50N/cm.sup.2 to the machine direction in order to
secure quality uniformity and production stability. More
preferably, the tensile strength ranges from 7 to 30N/curt if the
tensile strength applied to the sheet introduced into the stretcher
to the machine direction is less than 5N/cm.sup.2, the tensile
strength of the sheet is decreased during stretching to the machine
direction and the degree of the contact of the sheet to the roll is
reduced causing occurrences of slips of the sheet on the roll, thus
deteriorating quality uniformity and production stability. In
addition, due to slips, the sheet on the roll may move to right and
left directions or lean on one side, thus causing difficulty in
securing production stability. On the other hand, if the tensile
strength exceeding 50N/cm.sup.2 is applied, the tensile strength
applied to the sheet in the stretcher to the machine direction
during stretching may be directly transferred to the casted sheet,
in turn influencing a sheet forming process. As a result, a
thickness and a shape of the sheet may be not uniform, in turn
causing non-uniformity in a thickness and physical properties of
the sheet. Moreover, since the tensile strength of the sheet is
high even during stretching to the machine direction, stretching is
not performed by a difference of roll speed during preheating and
stretching but taken place by the tensile strength. Furthermore,
the stretching is executed in the overall stretcher to the machine
direction and non-uniformity of stretching is increased. Since the
stretching is not executed at a gap between rolls but in the
overall stretcher to the machine direction, a width holding ratio
is reduced and a width of a product is decreased, thus inhibiting
productivity. In order to ensure desirable quality uniformity and
production stability, a tensile strength in a machine direction of
a sheet between a rear end of the stretcher to the machine
direction and an inlet of the stretcher to the transverse direction
may range from 100 to 700N/cm.sup.2. Preferably, the tensile
strength ranges from 200 to 600N/cm.sup.2. When applying the
tensile strength of less than 100N/cm.sup.2, a stress in the
machine direction as decreased and the resin oriented by stretching
to the machine direction may undergo relaxation causing a diluent
to emit from the sheet and the occurrence of slips of the sheet on
a roll surface, thus inhibiting production stability. Furthermore,
an amount of the emitting diluent cannot be controlled, thus
inhibiting quality uniformity. On the other hand, when a tensile
strength exceeding 700N/cm.sup.2 is applied, stretching is
conducted by the tensile strength between the rear end of the
stretcher to the machine direction and the stretcher to the
transverse direction (a longer distance than a gap between rolls)
to inhibit quality uniformity. In addition, a width holding ratio
is reduced to deteriorate productivity, and leaning of the film,
caused by the tensile strength may occur, causing the film to
disengage out of a chuck of the stretcher to the transverse
direction, thus inhibiting production stability.
[0051] The film stretched according to the foregoing processes may
be subjected to extraction of the diluent contained in the film by
using an organic solvent and drying. The organic solvent used in
the present invention may include any organic solvent capable of
extracting the diluent, without being particularly limited. More
preferably, the organic solvent includes methylethylketone,
methylene chloride, hexane, or the like, which have high extraction
efficiency and are rapidly dried. The extraction may be performed
by any conventional extraction method using a solvent, such as
immersion, solvent spray, ultrasonic treatment, or the like, which
is used alone or as a combination thereof. A content of the diluent
residue after extraction must be not more than 2 wt %. If the
content of the diluent residue exceeds 2 wt %, physical properties
are deteriorated and permeability of the film is reduced. An amount
of the diluent residue (an extraction ratio) may significantly
depend on an extraction temperature and an extraction time. The
extraction temperature is preferably nigh to increase solubility of
the diluents and the solvent. However, in consideration of boiling
of the solvent, the extraction temperature may be 40.degree. C. or
less. The extraction time may depend on a thickness of a film to be
produced, and suitably range from 2 to 4 minutes if a typical
microporous film having a thickness of 10 to 30 .mu.m is produced.
The film obtained by substituting the diluent with the organic
solvent through extraction is subjected to final drying of the
organic solvent through drying, thereby fabricating a microporous
film. A tensile strength may be applied during the
extraction/drying processes, in order to control shrinkage property
and physical properties.
[0052] For the dried film, a heat setting process is executed by
removing a residual stress to reduce a shrinkage rate of the final
film. The heat setting process functions to forcedly grip the film,
which is shrinkable in a heated state with heat, thus removing the
residual stress. The shrinkage and the permeability of she film may
be influenced by a heat setting temperature and a heat setting
ratio. If the heat setting temperature is high, the stress of the
resin is reduced too low, in turn reducing the shrinkage ratio.
When the heat setting temperature is too high, the film partially
melts to close micropores formed in the film, thus reducing
permeability of the film. The heat setting temperature may be
selected in a range of temperatures at which 5 to 50 wt % of the
crystals in the film are molten. When the heat setting temperature
is selected in a range of temperatures of less than the temperature
at which 5 wt % of the crystals in the film are molten,
re-orientation of polyolefin molecules in the film is insufficient,
therefore, residual stress is not removed from the film. If the
heat setting temperature is selected in a range of temperatures of
more than the temperature at which 50 wt % of the crystals in the
film are molten, she film is partially molten to close micropores,
thus decreasing permeability of the film. In addition, the machine
of tenter type is used for a step-by-step heat setting process, as
described above, during heat setting, to thereby enhance mechanical
properties such as tensile strength, puncture strength, or the
like, while reducing a shrinkage ratio. At a first stage of the
heat setting process, stretching to the transverse direction is
conducted at 20 to 100% to increase permeability of the film and
enhance tensile strength and puncture strength. If the stretching
is excessively increased to exceed 100%, demerits such as increased
shrinkage ratio and excessively enlarged size of pores may be
generated, even though permeability and tensile strength are
improved. In a second stage, a width of the first stretched film
say be shrunk by about 5 to 50%. Transverse shrinking is conducted
under heat to alleviate the stress and orientation of the resin,
thereby reducing the shrinkage ratio. Here, if a width of a product
is shrunk by 50% or more, permeability and puncture strength are
decreased too much. On the other hand, if the shrinking is not more
than 5%, the stress and the resin orientation are not alleviated,
causing an increase in the shrinkage rate and allowing a large size
of the pore to be maintained, thus not securing stability of a
battery. The heat setting time may be varied to be relatively short
where the heat fixing temperature is high, while being extended
when the heat fixing temperature is low. Preferably, the heat
fixing time ranges from 10 seconds to 2 minutes.
[0053] Preferably the foregoing stretching, extraction, and heat
setting processes may be executed in a continuous mode.
Advantageous Effects of Invention
[0054] As described above, by adopting a combination of stretching
before extraction and a specific stretching process according to
the present invention and using a heat setting process under
specific conditions, problems of quality uniformity and production
stability which were immediate causes of quality failures could be
overcome, although, other problems in actual production still
remain to be solved. Moreover, a microporous film having excellent,
quality may be provided,
BRIEF DESCRIPTION OF DRAWINGS
[0055] The above and other objects, features and advantages of the
present invention will become apparent from the following
description of preferred embodiments given in conjunction with the
accompanying drawings, in which:
[0056] FIG. 1 illustrates a stretching method using a simultaneous
stretching process; and
[0057] FIG. 2 illustrates a stretching method according to the
present, invention.
MODE FOR THE INVENTION
[0058] Hereinafter, exemplary embodiments of the present invention
will be described in detail with reference to accompanying
drawings. However, the scope of the present invention is not
restricted to the following embodiments.
[0059] (1) Molecular Weight
[0060] A molecular weight of a polyolefin resin is determined by a
high temperature GPC (Gel Permeation Chromatography) available from
Polymer Laboratory Co., which uses 1,2,4-trichlorobenzene (TCB) as
a solvent and is performed at 140.degree. C., As a standard sample
for measurement of molecular weight, polystyrene was used.
[0061] (2) Analysis of Thermal Characteristics
[0062] For a molded sheet by T-die to be stretched as well as a
dried film after extraction, analysis of thermal characteristics
was performed by differential scanning calorimetry (DSC; DSC-822E
manufactured by Mettler Toledo Co.). Analysis conditions of the
dried film after extraction as well as the molded sheet include
elevating a temperature of a sample having a weight of 5 mg at a
scanning rate of 10.degree. C./min until the molded sheet is
completely molten. Following this, by measuring DSC thermogram of
the sheet before stretching, a degree of melting resin crystals in
the sheet, in relation to temperature and a melting temperature
thereof were determined.
[0063] (3) Film Thickness
[0064] Using a TESA Mu-Hite Electronic Height Gauge available from
TESA Co., a thickness of a final film was determined with the
measuring pressure of 0.63N.
[0065] (4) Puncture Strength
[0066] After mounting a pin having a diameter of 1 mm and a radius
of curvature (RC) of 0.5 mm on a universal testing machine (UTM,
Instron Co.), a strength of a separator when the separator is
broken at a moving speed of 120 mm/min and 23.degree. C. was
determined.
[0067] (5) Gas Permeability
[0068] Gas permeability was measured by a porometer (CFP-1500-AEL,
PMI Co.). In general, the gas permeability is indicated by a Gurley
number; however, since the Gurley number cannot compensate for
influences of a thickness of the separator, it is difficult to
determine a relative permeability in relation to a pore structure
of the separator. In order to solve such a problem, the present
invention adopted Darcy's permeability constant. Darcy's
permeability constant may be calculated by the following Equation
and, in the present invention, nitrogen was used.
C=(8FTV)/(.pi.D.sup.2(P.sup.2-1))
[0069] wherein,
[0070] C is Darcy's permeability constant,
[0071] F is a flow rate,
[0072] T is a thickness of a sample,
[0073] V is a viscosity of a gas (0.1.85 for N2),
[0074] D is a diameter of a sample, and
[0075] P is a pressure.
[0076] According to the present invention, an average value of the
Darcy's permeability constants in a region of 100 to 200 psi was
used.
[0077] (6) Shrinkage Ratio
[0078] After preparing a separator by cutting a size of 15 cm by 15
cm, the prepared separator was marked in machine and transverse
directions at a gap of 10 cm. Then, the marked separator was
interposed between paper sheets, placed in an oven stabilized at
12015 and left for 60 minutes. Thereafter, a shrinkage ratio was
estimated by measuring a variation of the gap. Estimation of the
shrinkage ratio was performed by the following Equation.
Shrinkage ratio (%)=100(initial gap-gap after leaving at
120.degree. C. for 1 hour)/initial gap
[0079] (7) Production Stability
[0080] Production stability was determined by monitoring whether at
least 3000 m of the final products are continuously produced
without problems.
[0081] (8) Quality Uniformity
[0082] For the final product, a thickness deviation was determined
by measuring thickness of the location in the middle between the
center and edge to the transverse direction for 1000 m by 50 m
intervals (1/4 position among an overall width in a transverse
direction).
Quality uniformity(%)={Standard deviation of thickness/average
thickness}.times.100
Example 1
[0083] A resin composition included 97 wt % of a high density
polyethylene having a weight-average molecular weight of
3.0.times.10.sup.5 and a melting temperature of 135.degree. C. and
3 wt % of a homopolypropylene having a weight-average molecular
weight of 5.7.times.10.sup.5 and a melting temperature of
163.degree. C. A diluent was a paraffin oil having a kinetic
viscosity of 100 cSt at 40.degree. C. A sheet composition was
prepared by mixing the resin composition and the diluent in a ratio
by weight of 35:65; mixing, extruding and molding through a twin
screw compounder equipped with T-die at 250.degree. C.; and using a
casting roll set at 40.degree. C. to prepare a sheet having a width
of 300 mm and an average thickness of 1100 .mu.m.
[0084] The prepared sheet was introduced into a machine direction
stretcher while applying a tensile strength of 10.6N/cm.sup.2 in
the machine direction, and preheated in a preheating roll having
six (6) rolls and set at 115.degree. C. for 76 seconds. A
stretching roll which consists of four (4) rolls and is set at
118.degree. C., and in which each of the rolls has a roll contact
coefficient of 13.5 degree (of angle).times.m, was used. Also,
these rolls have a coefficient of non-contact section between rolls
of 17.9.times.10.sup.-3 min, 14.9.times.10.sup.-3 min,
12.4.times.10.sup.-3 min and 10.3.times.10.sup.-3 min,
respectively. Stretching was conducted in parts by these four
rolls, such that a maximum stretching ratio at one stretching roll
becomes 3.2 times and an overall stretching ratio in a machine
direction is 6 times, at a final speed of 12 m/min. last, a cooling
roll which consists of three (3) rolls, is set at 60.degree. C. and
rotates at the same speed as of the last stretching roll, was used
to cool the film for 7 seconds. A width holding ratio of the
machine direction stretched film was 74.6%.
[0085] The machine direction stretched film was introduced into a
transverse direction stretcher while applying a tensile strength of
250N/cm.sup.2 in the machine direction, and subjected to transverse
direction drawing at 118.degree. C. (using a preheating part, a
stretching part and a heat setting part) to reach 6 times. Thermal
relaxation was not carried out in the heat setting part.
[0086] The film completely stretched in machine and transverse
directions was treated by using methylene chloride at room
temperature to remove the diluent, extended up to 1.40% at
128.degree. C. in the transverse direction, by using heat setting
equipment of tenter type, and subjected to shrinking by 14.3%,
compared to a final width in the extension process.
[0087] For the resultant separator prepared as described above,
puncture strength, permeability, shrinkage ratio, average thickness
in a machine direction, a thickness deviation, and production
stability are listed in the following TABLE 1.
Example 2
[0088] A sheet composition was prepared by using a high density
polyethylene having a weight-average molecular weight of
3.0.times.10.sup.5 and a melting temperature of 135.degree. C., and
a paraffin oil having a kinetic viscosity of 100 cSt at 40.degree.
C. as a diluent in a ratio by weight of 30:70. The prepared sheet
composition was subjected to mixing, extruding and molding through
a twin screw compounder equipped with T-die at 250.degree. C. and
treated by using a casting roll set at 40.degree. C., thereby
resulting in a sheet having a width of 600 mm and an average
thickness of 2000 .mu.m.
[0089] The prepared sheet was introduced into a machine direction
stretcher while applying a tensile strength of 16.7N/cm.sup.2 in
the machine direction and preheated in a preheating roll having
eight (8) rolls and set at 110.degree. C. for 50 seconds. A
stretching roll which consists of six (6) rolls and is set at
108.degree. C., and in which each of the rolls has a roll, contact
coefficient of 13.5 degree (of angle).times.m, was used. Also,
these rolls have a coefficient of non-contact section between rolls
of 8.42.times.10.sup.-3 min, 7.66.times.10.sup.-3 min,
6.37.times.10.sup.-3 min, 4.83.times.10.sup.-3 min,
3.33.times.10.sup.-3 min. and 2.15.times.10.sup.-3 min,
respectively. Stretching was conducted in parts by these six rolls,
such that, a maximum stretching ratio at one stretching roll
becomes 1.7 times and an overall stretching ratio in a machine
direction is 7.5 times, at a final speed of 30 m/min. Last, a
cooling roll which consists of three (3) rolls, is set at 80 .mu.l
and rotates at the same speed as the last stretching roll, was used
to cool the film for 5 seconds. For a total of 17 rolls including
the preheating rolls, the stretching rolls, the cooling rolls and
the pinch rolls were used. A width holding ratio of the machine
direction stretched film was 72.3%.
[0090] The machine direction stretched film was introduced into a
transverse direction stretcher while applying a tensile strength of
392N/cm.sup.2 in the machine direction and subjected to transverse
direction stretching using a transverse direction stretcher, which
includes a preheating part set at 124.degree. C., a stretching part
set at 120.degree. C. and a heat setting part set at 116.degree.
C., to reach a maximum stretching ratio of 8.4 times (120%), Then,
thermal relaxation was carried out in the heat setting part to
reach 7 times, thus a final transverse direction stretching ratio
of 7 times.
[0091] The film completely stretched, in machine and transverse
directions was treated by using methylene chloride at room
temperature to remove the diluent, extended up to 145% at
129.degree. C. in the transverse direction, toy using heat setting
equipment of tenter type, and subjected to shrinking by 17.2%,
compared to a final width in the extension process.
[0092] For the resultant separator prepared as described above,
puncture strength, permeability, shrinkage ratio, average thickness
in a machine direction, a thickness deviation, and production
stability are listed in the following TABLE 1.
Example 3
[0093] A resin composition included 90 wt % of a high density
polyethylene having a weight-average molecular weight of
3.0.times.10.sup.5 and a melting temperature of 135.degree. C. and
10 wt % of calcium carbonate having an average particle size of
0.8/.mu.m. A diluent was a paraffin oil having a kinetic viscosity
of 100 cSt at 40.degree. C. A sheet composition was prepared by
mixing the resin composition and the diluent in a ratio by weight
of 40:60; mixing, extruding and molding through a twin screw
compounder equipped with T-die at 250.degree. C.; and using a
casting roll set at 40.degree. C. to prepare a sheet having a width
of 800 mm and an average thickness of 640 .mu.m.
[0094] The prepared sheet was introduced into a machine direction
stretcher while applying a tensile strength of 19.5N/cm.sup.2 in
the machine direction, and preheated in a preheating roll having
nine (9) rolls and set at 110.degree. C. for 91 seconds. A
stretching roll which consists of four (4) rolls and is set at
95.degree. C., and in which each of the rolls has a roll contact
coefficient of 13.5 degree (of angle).times.m, was used. Also,
these rolls have a coefficient of non-contact section, between
rolls of 13.9.times.10.sup.-3 min, 11.6.times.10.sup.-3 min,
8.27.times.10.sup.-3 min and 5.27.times.10.sup.-3 min,
respectively. Stretching was conducted in parts by these four
rolls, such that a maximum stretching ratio at one stretching roll
becomes 2.7 times and an overall stretching ratio in a machine
direction is 8.5 times, at a final speed of 20 m/min, last, a
cooling roll which consists of four (4) rolls, is set at 40.degree.
C. and rotates at the same speed as of the last stretching roll,
was used to cool the film for 5 seconds. A width holding ratio of
the machine direction stretched film was 67.7%.
[0095] The machine direction stretched film was introduced into a
transverse direction stretcher while applying a tensile strength of
427N/cm.sup.2 in the machine direction, and subjected to transverse
direction stretching using a transverse direction stretcher, which
includes a preheating part set at 114.degree. C., a stretching part
set at 110.degree. C. and a heat setting part set at 105.degree.
C., to reach a maximum stretching ratio of 7.7 times (110%). Then,
thermal relaxation was carried out in the heat setting part to
reach 7 times, thus a final transverse direction stretching ratio
was 7 times.
[0096] The film completely stretched in machine direction, and
transverse direction was treated by using methylene chloride at
room temperature to remove the diluent, extended up to 150% at
130.degree. C. in the transverse direction, by using heat setting
equipment of tenter type, and subjected to shrinking by 20%,
compared to a final width in the extension process.
[0097] For the resultant separator prepared as described above,
puncture strength, permeability, shrinkage ratio, average thickness
in a machine direction, a thickness deviation, and production
stability are listed in the following TABLE 1.
Comparative Example 1
[0098] A sheet composition was prepared by using a high density
polyethylene having a weight-average molecular weight of
3.0.times.10.sup.5 and a melting temperature of 135.degree. C., and
a paraffin oil having a kinetic viscosity of 100 cSt at 40.degree.
C. as a diluent in a ratio by weight of 40:60. The prepared sheet,
composition was subjected to mixing, extruding and molding through,
a twin screw compounder equipped with T-die at 250.degree. C. and
treated by using a casting roll set at 40.degree. C., thereby
resulting in a sheet having a width of 200 mm and an average
thickness of 1600 .mu.m.
[0099] Although the prepared sheet was stretched by using a
simultaneous stretcher at 117.degree. C. in machine and transverse
directions for 7 times, respectively, to reach a final speed of 5
m/min after stretching, the film disengaged out of the chuck as a
tensile strength to the film increased during progress of the
stretching. As a result, the drawing could not be completed.
Comparative Example 2
[0100] A sheet composition, was prepared by using a high density
polyethylene having a weight-average molecular weight of
3.0.times.10.sup.5 and a melting temperature of 135.degree. C., and
a paraffin oil having a kinetic viscosity of 100 cSt at 40.degree.
C. as a diluent in a ratio by weight of 35:65. The prepared sheet
composition was subjected to mixing, extruding and molding through
a twin screw compounder equipped with T-die at 250.degree. C. and
treated by using a casting roll set at 40.degree. C., thereby
resulting in a sheet having a width of 200 mm and an average
thickness of 1400 .mu.m.
[0101] The prepared sheet was drawn by using a simultaneous
stretcher at 118.degree. C. in machine and transverse directions
for 6.5 times, respectively, to reach a final speed of 5 m/min
after stretching.
[0102] The film completely stretched in machine and transverse
directions was treated by using methylene chloride at room
temperature to remove the diluent, extended up to 135% at
127.degree. C. in the transverse direction, by heat setting
equipment of tenter type, and subjected to shrinking by 11.1%,
compared to a final width in the extension process.
[0103] For the resultant separator prepared as described above,
puncture strength, permeability, shrinkage ratio, average thickness
in a machine direction, a thickness deviation, and production
stability are listed in one following TABLE 1.
Comparative Example 3
[0104] A sheet composition was prepared by using a high density
polyethylene having a weight-average molecular weight of
3.0.times.10.sup.5 and a melting temperature of 135.degree. C., and
a paraffin oil having a kinetic viscosity of 100 cSt at 40.degree.
C. as a diluent in a ratio by weight of 35:65. The prepared sheet
composition was subjected to mixing, extruding and molding through
a twin screw compounder equipped with T-die at 250.degree. C. and
treated by using a casting roll set at 40.degree. C., thereby
resulting in a sheet having a width of 700 mm and an average
thickness of 1200 .mu.m.
[0105] The prepared sheet was introduced into a machine direction
stretcher while applying a tensile strength of 17.3N/cm.sup.2 in
the machine direction, and preheated in a preheating roll having
eight (8) rolls and set at 115.degree. C. for 75 seconds. A
stretching roll which consists of two (2) rolls and is set at
115.degree. C., and in which each of the rolls has a roll contact
coefficient of 13.5 degree (of angle).times.m, was used. Also,
these rolls have a coefficient of non-contact section between rolls
of 14.3.times.10.sup.-3 min and 13.4.times.10.sup.-3 min,
respectively. Stretching was conducted in parts by these two rolls,
such that a maximum stretching ratio at one stretching roll is 6.9
times and an overall stretching ratio in a machine direction is 8.5
times, at a final speed of 20 m/min. Last, a cooling roll which
consists of three (3) rolls, is set at 50.degree. C. and rotates at
the same speed as the last stretching roll, was used to cool the
film for 4 seconds.
[0106] Since slips occurred at the stretching roll which stretches
6.9 times and, after machine direction stretching, a thickness and
a width of the film were unstable, transverse direction stretching
could nor be executed.
Comparative Example 4
[0107] A sheet composition was prepared by using a high density
polyethylene having a weight-average molecular weight of
3.0.times.10.sup.5 and a melting temperature of 135.degree. C., and
a paraffin oil having a kinetic viscosity of 100 cSt at 40.degree.
C. as a diluent in a ratio by weight of 30:70. The prepared sheet
composition was subjected to mixing, extruding and molding through
a twin screw compounder equipped with T-die at 250.degree. C. and
treated by using a casting roll set at 40.degree. C., thereby
resulting in a sheet having a width of 600 mm and an average
thickness of 1800 .mu.m.
[0108] The prepared sheet was introduced into a machine direction
stretcher while applying a tensile strength of 3.7N/cm.sup.2 in the
machine direction, and preheated in a preheating roll having eight
(8) rolls and set at 116.degree. C. for 94 seconds. A stretching
roll which consists of six (6) rolls and is set at 110.degree. C.,
and in which each of the rolls has a roll contact coefficient of
13.5 degree (of angle).times.m, was used. Also, these rolls have a
coefficient of non-contact section between rolls of
15.7.times.10.sup.-3 min, 12.1.times.10.sup.-3 min,
3.3.times.10.sup.-3 min, 7.10.times.10.sup.-3 min,
5.46.times.10.sup.-3 min and 3.90.times.10.sup.-3 min,
respectively. Stretching was conducted in parts by these six rolls,
such that a maximum stretching ratio at one stretching roll is 1.5
times and an overall stretching ratio in a machine direction is 7
times, at a final speed of 15 m/min. Last, a cooling roll which
consists of three (3) rolls, is set at 40.degree. C. and rotates at
the same speed as the last stretching roll, was used to cool the
film for 6 seconds.
[0109] Since slips of the sheet occurred during machine direction
stretching and the sheet leaned to one side, transverse direction,
stretching could not be executed.
Comparative Example 5
[0110] A sheet composition was prepared by using a high density
polyethylene having a weight-average molecular weight of
3.0.times.10.sup.5 and a melting temperature or 135.degree. C., and
dioctylphthalate as a diluent in a ratio by weight of 25:75, The
prepared sheet composition was subjected to mixing, extruding and
molding through a twin screw compounder equipped with T-die at
250.degree. C. and treated by using a casting toll set at
40.degree. C., thereby resulting in a sheet having a width of 300
mm and an average thickness of 1350 .mu.m.
[0111] The prepared sheet was introduced into a machine direction
stretcher while applying a tensile strength of 14.8N/cm.sup.2 in
the machine direction, and preheated in a preheating roll having
ten (10) rolls and set at 117.degree. C. for 338 seconds. A
stretching roll which consists of four (4) rolls and is set at
117.degree. C., and in which each of the rolls has a roll contact
coefficient of 13.5 degree (of angle).times.m, was used. Also,
these rolls have a coefficient of non-contact section between rolls
of 244.times.10.sup.-3 min, 174.times.10.sup.-3 min,
113.times.10.sup.-3 min and 66.8.times.10.sup.-3 min, respectively.
Stretching was conducted in parts by these four rolls, such that a
maximum stretching ratio at one stretching roll is 2.0 times and an
overall stretching ratio in a machine direction is 9 times, at a
final speed of 6 m/min, Last, a cooling roll which consists of
three (3) rolls, is set at 50.degree. C. and rotates at the same
speed as the last, stretching roll, was used to cool the film for
14 seconds. For one preheating roll located at the inlet of the
machine direction stretcher as well as three cooling rolls, pinch
rolls were used. A width holding ratio of the machine direction
stretched film was 44.7%.
[0112] The machine direction stretched film was introduced into a
transverse direction stretcher while applying a tensile strength of
525N/cm.sup.2 in the machine direction, and subjected to transverse
direction stretching using a transverse direction stretcher, which
includes a preheating part set at 125.5.degree. C., a stretching
part set at 125.5.degree. C. and a heat setting part set at
118.degree. C., to reach 5 times. Thermal relaxation was not
carried out.
[0113] The film completely stretched in machine and transverse
directions was treated by using methylene chloride at room
temperature to remove the diluent, extended up to 150% at
128.degree. C. in the transverse direction, by using heat setting
equipment of tenter type, and subjected to shrinking by 23.3%,
compared to a final width m the extension process.
[0114] The resultant separator prepared as described above had a
width of 60% (=134 mm/224 mm) compared to that of the product
according to Example 1, after machine direction stretching,
therefore, a width of the final product showed 60% or less of
productivity. For the width of the separator, puncture strength,
permeability, shrinkage ratio, average thickness in a machine
direction, a thickness deviation, and production stability are
listed in the following TABLE 1.
Comparative Example 6
[0115] A sheet composition was prepared by using a high density
polyethylene having a weight-average molecular weight of
3.0.times.10.sup.5 and a melting temperature of 135.degree. C. and
a paraffin oil having a kinetic viscosity of 100 cSt at 40.degree.
C. as a diluent in a ratio by weight of 30:70. The prepared sheet
composition was subjected to mixing, extruding and molding through
a twin screw compounder equipped with T-die at 250.degree. C. and
treated by using a casting roll set at 40.degree. C., thereby
resulting in a sheet having a width of 650 mm and an average
thickness of 1500 .mu.m.
[0116] The prepared sheet was introduced into a machine direction
stretcher while applying a tensile strength of 18.5N/cm.sup.2 in
the machine direction, and preheated in a preheating roll having
ten (8) rolls and set at 122.degree. C. for 61 seconds. A
stretching roll which consists of six (6) rolls and is set at
123.degree. C., and in which each of the rolls has a roll contact
coefficient of 13.5 degree (of angle).times.m, was used. Also,
these rolls have a coefficient of non-contact section between rolls
of 10.1.times.10.sup.-3 min, 7.49.times.10.sup.-3 min,
5.50.times.10.sup.-3 min, 4.05.times.10.sup.-3 min,
2.98.times.10.sup.-3 min and 2.19.times.10.sup.-3 mm, respectively.
Stretching was conducted in parts by these six rolls, such that a
maximum stretching ratio at one stretching roll becomes 1.4 times
and an overall stretching ratio in a machine direction is 7.5
times, at a final speed of 25 m/min. Last, a cooling roll which
consists of three (3) rolls, is set at 40.degree. C. and rotates at
the same speed as the last stretching roll, was used to cool the
film for 3 seconds.
[0117] In contrast to the stretching roll, since sheet sticking
occurred on a surface of the preheating roll during machine
direction stretching and impurities were deposited on the roll, the
film had poor appearance after stretching and the stretching was
stopped,
Comparative Example 7
[0118] A sheet composition was prepared by using a high density
polyethylene having a weight-average molecular weight of
3.0.times.10.sup.5 and a melting temperature of 135.degree. C., and
a paraffin oil having a kinetic viscosity of 100 cot at 40.degree.
C. as a diluent in a ratio by weight of 40:60, The prepared, sheet
composition was subjected to mixing, extruding and molding through
a twin screw compounder equipped with T-die at 250.degree. C. and
treated by using a casting roll set at 40.degree. C., thereby
resulting in a sheet having a width of 500 mm and an average
thickness of 1300 .mu.m.
[0119] The prepared sheet was introduced into a machine direction
stretcher while applying a tensile strength of 23.1N/cm.sup.2 in
the machine direction, and preheated in a preheating roll having
seven (7) rolls and set at 105.degree. C. for 53 seconds. A
stretching roll which consists of three (3) rolls and is set at
105.degree. C., and in which each of the rolls has a roll contact
coefficient of 13.5 degree (of angle).times.m, was used. Also,
these rolls have a coefficient of non-contact section between rolls
of 11.3.times.10.sup.-3 min, 7.09.times.10.sup.-3 min and
3.90.times.10.sup.-3 min, respectively. Stretching was conducted in
parts by these three rolls, such that a maximum stretching ratio at
one stretching roll becomes 2.0 times and an overall stretching
ratio in a machine direction is 6.5 times, at a final speed of 20
m/min. Last, a cooling roll which consists of three (3) rolls, is
set at 80.degree. C. and rotates at the same speed as the last
stretching roll, was used to cool the film for 4 seconds. A width
holding ratio of the machine direction stretched film was
73.6%.
[0120] Although the machine direction stretched film was introduced
into a transverse direction stretcher while applying a tensile
strength of 859N/cm.sup.2 in the machine direction, the film leaned
toward one side and dropped out of a chuck at one side of the
transverse direction stretcher, therefore, stretching could not be
executed.
Comparative Example 8
[0121] A sheet composition was prepared by using a nigh density
polyethylene having a weight-average molecular weight of
3.0.times.10.sup.5 and a melting temperature of 135.degree. C., and
a paraffin oil having a kinetic viscosity of 100 cSt at 40.degree.
C. as a diluent in a ratio by weight of 30:70. The prepared sheet
composition was subjected to mixing, extruding and molding through
a twin screw compounder equipped with T-die at 250.degree. C. and
treated by using a casting roll set at 40.degree. C., thereby
resulting in a sheet having a width of 300 mm and an average
thickness of 1500 .mu.m.
[0122] The prepared sheet was introduced into a machine direction
stretcher while applying a tensile strength of 11N/cm.sup.2 in the
machine direction, and preheated in a preheating roll having eight
(8) rolls and set at 112.degree. C. for 149 seconds. A stretching
roll which consists of six (6) rolls and is set at 112.degree. C.,
and in which each of the rolls has a roll contact coefficient of
13.5 degree (of angle).times.m, was used. Also, these rolls have a
coefficient of non-contact section between rolls of
24.8.times.10.sup.-3 min, 22.5.times.10.sup.-3 min,
18.8.times.10.sup.-3 min, 14.4.times.10.sup.-3 min,
9.6.times.10.sup.-3 min and 6.01.times.10.sup.-3 min, respectively.
Stretching was conducted in parts by these six rolls, such that a
maximum stretching ratio at one stretching roll becomes 1.85 times
and an overall stretching ratio in a machine direction is 9 times,
at a final speed of 12 m/min. Last, a cooling roll which consists
of three (3) rolls, is set at 100.degree. C. and rotates at the
same speed as the last stretching roll, was used to cool the film
for 7 seconds. A width holding ratio of the machine direction
stretched film was 73.3%.
[0123] Although the machine direction stretched film was introduced
into a transverse direction stretcher while applying a tensile
strength of 43.3/cm.sup.2 in the machine direction, the diluent
emitted from stretched film at the cooling rolls and was deposited
thereon, and the sheet leaned toward one side and disengaged out of
a chuck at one side of the transverse direction stretcher,
therefore, stretching could not be executed.
TABLE-US-00001 TABLE 1 Puncture Perme- Shrinkage Thickness strength
ability ratio (%) Production Quality (.mu.m) (N/.mu.m) (Darcy
.times. 10.sup.-5) MD TD stability uniformity Ex. 1 26 0.35 2.5 7 1
Pass 1.3% Ex. 2 33 0.45 2.1 8 4 Pass 1.5% Ex. 3 8 0.30 4.9 5 6 Pass
1.1% Com. Ex. 1 -- -- -- -- -- Fail -- Com. Ex. 2 25 0.32 2.8 10 14
Pass 2.5% Com. Ex. 3 -- -- -- -- -- -- -- Com. Ex. 4 -- -- -- -- --
Fail -- Com. Ex. 5 25 0.27 3.8 8 10 Pass 2.3% Com. Ex. 6 -- -- --
-- -- Fail -- Com. Ex. 7 -- -- -- -- -- Fail -- Com. Ex. 8 -- -- --
-- -- Fail --
[0124] As described above, by adopting a combination of stretching
before extraction and a specific stretching process according to
the present invention and using a heat setting process under
specific conditions, problems of quality uniformity and production
stability which were immediate causes of quality failures could be
overcome, although, other problems in actual, production still
remain to be solved. Moreover, a microporous film having excellent
quality may be provided
INDUSTRIAL APPLICABILITY
[0125] As described above, by adopting a combination of stretching
before extraction and a specific stretching process according to
the present invention and using a heat setting process under
specific conditions, problems of quality uniformity and production
stability which were immediate causes of quality failures could be
overcome, although, other problems in actual production still
remain to be solved. Moreover, a microporous film having excellent
quality may be provided.
* * * * *