U.S. patent number 3,914,354 [Application Number 05/399,138] was granted by the patent office on 1975-10-21 for process for producing fine fibrous structures.
This patent grant is currently assigned to Kabushiki Kaisha Oki Yuka Goeishi Kenkyujo. Invention is credited to Yoshimitsu Miyata, Shiro Ueki.
United States Patent |
3,914,354 |
Ueki , et al. |
October 21, 1975 |
**Please see images for:
( Certificate of Correction ) ** |
Process for producing fine fibrous structures
Abstract
An aqueous disperse system, preferably an aqueous emulsion,
comprising a molten linear polymer droplets dispersed in the
aqueous phase and containing a fine water-sorption agent and a
positive solvent with respect to the polymer is ejected from a
high-pressure region at a temperature above the polymer melting
point and below the critical temperature of the disperse system and
at a pressure above the saturated vapor pressure of the disperse
system into a low-pressure region at a temperature and pressure
permitting evaporation of a liquid phase within the disperse system
thereby to produce a fine fibrous structure of the polymer.
Inventors: |
Ueki; Shiro (Yokkaichi,
JA), Miyata; Yoshimitsu (Yokkaichi, JA) |
Assignee: |
Kabushiki Kaisha Oki Yuka Goeishi
Kenkyujo (Tokyo, JA)
|
Family
ID: |
13816490 |
Appl.
No.: |
05/399,138 |
Filed: |
September 20, 1973 |
Related U.S. Patent Documents
|
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
182524 |
Sep 21, 1971 |
|
|
|
|
Foreign Application Priority Data
|
|
|
|
|
Sep 25, 1970 [JA] |
|
|
45-83937 |
|
Current U.S.
Class: |
264/13;
162/157.5; 264/211; 264/205 |
Current CPC
Class: |
D21H
5/20 (20130101); D01D 5/11 (20130101); D21H
13/14 (20130101); D21H 5/202 (20130101) |
Current International
Class: |
D01D
5/00 (20060101); D01D 5/11 (20060101); B29C
023/00 () |
Field of
Search: |
;260/29.6XA,2.5,75T,78S,42.54,42.55 ;264/204,205,13,176F,24,211
;162/157 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Woo; Jay H.
Attorney, Agent or Firm: Wenderoth, Lind & Ponack
Parent Case Text
This is a continuation of application Ser. No. 182,524, filed Sept.
21, 1971, and now abandoned.
Claims
We claim:
1. A process for producing fine fibrous structures which comprises
the steps of:
1. preparing a heterogeneous aqueous dispersion system comprising a
molten polyolefin dispersed therein in a quantity of from 5 to 70
percent by weight of the aqueous dispersion system, water, and a
substantially water-immiscible positive solvent for the polymer,
said molten polyolefin containing water and a fine water-sorption
agent which is inherently solid in a quantity of from 20 to 80
percent by weight of the polyolefin; said positive solvent being in
a quantity of less than 50% by weight of the polymer, at least a
part of which is present within the molten polyolefin, and
2. passing said aqueous dispersion system from a high-pressure
region at a temperature above the melting point of the polymer and
below the critical temperature of said aqueous dispersion system
and at a pressure above the saturated vapor pressure of said system
into a low-pressure region at a temperature and pressure at which
the liquid phase within the dispersion system can evaporate thereby
to produce a fine fibrous structure of the polymer.
2. A process according to claim 1, wherein the positive solvent is
selected from the group consisting of n-pentane, n-hexane,
n-heptane, cyclopentane, cyclohexane, dichloromethane, benzene,
toluene, xylenes, decalin, tetralin, naphthalene, and mixtures
thereof.
3. A process according to claim 1 wherein the positive solvent is
present in a quantity of less than 30% by weight of the
polymer.
4. A process according to claim 1 wherein the molten polyolefin is
selected from the group consisting of high density polyethylene and
high density polypropylene and the heterogeneous aqueous dispersion
system is passed from a high pressure region in which the pressure
range is between 50 to 60 kg/cm.sup.2 and the temperature is
between 180.degree. to 200.degree.C to a low pressure region in
which the pressure is atmospheric pressure and the temperature is
room temperature.
5. A process for producing fine fibrous structures as claimed in
claim 1 in which the aqueous disperse system is an aqueous emulsive
liquid.
6. A process for producing fine fibrous structures as claimed in
claim 1 in which the water-sorption agent is a fine solid of a
member selected from the group consisting of nitrates, oxalates,
acetates, sulfates, sulfites, carbonates, phosphates, hydroxides,
and halides of alkali metals, alkaline earth metals (including
magnesium) and ammonium, and mixtures thereof.
7. A process for producing fine fibrous structures as claimed in
claim 1 in which the water-sorption agent is a water-insoluble
silicate.
8. A process for producing fine fibrous structures as claimed in
claim 1 in which the aqueous dispersion system is prepared by
blending the fine water-sorption agent with the polymer in a molten
or solution state, suspending the resulting blend in an aqueous
emulsion, and heating and pressurizing the resulting suspension to
and at a temperature above the melting point of the polymer and a
pressure above the critical pressure (Saturated Vapour Pressure) of
the suspension.
9. A process for producing fine fibrous structures as claimed in
claim 1 in which the aqueous dispersion system is prepared by
suspending a fine water-sorption agent which substantially does not
dissolve in water and the polymer in powder form in an aqueous
emulsion of the positive solvent and heating and pressurizing the
resulting suspension to and at a temperature above the melting
point of the polymer and a pressure above the critical pressure of
the suspension.
10. A process for producing fine fibrous structures as claimed in
claim 1 in which the polyolefin is a member selected from the group
consisting of homopolymers of ethylene, propylene, and butene-1;
copolymers of at least two of the monomers ethylene, propylene, and
butene-1; copolymers, wherein said monomers are predominant
constituents, of said monomers with other monomers co-polymerizable
therewith; and mixtures of said polymers.
11. A process for producing fine fibrous structures as claimed in
claim 1 in which the concentration of the polyolefin in the
dispersion system is from 5 to 70 percent by weight relative to the
quantity of the disperse system.
12. A process for producing fine fibrous structures as claimed in
claim 1 in which the polyolefin is a member selected from the group
consisting of polyethylenes, isotactic polypropylenes, and mixtures
thereof, and the positive solvent is a member selected from the
group consisting of aliphatic hydrocarbons, alicyclic hydrocarbons,
and aromatic hydrocarbons.
13. A process for producing fine fibrous structures as claimed in
claim 12 in which the aqueous dispersion system is prepared through
the use of a surfactant selected from the group consisting of
nonionic surfactants and anionic surfactants, said surfactants
being water-soluble and capable of forming an emulsive liquid in
the high pressure region.
Description
BACKGROUND
This invention relates generally to techniques in the production of
fine fibrous structures and more particularly to a new process for
producing fibrous structures for providing fine fibers suitable for
use in making synthetic papers.
Papers of a structure wherein fibers are in intertwined state are
known as one class of synthetic paper. A paper of this class is
made through the use of fibers of a synthetic polymer as one
constituent of a natural cellulosic paper-making material or as the
predominant paper-making material.
One advantageous feature of a synthetic paper of this class is that
its structure is substantially the same as that of conventional or
cellulosic papers. However, fibers for synthetic papers are
required to have a high degree of molecular orientation, to be
thin, and to have a highly fibrillated structure, and difficulties
are encountered in adapting synthetic polymeric fibers of the type
which have been generally used for fabrics and clothing to fulfill
these requirements. Furthermore, synthetic polymeric fibers of this
general character are deficient in hydrophilic property. For these
reasons, satisfactory synthetic papers of this class have not been
available.
On one hand, there is a known method for producing fine fibers
usable in making synthetic papers of this class which comprises
abruptly jetting or ejecting a solution of a crystalline polymer
under pressure and at a temperature above room temperature through
orifices into a low-pressure region and thereby reproducing the
polymer as a fine fibrous structure simultaneously with the
resulting evaporation of the solvent used.
By macerating or beating the fine fibrous structure thus obtained
by this spinning method, fine fibers of fibrillated structure
having ample fineness and ample strength due to molecular
orientation can be produced. When these fine fibers are used in
paper making, synthetic papers even more closely resembling
conventional paper can be produced.
Fine fibers of this character and the method for producing the
same, however, cannot be said to be entirely free of problems. More
specifically, for example, the choice of a usuable solvent is
limited since this solvent must have a low boiling point and,
moreover, must be used in a large quantity. Furthermore, fine
fibers produced in this manner lack hydrophilic property and,
consequently, cannot be easily used in paper making.
SUMMARY
It is an object of this invention to provide a relatively simple
process for producing fine fibrous structures wherein the above
described difficulties and problems are overcome. We have found
that this object can be achieved by ejecting an aqueous dispersion
or disperse system of a molten linear polymer droplets dispersed in
the aqueous phase under pressure into a low-pressure region.
In the production of fine fibers by diminution of mass of polymer,
the fine fibers can be produced by dispersing blowing agent in the
polymer mass and subjecting the blowing agent-containing polymer
mass to a lower pressure to allow the expansion of the blowing
agent thereby to split the polymer mass into fine fibers. For this,
it is the most important to employ a blowing agent having a large
expansion capacity and to disperse the blowing agent in a polymer
mass finely enough to split the polymer mass to desired fine
fibers.
Further, in order to obtain a molecularly oriented polymer, it is
desirable to finely-disperse a large amount of blowing agent which
has a large expansion capacity in the polymer mass and improved
wettability at the interface between the blowing agent and the
polymer, and to quench the blown polymer by means of latent heat of
vaporization of the blowing agent and Joul-Thomson effect by the
gas generated by the blowing agent thereby to fix the molecular
orientation.
The most important features of this invention thus reside in the
use as the blowing agent of water which has a large expansion
capacity and has a large latent heat of vaporization; the
improvement in dispersion of the water finely in the polymer mass
by the use of a water-sorption agent; and the improvement is
wettability at the surface of the water and the polymer by the use
of a surface active agent.
According to this invention, briefly summarized, there is provided
a process for producing fine fibrous structures wherein an aqueous
disperse system comprising a molten linear polymer containing a
fine water-sorption agent and a positive solvent with respect to
the polymer is ejected from a high-pressure region at a temperature
above the melting point of the polymer and below the critical
temperature of the disperse system and at a pressure above the
saturated vapor pressure of the disperse system into a low-pressure
region at a temperature and pressure conducive to evaporation of a
liquid phase within the disperse system thereby to produce a fine
fibrous structure of the polymer.
The nature, principle, utility, and further features of the
invention will be apparent from the following detailed description
beginning with a consideration of general aspects of the invention
and concluding with specific examples of practice illustrating
preferred embodiments of the invention.
DETAILED DESCRIPTION
In accordance with this invention, as mentioned hereinabove, an
aqueous disperse system is used as a "spinning solution" of the
linear polymer to be spun by ejection into a low-pressure region.
The droplets or particles of the polymer within the aqueous
disperse system contain a fine water-soluble or water-adsorptive or
water-absorptive material, that is, a water-sorption agent. Since
the droplets of molten polymer contain a hydrophilic substance of
this nature within an aqueous disperse system, these droplets
contain therewithin a substantial quantity of water.
Accordingly, by the practice of this invention, the following
desirable effects and results are afforded.
1. Blowing effect
The blowing effect of the water contained within the polymer
droplets is utilized. More specifically, when the aqueous disperse
system is ejected into the "low-pressure region," the pressure on
this water within the droplets is abruptly released, whereby this
water vaporizes instantaneously and exhibits a blowing effect. This
abrupt pressure release is accompanied by a rapid cooling effect
(Joule-Thomson effect and latent heat of vaporization), whereby the
molten polymer is cooled simultaneously with its blowing
action.
The water within the molten polymer fluid droplets may be broadly
classified into two kinds as distinguished by their states of
existence. That is, the first kind is water with a water-sorption
agent as its center which exists as a dispersed phase within a
continuous phase of the molten polymer, while the second kind is
the water corresponding to the case where this dispersed phase has
consolidated considerably and become communicative with the outer
side of the polymer droplets. The blowing effect is particularly
pronounced with the former kind of water, that is, the water which
is enveloped by the walls of the molten polymer.
In the case where a positive solvent with respect to the polymer is
used in the preparation of the aqueous disperse system of the
polymer, a further blowing effect can be expected also from the
evaporation in the "low-pressure region" of the positive solvent
which has infiltrated into the interior of the polymer fluid
droplets.
2. Molecular orientation effect
Two kinds of water exist in this polymer disperse system, namely,
water which has infiltrated into the interior of the above
mentioned polymer droplets and water which has not so infiltrated
and is present outside of the droplets.
The latter water evaporates at the instant when the disperse system
is extruded or ejected into the low-pressure region and becomes a
stream of water vapor, which advances with extremely high energy in
the ejection direction. This stream of water vapor exerts a great
stretching action on the polymer in the ejection or spinning
direction.
Since the quantity of the former water becomes considerable in
accordance with this invention, the contribution of the evaporation
of this water to the stretching action also amounts to a
considerable degree.
The abrupt evaporation of the water (and positive solvent) inside
and outside of the polymer droplets as described above also gives
rise to a rapid cooling of the interior and exterior of the
polymer, which thereupon solidifies. These blowing, stretching, and
cooling actions take place substantially simultaneously, whereby a
structure comprising fine fibers which has a highly orientated
structure and, moreover, is highly fibrillated is produced.
The degree of orientation and stiffness of these fine fibers differ
with whether or not the water enclosed within the molten polymer
droplets is existing as a dispersed phase within the continuous
phase of the molten polymer. More specifically, in the former case,
the contribution toward polymer stretching due to the evaporation
and expansion of the enclosed water is great, whereby fine fibers
of high orientation and high stiffness are produced. Accordingly,
beating is facilitated, and, moreover, the stiffness of a synthetic
paper made from these fibers is comparable to that of a natural
pulp paper.
On the other hand, in the latter case wherein the water enclosed
within the polymer droplets is not existing as a dispersed phase,
the enclosed water is communicative with the water (dispersion
medium of the aqueous disperse system) outside of the droplets. For
this reason, the evaporation and expansion action of the enclosed
water at the time of the ejection into the low-pressure region is
less than that in the former case, and the orientation of the
polymer due to the stretching action of the water outside of the
polymer droplets becomes predominant.
Consequently, the degree of orientation of the resulting fine
fibers is somewhat lower than that in the former case, but
synthetic papers made with these fibers are highly useful depending
on the use, such as, for example, uses where pliability and
softness are required and uses as disposables.
3. Reduction of quantity of solvent used
For the "spinning solution" in the practice of this invention, a
solution of the polymer in an organic solvent is not used, and the
polymer droplets within the intended aqueous disperse system of
emulsive liquid moreover, are not in the form of a solution of the
polymer but are in molten state. Accordingly, in such a mode of
utilization of the polymer, a solvent is not absolutely
necessary.
According to this invention, however, a positive solvent with
respect to the polymer used is used for the purposes of
facilitating the preparation of the aqueous disperse system and
facilitating the infiltration of water into the fine water-sorption
agent within the polymer droplets in the disperse system.
In view of these purposes of use of a solvent, the quantity used
thereof is remarkably small, being less than 100 percent,
preferably less than 50 percent and ordinarily less than 30
percent, of the weight of the polymer used.
As mentioned hereinabove, this invention contemplates the use of a
molten substance in the form of fluid droplets of the polymer
instead of a solution of the polymer. However, the coexistence,
albeit in a small quantity, of a positive solvent in the
"high-pressure region" under high-temperature and high-pressure
conditions gives rise to the possibility of the existence of the
polymer within the liquid droplets in a swollen state or the form
of a solution to some extent. Accordingly, according to this
invention the term "polymer droplets" is intended to include the
case of a solution of the polymer.
4. Extension of the range of usable solvents
By the conventional spinning process wherein a spinning solution is
ejected into a low-pressure region, it has not been feasible to use
a solvent of high boiling point because of difficulties relating to
the blowing force and the removal of residual solvent.
By the practice of this invention, however, high-boiling-point
solvents can also be used. Even if a high-boiling-point solvent
remains within the product polymer, it can removed with relative
ease by washing the product with water containing an emulsifier.
The emulsified liquid containing a small quantity of the solvent
and formed during this washing can be effectively utilized as a
starting material for the preparation of a polymer emulsive
liquid.
5. Hydrophilic property
In accordance with a preferred embodiment of this invention, an
emulsifier is used for preparing a stable polymer disperse
system.
This emulsifier and the water-sorption material used remains within
the polymer even when water evaporates in the low-pressure region.
Accordingly, the fine fibrous structure obtained in this case has
excellent hydrophilic property and has ample water-dispersibility
even without the addition of a dispersing agent. Furthermore, this
fibrous structure is not accompanied by problems such as foaming
and can be readily sent to the succeeding process steps of
macerating or beating and paper making. Furthermore, the fibers of
this fibrous structure can be used to make synthetic papers having
excellent "water wettability" which was unattainable in the prior
art.
1. Materials:Linear Polymer
For the polymer to be used in accordance with this invention, any
linear polymer capable of forming fibers can be used. For full
utilization of the molecular orientation effect, a crystalline
polymer is desirable. Furthermore, in view of the fact that this
polymer is mostly placed in the state of an aqueous disperse system
under pressurize and heated conditions, and in consideration of
hydrolysis which may occur, it may be said, if a choice is to be
made, that a polymer produced by polyaddition is preferable to a
polymer produced by polycondensation.
Examples of such linear polymers are polyolefin resins,
polychloroethylene resins, polyvinyl aromatic resins, polyamide
resins, polyester resins, polyimide resins, and polycarbonate
resins, as homopolymers and copolymer. Of these, polyolefin resins
such as homopolymers of ethylene, propylene, and butene-1;
copolymers of at least two of the monomers of ethylene, propylene
and butene-1 such as ethylene-propylene copolymers; copolymers,
wherein said monomer or monomers are predominant constituents, of
said monomers with other monomers copolymerized therewith such as
ethylenevinylacetate copolymers, ethylene-acrylate copolymers; and
mixtures of said polymers, are representative, and among these,
isotactic polypropylenes and high-density polyethylenes are most
typical. These polymers can be used singly or as mixtures
thereof.
Water-sorption agent
Another important feature of this invention is the fine
watersorption agent caused to exist within the droplets of the
molten polymer in the aqueous disperse system.
The water-sorption agents usable according to this invention may be
broadly classified into water-soluble materials a) and materials b)
which are difficult to dissolve or are insoluble in water and which
sorb, namely adsorb or absorb, water. These agents may be materials
which decompose when they contact water which has infiltrated into
the droplets of the molten polymer in the "high-pressure
region".
a. Water-soluble materials
Inorganic compunds and organic compunds which dissolve in water or
which dissolve water in the "high-pressure region" are usable.
Specific examples of usable water-soluble materials are inorganic
materials such as nitrates, acetates, sulfates, sulfites,
carbonates, phosphates, hydroxides, and halides of alkali metals,
alkaline earth metals, and ammonium and complex salts or double
salts thereof, as, for example, NaNO.sub.3, CH.sub.3 COONa,
MgSO.sub.4, Na.sub.2 CO.sub.3, NaH.sub.2 PO.sub.4, NaOH, NaCl, and
(NH.sub.4) Al (SO.sub.4).sub.2, and organic water-soluble materials
such as CMC, starch, gum arabic, agar, polyacrylamide, polyacrylic
acid or Na salt thereof, polyethylene imine, polyethylene oxide,
polyvinyl pyrrolidone, and polyvinyl alcohols. While liquid
materials such as ethylene glycol and glycerine are also effective,
it is difficult to blend these substances to a high
concentration.
Of these compounds, particularly salts having water of
crystallization as, for example, MgSO.sub.4.7H.sub.2 0, Na.sub.2
SO.sub.4.1OH.sub.2 O, and Na.sub.2 SO.sub.4.7H.sub.2 O, exhibit
pronounced effectiveness in forming fine fibers. The transformation
of the polymer into fine fibers is accomplished by the expansion of
the water enclosed within the polymer droplets and by the
stretching effect of the water outside of the droplets, as
mentioned hereinbefore. The splitting force of the polymer droplets
when a salt having water of crystallization is used is equal to the
splitting force of an expanding organic solvent in the case where a
solution of the polymer in the organic solvent is spun by ejection
into a low-pressure region.
That is, one percent by volume of the water within the polymer
droplets in the process of this invention corresponds to one
percent by volume of the solvent in the process wherein an organic
solvent solution of polymer is used. Thus, by the practice of this
invention, the same effectiveness in forming fine fibers as in the
conventional method of flash spinning a polymer solution through
the use of an organic solvent of lower boiling point than water is
attained. This is an important feature of this invention.
b. Water-insoluble material
Inorganic materials and organic materials which, although incapable
of being dissolved in water or of dissolving water in the
"high-pressure region," adsorb or absorb water.
In this case, since the quantity of the water enclosed within the
polymer droplets is small, the splitting effect decreases somewhat,
but the fibrilation in the beating process step is facilitated by
the material remaining in the fine fibers. Accordingly, the fine
fibers finally obtained are identical to five fibers obtained by
blending a water-soluble material.
Specific examples of usable water-insoluble materials are inorganic
and organic "fillers" such as calcium carbonate, waterinsoluble
solids comprising silicates such as clays (Kaoline, Pyrophyllite),
white carbon (or silica amorphous), talc Mica, Fuller earth, and
diatomaceous earth (or siliceous marl), basic magnesium carbonate,
cellulose powder and pulp, and hydrates which are difficult to
dissolve in water such as magnesium oxalate and magnesium
phosphate. For sorption of water in large quantity, porous
substances are particularly effective.
Positive solvent
In order to disperse the linear polymer in a stable manner as fluid
droplets in molten state in a water phase and, moreover, to
facilitate the infiltration of water into the fine water-sorption
agent within the polymer droplets in the aqueous disperse system, a
solvent, more specifically, a positive solvent, is preferably
used.
The term "positive solvent" is herein used to designate a solvent
in which the given molten polymer is at least partially soluble
under the temperature and pressure conditions of the "high-pressure
region". Accordingly, this solvent may or may not have a positive
characteristic of this nature in the "low-pressure region" or under
the conditions of room temperature and atmospheric pressure. In
general, however, this solvent is probably capable of causing the
given solid polymer to at least swell at least under heating.
Solvents capable of promoting the infiltration of water (and an
emulsifier) into the droplets of molten polymer are all usable. For
example, with polyolefin polymers, aliphatic hydrocarbons,
alicyclic hydrocarbons, aromatic hydrocarbons, halogenated
hydrocarbons, and the like, such as, for example, n-pentane,
n-hexane, n-heptane, cyclopentane, cyclohexane, dichloromethane,
benzene, toluene, xylenes, decalin, tetralin, napthalene, are used
singly or as mixtures.
Emulsifier
In accordance with a preferred mode of practice of this invention,
the aqueous disperse system is an aqueous emulsive liquid or
aqueous emulsion of molten polymer prepared by the use of an
emulsifier. Any emulsifier is usable provided that it is capable of
forming a stable emulsive liquid in the "high-pressure region."
Accordingly, a suitable emulsifier may be selected from those
generally sold on the market.
Specific examples of suitable emulsifiers are non-ionic, anionic,
cationic, amphoteric, and surfactants used singly or as
mixtures.
In the resulting aqueous emulsive liquid or aqueous emulsion of
polymer, the polymer may be present in the form of fine particles
or of larger or agglomerated particles.
2. Polymer aqueous disperse system
In the practice of this invention, use is made of a special polymer
aqueous disperse system. More specifically, the droplets of the
molten polymer contain a fine water-sorption agent, which makes
possible the enclosure of water therewithin.
As mentioned hereinbefore, this enclosed water exists as a
dispersed phase within the continuous phase of molten polymer or
exists in a state wherein it is communicating with the outside of
the polymer droplets because of the consolidation of this dispersed
phase. Whichever state this enclosed water assumes is determined by
the quantity of the enclosed water. On one hand, this quantity of
the enclosed water is determined by the quantity of the
watersorption agent within the polymer droplets.
More specifically, when the (water + water-sorption agent) content
within the droplets is up to the order of approximately 60 percent,
the former state is assumed, and the enclosed water exists as
independent cells. When this content exceeds approximately 60
percent and is of a value up to approximately 80 percent, the
enclosed water exists in the latter state.
The lower limit of the content of the water-sorption agent is
approximately 20 percent, preferably approximately 30 percent. The
above stated percentages are by weight. While this enclosed water
is composed principally of water, it ordinarily contains the
water-sorption agent and the emulsifier.
The aqueous dispersion of molten polymer of this character can be
prepared, in general, by any method by which the desired disperse
system can be prepared. That is, it is desirable to make a stable
disperse system and, moreover, to prepare it in the form of an
aqueous emulsive liquid by using an emulsifier and a positive
solvent relative to the polymer thereby to facilitate the
infiltration of water into the droplets of molten polymer.
Examples of suitable methods for preparing the aqueous disperse
system of the molten polymer are set forth below.
1. Preparatory forming method
1.1 Preparatory mixing
First, the polymer and the water-sorption agent are uniformly
blended beforehand by an ordinary method wherein additives such as
a pigment, a filler, a stablizer against oxidation, an antistatic
agent, and a reinforcing agent are blended with a thermoplastic
polymer. For this blending, a mixing machine such as an extruder,
kneader, rolls, a Banbury mixer, and a co-kneader is used.
While the polymer blend after mixing may be in the state of lumps,
granules, fine powder, and other forms, it is preferably in a fine
powder form of an average particle diameter of from 50 to 300
microns. If the particles are made excessively fine, however, the
dropping-out phenomenon of the mixed materials will tend to become
remarkable, whereby care must be exercised with respect to this
tendency.
Blending with the solvent is also effective particularly for
elevating the degree of mixing. Furthermore, as a special mixing
method the water-sorption agent and the fine polymer powder to be
mixed may be formed in a semi-molten state under a high pressure
into a lumpy substance.
1.2 Forming the aqueous disperse system
The polymer blend after mixing is caused to be suspended in an
emulsive liquid prepared by emulsifying a small quantity of a
positive solvent in water. The suspension thus formed is heated to
a temperature above the melting point of the polymer and subjected
to a pressure above the critical pressure of this emulsive liquid
system.
The action of the solvent and the emulsifier causes water to
infiltrate into the interior of the polymer droplets and to
dissolve the admixed water-sorption agent or be adsorbed on the
water-sorption agent to be captured within the polymer. In
addition, with this water as a nucleus, a portion of the water is
caused by the positive solvent and the emulsifier to penetrate into
the interior of the polymer droplets.
In this manner, water is a quantity corresponding to the volume or
sorbed quantity of the admixed water-sorption agent and the
quantity of infiltration due to the action of the positive solvent
and emulsifier is held within the polymer droplets.
Particularly in the case of a blend of the polymer in the state of
a fine powder, the molten polymer undergoes recombination enclosing
excess water existing on the outer peripheral surface, whereby
polymer droplets are formed. Furthermore, the capillaries produced
at the time of water infiltration are closed by variations in the
system conditions such as pressure and temperature, whereby
independent cells can be formed.
2. Direct forming method
In this method, the enclosure of water and water-sorption agent
existing at the outer periphery due to mutual refusion of polymers
is utilized.
A water-sorption agent which is difficult to dissolve in water and
a polymer powder are suspended in an emulsive liquid comprising
water, a positive solvent, and an emulsifier, and the resulting
suspension is heated and pressurized to a high temperature above
the melting point of the polymer and above the saturated vapor
pressure of the emulsive liquid.
A small quantity of the water is caused by the action of the
positive solvent and emulsifier in the emulsive liquid to
infiltrate into the interior of the polymer droplets. At a
temperature above its melting point, the polymer undergoes coupling
in a state wherein it is enclosing water and the water-sorption
agent existing at the outer peripheries of the fine polymer
particles, whereby an aqueous disperse system of molten polymer in
a state similar to that in the case (1.1) where preparatory mixing
is carried out. In the instant case, the finer and more porous the
polymer powder is, the better is the resulting droplet structure,
i.e., the formation of the enclosed water cells.
In all of the above described methods, pigments, reinforcing
agents, stabilizers, and other additives for polymers may be added
to the polymer. Furthermore, this polymer aqueous disperse system
may contain other auxiliary ingredients depending on the necessity.
For example, in addition to the above mentioned emulsifier,
water-soluble salts, water-soluble polymers, and other additives
can be added for the purpose of adjusting characteristics such as
the viscosity and the stability of the emulsive liquid and for
other purposes. The water-soluble polymers can be removed by
washing from the resulting fine fibrous structures or rendered
insoluble in water.
Furthermore, other materials such as fine fillers and blowing
agents can be added. In the case where this disperse system is an
aqueous suspension, a suspension stabilizer can be used.
The composition of this aqueous disperse system of a polymer is
preferably as follows. The polymer concentration within the
disperse system is from 5 to 70 percent, preferably from 20 to 30
percent. The quantity of the water-sorption agent relative to that
of the polymer is from 20 to 80 percent, preferably from 30 to 50
percent. The quantity of the positive solvent relative to that of
the polymer is greater than zero percent and of a value less than
100 percent, preferably less than 50 percent and ordinarily less
than 30 percent. The above stated percentages are all by weight.
When an emulsifier is used, its content in the aqueous disperse
system (emulsive liquid) of the polymer is of the order of less
than a number of percent.
3. Spinning
The "high-pressure region" in which the above described aqueous
disperse system of the molten polymer initially exists should be at
a temperature sufficient for the existence therein of the polymer
as droplets in molten state. Furthermore, since this aqueous
disperse system should exist as a disperse system, this temperature
should be below the critical temperature of the disperse system,
and, at the same time, the pressure of the region should be at a
value above the saturated vapor pressure of the water (and solvent)
at that temperature.
Since the blowing action of water is principally utilized in the
practice of this invention, the temperature and pressure conditions
of the "high-pressure region" are selected with consideration of
their relationships with the pressure and temperature conditions of
the "low-pressure region". Accordingly, in the case where the
"low-pressure region" is at atmospheric pressure, for example, the
blowing action of the water does not become sufficient at a
temperature of the "high-pressure region" of less than
130.degree.C.
In order to apply or sustain this pressure condition in the
"high-pressure region," any pressure-applying means can be used.
However, the ordinary measure is to introduce a pressurized gas,
which is preferably inert with respect to the disperse system. One
example of the conditions of the "high-pressure region" is that
wherein, in the case where an aqueous emulsive liquid of
high-density polyethylene or polypropylene is to be ejected into a
"low-pressure region" at room temperature and atmospheric pressure,
fine fibers which can be used to make paper can be produced at a
temperature of the order of from 180.degree. to 200.degree.C and at
a pressure of the order of from 50 to 60 kg/cm.sup.2.
The extrusion or ejection of the aqueous emulsive liquid of the
polymer from the "high-pressure region" to the "low-pressure
region" may be carried out through an ejection orifice device which
has a single orifice, a plurality of orifices, or orifices of slit
shape or some other shape. We have found that, while an ejection
velocity from the ejection orifice device is preferably above the
velocity of sound (330 meters/second), a velocity of approximately
one half of the velocity of sound or lower velocity may be
used.
While the "low-pressure region" is ordinarily at atmospheric
pressure and room temperature, it is also possible to maintain this
region under reduced pressure and heated conditions in order to
promote the evaporation of the liquid phase, particularly water,
within the emulsive liquid.
4. Product
The fine fibrous structure thus obtained is dried directly as it is
or is washed with an aqueous solution of an emulsifier and then
dried, whereupon the objective product is obtained.
This fine fibrous structure can be utilized as an open-mesh or
network structure, or by macerating or beating this fine fibrous
structure by a dry or wet process, it can be also utilized as a
staple fiber or as a starting material for paper making. According
to a preferred embodiment of this invention, as mentioned
hereinbefore, there are provided fine fibers of good hydrophilic
characteristic which are particularly suitable for use as a
starting material for paper making and, moreover, has excellent
compatibility with natural cellulosic pulp.
In order to indicate still more fully the nature and utility of
this invention, the following specific examples of practice
constituting preferred embodiments of the invention and results are
set forth, it being understood that these examples are presented as
illustrative only, and that they are not intended to limit the
scope of the invention.
EXAMPLE 1
Fifty parts of linear polyethylene of a melt index, MI, of 5 and a
density of 0.965 gram/cc. in powder form and 50 parts of magnesium
sulfate dried for 4 hours at a temperature of from 160 to
170.degree.C and passing through a 40-mesh sieve were blended in a
roll blender operated with a roll surface temperature of
175.degree.C. The mixture thus blended was pelletized, and then the
pellets were pulverized into a powder in a mill.
Separately, one part of a non-ionic emulsifier of a HLB 18 was
dissolved in 83 parts of water, and then one part of n-pentane was
added to the resulting solution to prepare a homogeneous emulsive
liquid. To this liquid, 15 parts of the above described powder of
the blend was added and uniformly dispersed, whereupon an aqueous
mixture was obtained.
This aqueous mixture was placed in a sealed vessel, the interior
pressure of which was increased to 40 kg/cm.sup.2 with pressurized
nitrogen. Then, as the mixture was agitated, it was heated to and
at 180.degree.C. After 50 minutes, the pressure within the vessel
rose to 53 kg/cm.sup.2 because of the heating. The interior of the
sealed vessel was communicative through a gate valve to a slit
nozzle of a width of 0.5 mm. and a length of 10 mm.
After 50 minutes, the system pressure was further increased with
pressurized nitrogen to 70 kg/cm.sup.2, and the gate valve was
abruptly opened to eject the system mixture into the atmosphere. As
a result, a mass of a fine fiber having a highly orientated
structure was obtained.
EXAMPLE 2
Fifteen parts of a linear polyethylene of MI of 5 and a density of
0.965 gram/cc. was dissolved at a temperature of from 120.degree.
to 140.degree.C in 70 parts of xylene. To the resulting solution,
15 parts of sodium chloride dried for 4 hours at a temperature of
from 160.degree. to 170.degree.C and passing through a 40-mesh
sieve was added while the solution was vigorously agitated.
After thorough agitation, the resulting mixture was poured
gradually into methyl alcohol to cause a blend of the polyethylene
and sodium chloride to precipitate. This precipitate was lightly
pulverized in a mixer to obtain a blend in powder form, which was
then washed from 2 to 3 times with methyl alcohol to remove the
xylene. The resulting mass was then dried at 60.degree.C for 24
hours for complete removal of the solvents.
15 parts of the blend thus obtained was added to an emulsive liquid
comprising 81 parts of water, 3 parts of n-pentane, and 1 part of a
non-ionic emulsifier of a HLB 14 thereby to form an aqueous
mixture, which was then process in accordance with the procedure
set forth in Example 1. As a result a three-eimensional network
structure of fibers each having a high degree of orientation was
produced.
EXAMPLE 3
Fifty parts of a linear polyethylene of a MI of 5 and a density of
0.965 gram/cc. and 50 parts of a clay dried for 4 hours at a
temperature of from 160.degree. to 170.degree.C and consisting of
particles of an average diameter of 5 microns were blended in a
roll blender and then pulverized.
15 parts of the resulting blend was added to an emulsive liquid
comprising 81 parts of water, 3 parts of n-pentane, and one part of
a non-ionic emulsifier of a HLB 14 to form an aqueous mixture,
which was processed according to the procedure specified in Example
1. As a result, a fine fibrous structure was produced.
EXAMPLE 4
Fifty parts of an isotactic polypropylene of a MI of 9 in powder
form and 50 parts of magnesium sulfate dried for 4 hours at a
temperature of from 160.degree. to 170.degree.C and passing through
a 40-mesh sieve were blended by means of a roll blender operated
with a roll surface temperature of 210.degree.C. The mixture thus
blended was pelletized and then pulverized into a powder in a
mill.
Separately, a homogeneous emulsive liquid was prepared by
dissolving one part of a non-ionic emulsifier of a HLB 18 in 83
parts of water and then adding one part of heptane to the resulting
solution.
To this emulsive liquid, 15 parts of the above described blended
powder was added to form an aqueous mixture, which was then
processed for 50 minutes in an autoclave at 180.degree.C and 50
kg/cm.sup.2 pressure and then ejected into the atmosphere. As a
result, a fine fibrous structure having stiffness was produced.
EXAMPLE 5
Seventy parts of Nylon-6 and 30 parts of sodium sulfite dried for 4
hours at a temperature of from 160.degree. to 170.degree.C were
granulated at a maximum temperature of 270.degree.C by means of a
45 mm .phi. extruder, and then the resulting granules were
pulverized.
Separately, a homogeneous emulsive liquid was prepared by
dissolving one part of an anionic surfactant of a HLB 18 in 83.5
parts of water and then adding 0.5 part of cresol to the resulting
solution.
In this emulsive liquid, 15 parts of the above described powder was
uniformly dispersed to form an aqueous mixture. This mixture was
placed in a sealed vessel, the interior pressure of which was
increased with pressurized nitrogen to 40 kg/cm.sup.2, and the
aqueous mixture was heated to and at 240.degree.C as it was
agitated.
After 60 minutes, the pressure within the vessel had increased to
65 kg/cm.sup.2, at which point a discharge valve of the vessel was
abruptly opened to eject the aqueous emulsive liquid of the polymer
into the atmosphere. As a result, fine fibers having a highly
orientated and fibrillated structure of substantial stiffness were
produced.
EXAMPLE 6
Fifteen parts of the blended mixture of a polyethylene and
magnesium sulfate prepared according to Example 1 was added to a
solution prepared by dissolving one part of an anionic
surface-active emulsifier of a HLB 12 in 84 parts of water thereby
to form an aqueous mixture in which the blended mixture was
uniformly dispersed.
This aqueous mixture was placed in a sealed vessel, and the
pressure within the vessel was increased with pressurized nitrogen
to 45 kg/cm.sup.2. The aqueous mixture was then heated to and at
180.degree.C as it was agitated. After 120 minutes, the vessel
interior pressure had risen to 55 kg/cm.sup.2, at which point a
discharge valve of the vessel was opened to discharge the polymer
aqueous emulsive liquid into the atmosphere. As a result, a foamed
structure having as a major part, uniform cells foamed from 5 to 10
times and, as one part, fine fibers having a fibrillated
structure.
EXAMPLE 7
A homogeneous aqueous suspension was prepared by dissolving 2 parts
of an anionic surface-active emulsifier of a HLB 18 in 35 parts
water and adding to the resulting solution 25 parts of calcium
carbonate and 40 parts of an isotactic polypropylene of a MI of 5
in pelletized form.
This suspension was placed in a sealed vessel and, after the
pressure within the vessel was raised to 45 kg/cm.sup.2 with
pressurized nitrogen, was heated to and at 180.degree.C under
agitation. After 120 minutes, the pressure within the vessel had
increase to 55 kg/cm.sup.2, at which point, a discharge valve of
the vessel was opened to discharge the suspension into the
atmosphere. As a result, fine fibers haveing a fibrillated
structure and stiffness were produced.
* * * * *