JPS6242046B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to poly(p-phenylene sulfide)
The purpose is to efficiently produce microporous hollow fibers with excellent heat resistance and chemical resistance by a combination of melt spinning, heat treatment stretching, etc. Our goal is to provide the following. BACKGROUND ART Microporous hollow fibers have traditionally been used as polymeric materials, and microporous hollow fibers made from polymeric materials have been used in many fields. For example, it is used as an ultrafiltration membrane for separation, purification, and recovery of water, waste fluids, and solutions, and for medical devices such as artificial kidneys. All of these methods use the microporous hollow fibers mentioned above to function as a diaphragm separation membrane, but the membrane materials that have been actually commercially available include cellulose, cellulose acetate, aromatic polyamide, polyacrylonitrile, and polysulfone. Ta. However, all of these materials have shortcomings in one of their properties regarding heat resistance and chemical resistance, and there has been a strong demand from users for membrane materials with excellent heat resistance and chemical resistance. That is, in terms of heat resistance, it is desirable to have heat resistance of 80°C for regular use and 98 to 100°C for short periods of time, but in reality, it is impossible for conventional membrane materials on the market to resist 80°C for regular use. On the other hand, regarding chemical resistance, we have strong acid resistance, strong alkali resistance, chlorine resistance (withstands concentrations of 300 ppm or more), oxidant resistance (withstands organic substance removal cleaning agents), and organic solvent resistance. The disadvantage of conventional commercially available membrane materials is that they are weak in some characteristics. On the other hand, conventional methods for producing microporous hollow fibers involve wet spinning a solution of a material and its good solvent from a hollow fiber spinneret, then coagulating it in a coagulation bath containing a poor solvent, and washing and desorbing it. Solvent and make hollow fibers
The molding method was a so-called semi-dry wet method or wet spinning. The disadvantages of this method include that the production is complicated due to the use of solvents, and that the production speed is less than 50 m/min, resulting in extremely low productivity. The present inventors have particularly focused on heat resistance,
As a result of searching for materials with excellent chemical resistance and mechanical strength, and investigating methods for manufacturing microporous hollow fibers from these materials, we found that poly(p-phenylene sulfide) (hereinafter abbreviated as PPS) was the main material. It was discovered that the raw resin used as a component is suitable as a material. PPS is a crystalline polymer and has thermoplasticity, so it can be melt-spun. By effectively utilizing this feature, the hollow fiber obtained by melt spinning is heat-treated to generate crystals, then the crystals are smoothly stretched to generate microporous, and finally the microporous structure is heat-set. The method is to do so. This method can be said to be unique because the mechanism for forming micropores is completely different from conventional semi-dry or wet methods. Thus, the present inventors' proposal is to form hollow fibers by melt-spinning a raw material resin containing 65% by weight or more of poly(p-phenylene sulfide) through a hollow fiber spinneret at a draft rate of 25 or more. , the hollow fiber is stretched at a stretching ratio DR ₁ =1.0 to 3.3 and a temperature T ₁ =20 to
Stretch at (Tg+30)℃ (Tg is the glass transition temperature of the polymer in degrees Celsius), and then the tension is DR ₂ = 0.5~
1.5, after heat treatment at temperature T ₂ = (Tg + 20) to (Tg + 180) °C, the hollow fiber was stretched at a stretching ratio DR ₃ = 1.05.
~2.8, stretched at temperature T ₃ = 10 ~ (Tg + 10) °C,
Subsequently, the stretching ratio DR ₄ = 1.0 to 2.5, the temperature T ₄ = (Tg
+10) ~ (Tg + 180) °C, and finally, tension degree DR ₅ = 0.7 ~ 1.3, temperature T ₅ = (Tg + 110) ~
In addition to heat setting at (Tg + 180) °C, the total draw ratio (hollow fiber length after heat setting/hollow fiber length after spinning) during the entire process is DR _t , the draft rate during spinning is Df , and the yarn breakage draft Taking the rate as Df _nax , 25
0.8DR _t 7.0 if Df<0.4Df _nax , and
0.4Df _nax Df0.97Df _nax 0.7DR _t 4.0
By doing so, the present invention provides a method for producing microporous hollow fibers, which is characterized by forming micropores in the hollow fibers. The fiber is a microporous hollow fiber obtained by melt-extruding and stretch-molding a crystalline polymer material of which 65% by weight or more is poly(p-phenylene sulfide), and the hollowness ratio according to the fiber cross-sectional area ratio is 8 to 8. 85%, and the hollow fiber has many micropores that communicate from the outer surface to the inner surface, and the average pore diameter of the micropores is 0.003 μm to 3.
.mu.m, and the microporous hollow fiber is characterized in that the microporous hollow structure is heat-set. Here, the average pore diameter of the micropores is 0.003 μm.
Hollow fibers smaller or larger than 3 μm can also be produced, but hollow fibers with pore diameters less than 0.003 μm are impractical due to extremely low gas and liquid permeation rates, and those with pore diameters larger than 3 μm have poor pore distribution. Due to its low density, it becomes a membrane with poor performance, and cannot be said to be advantageous compared to non-woven fabrics and others. The poly(p-phenylene sulfide) of the present invention refers to a polymer containing 90 mol% or more of p-phenylene sulfide as the main structural unit of the polymer. Other structural units that can be contained in less than 10 mol% include metaphenylene sulfide, 3
Functional phenyl sulfide

[Formula], diphenyl ether sulfide, diphenyl ketone sulfide, diphenyl sulfone sulfide, diphenyl sulfide, substituted phenyl sulfide

Examples include [Formula] (R: any one of alkyl, phenyl, alkoxy, nitro, and halogen group). In addition, the principle of microporous formation in the present invention is to crystallize melt-spun hollow fibers and forcibly stretch the crystallized product to form micropores. By crystallizing hollow fibers made from a blend of raw materials, PPS has a fine structure.
When a multi-phase structure consisting of a microcrystalline region and another polymer region is formed and this structure is stretched, the desired microporous structure may be formed. The amount of other polymers that can be blended into PPS is 35%
less than If other polymers account for 35% or more, defects in microporous formation, heat resistance, chemical resistance, mechanical properties, etc. will occur, and the characteristics of PPS will disappear. Other polymers that can be blended include:
Polyethylene terephthalate, polybutylene terephthalate, nylon-6, nylon-66, polycarbonate, polyoxymethylene, polyphenylene oxide, poly-4-methylpentene-1,
Examples include crystalline polymers such as polypropylene, polytetrafluoroethylene, and polyetheretherketone, and amorphous polymers such as polysulfone and polyethersulfone. Further, such raw material resin may contain appropriate amounts of additives such as antioxidants, antistatic agents, antibacterial agents, lubricants, and surfactants, as required. The spinneret used when melt-spinning the PPS-based polymer specified above into hollow fibers is as follows:
Either a conventionally known annular nozzle or a slit-shaped nozzle may be used, but a slit-shaped nozzle is more suitable for spinning a large number of hollow fibers from a multi-hole nozzle. The draft rate Df during melt spinning must be 25 or more. Here, the draft rate is the polymer discharge speed at the nozzle.
The relational expression between V ₀ and hollow fiber take-up speed V ₁ is Df = V ₁ /
V is ₀ . When Df<25, it is difficult to develop a microporous structure in the subsequent process. That is, hollow fibers that have undergone heat treatment for crystallization are brittle and have no elongation, making crystal stretching difficult. Df is 25 or more, preferably 50 or more. The spinning temperature (polymer temperature at the nozzle part) is desirably as low as possible within the range of spinnability, and is suitably around 300°C. In the case of raw materials containing 100% PPS, a temperature range of 285 to 310°C is suitable. The reason for this is that, as will be explained later, it is necessary to perform heat treatment to develop lamellae in the post-process, and in the present invention, it is desirable to have a higher molecular orientation state. This is because it is desirable that the amorphous orientation of the undrawn hollow fibers is also higher. As mentioned above, the production method of the present invention involves spinning at a slightly low temperature, but the melt viscosity of the polymer at the time of discharge from the spinneret is 500 to 10,000 poise, preferably
It is 3000-5000 poise. In order to provide such melt viscosity and spinnability, the polymer must have a molecular weight above a certain level. In the case of PPS100% raw material, the molecular weight is 205 in α-chloronaphthalene solution.
Intrinsic viscosity measured at °C is 0.25-0.80, preferably
It has a high molecular weight of 0.30 to 0.50. PPS
The intrinsic viscosity of the other polymer blended with is 0.30
The above is desirable. The outer diameter of the spun hollow fibers is preferably 30 μm to 5 mm. The outer diameter and hollowness ratio can be set depending on the purpose of use. However, hollow fibers with an outer diameter of less than 30μm,
It is actually difficult to form hollow fibers with a diameter exceeding mm, even if the hollow fiber die, spinning temperature, etc. are adjusted. The undrawn hollow fibers formed as described above are then
Stretching ratio DR ₁ = 1.0 to 3.3, temperature T ₁ = 20 to (Tg+
Stretch at 30)°C. The purpose of this step is to improve the orientation of the molecular chains of the undrawn fibers, which is necessary for oriented crystallization to sufficiently develop lamellae, by the heat treatment in the next step. In the above melt spinning, when the draft rate is gradually increased, a certain draft rate Df _nax
(For example, 450 times as much as in Comparative Example 2 described later), yarn breakage occurs. High draft spinning i.e. 0.4Df _nax Df
In the case of 0.97Df _nax , the stretching step (amorphous stretching) at this stage may be omitted (DR ₁ =1.0 means this omission). However, in the case of 25Df<0.4Df _nax , the stretching ratio is 1.0<DR ₁ 3.3, and the temperature T ₁ = 20
It is necessary to stretch at ~(Tg+30)°C. Here, the stretching ratio refers to the ratio of the length after stretching to the original length before stretching. When DR ₁ >3.3, the degree of orientation of molecular chains due to amorphous stretching increases too much, making it difficult to generate micropores. The stretching temperature T ₁ is 20T ₁ (Tg + 30) ℃, preferably (Tg
−20) T ₁ (Tg+10)℃. When T ₁ <20°C, the undrawn hollow fibers become white and voids are generated extensively, and the development of lamellae due to heat treatment in the next step is inhibited. On the other hand, when T ₁ >(Tg+30)° C., fluid stretching tends to occur, and the desired degree of orientation of amorphous molecular chains does not increase. Stretching may be carried out between a pair of rotating rolls by using the supply roll as a hot roll and making the circumferential speed of the drive roll faster than the circumferential speed of the supply roll. The peripheral speed of the supply roll can be set to a high speed of 50 m/min or more, usually around 150 m/min, so the productivity of the microporous hollow fiber of the present invention is extremely high. This point is one of the features of the present invention. Next, in order to develop lamellae by oriented crystallization, the tension DR ₂ = 0.5 to 1.5 and the temperature T ₂ = (Tg
+20) to (Tg+180)°C. Here, the degree of tension is the magnification of the length while being held in the heat treatment apparatus during heat treatment with respect to the original length before heat treatment. Therefore, DR ₂ =0.9 means applying a 10% contraction, and DR ₂ =1.1 means applying a 10% elongation. Tension is preferably 0.9DR ₂ 1.1
It is. When DR ₂ <0.5, the orientation of the developed lamellae becomes random and spherulites occur, making it impossible to form micropores in the crystal stretching in the next step. Furthermore, when DR ₂ >1.5, lamellae are difficult to develop. The heat treatment temperature T ₂ is finally (Tg + 110)
Preferably, the temperature is T ₂ (Tg+160)°C. As a heat treatment method, the temperature is first introduced at a temperature around (Tg + 20) °C, the temperature is gradually raised, and the final treatment is carried out at (Tg + 110) ~ (Tg + 160) °C, or (Tg + 20) ~ Even if treated at a constant temperature within the range of (Tg + 180) °C, or (Tg + 20)
Within the range of ~(Tg+180)℃, divided into several stages,
The temperature may be gradually increased. When T ₂ <(Tg+20)°C, there is virtually no lamella development. On the other hand, T ₂ >
When the temperature is (Tg+180)°C, the drawbacks are that the lamellae become random and the crystallization rate becomes slow. The heat treatment time is 2 to 60 minutes, preferably 5 to 30 minutes. The heat treatment is carried out by setting the degree of tension between a pair of rolls by adjusting the circumferential speeds of the supply roll and take-up roll, and inserting the roll into a hot bath such as hot air or far infrared rays between the pair of rolls. It is preferable to treat it as follows. The hollow fibers that have developed relatively oriented lamellae through the above heat treatment are then drawn at a draw ratio of DR ₃ = 1.05 ~
2.8. Stretch at a temperature T ₃ = 10 (Tg + 10)°C with a slight cold stretching. This stretching is crystal stretching, and micropores begin to be generated by this process. The pore size of the micropores is approximately determined by the combination of the previous heat treatment conditions and the stretching conditions of this step. The stretching ratio refers to the ratio of the length after stretching to the original length before stretching. Since the basic idea of the present invention is crystal stretching that deforms the lamellae, the stretching temperature is preferably 15T ₃ (Tg-30)° C. for stretching with a slight cold stretching effect.
This is a characteristic feature that is different from ordinary fiber or film stretching. When DR ₃ = 1.05 to 1.5, the average pore diameter of the generated micropores is 0.003 to 0.06μ.
m, and when DR ₃ =1.5 to 2.0, the average pore size is 0.06 to 0.6 μm, and when DR ₃ =2.0 to 2.8, the average pore size is 0.6 to 3 μm. Of course, delicate design and adjustment of the pore diameter requires delicate adjustment of the conditions of the entire process. When DR ₃ <1.05, it is virtually impossible to form micropores. When DR ₃ >2.8, the structure is destroyed by macroscopic voids in the hollow fibers, making it impossible to form micropores. When T ₃ <10°C, crystal stretching becomes difficult; on the other hand, when T ₃ > (Tg + 10)
When the temperature is ℃, it is difficult to form micropores. Subsequently, the hollow fibers with microporous formed by the above stretching were stretched at a stretching ratio DR ₄ =1.0 to 2.5 and a temperature T ₄ =
Stretching is carried out at (Tg+10) to (Tg+180)°C with a slight hot stretching effect. When the average pore diameter of the micropores formed by stretching at the stretching ratio DR ₃ is small, that is, from 0.003 to
When the pore diameter is 0.06 μm, there is almost no problem in forming micropores even if the stretching in the subsequent main step is omitted (that is, DR ₄ = 1.0), but when the pore diameter exceeds 0.06 μm, the hot stretching in the main step is not necessary. By applying this, micropores can be formed more smoothly. However, the stretching ratio in this process is not too large, and DR ₄ =
1.0 to 2.5, preferably 1.1DR ₄ 1.5. _DR4
>2.5, the micropores that were painstakingly formed during the previous stretching at a stretching ratio of DR ₃ are deformed and disappear. The preferred stretching temperature is (Tg+20)T ₄ (Tg
+80)℃. When T ₄ < (Tg + 10) °C, there is little effect on the smooth formation of micropores, and on the other hand,
When T ₄ >(Tg+180)°C, the micropores deform and disappear. In this way, the formed micropores are finally
DR ₅ = 0.7 ~ 1.3, temperature T ₅ = (Tg + 110) ~ (Tg +
Heat treatment is performed at 180)℃ for heat fixation. Similar to the heat treatment in the previous step, the tension is the magnification of the grip length of the heat treatment device during heat treatment with respect to the original length before heat treatment. Preferably, the tension level is DR ₅ .
0.9DR ₅ 1.1, processing temperature T ₅ is (Tg + 130) T ₅
(Tg+170)°C, time is 5 seconds to 5 minutes. If the heat setting treatment of this step is not performed, the formed microporous structure will change over time, resulting in problems such as the pore diameter gradually becoming smaller, the pore shape changing, and heat-resistant dimensional stability being poor. For example, when heat-setting is not performed, the heat shrinkage rate is 25-35% when left in an air bath at 150℃ for 30 minutes, but the heat-shrinkage rate after heat-setting treatment is as high as 2-4%. The width decreases, and the pore shape and diameter remain almost the same as before. Therefore, it is clear that it has excellent heat resistance and heat-resistant dimensional stability when compared with microporous hollow fibers produced by semi-dry or wet spinning using conventional membrane materials. In addition, in the production method of the present invention, the total stretching ratio (hollow fiber length after heat setting/hollow fiber length after spinning) through all the steps such as the above-mentioned stretching and heat treatment, etc.
As DR _t , 25 which corresponds to relatively low draft spinning
When Df<0.4Df _nax , DR _t satisfies 0.8DR _t 7.0, preferably 1.2DR _t 3.5, or 0.4Df _nax Df0.97Df _nax which corresponds to relatively high draft spinning
If DR _t is 0.7DR _t 4.0, preferably 0.9
Must satisfy DR _t 2.0. The microporous hollow fiber produced by the above method is
Within the membrane layer from the outer surface to the inner surface, there are almost no micropores that are independent from the surroundings, and most of them are communicating pores that communicate from the outer surface to the inner surface.
This is confirmed by observing an electron micrograph of a cross section of the fiber. When observing the cross section of the microporous hollow fiber of the present invention,
The pore diameter of the micropores and the distribution density of the micropores are almost uniform from the outer surface to the inner surface with almost no density. Therefore, conventional semi-dry or wet-spun hollow fibers consist of a so-called skin layer and a core layer.
This is in contrast to the heterogeneous structure with density. The number of micropores in the hollow fiber of the present invention varies depending on the pore diameter and porosity, but the number of micropores on the outer surface of the fiber is 10 ⁷ to 10 ¹¹ /
It can be determined that the size is on the order of cm by statistical observation of electron micrographs. Furthermore, by combining and selecting the manufacturing conditions of the present invention, the average pore diameter of the hollow fibers obtained can be
It can range from 0.003 to 3 μm. The average pore size is
It can be designed as appropriate depending on the use and purpose. The average pore diameter is determined from a scanning electron micrograph of the outer surface of the hollow fiber or a replica photograph taken using a transmission electron microscope.
100 holes were measured and averaged. Because the micropores of the hollow fibers are connected from the outer surface to the inner surface, the density of non-porous PPS hollow fibers is approximately 1.335 to 1.360 g/cm ³ (at 20°C).
The apparent density of the hollow fibers of the present invention is quite low at 0.13 to 1.22 g/cm ³ . The apparent density in this case is determined by sampling a certain amount of microporous hollow fibers, weighing them, immersing the sample in mercury at 20°C under atmospheric pressure, measuring the volume of the sample, and measuring the hollowness ratio. The volume of the membrane including the micropores can be obtained by The porosity calculated from the apparent density and true density (=100 x apparent density/true density) is 15
~85%. The outer diameter of the hollow fibers of the present invention can range from 35 μm to 3 mm. The outer diameter and inner diameter were averaged by measuring the outer diameter and inner diameter of 20 hollow fibers from cross-sectional photographs taken with an optical microscope or scanning electron microscope. When a slit-type nozzle is used as a nozzle for hollow fibers, the cross section of the obtained hollow fibers is not a perfect circle, but is almost circular, and the outer diameter and inner diameter can be easily measured. The hollow fiber of the present invention can have a hollow ratio in the range of 8 to 85% by selecting and combining manufacturing conditions. The hollowness ratio is determined from the average outer diameter _p and the average inner diameter _i statistically measured using a microscope, and the hollowness ratio = ( _i /
_p ) Calculated as ² × 100 (%). When using diaphragm separation to apply a pressure of about 50 to 100 Kg/ ^cm2 , the hollow ratio should be 8 to 40%, and when applying a low pressure such as 1 to 5 Kg/ ^cm2 , the hollow ratio should be set to 8 to 40%. can be increased to 70-85%. The film thickness between the outer diameter and inner diameter of the hollow fiber is a value determined from the outer diameter and hollow ratio settings determined depending on the application. When using hollow fibers for diaphragm separation and applying pressure, the pressure P at which the hollow fibers deform and break
are the outer diameter _p of the hollow fiber, the Young's modulus E, the film thickness t,
It is generally believed that the following relationship holds true with Poisson's ratio v. P=2E _t ³ /(1-v ² ) D _p ³ In the case of PPS, v≒0.3, E≒300Kg/mm ² ,
The above formula is used for application design. When the outer diameter of the hollow fiber is 35 μm, the film thickness must be at least 5 μm (50% hollow ratio) in practice, regardless of the applied pressure. On the other hand, in the case of a thicker outer diameter of 3mm, the film thickness is 150μ
m (hollowness ratio 80%) is practically necessary. The microporous hollow fiber of the present invention has particularly excellent heat resistance and chemical resistance. In air, e.g. at 200℃6
The tensile strength retention rate after being left for several months is over 50%, demonstrating outstanding heat resistance. Conventional hollow fibers produced by semi-dry or wet spinning of commercially available materials cannot be heated above 80°C in regular use, but this has become possible with the present invention. In addition, almost all organic chemicals, ammonia water, alkaline aqueous solutions such as caustic soda aqueous solution, hydrochloric acid, sulfuric acid with a concentration of 50% or less, nitric acid with a concentration of 30% or less,
It is completely unaffected by inorganic chemicals such as hydrofluoric acid at room temperature. The microporous hollow fibers of the present invention can be incorporated into a module in large numbers and used for ultrafiltration and precision diaphragm separation. In particular, it has excellent heat resistance and chemical resistance, so it can be used for electrodeposition coating of automobiles, home appliances, etc.
Industrial wastewater treatment, such as recovery of valuables and water reuse from chemical products, pulp, and dye wastewater, plating, pickling, and surface treatment, recovery of metals and inorganic salts from wastewater, and water reuse, as well as pharmaceutical and fermentation Proteins, enzymes, in industry
Rationalization of manufacturing processes such as separation and purification of sugars, production of ultrapure water in the electronics industry, concentration, brine removal, and clarification in the food industry, as well as solvent recovery in paint, painting, and dye factories, and production of ultrapure water in the electronics industry. Chemistry/
It can demonstrate its characteristics in organic solvent processing in the chemical industry. Furthermore, using the microporous hollow fibers of the present invention as a support for a separation membrane, the hollow fibers of the present invention are immersed in a solution of a relatively heat-resistant polymer such as polysulfone or aromatic polyamide, taken out, and dried. If a composite membrane is prepared in which a dense skin layer of these polymers with a thickness of 0.1 to 1.5 μm is formed on the surface of the hollow fiber of the present invention by removing the solvent, it can also be used for reverse osmosis separation. In the future, improving the permeation rate and rejection rate using such composite membranes will be a challenge for the industry, but there is a need for inexpensive support membranes that have excellent heat and chemical resistance and are highly productive. The microporous hollow fiber of the present invention can meet such demands. Furthermore, the polymer used in the present invention has PPS as its main component, and PPS has unpaired electrons in the sulfur in its main chain. Using this, it can be chemically modified or used as a complex. For example, enzymes are immobilized on microporous hollow fibers and used as enzyme-immobilized membranes in bioreactors.
It can be made into a highly functional diaphragm. Also,
Electron acceptors such as AsF ₅ , SbF ₅ , I ₂ , H ₂ SO ₄ , SO ₃ , Li, K, sodium naphthalene, N
When an electron donor such as (C ₄ H ₉ )・ClO ₄ is doped into the microporous hollow fiber of the present invention, there is an effect of dramatically increasing the membrane area due to the microporous structure, and the presence of benzene rings and sulfur in the main chain. Therefore, the electrical conductivity is
Utilizing the improvement to 10 ^-8 mho/cm (25°C) or higher, selective permeation is used to recover precious metals and heavy metals, to separate specific substances from electrodialysis membranes, electrolyte aqueous solutions, or solutions consisting of electrolytes and non-electrolytes. membrane, polarity,
It can be used to separate a specific gas from a non-polar mixed gas system, or to use changes in electrical resistance or electromotive force; for example, it can be used in humidity sensors, gas sensors, etc. In addition, since it is a hollow fiber with continuous microporous holes, it can be used as clothing by adsorbing sweat from the outer surface of the fiber, transferring it to the inside of the hollow fiber, and evaporating sweat from the inside of the hollow fiber, so it can be cut into short fibers and knitted. The knitted and woven fabrics can also be used as sweat-absorbing clothing and medical bandages. In particular, since it has excellent heat resistance, it is suitable for firefighting uniforms and work clothes for hot work sites. Furthermore, since it is a hollow fiber, it has heat insulating properties and has good heat resistance, so it can be used as a heat insulating material. Furthermore, since it is a microporous hollow fiber, it has a large ability to absorb and retain oil, and can be used as an oil fence in the event of an oil spill accident at sea or on water. As detailed above, the microporous hollow fiber of the present invention has particularly excellent heat resistance and chemical resistance, and in addition to having unpaired electrons in the sulfur atom, it can be manufactured by melt spinning, heat treatment, and drawing. Because it uses a highly flexible manufacturing method, it is also inexpensive, and in addition to conventional fields of use, it opens up new fields of use that have never existed before. Of course, the uses of the microporous hollow fiber of the present invention are not limited to the above examples. Examples of the present invention are shown below, but the present invention is not limited thereto. Examples 1 to 16 and Comparative Examples 1 to 16 Using a Koka type flow tester, the base was 1 mmφ
Melt viscosity measured at 10 mm ^L , temperature 305 °C, shear rate 200 sec ^-1 was 7500 poise, measured by differential calorimeter (DSC) (sample amount 15 mg, heating rate 10 °C/
Poly(p-
The raw material was powder of phenylene sulfide (PPS). This PPS was applied at 60℃ for 1hr, followed by 150℃ for 3hrs.
After drying with hot air, using a melt extrusion spinning machine with a screw diameter of 30 mmφ, the fibers were passed through a hollow fiber nozzle (4-piece slit type nozzle, nozzle outer diameter 5 mmφ, number of filaments: 12), and a discharge rate of 70 g/min was achieved at a nozzle temperature of 310°C. Hollow fibers were spun by varying the draft rate Df by changing the take-up speed while keeping it fixed. Here, the draft rate Df is the hollow fiber spinning take-off speed Vm (cm/min)
and the polymer discharge linear velocity Vo (cm/min) Df
=Vm/Vo. The discharge linear velocity Vo was determined by measuring the following quantities. Vo=Q/Sfρ, where Q: Polymer discharge rate (g/min) S: Cross-sectional area of slit-type die (cm ² ) f: Number of filaments ρ: Molten polymer density (g/cm ³ ) Obtained hollow fiber The stretching ratio between a set of rolls
Stretching was carried out by varying the DR ₁ and supply roll temperature (T ₁ °C). DR ₁ refers to the ratio of the length after stretching to the original length before stretching (stretching). Next, an electric heater bath (temperature T ₂ °C) was placed between a set of rolls, and heat treatment was performed by varying the tension DR ₂ between the rolls and varying the temperature T ₂ in the heater bath. Tension DR ₂ refers to the magnification of the length after heat treatment using rolls relative to the original length before heat treatment. Next, a stretching ratio of DR ₃ between a set of rolls,
Stretching was carried out using various supply rolls (temperature T ₃ ° C.) (stretching). Subsequently, the stretching ratio is increased between a set of rolls.
Stretching was carried out at various DR ₄ and supply roll temperatures (T ₄ °C) (stretching). However, when heating at a temperature exceeding 200°C was desired, an electric heater bath was placed between a set of rolls and the temperature of the heater bath was set at T ₄ °C for stretching. Finally, an electric heater bath (temperature T ₅ ° C.) was placed between a set of rolls, and heat fixation was carried out by varying the tension DR ₅ between the rolls and the temperature T ₅ in the heater bath. The fiber outer diameter (ODμm) and inner diameter (IDμm) of the obtained hollow fiber were statistically determined from the optical micrograph of the cross section of the hollow fiber detailed above, and the hollowness ratio was (ID/OD) ² × 100 ( %). The average pore diameter of the micropores was statistically determined from scanning electron micrographs as detailed above. However, the average pore size
In the case of 0.01 μm or less, it was statistically determined from transmission electron micrographs (carbon replica method). Molding conditions, outer diameter of microporous hollow fiber, hollow ratio,
The average pore diameter is shown in Table 1. In Comparative Example 1, the draft rate was too low to be collected. When the draft rate is relatively low as in Examples 1 and 2, stretching () is necessary to achieve amorphous orientation, but when the draft rate is relatively low as in Examples 3 to 16 and Comparative Examples 3 to 16, If it is relatively high, omit stretching () (DR ₁ = 1.0)
can. Comparative Example 2 is a case where the draft rate was high and yarn breakage occurred. As in Comparative Example 3, if the relaxation during heat treatment is too large, spherulites are generated during heat treatment, making subsequent stretching () impossible. If the temperature during heat treatment is too low, no matter how the subsequent conditions are manipulated, micropores are not generated (Comparative Example 4), but the _T2 temperature changes the micropore diameter significantly (Examples 6 to 8). If the heat treatment temperature _T2 is too high, the next stretching () becomes impossible (Comparative Example 5). If the degree of tension during heat treatment is too high, micropores are not generated (Comparative Example 6). Even if the low-temperature stretching () is omitted and only the high-temperature stretching () is performed, no microporosity is generated (Comparative Example 7). The stretching ratio DR ₃ of stretching () greatly influences the pore diameter of the micropores (Examples 9 to 12). However, if DR ₃ is too large, yarn breakage occurs and stretching becomes impossible (Comparative Example 8). If the stretching temperature _T3 is too low or too high, stretching becomes impossible or microporous is not generated (Comparative Examples 9 and 10). As in Example 14, microporous hollow fibers can be obtained even if high-temperature stretching () is omitted (DR ₄ = _1.0 );
>1.0), essential when drilling large holes.
However, the stretching ratio DR ₄ of stretching () cannot be set to a large value (Comparative Example 11). If the temperature T ₄ of stretching () is too high, microporous is not generated (Comparative Example 12). During heat fixation, if the relaxation is too large (Comparative Example 13) or the tension is too large (Comparative Example 14),
No micropores are generated. If the heat setting temperature _T5 is too low, the thermal dimensional stability is poor (Comparative Example 15). On the other hand, if T ₅ is too high, microporous will not be generated. Examples 1 to 16 are all microporous hollow fibers molded by the method of the present invention. these at 100℃
The tensile strength retention rate (immersion Strength after dipping/strength before dipping x 100%) was measured. The retention rate in all cases is 50-75%. It had extremely excellent mechanical properties, heat resistance, and chemical resistance.

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Claims (1)

[Claims] 1 A raw material resin consisting of poly(p-phenylene sulfide) of 65% or more by weight is melt-spun through a hollow fiber spinneret at a draft rate of 25 or more to form hollow fibers, and the hollow fibers are drawn at a draw ratio of DR _1. =1.0~
3.3, stretching at temperature T ₁ = 20 to (Tg + 30) °C (Tg is the glass transition temperature of the polymer °C), then stretching at tension DR ₂ = 0.5 to 1.5, temperature T ₂ = (Tg + 20) to (Tg
After heat treatment at +180)°C, the hollow fibers were subjected to stretching ratio DR ₃ = 1.05 to 2.8 and temperature T ₃ = 10 to (Tg + 10).
Stretched at ℃ and then stretched at a stretching ratio DR ₄ = 1.0 ~
2.5, stretching at temperature T ₄ = (Tg + 10) ~ (Tg + 180) °C, and finally, tension degree DR ₅ = 0.7 ~ 1.3, temperature T ₅
= (Tg + 110) ~ (Tg + 180) While heat setting at ℃, the total stretching ratio (hollow fiber length after heat setting / hollow fiber length after spinning) throughout the entire process.
DR _t is 0.8 when 25Df<0.4Df _nax , where the draft rate during spinning is Df and the yarn breakage draft rate is Df _nax .
DR _t 7.0, and 0.7DR _t 4.0 in the case of 0.4Df _nax Df0.97Df _nax , thereby forming microporous hollow fibers in the hollow fiber.