JP2010144055A - Device for producing polymer bead, and method of producing polymer bead - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a device and method for producing polymer beads capable of controlling the particle diameter of the polymer beads by using a simple means. <P>SOLUTION: This device for producing the polymer beads is provided with a polymer stock solution-dripping device 10 equipped with a nozzle 12 for dripping a polymer solution obtained by dissolving high polymer resin in a compatible solvent, and a slit 14 of a gas-ejection means for ejecting gas along the outer circumference of the nozzle. Thereby, the polymer beads having a smaller particle diameter are obtained even by using a same nozzle dimension, since the gas is blown to the droplets of the polymer solution formed at the tip end of the nozzle 12 and the droplets of the polymer solution fall down before the falling down of the polymer liquid by the weight of itself. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polymer bead manufacturing apparatus and a polymer bead manufacturing method.

  In recent years, a blood purification technique called apheresis has been developed. Among these, direct blood perfusion therapy (DHP: Direct Hemo Perfusion) is able to purify the blood by directly contacting the patient's blood with the adsorbent, so that separation was performed using a conventional plasma separation membrane. It is simpler than the plasma adsorption method (PA: Plasma Adsorption) in which plasma is brought into contact with an adsorbent, and globulin using a secondary membrane from plasma once separated using a plasma separation membrane (primary membrane) Double membrane filtration plasma exchange (DFPP) etc. that separate and remove substances with large molecular weight including other etiology (related), and recover molecular weight substances below etiological (related) substances centering on albumin, etc. (DFPP: Double Filtration Plasmapheresis) Compared to the direct blood perfusion therapy, It is becoming popular.

  As an adsorbent for the direct blood perfusion therapy described above, beads, non-woven fabrics, woven and knitted fabrics, etc. have been devised. “Rixel” used (manufactured by Kaneka Corporation) is a bead-shaped adsorbent. On the other hand, “Cellsorva” (made by Asahi Kasei Kuraray Medical Co., Ltd.) used for leukocyte adsorption therapy is a non-woven adsorbent. is there.

  However, among the various adsorbents described above, the bead-shaped adsorbent has less pressure loss in the adsorption module configured by accommodating the adsorbent in the case than the other forms of adsorbent, There is little bias in blood flow. Therefore, in the adsorption module loaded with the bead-shaped adsorbent, the pressure increase due to blood coagulation in the adsorption module during treatment is suppressed, and the performance variation due to the uneven blood flow in the adsorption module is reduced. Is done. For this reason, the shape of the adsorbent is preferably a bead shape.

  Adsorbents used for direct blood perfusion therapy also ensure a certain effective surface area that can be contacted with blood in order to improve adsorption efficiency and minimize the size of the adsorption module containing the adsorbent. There is a need.

  As a method for obtaining a bead-shaped adsorbent suitable for the direct blood perfusion therapy described above, for example, a polymer solution obtained by dissolving a polymer, which is a raw material of the adsorbent, in a solvent is dropped onto a coagulation liquid from a nozzle, and the bead-shaped adsorbent is obtained. “Drip solidification methods” for obtaining materials have been proposed (see, for example, Patent Document 1 to Patent Document 5).

JP-A-1-278541 Japanese Patent Publication No. 6-22631 JP-A-7-247365 Japanese Patent Laid-Open No. 11-322997 JP 2007-191512 A

  Patent Document 2 to Patent Document 5 described above do not disclose any method for controlling the diameter of the bead-shaped adsorbent. On the other hand, in Patent Document 1, an electrode is installed in front of the nozzle and a DC voltage is applied, thereby applying a vibration of 1,000 to 40,000 Hz to the polymer solution ejected from the nozzle to enter the gas phase from the nozzle. There has been proposed a production method for ejecting droplets and charging the droplets with the same sign to suppress coalescence of the droplets to obtain porous uniform polymer particles having a uniform size.

  However, in the manufacturing method described in Patent Document 1, it is necessary to install an electrode at a predetermined distance from the nozzle in order to be ejected from the nozzle and charged with the same sign, which complicates the manufacturing apparatus, and the droplets to be charged. Is limited to a small particle size.

  An object of the present invention is to provide a polymer bead manufacturing apparatus and a polymer bead manufacturing method capable of arbitrarily adjusting the particle size of the polymer beads with a simple manufacturing apparatus configuration.

  As a result of intensive studies to solve the above problems, the present inventors have completed the present invention shown below. The present invention has the following features.

  (1) A polymer bead manufacturing apparatus comprising a nozzle for dropping a polymer solution and a gas discharge means for discharging gas toward an opening of the nozzle.

  (2) The polymer bead manufacturing apparatus according to (1), further including a flow rate control device that controls a flow rate of the gas discharged from the gas discharge unit.

  (3) In the above (1) or (2), the nozzle has a double tube structure, the polymer solution is dropped from an inner nozzle, and the gas is discharged from an outer slit. It is an apparatus for producing the described polymer beads.

  (4) A polymer bead that is sprayed from a nozzle and blows a gas onto a droplet of a polymer solution formed at the tip of the nozzle, and drops the droplet in a coagulation liquid composed of a poor solvent with respect to the polymer of the polymer solution before dropping its own weight. It is a manufacturing method.

  (5) The method for producing polymer beads according to (4), wherein the particle size of the beads is further controlled by controlling the flow rate of the gas blown to the droplets of the polymer solution formed at the tip of the nozzle.

  (6) The polymer solution according to (4) or (5), wherein the polymer solution contains a polymer having a number average molecular weight of 10,000 or more and a solvent having compatibility with each polymer. is there.

  According to the present invention, the diameter of the polymer beads can be arbitrarily adjusted by controlling the flow rate of the discharged gas.

  The polymer bead manufacturing apparatus and the polymer bead manufacturing method in the embodiment of the present invention will be described below.

  FIG. 1 shows a schematic configuration of an example of a polymer bead manufacturing apparatus in the present embodiment. However, it is not limited to the following contents. As shown in FIG. 1, the apparatus for producing polymer beads in the present embodiment is for dropping a polymer solution (hereinafter also referred to as “polymer bead stock solution”) obtained by dissolving a polymer resin in a compatible solvent. It has a polymer original droplet dropping device 10 provided with a nozzle and gas discharge means for discharging gas along the outer periphery of the nozzle. In this embodiment, a slit 14 provided on the outer periphery of the nozzle is used as the gas discharge means, and the slit 14 surrounds the outer peripheral surface of the nozzle so that gas is discharged toward the opening of the nozzle. It is only necessary to be provided at least at a part, but it is preferable to provide several at equal intervals along the circumferential direction, and it is more preferable to provide the entire circumference of the nozzle. That is, a double tube structure is preferable. In addition, in this embodiment, the polymer original droplet dropping apparatus 10 has a double tube structure, and has a structure in which the inner nozzle protrudes from the outer slit end face.

  Furthermore, the polymer bead manufacturing apparatus according to the present embodiment includes a polymer stock solution storage tank 20 in which the polymer stock solution is stored, and a polymer stock supply that supplies the polymer stock solution from the polymer stock solution storage tank 20 to the nozzles of the polymer stock droplet dropping apparatus 10. The polymer stock solution supply passage 22 is provided with a pump 26 and a valve 24 for feeding the polymer stock solution. In addition, the polymer bead manufacturing apparatus according to the present embodiment includes a gas storage unit 50 in which gas is stored, a gas supply path 52 for supplying gas from the gas storage unit 50 to the slit 14, and a method for compressing the gas. The compressor 54 is provided, and the gas supply path 52 is provided with a flow meter 56 and a valve 28 for measuring the flow velocity of the supplied gas. The control unit (not shown) controls the gas flow rate by adjusting the amount of air supplied to the compressor 54 and the degree of opening and closing of the valve 28 based on the gas flow rate measured by the flow meter 56. In addition, the polymer bead manufacturing apparatus according to the present embodiment includes a coagulating liquid tank 30 provided below the original polymer droplet dropping apparatus 10 and storing a coagulating liquid 32 that is a poor solvent for the polymer in the polymer stock solution. . In addition, when using air as said gas, the gas storage part 50 mentioned above is not necessarily required.

  Next, an example of a method for producing polymer beads in the present embodiment will be described with reference to FIGS. First, the valve 24 is opened, the pump 26 is driven, and the polymer stock solution is supplied from the polymer stock solution storage tank 20 into the nozzle 12 of the polymer stock droplet dropping apparatus 10 via the polymer stock solution supply path 22. Thereby, a droplet of the polymer stock solution is formed at the tip of the nozzle 12. On the other hand, the valve 28 is opened, the compressor 54 is driven, and the gas is sent from the gas storage unit 50 to the slit 14 of the polymer original droplet dropping apparatus 10 while the flow rate of the gas is measured by the flow meter 56. The gas discharged from the slit 14 hits a droplet formed at the tip of the nozzle 12, and the droplet of the polymer stock solution is forcibly dropped into the coagulating liquid 32 in the coagulating liquid tank 30 before dropping its own weight, and the coagulating liquid 32. The polymer solidifies therein, and polymer beads 40 are formed.

  Here, the polymer solution contains a polymer having a number average molecular weight of 10,000 or more and a solvent having compatibility with each polymer. If necessary, the polymer solution contains, for example, at least two polymers having a number average molecular weight of 10,000 or more and different coagulation values, and a solvent having compatibility with each polymer. A polymer solution may be used. In such a case, each polymer having a different coagulation value has a different coagulation rate in the coagulation liquid. As a result, a time difference occurs until each polymer is precipitated, and a polymer having a relatively low coagulation value first aggregates and starts to precipitate. However, since the polymer having a relatively high coagulation value is in a dissolved state at that time, the movement of the polymer having a relatively low coagulation value is hindered by the polymer having a relatively large coagulation value. The agglomeration rate of a relatively small polymer is slower than that of a single polymer, resulting in non-uniform agglomeration of the entire polymer system. As a result, a large number of pores are formed in the solidified polymer, and porous beads are obtained.

  The polymer beads (including the porous beads) 40 are separated from the coagulation liquid 32, and later washed with purified water and dried.

  Furthermore, the structure of the polymer original droplet dropping apparatus 10 in the polymer bead manufacturing apparatus in the present embodiment will be described with reference to FIG. FIG. 3 shows an example of a conventional apparatus configuration. As shown in FIG. 2, the polymer raw droplet dropping device 10 includes a nozzle 12 for supplying and dropping a polymer raw solution, and a slit 14 for discharging gas. On the other hand, the apparatus of FIG. Here, the polymer stock solution usually has a certain viscosity, and as shown in FIG. 3, conventionally, the liquid droplets pushed out from the nozzle 12 and formed at the tip of the nozzle 12 fall into the coagulating liquid 32 by its own weight. The size of the droplet 142 when dropped was much larger than the diameter of the nozzle 12 and the diameter of the polymer beads 140 obtained was also large. However, as shown in FIG. 2, by discharging gas from the slit 14, the gas hits the droplet formed at the tip of the nozzle 12, and can be dropped before the droplet falls by its own weight. Therefore, as shown in FIG. 2, the droplet 42 having a diameter smaller than that of the droplet 142 can be dropped at the time of dropping shown in FIG. 3, and the diameter of the resulting polymer beads 40 can be made smaller than the conventional one. Furthermore, the diameter of the dropped droplet 42 can be controlled according to the flow rate of the gas discharged from the slit 14. Even when the flow velocity of the gas discharged from the slit 14 is small, if the gas hits the side surface portion of the droplet at the tip of the nozzle 12 that has grown to a diameter greater than or equal to the outer diameter of the nozzle 12, the droplet is self-weighted. Before dropping, it is detached from the nozzle 12 and dropped. In addition, for example, when a polymer stock solution having a high viscosity is dropped from a nozzle, even if the inner diameter of the nozzle is increased, a droplet having a smaller particle diameter can be dropped by gas discharge from a slit. Productivity is also improved.

  In the present embodiment, the viscosity of the polymer stock dropped from the nozzle 12 is 0.1 Pas to 2.0 Pas, while the inner diameter of the nozzle 12 is 0.1 mm or more and 0.3 mm or less. The outer diameter is 0.2 mm or more and 0.6 mm or less, and the ratio of the inner diameter to the outer diameter of the nozzle 12 is 2/6 to 5 in order to generate polymer beads having a particle diameter equal to or smaller than the outer diameter of the nozzle 12. / 6, and the nozzle protrusion length is 1 mm to 5 mm. The slit interval of the slit 14 through which gas is discharged along the outer periphery of the nozzle 12 is 0.05 mm to 2.0 mm, and the flow rate of the gas discharged from the slit 14 is from 0.05 L / min to 0.00 mm. 3 L / min.

  Furthermore, in the present embodiment, a configuration for giving vibration to the nozzle 12 may be added, and the vibration frequency at that time is preferably 10 kHz to 100 kHz.

  Furthermore, as a polymer contained in the polymer stock solution in the present embodiment, for example, polyarylate resin (PAR), polyether sulfone resin (PES), polysulfonic acid resin (PES), cellulose acetate, porstyrene resin, polymethyl methacrylate resin A combination of polymers of these resins can also be used.

  The polyarylate resin is a resin having a repeating unit represented by the following chemical formula (1).

  In the chemical formula (1), R1 and R2 are lower alkyl groups having 1 to 5 carbon atoms, and R1 and R2 may be the same or different. Examples of R1 and R2 include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Preferred R1 and R2 are methyl groups.

The polyethersulfone resin is a resin having a repeating unit represented by the following chemical formula (2) or chemical formula (3).

  In the chemical formula (2), R3 and R4 are lower alkyl groups having 1 to 5 carbon atoms, and R3 and R4 may be the same or different. Examples of R3 and R4 include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Preferred R1 and R2 are methyl groups.

  Examples of the gas sprayed on the droplets in the present embodiment include air, nitrogen, carbon dioxide, and argon. Gases other than air are normally stored in the gas storage unit 50 shown in FIG.

  In the present embodiment, one nozzle 12 is illustrated in FIG. 1, but the present invention is not limited to this, and a multi-nozzle including a plurality of nozzles 12 may be used. Is arbitrarily selected within the range of 500 to 500. Moreover, when arrange | positioning the multiple nozzle 12, it is arrange | positioned arbitrarily, such as circumferential shape and a grid | lattice form. Further, when a plurality of nozzles 12 are arranged, each nozzle 12 is provided with a slit 14 which is a gas discharge means in order to suppress variation in particle size and to adjust the particle size arbitrarily with high accuracy.

  Next, a polymer bead manufacturing apparatus according to another embodiment of the present invention will be described below. In addition, since the polymer bead manufacturing apparatus in the other embodiments has the same configuration except that the configuration is different from that of the above-described polymer original droplet dropping apparatus 10 (shown in FIG. 1), the same reference numerals are given to the same configurations. The description is omitted.

  As shown in FIG. 4, the polymer droplet dropping apparatus 100 according to another embodiment includes a nozzle 12a having a beveled end face 16 in which the nozzle tip is cut obliquely with respect to the nozzle length, and a gas along the outer periphery of the nozzle. A slit 14 for discharging is provided. Therefore, even if the flow rate of the gas discharged from the slit 14 is the same, the droplet formed on the oblique end surface 16 of the tip of the nozzle 12a is more relative to the droplet formed on the tip of the nozzle 12 shown in FIG. A lot of gas is sprayed. For this reason, compared with the polymer bead manufacturing apparatus 10 shown in FIG. 2, the polymer original droplet dropping apparatus 100 shown in FIG. The droplet diameter can be made smaller than that of the nozzle 42. Further, by controlling the flow rate of the gas discharged from the slit 14, the droplet 44 having a smaller particle diameter smaller than the outer diameter of the nozzle 12a can be generated.

  As the angle formed between the oblique end surface 16 of the nozzle 12a and the nozzle length direction is an acute angle, polymer beads having a smaller particle diameter can be manufactured. In this embodiment, the angle formed between the oblique end surface 16 of the nozzle 12a and the nozzle length direction is preferably 10 ° to 80 °, more preferably 10 ° to 45 °.

  In other embodiments, the dimensions of the nozzles 12a, the number of nozzles 12a, the arrangement of the nozzles 12a, and the arrangement of the slits 14 are the same as in the case of the nozzles 12 described above. Since specific examples of the polymer stock solution and gas used are the same, the description thereof is omitted here.

  Further, a polymer bead manufacturing apparatus according to still another embodiment of the present invention will be described below. In addition, since the polymer bead manufacturing apparatus in the other embodiments has the same configuration except that the configuration is different from that of the above-described polymer original droplet dropping apparatus 10 (shown in FIG. 1), the same reference numerals are given to the same configurations. The description is omitted.

  As shown in FIG. 5, in another embodiment, in addition to the polymer original droplet dropping device 10, a side gas ejection device 60 that ejects gas from the side surface direction of the polymer stock droplet dropped from the nozzle 12 is provided. Yes. The side gas discharge device 60 discharges gas intermittently or in communication. Therefore, even if the flow rate of the gas discharged from the slit 14 is the same, the droplet formed at the tip of the nozzle 12 is caused by the gas discharged from the side gas discharge device 60 by the gas discharged from the side gas discharge device 60. The liquid droplets fall into the coagulation liquid 32 with a relatively small particle size than the droplets formed on the surface. Here, an infrared sensor or the like may be used to control the gas discharge timing and the discharge amount from the side gas discharge device 60 while monitoring the size of the droplet formed at the tip of the nozzle 12. Further, in FIG. 5, the side gas discharge device 60 is arranged to discharge gas from a direction substantially orthogonal to the nozzle length of the nozzle 12, but is not limited to this, and in the discharge direction of the slit 14. On the other hand, it should just be arrange | positioned so that gas may be discharged from the angle of at least 1 degree and 180 degrees or less.

  In the above embodiment, the dimensions of the nozzle 12, the number of nozzles 12, the arrangement of the nozzles, and the arrangement of the slits 14 are the same as those of the nozzle 12 described with reference to FIGS. Specific examples of the polymer stock solution and the gas used in the embodiment are also the same as described above, and the description thereof is omitted here.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.

[Example 1]
A polymer stock solution was prepared using polyarylate resin (hereinafter, PAR, number average molecular weight 25,000, manufactured by Unitika, trade name: U polymer) and N-methylpyrrolidone (NMP). The mass mixing ratio of PAR and NMP was 14.0: 86.0. An aqueous solution of N-methylpyrrolidone (mixed 60% of NMP in water) was used as a coagulation liquid. The polymer solution was discharged from a nozzle 12 (FIG. 1) having a nozzle length of 5 mm, an inner diameter of 0.19 mm, and an outer diameter of 0.36 mm, and simultaneously a flow rate (flow rate) from a slit 14 (FIG. 1) having a slit interval of 0.15 mm. Gas was discharged at 0.15 L / min, and a droplet of the polymer stock solution was dropped into the coagulation bath. In Example 1, the discharge amount of the polymer stock solution was 72 mg / min. After sufficiently coagulating in the coagulating liquid, it was washed with distilled water to obtain polymer beads having a spherical shape with an outer diameter of 1.0 mm.

[Example 2]
As a polymer stock solution, polyarylate resin (hereinafter PAR, number average molecular weight 25,000, manufactured by Unitika, trade name: U polymer) and polyethersulfone resin (hereinafter PES, grade 4800P, number average molecular weight 21,000, manufactured by Sumitomo Chemical Co., Ltd.) , Trade name: Sumika Excel PES) and N-methylpyrrolidone (NMP), except that the mass mixing ratio of PAR, PES, and NMP was 7.0: 7.0: 86.0. According to 1, porous polymer beads were produced. The obtained porous polymer beads were porous polymer beads having a spherical shape with an outer diameter of 0.8 mm.

[Example 3]
Example except that a nozzle having a nozzle length of 5 mm, an inner diameter of 0.13 mm and an outer diameter of 0.31 mm was used as the nozzle 12 (FIG. 1), and the flow rate of air discharged from the slit 14 was changed to 0.1 L / min. According to 1, polymer beads were produced. The obtained polymer beads were polymer beads having a spherical shape with an outer diameter of 1.2 mm.

[Example 4]
As the nozzle 12 (FIG. 1), a nozzle having a nozzle length of 5 mm, an inner diameter of 0.3 mm, and an outer diameter of 0.55 mm is used, and the flow rate of air discharged from the slit 14 having a slit interval of 2.0 mm is changed to 0.3 L / min. Except for the above, polymer beads were produced according to Example 1. The obtained polymer beads were polymer beads having a spherical shape with an outer diameter of 0.7 mm.

[Comparative example]
Polymer beads were produced according to Example 1 except that air was not discharged from the slits 14. The obtained polymer beads were polymer beads having a spherical shape with an outer diameter of 2.0 mm.

[Example 5]:
As the nozzle 12a (FIG. 4), an angle formed by the oblique end surface of the nozzle tip and the nozzle length direction is 45 °, and a nozzle having a nozzle length of 5 mm, an inner diameter of 0.19 mm, and an outer diameter of 0.36 mm is used. Polymer beads were produced according to Example 1. The obtained polymer beads were polymer beads having a spherical shape with an outer diameter of 0.8 mm.

  The present invention is suitable for use in producing polymer beads.

It is a schematic block diagram which shows an example of the manufacturing apparatus of the polymer bead in embodiment of this invention. It is a figure explaining the structure of an example of the polymer original droplet dropping apparatus of the manufacturing apparatus of the polymer bead in embodiment of this invention. It is a figure explaining the structure of an example of the polymer original droplet dropping apparatus of the conventional polymer bead manufacturing apparatus. It is a figure explaining the structure of the other polymer original droplet dropping apparatus of the polymer bead manufacturing apparatus in embodiment of this invention. It is a figure explaining the structure of the other polymer original droplet dropping apparatus of the polymer bead manufacturing apparatus in embodiment of this invention.

Explanation of symbols

  10,100 Polymer raw liquid dropping device, 12, 12a Nozzle, 14 slit, 16 Bevel end surface, 20 Polymer stock solution storage tank, 22 Polymer stock solution supply path, 24, 28 Valve, 26 Pump, 30 Coagulation solution tank, 32 Coagulation solution, 40 , 140 polymer beads, 42, 44, 142 droplets, 50 gas reservoir, 52 gas supply path, 54 compressor, 56 flow meter, 60 side gas discharge device.

Claims (6)

A nozzle for dropping the polymer solution;
Gas discharge means for discharging gas toward the opening of the nozzle;
An apparatus for producing polymer beads, comprising:   The apparatus for producing polymer beads according to claim 1, further comprising a flow rate control device that controls a flow rate of the gas discharged from the gas discharge means.   3. The polymer bead according to claim 1, wherein the nozzle has a double tube structure, the polymer solution is dropped from an inner nozzle, and the gas is discharged from an outer slit. 4. Manufacturing equipment.   A gas is blown to a droplet of a polymer solution extruded from a nozzle and formed at the tip of the nozzle, and the droplet is dropped into a coagulating liquid composed of a poor solvent with respect to the polymer of the polymer solution before dropping its own weight. Production method of polymer beads.   5. The method of producing polymer beads according to claim 4, further comprising controlling the particle size of the beads by controlling the flow rate of the gas sprayed onto the droplets of the polymer solution formed at the tip of the nozzle.   The method for producing polymer beads according to claim 4 or 5, wherein the polymer solution contains a polymer having a number average molecular weight of 10,000 or more and a solvent having compatibility with each polymer. .

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