JP2011132395A - Gel manufacturing method - Google Patents

Gel manufacturing method Download PDF

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JP2011132395A
JP2011132395A JP2009294055A JP2009294055A JP2011132395A JP 2011132395 A JP2011132395 A JP 2011132395A JP 2009294055 A JP2009294055 A JP 2009294055A JP 2009294055 A JP2009294055 A JP 2009294055A JP 2011132395 A JP2011132395 A JP 2011132395A
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gel
solvent
size
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droplet discharge
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JP2011132395A5 (en
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Takashi Hiruma
敬 蛭間
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Seiko Epson Corp
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Abstract

<P>PROBLEM TO BE SOLVED: To produce a gel of a uniform size in which variation in a size of the gel is suppressed and controlled. <P>SOLUTION: A size controlling process is carried out after a droplet discharge process, a time T to immerse the gel 10 in a second solvent 2 is managed, thereby the going of the reaction (crosslinking condensation) of a calcium chloride aqueous solution which is a second solvent 2 and sodium alginate left behind in the gel 10 is controlled, and the rate of change% of the size of the gel 10 can be made to be controlled. By this, the smaller gel 10 can be obtained comparing with the size of the gel 10 produced in the droplet discharge process or the size of a first solvent 1 which has been droplet discharged. In addition, when there is variation in the size of the gel 10 produced in the droplet discharge process, a time T to immerse in the second solvent 2 is managed, the rate of change% of the size of the gel 10 is controlled, thereby the variation in the size of the gel 10 is suppressed, and the gel 10 of a uniform size can be obtained. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

本発明は、ゲル製造方法に関する。   The present invention relates to a method for producing a gel.

従来から、第１溶剤と第２溶剤とを反応させゲルを生成する方法が知られている。このようにゲルを生成する方法として、流れる連続相（第２溶剤）に、分散相（第１溶剤）を交差させ、連続相のせん断力により、微小液滴またはゲルを生成する方法が開示されている（たとえば、特許文献１参照）。   Conventionally, a method of generating a gel by reacting a first solvent and a second solvent is known. As a method for generating a gel in this way, a method is disclosed in which a dispersed phase (first solvent) is intersected with a flowing continuous phase (second solvent) and a microdroplet or gel is generated by the shear force of the continuous phase. (For example, refer to Patent Document 1).

ＷＯ２００２／０６８１０４号明細書（６頁、図２）WO2002 / 068104 specification (6 pages, FIG. 2)

しかしながら、せん断力を一定に保つことは困難であり、せん断力が変化することにより、生成されるゲルの大きさにバラツキが発生し、せん断力によりゲルの大きさを制御して生成することは困難という課題がある。   However, it is difficult to keep the shearing force constant. As the shearing force changes, the size of the generated gel varies, and it is possible to generate the gel by controlling the size of the gel by the shearing force. There is a problem of difficulty.

本発明は、上記課題の少なくとも一部を解決するためになされたものである。以下の形態または適用例により実現することが可能である。   The present invention has been made to solve at least a part of the above problems. It can be realized by the following forms or application examples.

［適用例１］本適用例にかかるゲル製造方法は、第１溶剤を第２溶剤に向けて液滴吐出し、前記第１溶剤と前記第２溶剤とを反応させゲルを生成する液滴吐出工程と、前記ゲルを前記第２溶剤に浸漬し、前記ゲルの大きさを制御するサイズ制御工程とを備えることを要旨とする。   [Application Example 1] In the gel manufacturing method according to this application example, the first solvent is discharged toward the second solvent, and the first solvent and the second solvent are reacted to generate a gel. The present invention includes a step and a size control step of immersing the gel in the second solvent to control the size of the gel.

これによれば、液滴吐出工程の後に、サイズ制御工程を実施することで、第２溶剤とゲル内に残されているアルギン酸ナトリウムとの反応が進み、ゲルの大きさを制御することができる。たとえば、液滴吐出工程において生成されたゲルの大きさに比べて、小さいゲルを得ることができる。   According to this, by carrying out the size control step after the droplet discharge step, the reaction between the second solvent and the sodium alginate remaining in the gel proceeds, and the size of the gel can be controlled. . For example, a gel smaller than the size of the gel generated in the droplet discharge process can be obtained.

本実施形態のゲルを示す概略側面図。The schematic side view which shows the gel of this embodiment. 本実施形態のゲル製造方法を示すフローチャート。The flowchart which shows the gel manufacturing method of this embodiment. 本実施形態のゲル製造方法を示す概略工程図。The schematic process drawing which shows the gel manufacturing method of this embodiment. ゲルを第２溶剤に浸漬する時間と変化率との関係を示すグラフ。The graph which shows the relationship between the time which immerses a gel in a 2nd solvent, and a change rate.

（実施形態）
以下、本実施形態について、図１から図４を参照して説明する。 (Embodiment)
Hereinafter, the present embodiment will be described with reference to FIGS. 1 to 4.

まず、本実施形態のゲル製造方法により形成されるゲルについて説明する。
図１（ａ）に示すように、ゲル１０は、弾性を有した球体形状をしている。または、図１（ｂ）に示すように、弾性を有した円盤形状で中央部に破線で示した窪みがある形状、たとえば赤血球のような形状をしている。または、破線で示した窪みを有しない円盤形状であってもよい。 First, the gel formed by the gel manufacturing method of this embodiment will be described.
As shown in FIG. 1A, the gel 10 has a spherical shape having elasticity. Or as shown in FIG.1 (b), it has the shape which has the hollow shown by the broken line in the center part, for example, the shape of a red blood cell, with an elastic disk shape. Or the disk shape which does not have the hollow shown with the broken line may be sufficient.

以下、本実施形態のゲル製造方法について、図２および図３を参照して説明する。
図２に示すように、ゲル製造方法は、液滴吐出工程（Ｓ１０１）と、サイズ制御工程（Ｓ１０２）とを備えている。図３は、それぞれの工程の概略を示している。 Hereinafter, the gel manufacturing method of this embodiment is demonstrated with reference to FIG. 2 and FIG.
As shown in FIG. 2, the gel manufacturing method includes a droplet discharge step (S101) and a size control step (S102). FIG. 3 shows an outline of each step.

図３（ａ）に示すように、液滴吐出工程（Ｓ１０１）を実施する。具体的には、第１溶剤１を、容器５０に収納された第２溶剤２に向けて液滴吐出し、第１溶剤１と第２溶剤２とを反応させゲル１０を生成する。
ここで、図３（ａ）および（ｂ）では、液滴吐出される第１溶剤１の速度が、遅い場合Ｓ（図示左側）と、速い場合Ｆ（図示右側）とを図示する。 As shown in FIG. 3A, a droplet discharge step (S101) is performed. Specifically, the first solvent 1 is ejected in droplets toward the second solvent 2 stored in the container 50, and the first solvent 1 and the second solvent 2 are reacted to generate the gel 10.
Here, in FIGS. 3A and 3B, the case where the speed of the first solvent 1 to be ejected is slow is S (the left side in the figure) and the case where it is fast is the F (the right side in the figure).

第１溶剤１は、アルギン酸塩であり、たとえばアルギン酸ナトリウムが一例として挙げられる。または、フィブリノーゲン、ホウ酸水溶液などが挙げられる。   The first solvent 1 is an alginate, for example, sodium alginate. Or a fibrinogen, boric-acid aqueous solution, etc. are mentioned.

第２溶剤２は、アルカリ土類金属塩であり、塩化カルシウム、塩化マグネシウム、または塩化バリウムなどの水溶液が一例として挙げられる。または、トロビンと塩化カルシウムなどのカルシウム塩とを含む水溶液、ポリビニルアルコール水溶液などが挙げられる。   The second solvent 2 is an alkaline earth metal salt, and examples thereof include aqueous solutions of calcium chloride, magnesium chloride, barium chloride, and the like. Alternatively, an aqueous solution containing trobin and a calcium salt such as calcium chloride, an aqueous polyvinyl alcohol solution, and the like can be given.

たとえば、第１溶剤１としてアルギン酸ナトリウム水溶液を用い、第２溶剤２として塩化カルシウム水溶液を用いる。アルギン酸ナトリウム水溶液を塩化カルシウム水溶液に向けて吐出させることで、アルギン酸ナトリウムと塩化カルシウムとが化学反応し、アルギン酸カルシウムからなるゲル１０が生成される。   For example, a sodium alginate aqueous solution is used as the first solvent 1, and a calcium chloride aqueous solution is used as the second solvent 2. By discharging the sodium alginate aqueous solution toward the calcium chloride aqueous solution, the sodium alginate and the calcium chloride chemically react to generate the gel 10 made of calcium alginate.

図３（ｂ）に示すように、サイズ制御工程（Ｓ１０２）を実施する。具体的には、ゲル１０を、容器５５に収納された第２溶剤２である塩化カルシウム水溶液に浸漬し、ゲル１０の大きさを制御する。これにより、アルギン酸カルシウムからなるゲル１０は、２価の金属イオンにより、さらなるゲル化が誘発される。この場合、２価の金属イオンであるカルシウムイオン（Ｃａ2+）が、ゲル１０内に残されたアルギン酸ナトリウムのナトリウムイオン（Ｎａ+）と置換されることで、ゲル化が進行する。このとき、ナトリウムイオン（Ｎａ+）は１価であり、カルシウムイオン（Ｃａ2+）は２価であるので、２個のナトリウムイオン（Ｎａ+）に対して、１個のカルシウムイオン（Ｃａ2+）が置換される。このとき、ゲル１０の中心部分に残るアルギン酸ナトリウムは、２つのアルギン酸ナトリウム間において、２つのナトリウムイオン（Ｎａ+）が脱離して、２価の金属イオンである１つのカルシウムイオン（Ｃａ2+）に置換されることで、２つのアルギン酸ナトリウム間を橋架けする架橋凝縮が起こり、ゲル化する。これにより、ゲル１０の大きさを、凝縮させる、つまり小さくさせる。
ここで、第２溶剤２は、容器５５に収納されるとして図示および説明したが、これに限るものではなく、液滴吐出工程（Ｓ１０１）において図３（ａ）に示すように、第２溶剤２は容器５０に収納されるとしてもよい。 As shown in FIG. 3B, the size control step (S102) is performed. Specifically, the gel 10 is immersed in a calcium chloride aqueous solution that is the second solvent 2 housed in the container 55, and the size of the gel 10 is controlled. Thereby, the gel 10 made of calcium alginate is further gelled by divalent metal ions. In this case, gelation proceeds by replacing calcium ions (Ca 2+ ), which are divalent metal ions, with sodium ions (Na + ) of sodium alginate remaining in the gel 10. At this time, the sodium ion (Na + ) is monovalent and the calcium ion (Ca 2+ ) is divalent. Therefore, one calcium ion (Ca 2 ) with respect to two sodium ions (Na + ). + ) Is replaced. At this time, the sodium alginate remaining in the central portion of the gel 10 is desorbed between two sodium alginate so that two sodium ions (Na + ) are desorbed and one calcium ion (Ca 2+ ) which is a divalent metal ion. By the substitution, cross-linking condensation that bridges between two sodium alginate occurs and gels. Thereby, the magnitude | size of the gel 10 is condensed, ie, made small.
Here, the second solvent 2 has been illustrated and described as being contained in the container 55, but the present invention is not limited to this, and as shown in FIG. 3A, the second solvent is not limited thereto. 2 may be stored in the container 50.

架橋凝縮が起こりゲル化する際に、ゲル１０は、その表面張力により、第２溶剤２である塩化カルシウム水溶液に浸漬する前の形状を維持しようする。このため、置換されるカルシウムイオン（Ｃａ2+）は、図３（ｂ）において矢印で示すように、ゲル１０の表面から中心部分へ、均一に入り込み、ナトリウムイオン（Ｎａ+）と置換される。これにより、ゲル化が進行し、ゲル１０は、均一に凝縮される。つまり、ゲル１０が球状の場合、球状を維持しつつ均一に凝縮される。そして、円盤形状で中央部に破線で示した窪みがある形状、または破線で示した窪みを有しない円盤形状の場合、その形状を維持しつつ均一に凝縮される。 When cross-linking condensation occurs and gelation occurs, the gel 10 tends to maintain its shape before being immersed in the aqueous solution of calcium chloride as the second solvent 2 due to its surface tension. For this reason, as shown by arrows in FIG. 3B, the calcium ions (Ca 2+ ) to be substituted uniformly enter the center portion from the surface of the gel 10 and are replaced with sodium ions (Na + ). . Thereby, gelation advances and the gel 10 is condensed uniformly. That is, when the gel 10 is spherical, it is condensed uniformly while maintaining the spherical shape. And in the shape of a disk and having a dent indicated by a broken line at the center or a disk shape not having a dent indicated by a broken line, the shape is uniformly condensed while maintaining the shape.

そして、第２溶剤２である塩化カルシウム水溶液に浸漬する時間Ｔを管理することにより、ゲル１０の大きさの凝縮の程度を制御し、ゲル１０の大きさを正確にする。   And the degree of condensation of the magnitude | size of the gel 10 is controlled by managing the time T immersed in the calcium chloride aqueous solution which is the 2nd solvent 2, and the magnitude | size of the gel 10 is made accurate.

本実施形態によれば、液滴吐出工程の後に、サイズ制御工程を実施して、ゲル１０を第２溶剤２に浸漬する時間Ｔを管理することにより、第２溶剤２である塩化カルシウム水溶液とゲル１０内に残されているアルギン酸ナトリウムとの反応（架橋凝縮）の進み具合を制御し、ゲル１０の大きさの変化率％を制御させることができる。これにより、液滴吐出工程において生成されたゲル１０の大きさ、または液滴吐出された第１溶剤１の大きさに比べて、小さいゲル１０を得ることができる。または、液滴吐出工程において生成されたゲル１０の大きさのバラツキがある場合、第２溶剤２に浸漬する時間Ｔを管理し、ゲル１０の大きさの変化率％を制御することで、ゲル１０の大きさのバラツキを抑え、均一な大きさのゲル１０を得ることができる。   According to this embodiment, the size control process is performed after the droplet discharge process, and the time T in which the gel 10 is immersed in the second solvent 2 is managed, whereby the calcium chloride aqueous solution that is the second solvent 2 and The progress of the reaction (crosslinking condensation) with the sodium alginate remaining in the gel 10 can be controlled, and the change rate% of the size of the gel 10 can be controlled. Thereby, the gel 10 smaller than the size of the gel 10 generated in the droplet discharging step or the size of the first solvent 1 discharged from the droplet can be obtained. Alternatively, when there is a variation in the size of the gel 10 generated in the droplet discharge process, the time T in which the gel 10 is immersed in the second solvent 2 is managed, and the change rate% of the size of the gel 10 is controlled. The gel 10 having a uniform size can be obtained by suppressing the variation of the size 10.

以下に、第１溶剤１と第２溶剤２とを反応させ生成されたゲル１０を、第２溶剤２に浸漬する時間Ｔと変化率％との関係について、実験を行った。その結果を、図４に示す。   Below, it experimented about the relationship between the time T and the rate of change% which immerse the gel 10 produced | generated by making the 1st solvent 1 and the 2nd solvent 2 react. The result is shown in FIG.

ここで、変化率％は、第２溶剤２に浸漬する前のゲル１０の大きさ（直径）を分母とし、ゲル１０を第２溶剤２に浸漬している間のゲル１０の大きさ（直径）を分子とした値である。ゲル１０の大きさが変化しない場合、変化率％は１００％であり、ゲル１０の大きさが小さくなると、変化率％は低下し、１００％以下の値になる。   Here, the rate of change% is the size (diameter) of the gel 10 before dipping in the second solvent 2, and the size (diameter) of the gel 10 while dipping the gel 10 in the second solvent 2. ) As a numerator. When the size of the gel 10 does not change, the rate of change% is 100%. When the size of the gel 10 is reduced, the rate of change% decreases to a value of 100% or less.

第１溶剤１は、３種類のアルギン酸水溶液Ａ，Ｂ，およびＣを用いた。そして、第２溶剤２は、塩化カルシウム水溶液を用いた。   As the first solvent 1, three kinds of aqueous solutions of alginate A, B, and C were used. And the 2nd solvent 2 used calcium chloride aqueous solution.

図４に示すように、３種類の第１溶剤１であるアルギン酸水溶液Ａ，Ｂ，およびＣのいずれの場合においても、第１溶剤１と第２溶剤２とを反応させて生成されたゲル１０は、浸漬する時間Ｔが経過するとともに、変化率％が低下し、ゲル１０の大きさ（直径）が収縮していることが確認できる。   As shown in FIG. 4, the gel 10 formed by reacting the first solvent 1 and the second solvent 2 in any of the three types of the first solvent 1, the alginic acid aqueous solutions A, B, and C. It can be confirmed that the rate of change% decreases and the size (diameter) of the gel 10 is contracted as time T for immersing elapses.

このように、実験において、上述の効果を奏することが確認できた。   As described above, it was confirmed in the experiment that the above-described effects were achieved.

上述のゲル製造方法により形成されるゲルは、医薬品、化粧品、農薬、生体材料解析、さらには再生医療など幅広い分野で、好適に利用することができる。   The gel formed by the above-described gel production method can be suitably used in a wide range of fields such as pharmaceuticals, cosmetics, agricultural chemicals, biomaterial analysis, and regenerative medicine.

なお、上記課題の少なくとも一部を解決できる範囲での変形、改良などは前述の実施形態に含まれるものである。   In addition, the deformation | transformation in the range which can solve at least one part of the said subject, improvement, etc. are contained in above-mentioned embodiment.

たとえば、サイズ制御工程（Ｓ１０２）において、ゲル１０を凝縮させる条件として、ゲル１０を第２溶剤２に浸漬する時間Ｔを用いたが、これに限定するものではなく、第２溶剤２の温度、第２溶剤２の溶質濃度、または第２溶剤２の水素イオン指数ｐＨを凝縮させる条件として、実施することが可能である。   For example, in the size control step (S102), the time T for immersing the gel 10 in the second solvent 2 is used as a condition for condensing the gel 10, but the present invention is not limited to this, and the temperature of the second solvent 2, It can be carried out as a condition for condensing the solute concentration of the second solvent 2 or the hydrogen ion exponent pH of the second solvent 2.

２価の金属イオンとしてカルシウムイオン（Ｃａ2+）を用いて説明したが、マグネシウムイオン（Ｍｇ2+）またはバリウムイオン（Ｂａ2+）などのアルカリ土類金属であればよく、その場合、塩化カルシウムの代わりに、塩化マグネシウムまたは塩化バリウムを用いることができる。 Although description has been made using calcium ions (Ca 2+ ) as divalent metal ions, alkaline earth metals such as magnesium ions (Mg 2+ ) or barium ions (Ba 2+ ) may be used. Instead of calcium, magnesium chloride or barium chloride can be used.

なお、第１溶剤１および第２溶剤２の材料を上述のように示したが、どちらを第１溶剤１、どちらを第２溶剤２としてもよく、インクジェットで安定して液滴吐出するために粘度の低い液を第１溶剤１とすることが好ましい。   In addition, although the material of the 1st solvent 1 and the 2nd solvent 2 was shown as mentioned above, whichever may be the 1st solvent 1 and which is the 2nd solvent 2, in order to discharge a droplet stably with an inkjet A liquid having a low viscosity is preferably used as the first solvent 1.

また、上述の実施形態においては、第２溶剤２を流動させずに静止状態で、容器５０および容器５５に収納しているとして説明したが、これに限るものではなく、容器５０および容器５５へと第２溶剤２を流動させる構成であってもよい。この場合、上述の実施形態と同様に、サイズ制御工程（Ｓ１０２）において、ゲル１０を第２溶剤２に浸漬する時間Ｔ、第２溶剤２の温度、第２溶剤２の溶質濃度、または第２溶剤２の水素イオン指数ｐＨを管理することで、上述の効果を奏することができる。   In the above-described embodiment, the second solvent 2 is described as being stored in the container 50 and the container 55 in a stationary state without flowing, but the present invention is not limited to this. Alternatively, the second solvent 2 may flow. In this case, similarly to the above-described embodiment, in the size control step (S102), the time T for immersing the gel 10 in the second solvent 2, the temperature of the second solvent 2, the solute concentration of the second solvent 2, or the second By controlling the hydrogen ion exponent pH of the solvent 2, the above-described effects can be achieved.

１…第１溶剤、２…第２溶剤、１０…ゲル、５０，５５…容器。   DESCRIPTION OF SYMBOLS 1 ... 1st solvent, 2 ... 2nd solvent, 10 ... Gel, 50,55 ... Container.

Claims (1)

第１溶剤を第２溶剤に向けて液滴吐出し、前記第１溶剤と前記第２溶剤とを反応させゲルを生成する液滴吐出工程と、
前記ゲルを前記第２溶剤に浸漬し、前記ゲルの大きさを制御するサイズ制御工程とを備えることを特徴とするゲル製造方法。 A droplet discharge step of discharging a droplet toward the second solvent and generating a gel by reacting the first solvent and the second solvent;
A gel manufacturing method comprising: immersing the gel in the second solvent; and controlling a size of the gel.
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CN114539563A (en) * 2022-03-04 2022-05-27 浙江大学 Method for synthesizing hydrogel pellets with different shapes and sizes

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JPH01115901A (en) * 1987-10-29 1989-05-09 Kibun Kk Production of gel or hardened gel
JPH09157433A (en) * 1995-12-07 1997-06-17 Unitika Chem Kk Production of polyvinyl alcohol-based gel molding and microorganism-immobilized molding
JPH09192471A (en) * 1996-01-24 1997-07-29 Kirin Brewery Co Ltd Production of alginate gel sphere
JP2006525108A (en) * 2003-05-09 2006-11-09 ジボダン エス エー Alginate matrix particles

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JPH01115901A (en) * 1987-10-29 1989-05-09 Kibun Kk Production of gel or hardened gel
JPH09157433A (en) * 1995-12-07 1997-06-17 Unitika Chem Kk Production of polyvinyl alcohol-based gel molding and microorganism-immobilized molding
JPH09192471A (en) * 1996-01-24 1997-07-29 Kirin Brewery Co Ltd Production of alginate gel sphere
JP2006525108A (en) * 2003-05-09 2006-11-09 ジボダン エス エー Alginate matrix particles

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114539563A (en) * 2022-03-04 2022-05-27 浙江大学 Method for synthesizing hydrogel pellets with different shapes and sizes

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