JP6498383B2 - Nonwoven sheet, cell culture scaffold, and method for producing nonwoven sheet - Google Patents
Nonwoven sheet, cell culture scaffold, and method for producing nonwoven sheet Download PDFInfo
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- JP6498383B2 JP6498383B2 JP2014033225A JP2014033225A JP6498383B2 JP 6498383 B2 JP6498383 B2 JP 6498383B2 JP 2014033225 A JP2014033225 A JP 2014033225A JP 2014033225 A JP2014033225 A JP 2014033225A JP 6498383 B2 JP6498383 B2 JP 6498383B2
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Description
本発明は、不織布シート、細胞培養足場材、及び、不織布シートの製造方法に関する。 The present invention relates to a nonwoven sheet, a cell culture scaffold, and a method for producing a nonwoven sheet.
現在、多数の微細な開孔を備えた多孔膜は種々の分野で使用されており、例えば、歯周組織再生医療用途においては、ＰＤＬＬＡ（ｐｏｌｙ−ＤＬ−ｌａｃｔｉｃ ａｃｉｄ：ポリＤＬ−乳酸）製で多数の微細な開孔を備えた多孔シートが使用されている（例えば、特許文献１）。このような多孔フィルムの作製において多数の微細な貫通孔は、例えば、レーザ加工により１個ずつ形成されている。そのため、生産性に劣るとの課題があった。 At present, a porous membrane having a large number of fine pores is used in various fields. For example, in a periodontal tissue regenerative medicine application, it is made of PDLLA (poly-DL-lactic acid: polyDL-lactic acid). A perforated sheet having a large number of fine openings is used (for example, Patent Document 1). In the production of such a porous film, a large number of fine through holes are formed one by one, for example, by laser processing. Therefore, there was a problem that the productivity was inferior.
また、歯周組織再生医療用途等、生体適合材料に使用される多孔シートは、溶媒や不純物の残留が忌避される。そのため、クリーンな環境下で製造することが要求される。 Also, porous sheets used for biocompatible materials such as periodontal tissue regenerative medical applications are repelled from residual solvents and impurities. Therefore, manufacturing in a clean environment is required.
本発明は、多数の貫通孔を備えた不織布シートを高い生産性で提供することを目的とする。 An object of this invention is to provide the nonwoven fabric sheet provided with many through-holes with high productivity.
上述したような現状を踏まえ、本発明者らは、高い生産性で製造することができる多数の微細な開孔を備えた多孔シートについて鋭意検討を行い、レーザ溶融静電紡糸法により製造された不織布シートであれば、製造時の捕集部材（コレクター）として特定の形状を有する捕集部材を用いることにより、多数の微細な開孔を備えた不織布シートとすることができ、このような不織布シートは、別途、開孔を設ける工程を経ることなく製造することができるため、生産性にも優れることを見出し、本発明を完成した。 Based on the present situation as described above, the present inventors have conducted intensive studies on a porous sheet having a large number of fine holes that can be produced with high productivity, and have been produced by a laser melting electrospinning method. If it is a nonwoven fabric sheet, it can be set as the nonwoven fabric sheet provided with many fine holes by using the collection member which has a specific shape as a collection member (collector) at the time of manufacture, Such a nonwoven fabric Since the sheet can be manufactured without going through a process of providing an opening separately, it was found that the sheet is excellent in productivity, and the present invention was completed.
すなわち、本発明は、厚さ方向に貫通した複数の貫通孔を備えた不織布シートであって、熱可塑性樹脂からなるシート状物にレーザ光を照射して上記シート状物の端部を加熱溶融させるとともに、上記シート状物の加熱溶融した部分と捕集部材との間に電位差を設け、繊維を上記捕集部材の方向に飛翔させ、上記捕集部材上に積層させることにより製造された不織布シートであり、上記捕集部材は、複数の貫通孔を有する捕集部材であることを特徴とする不織布シートに関する。 That is, the present invention is a non-woven sheet having a plurality of through-holes penetrating in the thickness direction, and the sheet-like material made of thermoplastic resin is irradiated with laser light to heat and melt the end portion of the sheet-like material. And a non-woven fabric produced by providing a potential difference between the heated and melted portion of the sheet-like material and the collecting member, causing the fibers to fly in the direction of the collecting member, and laminating on the collecting member It is a sheet | seat and the said collection member is a collection member which has a some through-hole, It is related with the nonwoven fabric sheet characterized by the above-mentioned.
前記不織布シートが備える貫通孔の開口径は、５μｍ〜２．０ｍｍであることが好ましい。 It is preferable that the opening diameter of the through-hole with which the said nonwoven fabric sheet is provided is 5 micrometers-2.0 mm.
前記不織布シートが備える貫通孔の壁面において、繊維同士が融着していないことが好ましい。 In the wall surface of the through hole provided in the nonwoven fabric sheet, it is preferable that the fibers are not fused.
前記繊維は、平均繊維径が２０μｍ以下であることが好ましい。 The fibers preferably have an average fiber diameter of 20 μm or less.
前記繊維は、生体適合性樹脂を含んでなる繊維であることが好ましい。 The fiber is preferably a fiber comprising a biocompatible resin.
前記生体適合性樹脂は、ポリ乳酸、ポリグリコール酸、ポリ乳酸−ポリグリコール酸共重合体、ポリカプロラクトンからなる群より選択される少なくとも１種である。 The biocompatible resin is at least one selected from the group consisting of polylactic acid, polyglycolic acid, polylactic acid-polyglycolic acid copolymer, and polycaprolactone.
さらに、本発明は、本発明の不織布シートからなることを特徴とする細胞培養足場材に関する。 Furthermore, this invention relates to the cell culture scaffold characterized by consisting of the nonwoven fabric sheet of this invention.
また、本発明は、上述した不織布シートを製造する方法であって、熱可塑性樹脂からなるシート状物にレーザ光を照射して上記シート状物の端部を加熱溶融させるとともに、上記シート状物の加熱溶融した部分と複数の貫通孔を有する捕集部材との間に電位差を設け、繊維を上記捕集部材の方向に飛翔させることにより、繊維を上記捕集部材上に積層させることを特徴とする不織布シートの製造方法に関する。 Further, the present invention is a method for producing the above-mentioned nonwoven fabric sheet, wherein the sheet-like material made of a thermoplastic resin is irradiated with laser light to heat and melt the end portion of the sheet-like material, and the sheet-like material A potential difference is provided between the heated and melted portion of the material and the collecting member having a plurality of through holes, and the fibers are stacked on the collecting member by flying the fibers in the direction of the collecting member. The present invention relates to a method for producing a nonwoven fabric sheet.
本発明の不織布シートの製造方法において、上記捕集部材は、パンチングメタルであることが好ましい。 In the manufacturing method of the nonwoven fabric sheet of this invention, it is preferable that the said collection member is a punching metal.
本発明の不織布シートの製造方法では、上記繊維が飛翔する空間の温度を２０〜３００℃とすることが好ましい。 In the manufacturing method of the nonwoven fabric sheet of this invention, it is preferable that the temperature of the space where the said fiber flies is 20-300 degreeC.
本発明の不織布シートの製造方法では、上記繊維が飛翔する空間の湿度が５０％以上となるように加湿することが好ましい。 In the manufacturing method of the nonwoven fabric sheet of this invention, it is preferable to humidify so that the humidity of the space where the said fiber flies may be 50% or more.
本発明の不織布シートは、レーザ溶融静電紡糸法により製造された不織布シートであり、製造時に捕集部材（コレクター）として複数の貫通孔を有する捕集部材を使用するため、多数の繊維をシート状に成形すると同時に、当該シートに多数の貫通孔（開孔）が設けられる。そのため、上記不織布シートは、高い生産性で製造された不織布シートとなる。
また、上記不織布シートは、レーザ溶融静電紡糸法により製造されたシートであるためシート内に溶剤が残留しないシートとすることができ、不純物の混入の回避も容易であり、また、材料樹脂の選択の自由度も高いため、生体適合性に優れた不織布シートや細胞培養足場材として好適な不織布シートとすることも容易である。
The nonwoven fabric sheet of the present invention is a nonwoven fabric sheet produced by a laser melt electrostatic spinning method. Since a collecting member having a plurality of through holes is used as a collecting member (collector) during production, a sheet of a large number of fibers is used. At the same time, the sheet is provided with a number of through holes (open holes). Therefore, the said nonwoven fabric sheet turns into a nonwoven fabric sheet manufactured with high productivity.
Further, since the nonwoven fabric sheet is a sheet manufactured by a laser melt electrostatic spinning method, it can be a sheet in which no solvent remains in the sheet, it is easy to avoid contamination of impurities, and the material resin Since the degree of freedom of selection is also high, it is easy to obtain a nonwoven sheet excellent in biocompatibility and a nonwoven sheet suitable as a cell culture scaffold.
また、本発明の不織布シートの製造方法によれば、本発明の不織布シートを好適に製造することができる。 Moreover, according to the manufacturing method of the nonwoven fabric sheet of this invention, the nonwoven fabric sheet of this invention can be manufactured suitably.
以下、本発明について、図面を参照しながら説明する。
本発明の不織布シートは、厚さ方向に貫通した複数の貫通孔を備えた不織布シートであって、熱可塑性樹脂からなるシート状物にレーザ光を照射して上記シート状物の端部を加熱溶融させるとともに、上記シート状物の加熱溶融した部分と捕集部材との間に電位差を設け、繊維を上記捕集部材の方向に飛翔させ、上記捕集部材上に積層させることにより製造された不織布シートであり、上記捕集部材は、複数の貫通孔を有する捕集部材であることを特徴とする。ここで、複数の貫通孔を有する捕集部材の代わりに、マスキングを捕集部材上に設置すること、捕集部材を局所的に加熱すること、または、剣山のような凹凸物を有する捕集部材を使用することによっても、不織布上に複数の貫通孔を設けることができる。
Hereinafter, the present invention will be described with reference to the drawings.
The nonwoven fabric sheet of the present invention is a nonwoven fabric sheet having a plurality of through holes penetrating in the thickness direction, and heats the end of the sheet material by irradiating the sheet material made of thermoplastic resin with laser light. Produced by melting and providing a potential difference between the heated and melted part of the sheet-like material and the collecting member, causing the fibers to fly in the direction of the collecting member, and laminating on the collecting member It is a nonwoven fabric sheet, The said collection member is a collection member which has a some through-hole, It is characterized by the above-mentioned. Here, instead of a collecting member having a plurality of through holes, masking is set on the collecting member, the collecting member is locally heated, or a collecting member having unevenness like a sword mountain. Also by using a member, a plurality of through holes can be provided on the nonwoven fabric.
図１は、本発明の不織布シートの一例を模式的に示す斜視図である。図１に示すように、本発明の不織布シート１は、厚さ方向に貫通した複数の貫通孔２を備えている。 FIG. 1 is a perspective view schematically showing an example of the nonwoven fabric sheet of the present invention. As shown in FIG. 1, the nonwoven fabric sheet 1 of this invention is equipped with the several through-hole 2 penetrated in the thickness direction.
上記不織布シートでは、上記貫通孔の壁面において、繊維同士が融着していないことが好ましい。上記不織布シートが歯周組織再生医療で使用される不織布シート等、細胞培養足場材である場合に求められる一つの重要な特性として多孔質性がある。多孔質性は組織を再生させるのに必要な細胞への十分な酸素および栄養を補給し、二酸化炭素や老廃物を速やかに排出する意味において重要である。繊維同士が融着した場合、貫通孔の壁面において融着面の繊維同士が接着して、水掻き状やフィルム状になり、多孔質性が失われてしまうからである。もう一つの重要な特性として、細胞接着性が挙げられる。本発明の不織布シートは、レーザ溶融静電紡糸法により製造された平均繊維径が好ましくは２０μｍ以下の繊維で形成されており、比表面積が大きく細胞接着性が高い。また、繊維の任意の横断面は異形であり、円横断面繊維の比面積よりさらに増大しており、細胞が繊維表面に接着する十分な面積をとることができる。繊維同士が融着した場合、貫通孔の壁面において融着面の繊維同士が接着して水掻き状やフィルム状になることで比表面積が小さくなり、その細胞接着性が低くなる。なお、本発明の不織布シートは、後述する方法により製造されたものであるため、通常、上記貫通孔の壁面において、繊維同士が融着していない不織布シートとなる。 In the said nonwoven fabric sheet, it is preferable that the fibers are not melt | fused in the wall surface of the said through-hole. One important characteristic required when the nonwoven fabric sheet is a cell culture scaffold such as a nonwoven fabric sheet used in periodontal tissue regenerative medicine is porosity. Porousness is important in terms of providing sufficient oxygen and nutrients to the cells necessary to regenerate the tissue and expelling carbon dioxide and waste products quickly. This is because when the fibers are fused together, the fibers on the fused surface are bonded to each other on the wall surface of the through-hole to form a web-like shape or a film shape, and the porous property is lost. Another important property is cell adhesion. The nonwoven fabric sheet of the present invention is formed of fibers having an average fiber diameter of preferably 20 μm or less produced by a laser melt electrostatic spinning method, and has a large specific surface area and high cell adhesion. In addition, the arbitrary cross section of the fiber is irregular and is larger than the specific area of the circular cross section fiber, so that a sufficient area for cells to adhere to the fiber surface can be taken. When the fibers are fused together, the specific surface area is reduced by bonding the fibers on the fused surface to each other on the wall surface of the through-hole to form a web-like shape or a film shape, and the cell adhesion is lowered. In addition, since the nonwoven fabric sheet of this invention is manufactured by the method mentioned later, normally, in the wall surface of the said through-hole, it becomes a nonwoven fabric sheet in which fibers are not melt | fused.
上記不織布シートが有する貫通孔の好ましい開口径は、好ましくは５μｍ〜２．０ｍｍ、より好ましくは２０μｍ〜１．５ｍｍ、とくに好ましくは５０μｍ〜１．０ｍｍである。特に、上記不織布シートが歯周組織再生医療で使用される不織布シート等、細胞培養足場材である場合には、上記貫通孔の開口径は、５０μｍ〜１．０ｍｍが好ましい。培養細胞への栄養と空気（酸素）の供給、および培養細胞からの代謝老廃物の回収を高い効率で行うことができれば、優れた細胞培養足場材になると期待され、この機能を発揮するには血液成分の通過が可能な開孔径が必須である。血液成分である赤血球は、７〜８μｍ、白血球は、６〜５０μｍであることから、血液成分の通過させには５０μｍ以上を確保し、かつ外部からの異物進入を防ぐ機能を併せ持たせるには１．０ｍｍ以下の細孔径を確保することが必要条件となるからである。 The preferable opening diameter of the through-hole which the said nonwoven fabric sheet has becomes like this. Preferably they are 5 micrometers-2.0 mm, More preferably, they are 20 micrometers-1.5 mm, Most preferably, they are 50 micrometers-1.0 mm. In particular, when the nonwoven fabric sheet is a cell culture scaffold such as a nonwoven fabric sheet used in periodontal tissue regenerative medicine, the opening diameter of the through hole is preferably 50 μm to 1.0 mm. If the nutrient and air (oxygen) supply to the cultured cells and the recovery of metabolic waste products from the cultured cells can be performed with high efficiency, it is expected to become an excellent cell culture scaffolding material. An aperture diameter that allows blood components to pass through is essential. Red blood cells, which are blood components, are 7-8 μm, and leukocytes are 6-50 μm. Therefore, it is necessary to secure 50 μm or more for the passage of blood components and to have the function of preventing foreign substances from entering from outside. This is because ensuring the pore diameter of 1.0 mm or less is a necessary condition.
上記貫通孔同士の間隔も特には限定されないが、好ましくは１０μｍ〜１．０ｍｍ、より好ましくは３０〜５００μｍ、とくに好ましくは５０〜３００μｍである。貫通孔同士の間隔が１０μｍより狭いと機械強度が低く、歯周組織再生手術などで負荷がかかった際、破損してしまい細胞培養足場材として好ましくない。なお、上記不織布シートにおいて、貫通孔の数は特に限定されない。 The interval between the through holes is not particularly limited, but is preferably 10 μm to 1.0 mm, more preferably 30 to 500 μm, and particularly preferably 50 to 300 μm. When the interval between the through holes is smaller than 10 μm, the mechanical strength is low, and when a load is applied in periodontal tissue regeneration surgery or the like, it is broken and is not preferable as a cell culture scaffold. In the nonwoven fabric sheet, the number of through holes is not particularly limited.
上記不織布シートを構成する繊維は、繊維径の小さい繊維であることが望ましく、平均繊維径は好ましくは２０μｍ以下、より好ましくは０．３〜１０μｍ、とくに好ましくは０．５〜５．０μｍである。また、このような平均繊維径を有する不織布シートには、例えば、５０〜１０００ｎｍ程度の繊維径を有する極細繊維や、１０μｍ以上の繊維が含まれていてもよい。さらに、上記繊維は、相対的に繊維径の大きい繊維と相対的に繊維径の小さい繊維とが混在していてもよい。さらに、繊維の任意の横断面が円横断面ではない異形断面繊維は、細胞接着性が高く好ましい。 The fibers constituting the nonwoven fabric sheet are desirably fibers having a small fiber diameter, and the average fiber diameter is preferably 20 μm or less, more preferably 0.3 to 10 μm, and particularly preferably 0.5 to 5.0 μm. . Moreover, the nonwoven fabric sheet which has such an average fiber diameter may contain the ultra fine fiber which has a fiber diameter of about 50-1000 nm, and the fiber of 10 micrometers or more, for example. Further, the fibers may include a fiber having a relatively large fiber diameter and a fiber having a relatively small fiber diameter. Furthermore, a modified cross-section fiber in which an arbitrary cross section of the fiber is not a circular cross section is preferable because of high cell adhesion.
また、上記不織布シートでは、不織布シートを構成する各繊維が、貫通孔非形成部において均質に分散し、かつ、三次元にランダムに配向していることが好ましい。不織布シートが歯周組織再生医療で使用される不織布シート等、細胞培養足場材である場合は、三次元的な細胞培養が可能で、培養細胞への栄養や空気（酸素）の供給および培養細胞からの代謝老廃物の除去を高い効率で行うことができるからである。繊維を配向させたシートや細胞培養ディッシュやプレートを用いた通常の培養では、配向した繊維方向のみに沿った一次元的な細胞培養や細胞培養ディッシュやプレート上での平面に沿った二次元的な細胞培養しか行えないのに対し、本発明の不織布シートは、繊維が三次元にランダムに配向しているため、培養細胞が該不織布シートの内部にまで入り込んで三次元的に付着増殖できるからである。また、生体内に移植して組織や骨などに対して形状追従性を付与するためには繊維がランダムに配向することが好ましく、形状の安定性を向上させるため、細胞培養時や歯周組織再生手術の操作性を向上させるには繊維が三次元にランダムに配向した不織布シートとすることが好ましい。 Moreover, in the said nonwoven fabric sheet, it is preferable that each fiber which comprises a nonwoven fabric sheet is uniformly disperse | distributed in a through-hole non-formation part, and is orientated at random in three dimensions. If the nonwoven sheet is a cell culture scaffold such as a nonwoven sheet used in periodontal tissue regenerative medicine, three-dimensional cell culture is possible, supplying nutrients to the cultured cells, supplying air (oxygen), and cultured cells This is because it is possible to remove metabolic waste from the plant with high efficiency. In normal culture using a fiber-oriented sheet, cell culture dish, or plate, one-dimensional cell culture along the direction of the oriented fiber or two-dimensional along a plane on the cell culture dish or plate The non-woven fabric sheet of the present invention can only be cultivated in a cell, but the fibers are randomly oriented in three dimensions, so that the cultured cells can penetrate into the non-woven fabric sheet and adhere and proliferate in three dimensions. It is. Further, in order to provide shape followability to a tissue or bone by transplanting into a living body, it is preferable that fibers are oriented randomly, and in order to improve the stability of the shape, cell culture or periodontal tissue In order to improve the operability of regenerative surgery, it is preferable to use a nonwoven fabric sheet in which fibers are randomly oriented in three dimensions.
上記不織布シートの厚さは特に限定されず、用途に応じて適宜選択すればよいが、複数の均一な貫通孔が形成され、均質な不織布シートとすることが容易な点から０．０１〜２．０ｍｍが好ましく、０．０５〜１．５ｍｍがより好ましく、０．１〜１．０ｍｍがとくに好ましい。 Although the thickness of the said nonwoven fabric sheet is not specifically limited, What is necessary is just to select suitably according to a use, From the point with which several uniform through-holes are formed and it is easy to set it as a uniform nonwoven fabric sheet, 0.01-2 0.0 mm is preferable, 0.05 to 1.5 mm is more preferable, and 0.1 to 1.0 mm is particularly preferable.
さらに、上記不織布シートの目付（貫通孔非形成部分の目付）も、用途に応じて選択でき、通常、１０〜５００ｇ／ｍ２であり、好ましくは５０〜４００ｇ／ｍ２、さらに好ましくは１００〜３００ｇ／ｍ２である。 Furthermore, the basis weight of the non-woven fabric sheet (the basis weight of the through-hole non-forming portion) can also be selected depending on the use, and is usually 10 to 500 g / m 2 , preferably 50 to 400 g / m 2 , more preferably 100 to 100%. 300 g / m 2 .
このような形状を有する本発明の不織布シートは、熱可塑性樹脂からなるシート状物にレーザ光を照射して上記シート状物の端部を加熱溶融させるとともに、上記シート状物の加熱溶融した部分と捕集部材との間に電位差を設け、繊維を上記捕集部材の方向に飛翔させ、上記捕集部材上に積層させることにより製造されたものである。このとき、捕集部材として、複数の貫通孔を有する捕集部材を用いることが重要であり、このような捕集部材を用いることにより、不織布シートを成形すると同時に多数の貫通孔を備えた不織布シートとすることができる。 The nonwoven fabric sheet of the present invention having such a shape is obtained by irradiating a sheet-like material made of a thermoplastic resin with a laser beam to heat and melt the end portion of the sheet-like material and at the same time the heated and melted portion of the sheet-like material. And a collecting member, a potential difference is provided, and the fibers are produced by flying in the direction of the collecting member and laminating on the collecting member. At this time, it is important to use a collecting member having a plurality of through-holes as a collecting member. By using such a collecting member, a non-woven fabric provided with a large number of through-holes at the same time as forming a non-woven sheet. It can be a sheet.
このような方法で製造された不織布シートは、溶媒型の静電紡糸法と異なり溶媒を使用しなくても得ることができ、また、レーザ光以外を熱源とする溶融型の静電紡糸法と異なり、紡糸時に熱可塑性樹脂の熱劣化がなく、クリーンで不純物の混入のない製造環境の構築が容易であるため、高品質な不織布シートとなる。 The nonwoven fabric sheet produced by such a method can be obtained without using a solvent unlike the solvent-type electrospinning method, and can be obtained by using a melt-type electrospinning method using a heat source other than laser light as a heat source. On the other hand, the thermoplastic resin is not thermally deteriorated during spinning, and it is easy to construct a production environment that is clean and free of impurities, so that a high-quality nonwoven fabric sheet is obtained.
以下、本発明の不織布シートが製造される方法を説明する。なお、このような製造方法自体も本発明の１つである。
図２（ａ）は、本発明の不織布シートを製造する方法を模式的に示す概略図である。上記不織布シートを製造する場合には、図２（ａ）に示すように、レーザ光源１１から出射したレーザ光１２を、レーザ光走査手段１５を介して保持部材１８に保持された熱可塑性樹脂からなるシート状物１７の端部１７ａを走査するように照射するとともに、電源２０により電圧を印加し、端部１７ａと、シート状物１７の端部１７ａに対向配置された捕集部材１９との間に電位差を生じさせる。その結果、図２（ｂ）に示すように、レーザ光１２の照射により、シート状物１７の端部１７ａが加熱溶融されるとともに、この加熱溶融した部分に電荷が付与されることとなる。そして、電荷が付与された加熱溶融部には、その表面に電荷が集まり反発することによって、次第に複数の針状突出部（以下、テーラーコーンともいう）１１７が形成され、電荷の反発力が表面張力を超えると、溶融した熱可塑性樹脂は、テーラーコーン１１７先端から静電引力により捕集部材１９に向かって繊維として吐出され、捕集部材１９方向に飛翔する。その結果、伸長した繊維は捕集部材１９上に堆積し、捕集される。
Hereinafter, the method by which the nonwoven fabric sheet of this invention is manufactured is demonstrated. Such a manufacturing method itself is also one aspect of the present invention.
Fig.2 (a) is schematic which shows typically the method of manufacturing the nonwoven fabric sheet of this invention. In the case of manufacturing the nonwoven fabric sheet, as shown in FIG. 2A, the laser light 12 emitted from the laser light source 11 is made from the thermoplastic resin held by the holding member 18 via the laser light scanning means 15. The end 17a of the sheet-like object 17 is irradiated so as to scan, and a voltage is applied by the power source 20, and the end part 17a and the collecting member 19 disposed opposite to the end 17a of the sheet-like object 17 A potential difference is generated between them. As a result, as shown in FIG. 2B, the end portion 17a of the sheet-like material 17 is heated and melted by the irradiation of the laser beam 12, and an electric charge is given to the heated and melted portion. In the heated and melted portion to which electric charge is applied, a plurality of needle-like protrusions (hereinafter also referred to as tailor cones) 117 are gradually formed by collecting and repelling the charge on the surface. When the tension is exceeded, the molten thermoplastic resin is discharged as fibers from the tip of the tailor cone 117 toward the collecting member 19 by electrostatic attraction, and flies in the direction of the collecting member 19. As a result, the elongated fibers are deposited on the collecting member 19 and collected.
捕集部材１９は、複数の貫通孔を有する。このような捕集部材の具体例としては、金属メッシュや、パンチングメタル等、導電性を有し、複数の貫通孔を有する捕集部材が挙げられる。両者のうちではパンチングメタルの方が好ましい。金属メッシュでは金属ワイヤが編み込まれているため、捕集面に凹凸（うねり）が存在することとなるが、パンチングメタルであれば捕集面が平坦であり、厚さや開口径の均一な不織布シートを作製するのにより適しているからである。金属メッシュやパンチングメタルの材質としては、鉄、ステンレス、真鍮、アルミニウム、銅、チタンなど、及びメッキ、表面処理、塗装などの前記金属板、前記金属の合金などが挙げられる。パンチングメタルの貫通孔に非導電性材料を埋め込んでも良い。飛翔した繊維が、非導電材料を避けて、導電性のパンチングメタル表面に捕集され、厚さや開口径の均一な不織布シートを作製するのにより適しているからである。 The collection member 19 has a plurality of through holes. Specific examples of such a collecting member include a collecting member having conductivity and a plurality of through holes, such as a metal mesh or a punching metal. Of these, punching metal is preferred. Since the metal mesh is woven into the metal mesh, there will be irregularities (undulations) on the collection surface, but if it is punched metal, the collection surface will be flat and the nonwoven fabric sheet with a uniform thickness and opening diameter It is because it is more suitable for producing. Examples of the material of the metal mesh or punching metal include iron, stainless steel, brass, aluminum, copper, titanium, and the like, the metal plate such as plating, surface treatment, and coating, and the metal alloy. A nonconductive material may be embedded in the through hole of the punching metal. This is because the flying fibers are collected on the surface of the conductive punching metal, avoiding the non-conductive material, and more suitable for producing a nonwoven fabric sheet having a uniform thickness and opening diameter.
上記捕集部材が樹脂等の非導電性材料からなる場合には、上記捕集部材の捕集面と反対側の面には金属部材を配設する。シート状物の端部と捕集面との間に電位差を設ける必要があるからである。この場合、金属部材の形状は、捕集部材と同一の平面形状を有するものとする。なお、捕集部材と金属部材とは一体化していてもよい。また、捕集部材（又は金属部材）は接地（アース）されていることが好ましい。製造された不織布シートの取り扱い性が向上するからである。 When the collection member is made of a non-conductive material such as resin, a metal member is disposed on the surface of the collection member opposite to the collection surface. This is because it is necessary to provide a potential difference between the end of the sheet-like material and the collection surface. In this case, the metal member has the same planar shape as the collecting member. The collecting member and the metal member may be integrated. Moreover, it is preferable that the collection member (or metal member) is grounded. It is because the handleability of the manufactured nonwoven fabric sheet improves.
本発明では、このような多数の貫通孔を有する捕集部材が用いられるため、シート状物の端部（テーラーコーン）から飛翔した繊維は捕集部材の貫通孔が形成されていない領域に積層されることとなる。そのため、上述した多数の貫通孔を備えた捕集部材を用いることにより、得られた不織布シートは、厚さ方向に貫通した複数の貫通孔を備えた不織布シートとなる。 In the present invention, since the collecting member having such a large number of through holes is used, the fibers flying from the end portion (tailor cone) of the sheet-like material are laminated in a region where the through holes of the collecting member are not formed. Will be. Therefore, the obtained nonwoven fabric sheet turns into a nonwoven fabric sheet provided with the several through-hole penetrated in the thickness direction by using the collection member provided with many through-holes mentioned above.
上記捕集部材が有する貫通孔について、その形状は、得られる不織布シートが備える貫通孔の形状とほぼ同一である。従って、上記捕集部材の貫通孔の開口径は特に限定されず不織布シートが有する貫通孔の形状に応じて適宜設定すればよい。 About the through-hole which the said collection member has, the shape is substantially the same as the shape of the through-hole with which the obtained nonwoven fabric sheet is equipped. Therefore, the opening diameter of the through hole of the collecting member is not particularly limited, and may be set as appropriate according to the shape of the through hole of the nonwoven fabric sheet.
レーザ光走査手段１５は、シート状物１７の端部１７ａを走査するようにレーザ光を照射するための光学部品の集合体であり、反射ミラー１３とポリゴンミラー１４とで構成されている。レーザ光源１１から出射したレーザ光を、反射ミラー１３を介して高速で回転するポリゴンミラー１４に導入することにより、ポリゴンミラー１４を介して、シート状物１７の端部１７ａを走査するように均一にレーザ光を照射することができる。 The laser beam scanning means 15 is an assembly of optical components for irradiating the laser beam so as to scan the end portion 17 a of the sheet-like material 17, and is constituted by a reflection mirror 13 and a polygon mirror 14. The laser light emitted from the laser light source 11 is introduced into the polygon mirror 14 that rotates at high speed via the reflection mirror 13, so that the end 17 a of the sheet-like object 17 is scanned uniformly via the polygon mirror 14. Can be irradiated with laser light.
また、図２（ａ）に示した例では、ポリゴンミラー１４を介してシート状物の端部全体にレーザ光を照射しているが、シート状物の端部全体にレーザ光を照射することができれば、他の方法でレーザ光をシート状物の端部に照射してもよく、例えば、ポリゴンミラー１４に代えて、ガルバノミラーを使用してレーザ光を照射してもよい。また、図２（ａ）に示した例では、シート状物１７を保持する保持部材１８が電極としての機能を兼ねており、高電圧発生装置２０により、保持部材１８に電圧が印加されると、シート状物１７の端部１７ａに電荷が付与されることとなる。 In the example shown in FIG. 2A, the entire end of the sheet is irradiated with laser light via the polygon mirror 14, but the entire end of the sheet is irradiated with laser light. If possible, the laser beam may be irradiated to the end of the sheet-like material by another method. For example, instead of the polygon mirror 14, the laser beam may be irradiated using a galvano mirror. In the example shown in FIG. 2A, the holding member 18 that holds the sheet-like material 17 also functions as an electrode, and when a voltage is applied to the holding member 18 by the high voltage generator 20. The electric charge is applied to the end portion 17 a of the sheet-like material 17.
また、保持部材１８では、シート状物１７の端部１７ａから繊維が吐出されるにしたがって、シート状物１７を捕集部材１９側に連続的に送り出す。上記シート状物を連続的に送り出す場合、その供給速度は特に限定されないが、通常、０．０１〜１５０．０ｍｍ／分であり、好ましくは０．０５〜１００．０ｍｍ／分、さらに好ましくは０．１〜６０．０ｍｍ／分である。速度を速くすれば生産性が高まるが、速すぎると、レーザ光照射部近傍での熱可塑性樹脂が充分溶融しないので繊維が紡糸されにくい。一方、速度が遅いと、熱可塑性樹脂が分解したり、生産性が低くなったりすることがある。 Further, in the holding member 18, the sheet-like material 17 is continuously sent out to the collecting member 19 side as the fibers are discharged from the end portion 17 a of the sheet-like material 17. When the sheet-like material is continuously fed out, the supply speed is not particularly limited, but is usually 0.01 to 150.0 mm / min, preferably 0.05 to 100.0 mm / min, and more preferably 0. 1-60.0 mm / min. Increasing the speed increases the productivity, but if the speed is too high, the thermoplastic resin in the vicinity of the laser beam irradiation portion does not melt sufficiently, so that the fibers are hardly spun. On the other hand, when the speed is low, the thermoplastic resin may be decomposed or the productivity may be lowered.
また、保持部材１８は、捕集部材１９と対向する側面に並列に配置された複数のＮ２ガス吐出口１８ｂを備えるとともに、Ｎ２ガス吐出口１８ｂを備える面と直交する側面に配置されたＮ２ガス供給口１８ａとを備えている。そして、Ｎ２ガス吐出口１８ｂとＮ２ガス供給口１８ａとは内部の配管（図示せず）を通じて連結されており、製造時にはＮ２ガス供給口１８ａよりＮ２ガスを導入し、シート状物の端部にＮ２ガスを供給することにより、熱可塑性樹脂の酸化分解を防止することができる。酸化分解を防止するガスは、Ｎ２ガスに限定されることはなく、ヘリウム、アルゴン等の不活性ガス、二酸化炭素などの非酸化性ガスであればいかなるガスであっても良い。なお、上記不織布シートを製造する際に、Ｎ２ガスは必ずしも供給しなくてもよい。 The holding member 18 includes a plurality of N 2 gas discharge ports 18b arranged in parallel on the side surface facing the collection member 19, and is also disposed on a side surface orthogonal to the surface including the N 2 gas discharge ports 18b. And an N 2 gas supply port 18a. Then, the N 2 gas discharge ports 18b and N 2 gas supply port 18a is connected through an internal pipe (not shown), the N 2 gas was introduced from the N 2 gas supply port 18a at the time of manufacture, sheet By supplying N 2 gas to the end portion of the thermoplastic resin, oxidative decomposition of the thermoplastic resin can be prevented. The gas for preventing oxidative decomposition is not limited to N 2 gas, and may be any gas as long as it is an inert gas such as helium or argon, or a non-oxidizing gas such as carbon dioxide. In producing the non-woven fabric sheet, N 2 gas may not necessarily supplied.
また、図２（ａ）に示した製造方法では、繊維の飛翔空間に加熱空気を供給するための加熱空気供給装置２２を使用している。このように、繊維の飛翔空間に加熱空気を供給することにより、飛翔させる繊維の繊維径を小さくすることができる。即ち、紡糸空間を加熱することにより、形成されつつある繊維の急激な温度低下を抑制することができ、これにより、繊維の伸長又は延伸を促進し、より極細な繊維からなる不織布シートとすることができるのである。なお、上記不織布シートを製造する際に、乾燥空気は必ずしも繊維の飛翔空間に供給しなくてもよい。 Moreover, in the manufacturing method shown to Fig.2 (a), the heating air supply apparatus 22 for supplying heated air to the flying space of a fiber is used. Thus, by supplying heated air to the flying space of the fibers, the fiber diameter of the fibers to fly can be reduced. That is, by heating the spinning space, it is possible to suppress a rapid temperature drop of the fiber being formed, thereby promoting the elongation or stretching of the fiber, and forming a nonwoven fabric sheet made of finer fibers. Can do it. In addition, when manufacturing the said nonwoven fabric sheet, dry air does not necessarily need to be supplied to the flight space of a fiber.
上記飛翔空間の温度は、シート状物の種類にも依存し特に限定はされないが、好ましくは２０〜３００℃、より好ましくは１００〜２５０℃、とくに好ましくは１５０〜２００℃である。繊維が飛翔する空間の温度が高くなれば、溶融された熱可塑性樹脂が飛翔空間内で溶融状態を保ちつつエレクトロスピニングできるので、目的の繊維径とすることが容易である。２０℃未満では、シート状物から飛翔した繊維が静電引力による伸長又は延伸によって細くなる前に固化してしまう場合があり、逆に３００℃を超えると、シート状物から飛翔した繊維が熱分解したり、溶融したまま捕集部材に到達して、フィルム状となり、多孔質性を有した不織布シートとならないことがある。 The temperature of the flying space depends on the type of the sheet-like material and is not particularly limited, but is preferably 20 to 300 ° C, more preferably 100 to 250 ° C, and particularly preferably 150 to 200 ° C. If the temperature of the space in which the fibers fly is high, the melted thermoplastic resin can be electrospun while maintaining the molten state in the flying space, so that the desired fiber diameter can be easily obtained. If the temperature is lower than 20 ° C, the fiber flying from the sheet-like material may solidify before becoming thin by stretching or stretching due to electrostatic attraction. Conversely, if the temperature exceeds 300 ° C, the fiber flying from the sheet-like material is heated. It may decompose or reach the collecting member while being melted to form a film and not a non-woven fabric sheet having a porous property.
上記加熱空気供給装置における加熱手段としては、例えば、ヒーター（ハロゲンヒーター等）等が挙げられる。また、加熱空気の温度は、熱可塑性樹脂の融点に応じて、例えば、５０℃以上の温度から熱可塑性樹脂の発火点未満までの温度範囲から選択できるが、紡糸性の点から、熱可塑性樹脂の融点未満の温度が好ましい。 Examples of the heating means in the heated air supply device include a heater (such as a halogen heater). The temperature of the heated air can be selected, for example, from a temperature range from 50 ° C. or higher to less than the ignition point of the thermoplastic resin, depending on the melting point of the thermoplastic resin. A temperature below the melting point of is preferred.
上記飛翔空間の湿度は特に限定されないが、好ましくは５０％以上、より好ましくは６０％以上、とくに好ましくは７０％以上である。湿度が高くなれば、繊維表面に水分子が吸着して表面に薄い水の層が形成され、沿面イオン伝道効果により表面抵抗が急速に小さくなる。沿面イオン伝道効果により、本来表面抵抗が高い熱可塑性樹脂であってもエレクトロスピニングが容易となると共に、捕集部に捕集された繊維表面の表面抵抗が低くなり、捕集部材の形状を反映した、複数の貫通孔を有する多数の微細な開孔を備えた、不織布シートとすることが容易になる。沿面イオン伝道効果の概念については、「株式会社朝倉書店発行「静電気工学シリーズ１静電気の基礎、Ｐ１３９−２．２沿面イオン伝道」に詳細が記載されている。一方、５０％未満では、沿面イオン伝道効果が非常に小さいため、表面抵抗が高い熱可塑性樹脂は、エレクトロスピニングが起こりにくくなり、且つ捕集部に捕集された繊維によって捕集部表面の表面抵抗が高くなり、捕集部材の形状を反映した貫通孔が形成できなくなる。 The humidity of the flying space is not particularly limited, but is preferably 50% or more, more preferably 60% or more, and particularly preferably 70% or more. When the humidity increases, water molecules are adsorbed on the fiber surface and a thin water layer is formed on the surface, and the surface resistance rapidly decreases due to the creeping ion transmission effect. The creeping ion transmission effect facilitates electrospinning even for thermoplastic resins that have inherently high surface resistance, and the surface resistance of the fiber surface collected in the collection section is reduced, reflecting the shape of the collection member. Thus, it becomes easy to obtain a nonwoven fabric sheet having a large number of fine openings having a plurality of through holes. The concept of the creeping ion evangelization effect is described in detail in “Asakura Shoten Co., Ltd.“ Static Engineering Series 1 Basics of Static Electricity, P139-2.2 Creeping Ion Evangelism ”. On the other hand, if it is less than 50%, the creeping ion transmission effect is very small. Therefore, the thermoplastic resin with high surface resistance is less likely to cause electrospinning, and the surface of the surface of the collecting part is collected by the fibers collected in the collecting part. Resistance becomes high, and a through hole reflecting the shape of the collecting member cannot be formed.
加湿の方法は特に特に限定されないが、ナノバブル水で加湿することが好ましい。ナノバブル水とは、超微細気泡を含む水であって、超微細気泡は、最頻粒子径が５００ｎｍ以下、好ましくは３００ｎｍ以下、最も好ましくは１５０ｎｍ以下であり、１ｍｌ当たり１０万個以上、好ましくは３０万個以上、より好ましくは５０万個以上、最も好ましくは１００万個以上存在する。超微細気泡内は空気、窒素、酸素、およびオゾンから選択される気体である。なお、本明細書中で言及される超微細気泡の数は、ナノ粒子解析システム ナノサイトシリーズ（ＮａｎｏＳｉｇｈｔ社製）により測定されたものである。 The method of humidification is not particularly limited, but it is preferable to humidify with nanobubble water. Nanobubble water is water containing ultrafine bubbles, and the ultrafine bubbles have a mode particle diameter of 500 nm or less, preferably 300 nm or less, most preferably 150 nm or less, and 100,000 or more per ml, preferably There are 300,000 or more, more preferably 500,000 or more, most preferably 1,000,000 or more. Inside the ultrafine bubbles is a gas selected from air, nitrogen, oxygen, and ozone. The number of ultrafine bubbles mentioned in the present specification is measured by the nanoparticle analysis system Nanosite Series (manufactured by NanoSight).
上述した方法で製造される不織布シートを連続的に製造する場合には、捕集部材をシート状物の端部に対して相対的かつ経時的に移動させればよい。このとき、捕集部材をシート状物の端部に対して移動させても良いし、シート状物の端部の位置を捕集部材に対して移動させても良く、両者を同時に移動させても良い。このとき、捕集部材やシート状物の端部の移動は連続的に行っても良いし、断続的に行っても良い。また、捕集部材をシート状物の端部に対して相対的させる態様としては、テーラーコーンから捕集部材に向かって飛翔中の繊維に、力学的、磁力的又は電気的な力を作用させることで捕集位置を移動させる態様、例えば、飛翔中の繊維にエアーを吹き付ける、捕集部の方向に吸引するなどの態様を採用することもできる。もちろん、これらの捕集部材をシート状物の端部に対して相対的に移動させる態様は、組合せて使用してもよい。 When continuously manufacturing the nonwoven fabric sheet manufactured by the method described above, the collection member may be moved relative to the end of the sheet-like material with time. At this time, the collecting member may be moved with respect to the end of the sheet-like material, or the position of the end of the sheet-like material may be moved with respect to the collecting member. Also good. At this time, the movement of the collecting member or the end of the sheet-like material may be performed continuously or intermittently. Moreover, as an aspect which makes a collection member relatively with respect to the edge part of a sheet-like thing, a mechanical, magnetic, or electrical force is made to act on the fiber in flight toward a collection member from a tailor cone. Thus, it is possible to adopt a mode in which the collection position is moved, for example, a mode in which air is blown on the flying fiber or suction is performed in the direction of the collection unit. Of course, a mode in which these collecting members are moved relative to the end of the sheet-like material may be used in combination.
上記捕集部材等の移動速度は特に限定されず、製造する繊維シートの目付等を考慮して適宜決定すればよい。例えば、目付１００ｇ／ｍ２のシート状物の供給速度が０．５ｍｍ／分である場合、捕集部材の移動速度を１００ｍｍ／分程度に設定することにより、目付０．５ｇ／ｍ２程度の不織布シートを連続的に製造することができる。 The moving speed of the collection member or the like is not particularly limited, and may be appropriately determined in consideration of the basis weight of the fiber sheet to be manufactured. For example, when the supply speed of the sheet-like material with a basis weight of 100 g / m 2 is 0.5 mm / min, by setting the moving speed of the collecting member to about 100 mm / min, the basis weight is about 0.5 g / m 2 . Nonwoven sheets can be produced continuously.
次に、電荷が付与されたシート状物の加熱溶融部にテーラーコーンが形成され、繊維が吐出される工程についてもう少し詳しく説明する。図２（ｂ）は、図２（ａ）の加熱溶融部に形成されたテーラーコーンの拡大上面図である。図２（ａ）、（ｂ）に示すように、電圧を印加した状態のシート状物１７の端部１７ａを走査するようにレーザ光１２を照射すると、シート状物１７の端部１７ａに線状の加熱溶融部が形成され、さらに、加熱溶融部の先端に波状の摂動（メニスカス不安定現象）が発生し、この摂動（メニスカス）が発達してテーラーコーン１１７が形成され、電荷の反発力が表面張力を超えると、テーラーコーン１１７から捕集部材１９側（図２（ｂ）中、右側）に向かって繊維が吐出される。 Next, the process in which the tailor cone is formed in the heated and melted portion of the sheet-like material to which electric charge has been applied and the fibers are discharged will be described in a little more detail. FIG.2 (b) is an enlarged top view of the tailor cone formed in the heating-melting part of Fig.2 (a). As shown in FIGS. 2A and 2B, when the laser beam 12 is irradiated so as to scan the end portion 17a of the sheet-like object 17 in a state where a voltage is applied, a line is applied to the end portion 17a of the sheet-like object 17. Further, a wave-like perturbation (meniscus instability phenomenon) occurs at the tip of the heat-melting portion, and this perturbation (meniscus) develops to form a tailor cone 117, and the repulsive force of charge Exceeds the surface tension, the fibers are discharged from the tailor cone 117 toward the collection member 19 side (right side in FIG. 2B).
本発明の不織布シートにおいて、原料となるシート状物の厚さは特に限定されないが、通常０．０１〜１０ｍｍであり、好ましくは、０．０３〜５．０ｍｍである。そして、上記シート状物の厚さを適宜変更することにより、テーラーコーンの数（テーラーコーンの間隔（図２（ｂ）中、Ｗ））を調整することができる。具体的には、シート状物の厚さが厚いほど、テーラーコーンの数が少なく（テーラーコーンの間隔が大きく）なる傾向にある。この理由は定かではないが、シート状物の厚さが厚くなると、シート状物の端部における溶融体の体積が増加することとなり、その結果、テーラーコーンがよく発達し、各テーラーコーン間の静電反発が大きくなるため、テーラーコーンの間隔が大きくなると考えられる。なお、テーラーコーンが発達するとは、テーラーコーンの高さ（図２（ｂ）中、Ｈ）が大きくなることを意味する。 In the nonwoven fabric sheet of the present invention, the thickness of the sheet material as a raw material is not particularly limited, but is usually 0.01 to 10 mm, preferably 0.03 to 5.0 mm. And the number of tailor cones (the interval between tailor cones (W in FIG. 2B)) can be adjusted by appropriately changing the thickness of the sheet-like material. Specifically, the thicker the sheet-like material, the smaller the number of tailor cones (the larger the tailor cone interval). The reason for this is not clear, but as the thickness of the sheet-like material increases, the volume of the melt at the end of the sheet-like material increases, and as a result, the tailor cones develop well, and between each tailor cone Since the electrostatic repulsion increases, it is considered that the interval between the tailor cones increases. The development of the tailor cone means that the height of the tailor cone (H in FIG. 2B) increases.
上記シート状物は、熱可塑性樹脂からなるものであり、熱可塑性樹脂製の繊維からなる繊維集合体（不織布、織物、編み物等）であってもよいし、熱可塑性樹脂を予め混練した後、成形して作製したシートであってもよい。また、その形状は、特に限定されず、例えば、フィルム、プレート、ボード等が挙げられる。 The sheet-like material is made of a thermoplastic resin, and may be a fiber assembly (nonwoven fabric, woven fabric, knitted fabric, etc.) made of thermoplastic resin fibers, or after kneading the thermoplastic resin in advance, It may be a sheet produced by molding. Moreover, the shape is not specifically limited, For example, a film, a plate, a board etc. are mentioned.
上記熱可塑性樹脂としては、生体適合性、または生体吸収性が高い樹脂であれば限定されず、ポリグリコール酸、ポリ乳酸（ポリＬ−乳酸、ポリＤ−乳酸、ポリＤＬ−乳酸）、ポリ乳酸−ポリグリコール酸共重合体、ポリカプロラクトン、ポリジオキサノン、ポリトリメチレンカーボネート、ポリブチレンサクシネート、ポリエチレンサクシネート、およびこれらの共重合体、Ｎ−メチルピロリドン、炭酸トリメチレン、パラジオキサノン、１，５−ジオキセパン−２−オンなどのホモポリマー、コポリマー又はこれらポリマーの混合物からなる群より選択される少なくとも一種である。好ましくは主として脂肪族ポリエステルからなる。脂肪族ポリエステルとしては、ポリグリコール酸、ポリ乳酸、ポリカプロラクトン、およびこれらの共重合体からなる群から選ばれる少なくとも一種であることが好ましい。これらの中でも、生体適合性、及び生体吸収性に優れるポリＤＬ−乳酸（ＰＤＬＬＡ）含む熱可塑性樹脂が好ましい。 The thermoplastic resin is not limited as long as it is a biocompatible or highly bioabsorbable resin. Polyglycolic acid, polylactic acid (poly L-lactic acid, poly D-lactic acid, poly DL-lactic acid), polylactic acid -Polyglycolic acid copolymer, polycaprolactone, polydioxanone, polytrimethylene carbonate, polybutylene succinate, polyethylene succinate, and copolymers thereof, N-methylpyrrolidone, trimethylene carbonate, paradioxanone, 1,5- It is at least one selected from the group consisting of homopolymers such as dioxepane-2-one, copolymers or mixtures of these polymers. Preferably, it consists mainly of aliphatic polyester. The aliphatic polyester is preferably at least one selected from the group consisting of polyglycolic acid, polylactic acid, polycaprolactone, and copolymers thereof. Among these, a thermoplastic resin containing poly DL-lactic acid (PDLLA) having excellent biocompatibility and bioabsorbability is preferable.
上記熱可塑性樹脂のなかでは、ナノ繊維等の極細繊維を形成し易い点からは、低粘度の熱可塑性樹脂が好ましい。また、電荷による電気的牽引力が発生しやすく、テーラーコーンを形成し易い点からは、極性を有する熱可塑性樹脂が好ましい。更に、歯周組織再生医療用途等で細胞培養足場材として使用する場合には、ポリ乳酸（ＰＬＡ）、特にポリＤＬ−乳酸（ＰＤＬＬＡ）が好ましい。細胞培養足場として好適だけではなく、力学特性と吸収特性の面で、歯周組織再生用膜にとって望ましい特性（程よい柔らかさとガラス転移点、吸収期間等）を持たせるためである。 Among the above thermoplastic resins, a low viscosity thermoplastic resin is preferable from the viewpoint of easily forming ultrafine fibers such as nanofibers. In addition, a thermoplastic resin having a polarity is preferable from the viewpoint of easily generating an electric traction force due to electric charges and easily forming a tailor cone. Furthermore, polylactic acid (PLA), particularly polyDL-lactic acid (PDLLA) is preferred when used as a cell culture scaffold for periodontal tissue regenerative medical applications and the like. This is not only suitable as a cell culture scaffold, but also has desirable characteristics (moderate softness and glass transition point, absorption period, etc.) for the periodontal tissue regeneration membrane in terms of mechanical characteristics and absorption characteristics.
なお、シート状物は、熱可塑性樹脂のみからなるものに限定されず、繊維に用いられる各種の添加剤、例えば、安定剤（酸化防止剤、紫外線吸収剤、熱安定剤等）、帯電防止剤、充填剤、滑剤、湿潤剤、可塑剤、増粘剤、分散剤、発泡剤、界面活性剤等を含有した熱可塑性樹脂組成物からなるものであってもよい。また、細胞の培養、組織の再生などに有効なタンパク質を添加剤として使用してもよい。例えば、サイトカイン、フィブロネクチン、ラミニン、コラーゲン、グリコサミノグリカン（ヘパラン硫酸、ヒアルロン酸など）、ヘパリン、キチン、コラーゲン、ポリリジン、ポリアルギニン、セリシン、セルロース、デキストラン、及びプルランなどがあげられる。これらの添加剤は、単独で又は二種以上組み合わせて含有することができる。さらに、本発明では、熱可塑性樹脂に加え、骨や生体組織の成長因子、ミノサイクリン、ドキシサイクリン等のテトラサイクリン系、クラリスロマイシン、アジスロマイシン等のマクロライド系、レボフロキサシン等のニューキノロン系、テリスロマイシン等のケトライド系などの抗菌性物質、フルルビプロフェン等の非ステロイド系、デキサメタゾン等のステロイド系等の抗炎症剤、アズレン等の天然由来物、ビスフォスホネート等の骨吸収阻害剤等の薬剤を適宜配合することができる。 The sheet-like material is not limited to a thermoplastic resin alone, and various additives used for fibers, such as stabilizers (antioxidants, ultraviolet absorbers, thermal stabilizers, etc.), antistatic agents. And a thermoplastic resin composition containing a filler, a lubricant, a wetting agent, a plasticizer, a thickener, a dispersant, a foaming agent, a surfactant and the like. A protein effective for cell culture, tissue regeneration, etc. may be used as an additive. For example, cytokine, fibronectin, laminin, collagen, glycosaminoglycan (eg, heparan sulfate, hyaluronic acid), heparin, chitin, collagen, polylysine, polyarginine, sericin, cellulose, dextran, pullulan and the like can be mentioned. These additives can be contained alone or in combination of two or more. Furthermore, in the present invention, in addition to thermoplastic resins, bone and biological tissue growth factors, tetracyclines such as minocycline and doxycycline, macrolides such as clarithromycin and azithromycin, new quinolones such as levofloxacin, and tethromycin Antibacterial substances such as ketolides, non-steroids such as flurbiprofen, steroids such as dexamethasone, natural products such as azulene, and bone resorption inhibitors such as bisphosphonates It can mix | blend suitably.
これらの添加剤のなかでは、界面活性剤を用いることが好ましい。シート状物に高電圧を印加して電荷を注入する際、熱可塑性樹脂からなるシート状物は電気絶縁性が高く、電気抵抗の低くなる熱溶融部までに電荷を注入しにくくなるが、熱可塑性樹脂の繊維からなる繊維集合体は、電気絶縁性の大きい繊維の表面に界面活性剤などを付与することでシート状物の電気抵抗が低下し、熱溶融部まで十分に電荷を注入できるからである。 Of these additives, a surfactant is preferably used. When injecting charges by applying a high voltage to the sheet material, the sheet material made of thermoplastic resin has high electrical insulation, and it becomes difficult to inject charges into the heat-melting part where the electrical resistance is low. A fiber assembly made of plastic resin fibers reduces the electrical resistance of the sheet-like material by adding a surfactant or the like to the surface of a fiber having a large electrical insulation property, and can sufficiently inject electric charges up to the heat melting part. It is.
これらの添加剤は、それぞれ、熱可塑性樹脂１００質量部に対して、５０質量部以下の割合で使用でき、好ましくは０．０１〜３０質量部、より好ましくは０．１〜５質量部である。 Each of these additives can be used at a ratio of 50 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin, preferably 0.01 to 30 parts by mass, more preferably 0.1 to 5 parts by mass. .
上記レーザ光源としては、例えば、ＹＡＧレーザ、炭酸ガス（ＣＯ２）レーザ、アルゴンレーザ、エキシマレーザ、ヘリウム−カドミウムレーザ等が挙げられる。これらのなかでは、電源効率が高く、熱可塑性樹脂の溶融性が高い点から、炭酸ガスレーザが好ましい。また、レーザ光の波長は、例えば、２００ｎｍ〜２０μｍ、好ましくは５００ｎｍ〜１８μｍ、さらに好ましくは５〜１５μｍ程度である。 Examples of the laser light source include a YAG laser, a carbon dioxide (CO 2 ) laser, an argon laser, an excimer laser, and a helium-cadmium laser. Among these, a carbon dioxide laser is preferable from the viewpoint of high power efficiency and high meltability of the thermoplastic resin. The wavelength of the laser light is, for example, about 200 nm to 20 μm, preferably about 500 nm to 18 μm, and more preferably about 5 to 15 μm.
また、上記レーザ光の出力は、加熱溶融部の温度が熱可塑性樹脂の融点以上となり、かつ、熱可塑性樹脂の発火点以下の温度となる範囲に制御すればよいが、吐出させる繊維の繊維径を小さくする観点からは高い方が好ましい。具体的なレーザ光の出力は、用いる熱可塑性樹脂の物性値（融点、ＬＯＩ値（限界酸素指数））や形状、熱可塑性樹脂の供給速度等に応じて適宜選択できる。また、加熱溶融部の温度は、熱可塑性樹脂の融点以上で、発火点以下の温度であれば特に限定されないが、通常１００〜６００℃程度であり、好ましくは２００〜４００℃である。 The output of the laser beam may be controlled within a range in which the temperature of the heating and melting portion is equal to or higher than the melting point of the thermoplastic resin and is equal to or lower than the ignition point of the thermoplastic resin. From the viewpoint of reducing the size, a higher value is preferable. The specific output of the laser beam can be appropriately selected according to the physical property values (melting point, LOI value (limit oxygen index)) and shape of the thermoplastic resin to be used, the supply rate of the thermoplastic resin, and the like. The temperature of the heat-melting part is not particularly limited as long as it is not lower than the melting point of the thermoplastic resin and not higher than the ignition point, but is usually about 100 to 600 ° C, preferably 200 to 400 ° C.
また、レーザ光の走査速度は、３０ｍ／ｓ以上が望ましい。走査速度が３０ｍ／ｓ未満では、シート状物の端部全体を同時に加熱溶融することができないことがあるからである。 The laser beam scanning speed is preferably 30 m / s or more. This is because if the scanning speed is less than 30 m / s, the entire end of the sheet-like material cannot be heated and melted at the same time.
このような不織布シートの製造方法において、上記シート状物の端部と上記捕集部材との間に発生させる電位差は放電しない範囲で高電圧であるのが好ましく、要求される繊維径、電極と捕集部材との距離、レーザ光の照射量等に応じて適宜選択できるが、通常０．１〜３０ｋＶ／ｃｍ程度であり、好ましくは０．５〜２０ｋＶ／ｃｍ、より好ましくは１〜１０ｋＶ／ｃｍである。 In such a method for producing a nonwoven fabric sheet, the potential difference generated between the end of the sheet-like material and the collecting member is preferably a high voltage within a range in which no discharge occurs, and the required fiber diameter, electrode and Although it can select suitably according to the distance with a collection member, the irradiation amount of a laser beam, etc., it is about 0.1-30 kV / cm normally, Preferably it is 0.5-20 kV / cm, More preferably, it is 1-10 kV / cm. cm.
熱可塑性樹脂の溶融部に電圧を印加する方法は、レーザ光の照射部（熱可塑性樹脂の加熱溶融部）と電荷を付与するための電極部とを一致させる直接印加方法であってもよいが、簡便に装置を作製できる点、レーザ光を有効に熱エネルギーに変換できる点、レーザ光の反射方向を容易に制御でき、安全性が高い点等から、レーザ光の照射部と電荷を付与するための電極部（図２（ａ）の例では、保持部材１８が電極部に相当）とを別個の位置に設ける間接印加方法（特に、熱可塑性樹脂の供給方向における下流側にレーザ光の照射部を設ける方法）が好ましい。特に、上述した不織布シートの製造方法では、電極部よりも下流側で熱可塑性樹脂にレーザ光を照射するとともに、電極部とレーザ光照射部との距離を特定の範囲（例えば、１０ｍｍ以下程度）に調整するのが好ましい。この距離は、熱可塑性樹脂の導電率、熱伝導率、ガラス転移点、レーザ光の照射量等に応じて選択でき、例えば、０．５〜１０ｍｍ、好ましくは１〜８ｍｍ、さらに好ましくは１．５〜７ｍｍ、特に好ましくは２〜５ｍｍ程度である。両者の距離がこの範囲にあると、レーザ光照射部近傍での熱可塑性樹脂の分子運動性が高まり、溶融状態の熱可塑性樹脂に充分な電荷を付与できるため、生産性を向上できる。 The method of applying a voltage to the melted portion of the thermoplastic resin may be a direct application method in which the laser light irradiated portion (heated melted portion of the thermoplastic resin) and the electrode portion for imparting electric charge are matched. The laser beam irradiation part and the charge are given from the point that the device can be easily manufactured, the laser beam can be effectively converted into thermal energy, the reflection direction of the laser beam can be easily controlled, and the safety is high. Indirect application method (in particular, irradiation with laser light downstream in the direction of thermoplastic resin supply) in which an electrode portion (in the example of FIG. 2A, the holding member 18 corresponds to the electrode portion) is provided at a separate position. The method of providing a part) is preferable. In particular, in the above-described method for producing a nonwoven fabric sheet, the thermoplastic resin is irradiated with laser light downstream from the electrode portion, and the distance between the electrode portion and the laser light irradiation portion is within a specific range (for example, about 10 mm or less). It is preferable to adjust to. This distance can be selected according to the electrical conductivity of the thermoplastic resin, the thermal conductivity, the glass transition point, the irradiation amount of the laser beam, etc., for example, 0.5 to 10 mm, preferably 1 to 8 mm, more preferably 1. The thickness is 5 to 7 mm, particularly preferably about 2 to 5 mm. If the distance between the two is within this range, the molecular mobility of the thermoplastic resin in the vicinity of the laser beam irradiation portion is increased, and a sufficient charge can be imparted to the molten thermoplastic resin, so that productivity can be improved.
また、上記シート状物の端部と上記捕集部材との距離は特に限定されず、通常、５ｍｍ以上であればよいが、効率良く不織布シートを製造するためには、好ましくは１０〜３００ｍｍ、より好ましくは１５〜２００ｍｍ、さらに好ましくは５０〜１５０ｍｍ、特に好ましくは８０〜１２０ｍｍ程度である。 In addition, the distance between the end of the sheet-like material and the collecting member is not particularly limited, and may be usually 5 mm or more, but in order to efficiently manufacture a nonwoven fabric sheet, preferably 10 to 300 mm, More preferably, it is 15-200 mm, More preferably, it is 50-150 mm, Most preferably, it is about 80-120 mm.
ここまで、図２を参照しながら説明した不織布シートの製造方法では、レーザ光は一方向のみからシート状物の端部に照射しているが、例えば反射ミラーを介してレーザ光を２方向からシート状物の端部に照射してもよい。シート状物の厚さが厚くても、その端部をより均一に溶融させることができるからである。また、複数枚の上記シート状物を平行に並べ、それを上記捕集部材の移動方向に沿って設置し、各シート状物の端部から繊維を同時に飛翔させてもよい。この場合、不織布シートの製造速度を複数倍に向上させることができる。 So far, in the method for manufacturing a nonwoven fabric sheet described with reference to FIG. 2, the laser light is applied to the end of the sheet-like material from only one direction. For example, the laser light is applied from two directions via a reflection mirror. You may irradiate the edge part of a sheet-like object. This is because even if the thickness of the sheet-like material is large, the end portion thereof can be melted more uniformly. Alternatively, a plurality of the sheet-like objects may be arranged in parallel, installed along the moving direction of the collecting member, and the fibers may be allowed to fly simultaneously from the end of each sheet-like object. In this case, the production rate of the nonwoven fabric sheet can be improved multiple times.
また、上記不織布シートの製造方法において、上記シート状物の端部と上記捕集部材との間の空間（繊維の飛翔空間）は、不活性ガス雰囲気であってもよい。飛翔空間を不活性ガス雰囲気とすることにより、繊維が発火することを抑制できるため、レーザ光の出力を高めることができる。不活性ガスとしては、例えば、窒素ガス、ヘリウムガス、アルゴンガス、炭酸ガス等が挙げられる。これらのうち、通常、窒素ガスを使用する。これらの不活性ガスは加熱されていてもよい。また、上記不活性ガスの使用により、加熱溶融部における酸化反応を抑制することができる。 Moreover, in the manufacturing method of the said nonwoven fabric sheet, inert gas atmosphere may be sufficient as the space (fiber flight space) between the edge part of the said sheet-like material, and the said collection member. By setting the flight space to an inert gas atmosphere, it is possible to suppress the firing of the fibers, so that the output of the laser beam can be increased. Examples of the inert gas include nitrogen gas, helium gas, argon gas, carbon dioxide gas, and the like. Of these, nitrogen gas is usually used. These inert gases may be heated. In addition, the use of the inert gas can suppress the oxidation reaction in the heating and melting part.
このような方法により製造される本発明の不織布シートは、溶媒等の不純物が残留していない、材料樹脂のみからなる不織布シートとすることができる。そのため、歯周組織再生医療等で使用される細胞培養足場材として好適に使用することができる。上記不織布シートは、貫通孔非形成部分が不織布であるため、樹脂フィルムに比べ、多孔質性があり、組織を再生させるのに必要な細胞への十分な酸素および栄養を補給し、二酸化炭素や老廃物を速やかに排出できる。また、平均繊維径が２０μｍ以下の繊維で形成されていれば、比表面積が大きく細胞接着性が高くなる。繊維の任意の横断面は異形であり、円横断面繊維の比面積よりさらに増大しており、細胞が繊維表面に接着する十分な面積をとることができる。本発明の不織布シートは、細胞培養足場材として好適である。本発明の不織布シートからなる細胞培養足場材もまた本発明の１つである。 The nonwoven fabric sheet of this invention manufactured by such a method can be made into the nonwoven fabric sheet which consists only of material resin in which impurities, such as a solvent, do not remain. Therefore, it can be suitably used as a cell culture scaffold used in periodontal tissue regenerative medicine and the like. The non-woven fabric sheet is a non-woven fabric in which the through-holes are not formed. Therefore, the non-woven fabric sheet is more porous than the resin film, and supplies sufficient oxygen and nutrients to cells necessary to regenerate the tissue. Waste products can be discharged quickly. Moreover, if it is formed with fibers having an average fiber diameter of 20 μm or less, the specific surface area is large and the cell adhesion is enhanced. Any cross-section of the fiber is irregular and is even greater than the specific area of the circular cross-section fiber, allowing sufficient area for cells to adhere to the fiber surface. The nonwoven fabric sheet of the present invention is suitable as a cell culture scaffold. A cell culture scaffold comprising the nonwoven fabric sheet of the present invention is also one aspect of the present invention.
また、上記不織布シートは、他の不織布（例えば、スパンボンド不織布等）や織編物、フィルム、ボードと積層一体化されたものであってもよい。 The non-woven fabric sheet may be laminated and integrated with other non-woven fabric (for example, spunbonded non-woven fabric), woven or knitted fabric, film or board.
本発明の不織布シートは、皮膚や歯周組織、顎骨などの組織再生・修復用の足場やテンプレートとしての細胞足場材料の成型体の一部あるいは全部、血管、軟骨、皮膚、角膜、腎臓、肝臓、筋肉、腱などの組織再生及び移植用組織形成に使用する足場材料用の成型体の一部あるいは全部、歯科材料、眼内レンズなどの生体内埋め込み用医療成型体の一部あるいは全部、外科用縫合糸、外科用補填材、外科用補強材、創傷保護材、骨折接合材、カテーテル、シリンジ、輸液・血液バッグ、血液フィルター、体外循環用材料などの医療行為に使用する成型体の一部あるいは全部として使用することができる。実際の医療行為以外にも医療につながる研究を目的とした用途にも使用することができる。例えば細胞培養、組織培養用のフラスコ、シャーレ、ウェル、プレート、多穴ウェル、多穴プレート、スライド、フィルム、バック、カラム、タンク、ボトル、中空糸、不織布など細胞培養用器具として使用される形状の基材上に本発明で得られる繊維の集合体を形成して使用することも可能である。また、セパレータや高性能フィルター産業用資材（油吸着材、皮革基布、セメント用配合材、ゴム用配合材、各種テープ基材等）、生活関連資材（ワイパー、印刷物基材、包装・袋物資材、収納材、等）、衣料用材、内装材用（断熱材、吸音材等）、等の分野で利用できる。 The nonwoven fabric sheet of the present invention is a part or all of a scaffold for tissue regeneration / restoration such as skin, periodontal tissue, and jaw bone, or a molded body of cell scaffold material as a template, blood vessel, cartilage, skin, cornea, kidney, liver , Part or all of a molded body for scaffold material used for tissue regeneration such as muscle and tendon and formation of tissue for transplantation, part or all of a medical molded body for in vivo implantation such as dental material and intraocular lens, surgery Parts of molded products used for medical activities such as surgical sutures, surgical fillers, surgical reinforcements, wound protection materials, fracture joint materials, catheters, syringes, infusion / blood bags, blood filters, extracorporeal circulation materials, etc. Or it can be used as a whole. In addition to actual medical practice, it can also be used for research purposes that lead to medical care. For example, cell culture, tissue culture flasks, petri dishes, wells, plates, multi-wells, multi-well plates, slides, films, bags, columns, tanks, bottles, hollow fibers, non-woven fabrics, etc. It is also possible to use an aggregate of fibers obtained by the present invention on a base material. In addition, separators and high-performance filter industrial materials (oil adsorbents, leather base fabrics, cement compounding materials, rubber compounding materials, various tape substrates, etc.), life-related materials (wipers, printed materials, packaging and bag materials) , Storage materials, etc.), clothing materials, interior materials (heat insulation materials, sound absorbing materials, etc.).
特に、再生医療で使用される細胞足場材料、生体内埋め込み用医療成型体、細胞培養足場材や等、クリーンで均質であることが求められる生体適合性シートとして好適である。 In particular, it is suitable as a biocompatible sheet that is required to be clean and homogeneous, such as a cell scaffold material used in regenerative medicine, a medical molded body for in vivo implantation, and a cell culture scaffold.
以下、本発明について実施例を掲げてさらに詳しく説明するが、本発明はこれらの実施例のみに限定されるものではない。 EXAMPLES Hereinafter, although an Example is hung up and demonstrated in more detail about this invention, this invention is not limited only to these Examples.
（シート状物の作製）
ＰＤＬＬＡ（ポリＤＬ−乳酸）のペレットを１４０℃で熱プレスし、厚さ０．３ｍｍ、幅８０ｍｍのＰＤＬＬＡシートを作製し、シート状物とした。
(Production of sheet-like material)
PDLLA (poly DL-lactic acid) pellets were hot-pressed at 140 ° C. to produce a PDLLA sheet having a thickness of 0.3 mm and a width of 80 mm to obtain a sheet.
（実施例１）
上記シート状物を使用し、図２に示した構成を備えた製造装置を用いて不織布シートを作製した。ここで、各部材としては以下のものを使用した。
レーザ光源：ＣＯ２レーザ（Ｕｎｉｖｅｒｓａｌ Ｌａｓｅｒ Ｓｙｓｔｅｍｓ社製、ＵＬＣＲ−１２０、波長１０．６μｍ、出力定格１２０Ｗ、空冷型、ビーム径５４ｍｍ）
レーザ光走査手段：ＡｕコートＣｕミラー（住友電工ハードメタル社製、ＴＲＤ５０−５Ａ、直径５０ｍｍ、厚み５ｍｍ）、ビームエキスパンダー（住友電工ハードメタル社製、ＢＸ３．８１−２５．４−２．０、倍率０．４倍）、及び、ポリゴンミラー（レーザックス社製、１５面体、外接円径４０ｍｍ）。電源：高圧電源（松定プレシジョン社製、ＨＡＲｂ−８０Ｐ１．２５、最大電圧８０ｋＶ、最大電流１．２５ｍＡ）。加熱空気供給装置：超音波加湿器；（良品計画社製、ＴＰＫ−ＭＪＵ１００、加湿量約１００ｍｌ／ｈ）。捕集部材：アルミニウム製パンチングメタル（開口径１．０ｍｍ、開口間隔０．５ｍｍ）。
Example 1
Using the above sheet-like material, a nonwoven fabric sheet was produced using a production apparatus having the configuration shown in FIG. Here, the following were used as each member.
Laser light source: CO 2 laser (Universal Laser Systems, ULCR-120, wavelength 10.6 μm, output rating 120 W, air-cooled type, beam diameter 54 mm)
Laser beam scanning means: Au-coated Cu mirror (manufactured by Sumitomo Electric Hardmetal Corp., TRD50-5A, diameter 50 mm, thickness 5 mm), beam expander (manufactured by Sumitomo Electric Hardmetal Corp., BX3.81-25.4-2.0, Magnification 0.4 times) and polygon mirror (manufactured by Laserx, 15-hedron, circumscribed circle diameter 40 mm). Power supply: High voltage power supply (Matsusada Precision Co., Ltd., HARb-80P1.25, maximum voltage 80 kV, maximum current 1.25 mA). Heated air supply device: ultrasonic humidifier; (Ryohin Keikaku Co., Ltd., TPK-MJU100, humidification amount: about 100 ml / h). Collection member: Aluminum punching metal (opening diameter 1.0 mm, opening interval 0.5 mm).
そして、走査幅２５０ｍｍ、走査速度１９１ｍ／ｓで、ビーム径１．６ｍｍのレーザ光（出力１３７Ｗ）を保持部材で保持したシート状物の端部に照射した。このとき、シート状物の端部と捕集部材の捕集面との距離は１０ｃｍとし、保持部材（電極）と捕集部材との間の電位差は４ｋＶ／ｃｍとした。また、シート状物の供給速度は、０．５ｍｍ／分とした。さらに、飛翔空間の温度は２００℃とし、湿度は水での加湿により６０％とした。また、保持部材からはＮ２ガスを供給した。なお、捕集部材は固定して不織布シートを製造した。 And the laser beam (output 137W) of beam diameter 1.6mm was irradiated to the edge part of the sheet-like material hold | maintained with the holding member with the scanning width of 250 mm and the scanning speed of 191 m / s. At this time, the distance between the end of the sheet-like material and the collecting surface of the collecting member was 10 cm, and the potential difference between the holding member (electrode) and the collecting member was 4 kV / cm. Moreover, the supply speed of the sheet-like material was 0.5 mm / min. Furthermore, the temperature of the flight space was 200 ° C., and the humidity was 60% by humidification with water. Moreover, N2 gas was supplied from the holding member. In addition, the collection member was fixed and the nonwoven fabric sheet was manufactured.
このような方法により、厚さ０．３ｍｍで、平均開口径１．０ｍｍのＰＤＬＬＡ繊維からなる目付（貫通孔非形成部分の目付）２１０ｇ／ｍ２の不織布シートを得た。ここで、上記ＰＤＬＬＡ繊維は、平均繊維径は３．５μｍであった。得られた不織布シートの顕微鏡拡大写真（５０倍像）を図３に示す。 By such a method, a nonwoven fabric sheet having a weight of 0.3 g and a basis weight of 210 g / m 2 made of PDLLA fibers having an average opening diameter of 1.0 mm was obtained. Here, the PDLLA fiber had an average fiber diameter of 3.5 μm. A microscope magnified photograph (50-fold image) of the obtained nonwoven fabric sheet is shown in FIG.
（実施例２）
捕集部材として、アルミニウム製パンチングメタル（開口径０．５ｍｍ、開口間隔０．５ｍｍ）を使用した以外は、実施例１と同様の方法を用いて、厚さ０．２ｍｍで、平均開口径０．５ｍｍのＰＤＬＬＡ繊維からなる目付（貫通孔非形成部分の目付）２０５ｇ／ｍ２の不織布シートを得た。ここで、ＰＤＬＬＡ繊維は、平均繊維径３．５μｍであった。得られた不織布シートの顕微鏡拡大写真（５０倍像）を図４に示す。
(Example 2)
Using the same method as in Example 1 except that aluminum punching metal (opening diameter 0.5 mm, opening interval 0.5 mm) was used as the collecting member, the average opening diameter was 0 mm with a thickness of 0.2 mm. A nonwoven fabric sheet having a basis weight of 205 mm / m 2 consisting of PDLLA fibers having a diameter of 5 mm (a basis weight of a through hole non-forming portion) was obtained. Here, the PDLLA fiber had an average fiber diameter of 3.5 μm. A microscope magnified photograph (50-fold image) of the obtained non-woven sheet is shown in FIG.
（実施例３）
捕集部材として、真鍮製の金属メッシュ（２０メッシュ／メッシュ間隔１．０ｍｍ）を使用した以外は、実施例１と同様の方法を用いて、厚さ０．８ｍｍで、平均開口径１．０ｍｍのＰＤＬＬＡ繊維からなる目付（貫通孔非形成部分の目付）２００ｇ／ｍ２の不織布シートを得た。ここで、上記ＰＤＬＬＡ繊維は、平均繊維径３．４μｍであった。得られた不織布シートの顕微鏡拡大写真（５０倍像）を図５に示す。
(Example 3)
Except for using a brass metal mesh (20 mesh / mesh spacing 1.0 mm) as the collecting member, the same method as in Example 1 was used, with a thickness of 0.8 mm and an average opening diameter of 1.0 mm. The nonwoven fabric sheet of 200 g / m < 2 > of fabric weight (weight of a through-hole non-formation part) which consists of PDLLA fiber of was obtained. Here, the PDLLA fiber had an average fiber diameter of 3.4 μm. A microscope magnified photograph (50-fold image) of the obtained nonwoven fabric sheet is shown in FIG.
（比較例１）
飛翔空間の温度を３５０℃とした以外は、実施例１と同様の方法を用いて紡糸した。厚さ０．２ｍｍで、平均開口径１．０ｍｍのＰＤＬＬＡ繊維からなる目付（貫通孔非形成部分の目付）２１０ｇ／ｍ２の不織布シートを得た。得られた不織布シートの顕微鏡拡大写真（５０倍像）を図６に示す。貫通孔の壁面において、繊維同士が融着した構造となっている。
(Comparative Example 1)
Spinning was performed using the same method as in Example 1 except that the temperature of the flight space was 350 ° C. A nonwoven fabric sheet having a thickness of 210 g / m 2 having a thickness of 0.2 mm and made of PDLLA fibers having an average opening diameter of 1.0 mm was obtained. The microscope magnified photograph (50 times image) of the obtained nonwoven fabric sheet is shown in FIG. On the wall surface of the through hole, the fibers are fused together.
（比較例２）
捕集部材をアルミニウム製プレートとした以外は、実施例１と同様の方法を用いて紡糸した。厚さ０．８ｍｍのＰＤＬＬＡ繊維からなる目付（貫通孔非形成部分の目付）１９０ｇ／ｍ２の不織布シートを得た。このシートをレーザで切断加工した。得られた不織布シートの顕微鏡拡大写真（５０倍像）を図７に示す。切断面において、繊維の切断面が露出すると共に繊維同士が融着した構造となっている。
(Comparative Example 2)
Spinning was performed using the same method as in Example 1 except that the collecting member was an aluminum plate. A nonwoven fabric sheet having a basis weight (weight per unit area of the through hole non-formed portion) of 190 g / m 2 made of PDLLA fibers having a thickness of 0.8 mm was obtained. This sheet was cut by laser. A microscope magnified photograph (50-fold image) of the obtained nonwoven fabric sheet is shown in FIG. The cut surface has a structure in which the cut surfaces of the fibers are exposed and the fibers are fused.
（比較例３）
捕集部材をアルミニウム製プレートとした以外は、実施例１と同様の方法を用いて紡糸した。厚さ０．８ｍｍのＰＤＬＬＡ繊維からなる目付（貫通孔非形成部分の目付）１９５ｇ／ｍ２の不織布シートを得た。このシートをトムソン刃で切断加工した。得られた不織布シートの顕微鏡拡大写真（５０倍像）を図８に示す。貫通孔の壁面において、切断面において繊維がカットされており、繊維が脱落しやすい構造となっている。
(Comparative Example 3)
Spinning was performed using the same method as in Example 1 except that the collecting member was an aluminum plate. Basis weight consisting of PDLLA fiber thickness of 0.8mm was obtained nonwoven fabric sheet (through hole non-basis weight of the formed portion) 195g / m 2. This sheet was cut with a Thomson blade. A microscope magnified photograph (50-fold image) of the obtained nonwoven fabric sheet is shown in FIG. In the wall surface of the through hole, the fiber is cut at the cut surface, so that the fiber is easily dropped.
（平均繊維径の測定）
不織布の表面を走査型電子顕微鏡（ＳＥＭ）により観察し、電子顕微鏡写真中の任意の２０５０本のナノファイバー表面の幅を計測し、その平均を平均直径とした。観察倍率は５００倍〜５万倍とした。また、繊維径は、画像解析ソフトを用いて行った。
(Measurement of average fiber diameter)
The surface of the nonwoven fabric was observed with a scanning electron microscope (SEM), the width of the surface of any 2050 nanofibers in the electron micrograph was measured, and the average was taken as the average diameter. The observation magnification was 500 to 50,000 times. The fiber diameter was measured using image analysis software.
（開口径の測定）
不織布の表面を走査型電子顕微鏡（ＳＥＭ）により観察し、電子顕微鏡写真中の任意の２０個の開口の幅を計測し、その平均を開口径とした。観察倍率は５０倍〜５００倍とした。
(Measurement of aperture diameter)
The surface of the nonwoven fabric was observed with a scanning electron microscope (SEM), the width of 20 arbitrary openings in the electron micrograph was measured, and the average was taken as the opening diameter. The observation magnification was 50 to 500 times.
１ 不織布シート
２ 貫通孔
１１ レーザ光源
１２ レーザ光
１３ 反射ミラー
１４ ポリゴンミラー
１５ レーザ光走査手段
１７ シート状物
１８ 保持部材
１９ 捕集部材
２０ 電源
２２ 加熱空気供給装置
１１７ テーラーコーン
DESCRIPTION OF SYMBOLS 1 Nonwoven fabric sheet 2 Through-hole 11 Laser light source 12 Laser beam 13 Reflection mirror 14 Polygon mirror 15 Laser beam scanning means 17 Sheet-like object 18 Holding member 19 Collection member 20 Power supply 22 Heated air supply device 117 Tailor cone
Claims (7)
熱可塑性樹脂からなるシート状物にレーザ光を照射して前記シート状物の端部を加熱溶融させるとともに、前記シート状物の加熱溶融した部分と複数の円形の貫通孔を有するパンチングメタルからなる捕集部材との間に電位差を設け、繊維を前記捕集部材の方向に水平に飛翔させることにより、繊維を前記捕集部材上に積層させることを特徴とする不織布シートの製造方法。 A method for producing a nonwoven fabric sheet having a plurality of through holes having an opening diameter of 5 μm to 2.0 mm penetrating in the thickness direction,
The sheet-like material made of thermoplastic resin is irradiated with laser light to heat and melt the end portion of the sheet-like material, and is made of a punching metal having a heat-melted portion of the sheet-like material and a plurality of circular through holes. A method for producing a non-woven fabric sheet, wherein a fiber is laminated on the collecting member by providing a potential difference between the collecting member and causing the fibers to fly horizontally in the direction of the collecting member.
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