JP6815002B2 - ε-Polylysine ultrafine fibers and fiber structures, their manufacturing methods - Google Patents
ε-Polylysine ultrafine fibers and fiber structures, their manufacturing methods Download PDFInfo
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- JP6815002B2 JP6815002B2 JP2016175476A JP2016175476A JP6815002B2 JP 6815002 B2 JP6815002 B2 JP 6815002B2 JP 2016175476 A JP2016175476 A JP 2016175476A JP 2016175476 A JP2016175476 A JP 2016175476A JP 6815002 B2 JP6815002 B2 JP 6815002B2
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- polylysine
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- 229920001410 Microfiber Polymers 0.000 title claims description 118
- 239000000835 fiber Substances 0.000 title claims description 84
- 108010039918 Polylysine Proteins 0.000 title claims description 40
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 238000000034 method Methods 0.000 claims description 47
- 238000009987 spinning Methods 0.000 claims description 35
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 29
- 125000001153 fluoro group Chemical group F* 0.000 claims description 22
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 17
- 229910052731 fluorine Inorganic materials 0.000 claims description 17
- 230000005684 electric field Effects 0.000 claims description 9
- 229920001351 ε-poly-L-lysine Polymers 0.000 description 67
- 238000001352 electron-beam projection lithography Methods 0.000 description 66
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- 239000002904 solvent Substances 0.000 description 12
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- 238000011282 treatment Methods 0.000 description 8
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- 125000002091 cationic group Chemical group 0.000 description 6
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- KSNKQSPJFRQSEI-UHFFFAOYSA-N 3,3,3-trifluoropropanoic acid Chemical compound OC(=O)CC(F)(F)F KSNKQSPJFRQSEI-UHFFFAOYSA-N 0.000 description 3
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
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- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
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- 241000187747 Streptomyces Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
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- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
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- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
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- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
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- 239000005017 polysaccharide Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- 108020004414 DNA Proteins 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical class O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000000560 biocompatible material Substances 0.000 description 1
- 229920000249 biocompatible polymer Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 230000010478 bone regeneration Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- NSQPPSOSXWOZNH-UHFFFAOYSA-L calcium benzoate Chemical compound [Ca+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 NSQPPSOSXWOZNH-UHFFFAOYSA-L 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 239000005452 food preservative Substances 0.000 description 1
- 235000019249 food preservative Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011087 fumaric acid Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229920002674 hyaluronan Polymers 0.000 description 1
- 229960003160 hyaluronic acid Drugs 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002799 interferon inducing agent Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000005426 pharmaceutical component Substances 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- LROWVYNUWKVTCU-STWYSWDKSA-M sodium sorbate Chemical compound [Na+].C\C=C\C=C\C([O-])=O LROWVYNUWKVTCU-STWYSWDKSA-M 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
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- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Artificial Filaments (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Description
本発明は、ε−ポリリジンを主成分とする極細繊維及び繊維構造体、それらを製造するための方法に関する。 The present invention relates to ultrafine fibers and fiber structures containing ε-polylysine as a main component, and methods for producing them.
近年、数十〜数百ナノメートル（ｎｍ）の直径を有する、いわゆるナノ繊維が注目され、ドラッグデリバリー、足場材料、創傷被覆材などのバイオメディカル分野、発光体用電子銃や各種センサーなどのエレクトロニクス分野、高性能フィルターなどの環境対応分野への応用が期待されている。特にバイオメディカルの分野においては、足場材料や細胞接着基材等への応用面からナノレベルでの構造制御が重要となるため、直径が極めて細い繊維（ナノ繊維）の作製が望まれている。そのような極細繊維を製造する方法としては、例えば電界紡糸法がある。 In recent years, so-called nanofibers having a diameter of several tens to several hundreds of nanometers (nm) have attracted attention, and are used in biomedical fields such as drug delivery, scaffolding materials, and wound dressings, and electronics such as electron guns for illuminants and various sensors. It is expected to be applied to fields and environment-friendly fields such as high-performance filters. Particularly in the field of biomedical fields, structural control at the nano level is important from the viewpoint of application to scaffolding materials, cell adhesion substrates, etc., and therefore, production of fibers (nanofibers) having extremely small diameters is desired. As a method for producing such ultrafine fibers, for example, there is an electric field spinning method.
また、ポリカチオンは、そのカチオン性と分子量効果（分子鎖の凝集力や、強度や接着性等の物理的特性など）の両方を利用し、医薬・抗体等の固定、化粧品、接着剤、塗料、紙力増強剤等に広く利用されている。これらはナノ繊維化することで、高い比表面積を有するようになるため、細胞接着性の向上や医薬・抗体等の固定サイト数増加などの効果が得られる。これらの特徴と天然由来である特性を活かして、天然由来のポリカチオンを繊維化する研究が進められている（特許文献１）。特許文献１は、セルロース又はキトサン等の多糖類を電界紡糸法によって極細繊維とする発明であり、これらの材料を有機溶媒に溶解したものを紡糸液とし、電界紡糸法によって極細繊維とした後、必要に応じてアルカリ処理をすることによって水不溶性のセルロース極細繊維ないしキトサン極細繊維を得たことが開示されている。 In addition, polycations utilize both their cationic properties and molecular weight effects (such as the cohesive force of molecular chains and physical properties such as strength and adhesiveness) to fix pharmaceuticals and antibodies, cosmetics, adhesives, paints, etc. , Widely used as a paper strength enhancer. By converting these into nanofibers, they have a high specific surface area, so that effects such as improvement of cell adhesion and increase in the number of fixed sites such as pharmaceuticals and antibodies can be obtained. Research is underway to fiberize naturally-derived polycations by taking advantage of these characteristics and naturally-derived characteristics (Patent Document 1). Patent Document 1 is an invention in which a polysaccharide such as cellulose or chitosan is made into ultrafine fibers by an electrospinning method. A spinning solution obtained by dissolving these materials in an organic solvent is used as a spinning solution, and then ultrafine fibers are produced by an electrospinning method. It is disclosed that water-insoluble cellulose ultrafine fibers or chitosan ultrafine fibers were obtained by subjecting them to alkali treatment as needed.
多糖類であるキトサンやポリアミノ酸であるポリリジン等は生体毒性が低く、特にポリリジンは優れた生体親和性から、医療機器のコーティング材、ドラッグデリバリー、医薬・抗体の固定担体、抗菌性、食品添加剤などの用途で有効に用いられる。 Chitosan, which is a polysaccharide, and polylysine, which is a polyamino acid, have low biotoxicity. In particular, polylysine has excellent biocompatibility, so it is used as a coating material for medical devices, drug delivery, fixed carriers for pharmaceuticals and antibodies, antibacterial properties, and food additives. It is effectively used in such applications.
ポリリジンには、α位のアミノ基とカルボキシル基等が縮合したα−ポリリジンと、ε位のアミノ基とカルボキシル基等が縮合したε−ポリリジンの２種類が存在する。α−ポリリジンは、ポリカチオンの特性により、バイオメディカル分野において、インターフェロン誘導物質の効果の向上、薬物透過性の向上、ＤＮＡ等とのポリイオンコンプレックス、遺伝子及び核酸等のデリバリーなどの用途に使用することができると報告されている。しかしながら、このような用途では生体毒性が重要となってくるが、α−ポリリジンは少なからず細胞毒性を示すという報告もある（非特許文献１）。上記用途では、α−ポリリジンのカチオン性を利用しており、天然由来のε−ポリリジンはα−ポリリジンの代替として適している。ε−ポリリジンを含有した極細繊維の例としては、他のポリマー中にポリリジンを含有することで作製した極細繊維の例があげられる（特許文献２）。特許文献２は、生体適合性繊維の不織布に骨補填材を含有する骨再生用材料に関する発明であり、生体適合性ポリマーの一例としてポリリジンが開示されている。但し、実施例には、ポリ乳酸不織布のみが示されており、ポリリジンを材料として繊維ないし不織布とした例はない。 There are two types of polylysine: α-polylysine, which is a condensation of an amino group at the α-position and a carboxyl group, and ε-polylysine, which is a condensation of an amino group at the ε-position and a carboxyl group. Due to the characteristics of polycations, α-polylysine should be used in the biomedical field for improving the effects of interferon inducers, improving drug permeability, delivering polyion complexes with DNA, genes, nucleic acids, etc. It is reported that it can be done. However, although biotoxicity is important in such applications, there is a report that α-polylysine exhibits not a little cytotoxicity (Non-Patent Document 1). In the above applications, the cationicity of α-polylysine is utilized, and naturally occurring ε-polylysine is suitable as a substitute for α-polylysine. Examples of ultrafine fibers containing ε-polylysine include ultrafine fibers produced by containing polylysine in other polymers (Patent Document 2). Patent Document 2 is an invention relating to a bone regeneration material containing a bone filling material in a non-woven fabric of biocompatible fibers, and polylysine is disclosed as an example of a biocompatible polymer. However, in the examples, only polylactic acid non-woven fabric is shown, and there is no example in which polylysine is used as a fiber or non-woven fabric.
特許文献３は、セルロース等の糖質とε−ポリリジンと電解質とを含む組成物の発明であり、この組成物を含有する繊維が開示されている。実施例においては、セルロースに対して０．１％のε−ポリリジンを含む、レーヨンビスコースの紡糸原液を湿式紡糸してε−ポリリジンを含有する繊維を得たことが開示されている。 Patent Document 3 is an invention of a composition containing a sugar such as cellulose, ε-polylysine, and an electrolyte, and a fiber containing this composition is disclosed. In the examples, it is disclosed that a rayon viscose spinning stock solution containing 0.1% ε-polylysine with respect to cellulose was wet-spun to obtain fibers containing ε-polylysine.
上記のとおり、ε−ポリリジンを繊維に一部含有させることやε−ポリリジンを添加した極細繊維は公知であった。しかしながら、ε−ポリリジンはその分子量が繊維化するには低すぎるためか、未だにε−ポリリジンを繊維化し、ε−ポリリジンを主成分として含む極細繊維は得られていなかった。
上記の状況に鑑み、本発明は、カチオン性ポリペプチドであるε−ポリリジンを主成分として含む極細繊維を提供することを課題とする。
As described above, it has been known that the fiber contains a part of ε-polylysine and the ultrafine fiber to which ε-polylysine is added. However, probably because the molecular weight of ε-polylysine is too low to be fiberized, ε-polylysine is still fiberized, and ultrafine fibers containing ε-polylysine as a main component have not been obtained.
In view of the above circumstances, it is an object of the present invention to provide ultrafine fibers containing ε-polylysine, which is a cationic polypeptide, as a main component.
本発明者らは、前述の従来技術の問題点に鑑み、鋭意研究を重ねた。その結果、トリフルオロ酢酸に溶解したε−ポリリジン溶液はコンプレックス構造を形成することで繊維化に必要な曳糸性を発現し、ε−ポリリジンを主成分とする極細繊維が得られることを見出した。この方法で得られた極細繊維は、そのカチオン性を巧みに利用して種々のポリアニオンとコンプレックスを作ることが可能であり、ポリイオンコンプレックスにより多岐な分野で利用可能である。 In view of the above-mentioned problems of the prior art, the present inventors have conducted intensive studies. As a result, it was found that the ε-polylysine solution dissolved in trifluoroacetic acid expresses the spinnability required for fibrosis by forming a complex structure, and ultrafine fibers containing ε-polylysine as a main component can be obtained. .. The ultrafine fibers obtained by this method can make a complex with various polyanions by skillfully utilizing their cationic properties, and can be used in various fields by the polyion complex.
本発明は以下によって構成される。
［１］ε−ポリリジンを３０重量％以上含有する、平均繊維径が１０ｎｍ以上２０００ｎｍ以下である極細繊維。
［２］ε−ポリリジンからなる前記［１］に記載の極細繊維。
［３］さらに、フッ素原子とカルボキシル基を有する化合物を含有する前記［１］または［２］に記載の極細繊維。
［４］前記［１］〜［３］のいずれか１項に記載の極細繊維を含む繊維構造体。
［５］前記［１］〜［３］のいずれか１項に記載の極細繊維を、電界紡糸法により形成する極細繊維の製造方法。
［６］ε−ポリリジンと、フッ素原子とカルボキシル基を有する化合物とを含む溶液を紡糸溶液として用いる、前記［５］に記載の極細繊維の製造方法。
［７］前記フッ素原子とカルボキシル基を有する化合物がトリフルオロ酢酸である、前記［６］に記載の極細繊維の製造方法。
The present invention comprises the following.
[1] An ultrafine fiber containing 30% by weight or more of ε-polylysine and having an average fiber diameter of 10 nm or more and 2000 nm or less.
[2] The ultrafine fiber according to the above [1], which is composed of ε-polylysine.
[3] The ultrafine fiber according to the above [1] or [2], which further contains a compound having a fluorine atom and a carboxyl group.
[4] A fiber structure containing the ultrafine fibers according to any one of the above [1] to [3].
[5] A method for producing ultrafine fibers, wherein the ultrafine fibers according to any one of the above [1] to [3] are formed by an electric field spinning method.
[6] The method for producing ultrafine fibers according to the above [5], wherein a solution containing ε-polylysine and a compound having a fluorine atom and a carboxyl group is used as a spinning solution.
[7] The method for producing ultrafine fibers according to the above [6], wherein the compound having a fluorine atom and a carboxyl group is trifluoroacetic acid.
本発明の極細繊維及び繊維構造体は、ε−ポリリジンを高濃度で含有する極細繊維であるので、生体親和性、抗菌性等のε−ポリリジンの効果をより発現する製品を提供することができる。 Since the ultrafine fiber and the fiber structure of the present invention are ultrafine fibers containing a high concentration of ε-polylysine, it is possible to provide a product that more exhibits the effects of ε-polylysine such as biocompatibility and antibacterial property. ..
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
（ε−ポリリジン極細繊維）
本発明は、ε−ポリリジン（以下、ＥＰＬと記述する。）を主成分として含む、具体的には、繊維に対して３０重量％以上のＥＰＬを含有する極細繊維である。ＥＰＬを主成分とすることにより、抗菌性などをはじめとするＥＰＬの性質を効果的に利用することが可能となる。また、フッ素原子とカルボキシル基を有する化合物を含有させることで、十分な紡糸性で極細繊維が得られるため、比表面積が大きく、ＥＰＬ極細繊維の特性を十分に引き出すことが可能となる。
(Ε-Polylysine ultrafine fiber)
The present invention is an ultrafine fiber containing ε-polylysine (hereinafter referred to as EPL) as a main component, specifically, containing 30% by weight or more of EPL with respect to the fiber. By using EPL as a main component, it becomes possible to effectively utilize the properties of EPL including antibacterial properties. Further, by containing a compound having a fluorine atom and a carboxyl group, ultrafine fibers can be obtained with sufficient spinnability, so that the specific surface area is large and the characteristics of EPL ultrafine fibers can be sufficiently brought out.
本発明の極細繊維は、ＥＰＬを主成分として構成されている。極細繊維におけるＥＰＬの構成比率は、主成分であれば、特に制限されるものではないが、繊維に対して３０重量％以上であり、５０重量％以上であることが好ましく、８０重量％以上であることがより好ましく、ＥＰＬのみで構成されていることが更に好ましい。ＥＰＬの本来の特徴である抗菌性や生体親和性、生体毒性の低さなどの特性を活かすためには、極細繊維におけるＥＰＬの構成比率が高いほど好ましい。 The ultrafine fiber of the present invention is composed mainly of EPL. The composition ratio of EPL in the ultrafine fiber is not particularly limited as long as it is the main component, but is 30% by weight or more, preferably 50% by weight or more, and 80% by weight or more with respect to the fiber. It is more preferable that there is, and it is further preferable that it is composed only of EPL. In order to utilize the original characteristics of EPL such as antibacterial property, biocompatibility, and low biotoxicity, it is preferable that the composition ratio of EPL in the ultrafine fiber is high.
また、ＥＰＬは分子量が低く、それ単独では満足できる紡糸性が得られない場合もあり、紡糸性を改善するために、ＥＰＬの特性を著しく損なわない範囲で、他の成分と混合して極細繊維を得ることも可能である。他の成分の種類は特に限定されないが、ポリフッ化ビニリデンやナイロン６、ナイロン６，６、ポリウレタン、ポリエチレングリコール、ポリビニルアルコール、ポリエチレンオキサイド、天然コラーゲン、ポリ乳酸、キトサンなどを例示することができる。ＥＰＬの生体親和性の高さを活かすためには、生体親和性に優れるポリビニルアルコールやポリエチレンオキサイド、キトサンなどが特に好ましい。 In addition, EPL has a low molecular weight, and in some cases, satisfactory spinnability cannot be obtained by itself. In order to improve spinnability, ultrafine fibers are mixed with other components within a range that does not significantly impair the characteristics of EPL. It is also possible to obtain. The types of other components are not particularly limited, and examples thereof include polyvinylidene fluoride, nylon 6, nylon 6, 6, polyurethane, polyethylene glycol, polyvinyl alcohol, polyethylene oxide, natural collagen, polylactic acid, and chitosan. In order to take advantage of the high biocompatibility of EPL, polyvinyl alcohol, polyethylene oxide, chitosan, etc., which have excellent biocompatibility, are particularly preferable.
また、ＥＰＬは潮解性を有しており、潮解性の制御が必要な場合もあり、潮解性を抑制するために、ＥＰＬの特性を著しく損なわない範囲で、他の成分と混合して極細繊維を得ることも可能である。他の成分の種類は特に限定されるものではなく、前述のポリマー等が使用できる。 In addition, EPL has deliquescent property, and it may be necessary to control deliquescent property. In order to suppress deliquescent property, ultrafine fibers are mixed with other components within a range that does not significantly impair the characteristics of EPL. It is also possible to obtain. The types of other components are not particularly limited, and the above-mentioned polymers and the like can be used.
本発明の極細繊維に用いるＥＰＬを得る方法は、特に制限はなく、微生物を用いる製造法、化学合成法等、いかなる製造法によるものでもよい。なかでも、微生物を用いて製造されるＥＰＬ、例えば、特開２００５−３１８８１５号公報等に記載されたε−ポリ−Ｌ−リジンの製造法によって得られるＥＰＬ、すなわち、ストレプトマイセス属に属するＥＰＬ生産菌であるストレプトマイセス・アウレオファシエンス（Streptomyces aureofaciuens）を培地に培養し、得られる培養物からＥＰＬを分離、採取することによって得られたＥＰＬが特に好ましい。また、ＥＰＬは市販品をそのまま利用してもよく、カチオン性ポリマーとしての機能を失わない程度に、化学修飾等を実施して使用してもよい。 The method for obtaining the EPL used for the ultrafine fibers of the present invention is not particularly limited, and may be any production method such as a production method using a microorganism or a chemical synthesis method. Among them, EPL produced by using a microorganism, for example, EPL obtained by the method for producing ε-poly-L-lysine described in JP-A-2005-318815, that is, EPL belonging to the genus Streptomyces. EPL obtained by culturing the producing bacterium Streptomyces aureofaciuens in a medium and separating and collecting EPL from the obtained culture is particularly preferable. Further, the EPL may be a commercially available product as it is, or may be used after being chemically modified to the extent that the function as a cationic polymer is not lost.
本発明において使用するＥＰＬは、遊離の形で用いることができるが、アミノ基が塩の状態であっても、同等の効果を奏する。ＥＰＬの塩は、無機塩であっても有機酸塩であってもよい。無機塩としては、塩酸、硫酸、およびリン酸などを挙げることができる。また、有機塩としては、クエン酸、グルコン酸、酢酸、酒石酸、乳酸、フマル酸、コハク酸、リンゴ酸、アジピン酸、プロピオン酸、ソルビン酸、安息香酸のナトリウム塩、カリウム塩、カルシウム塩、鉄塩等が挙げることができる。これら無機酸および有機酸も１種または２種以上混合して用いることができる。得られるＥＰＬの極細繊維は、遊離の形でも、塩の形でも、差異はない。 The EPL used in the present invention can be used in a free form, but the same effect can be obtained even when the amino group is in a salt state. The salt of EPL may be an inorganic salt or an organic acid salt. Examples of the inorganic salt include hydrochloric acid, sulfuric acid, phosphoric acid and the like. The organic salts include citric acid, gluconic acid, acetic acid, tartaric acid, lactic acid, fumaric acid, succinic acid, malic acid, adipic acid, propionic acid, sorbic acid, sodium salt of benzoic acid, potassium salt, calcium salt and iron. Salt and the like can be mentioned. These inorganic acids and organic acids can also be used alone or in admixture of two or more. The resulting EPL microfibers are no different in free form or salt form.
本発明の極細繊維は、１０ｎｍ〜２０００ｎｍ、好ましくは３０ｎｍ〜１０００ｎｍの繊維径を有する、長繊維又は短繊維である。極細繊維の繊維径が小さくなると繊維比表面積が大きくなるので好ましいが、繊維径が２０００ｎｍ以下であれば十分な高比表面積を生かした高い抗菌性等の効果が得られるので好ましく、１０００ｎｍ以下であれば更に好ましい。また、繊維径が大きくなると繊維１本あたりの力学強力が高くなるが、繊維径が１０ｎｍ以上であれば満足できる材料強度やハンドリング性を示すようになるので好ましく、３０ｎｍ以上であれば十分な特性となるのでより好ましい。本発明の極細繊維の繊維長は特に制限されず、図１に示される写真のように繊維の長さ方向に延在する構造を有するものであればよく、フィブリルは含まない。 The ultrafine fibers of the present invention are long fibers or short fibers having a fiber diameter of 10 nm to 2000 nm, preferably 30 nm to 1000 nm. When the fiber diameter of the ultrafine fiber is small, the specific surface area of the fiber is large, which is preferable. However, when the fiber diameter is 2000 nm or less, an effect such as high antibacterial property utilizing a sufficiently high specific surface area can be obtained, and it is preferable that the fiber diameter is 1000 nm or less. Is even more preferable. Further, as the fiber diameter increases, the mechanical strength per fiber increases, but it is preferable that the fiber diameter is 10 nm or more because it exhibits satisfactory material strength and handleability, and 30 nm or more is sufficient characteristics. It is more preferable because it becomes. The fiber length of the ultrafine fiber of the present invention is not particularly limited as long as it has a structure extending in the fiber length direction as shown in the photograph shown in FIG. 1, and does not include fibril.
本発明の極細繊維は、単一繊維であってもよいし、複合繊維あるいは２種以上の繊維が混合されてなる混合繊維であってもよい。 The ultrafine fibers of the present invention may be single fibers, composite fibers, or mixed fibers obtained by mixing two or more kinds of fibers.
本発明の極細繊維は、特に限定されるわけではないが、フッ素原子とカルボキシル基を有する化合物を含有することが好ましい。ここで、フッ素原子とカルボキシル基を有する化合物とは、構造中にフッ素原子とカルボキシル基を有する化合物をいう。該化合物は、例えば、繊維化の過程で使用する、ＥＰＬを溶解するために使用した溶媒に由来するものである。特定の理論に拘束されるものではないが、繊維化の過程で溶媒を十分に除去しても得られた極細繊維にフッ素原子が残存するという事実は、ＥＰＬとフッ素原子とカルボキシル基を有する化合物とがコンプレックスを形成し、得られた極細繊維においてもかかるコンプレックスが保持されていることを示していると推定される。より詳しくは、紡糸溶液の状態で、ＥＰＬのアミノ基と、フッ素原子とカルボキシル基を有する化合物のカルボキシル基とがイオン結合でコンプレックスを形成し、続く電界紡糸においては電界の力によって凝集が促進され、分子集合体様の挙動をする、と推定される。またこのコンプレックスの形成によって、ＥＰＬを主体とする極細繊維を得るために必要な、十分な曳糸性が得られるようになると考えられる。すなわち、本発明のＥＰＬを主成分とする極細繊維がフッ素原子を含む場合には、特に優れた紡糸性で極細繊維が得られたことを意味している。 The ultrafine fiber of the present invention is not particularly limited, but preferably contains a compound having a fluorine atom and a carboxyl group. Here, the compound having a fluorine atom and a carboxyl group means a compound having a fluorine atom and a carboxyl group in the structure. The compound is derived from, for example, the solvent used to dissolve EPL, which is used in the process of fibrosis. Although not bound by a specific theory, the fact that fluorine atoms remain in the obtained ultrafine fibers even after sufficient removal of the solvent during the fibrosis process is a compound having EPL, fluorine atoms and a carboxyl group. It is presumed that and forms a complex, and that the obtained ultrafine fibers also retain such a complex. More specifically, in the state of the spinning solution, the amino group of EPL and the carboxyl group of the compound having a fluorine atom and a carboxyl group form a complex by an ionic bond, and in the subsequent electrospinning, aggregation is promoted by the force of the electric field. , It is presumed that it behaves like a molecular assembly. Further, it is considered that the formation of this complex makes it possible to obtain sufficient spinnability necessary for obtaining ultrafine fibers mainly composed of EPL. That is, when the ultrafine fiber containing EPL as a main component of the present invention contains a fluorine atom, it means that the ultrafine fiber was obtained with particularly excellent spinnability.
本発明で利用できるフッ素とカルボキシル基を有する化合物としては、トリフルオロ酢酸、３，３，３−トリフルオロプロピオン酸、トリフルオロメタンスルホン酸、ペンタフルオロプロピオン酸等を例示することができ、これらの化合物は、ＥＰＬの紡糸溶液の溶媒として使用することができる。これらのなかでも、トリフルオロ酢酸を使用した場合には、その揮発性が高いためにＥＰＬの凝集性が高まり、かつ、ＥＰＬとトリフルオロ酢酸がコンプレックス構造を形成するためか、特に優れた紡糸性を発現するため、より好ましい。トリフルオロ酢酸とのコンプレックスにより極細繊維中に含まれるフッ素原子の量は、特に限定されないが、電界紡糸過程の安定性や得られる極細繊維の特性を鑑みて、適宜設定することができるが、繊維に対して０．１〜１０重量％の範囲を例示することができる。 Examples of the compound having fluorine and a carboxyl group that can be used in the present invention include trifluoroacetic acid, 3,3,3-trifluoropropionic acid, trifluoromethanesulfonic acid, pentafluoropropionic acid and the like, and these compounds can be exemplified. Can be used as a solvent for the spinning solution of EPL. Among these, when trifluoroacetic acid is used, the cohesiveness of EPL increases due to its high volatility, and EPL and trifluoroacetic acid form a complex structure, which is why the spinnability is particularly excellent. Is more preferable because it expresses. The amount of fluorine atoms contained in the ultrafine fibers due to the complex with trifluoroacetic acid is not particularly limited, but can be appropriately set in consideration of the stability of the electrospinning process and the characteristics of the obtained ultrafine fibers. The range of 0.1 to 10% by weight can be exemplified.
本発明のＥＰＬ極細繊維中にフッ素とカルボキシル基を有する化合物が含有される場合、例えば、赤外吸収スペクトル測定や元素分析によってＣ−Ｆ結合の存在を確認することができ、具体的な方法は後述の実施例に示される。 When a compound having fluorine and a carboxyl group is contained in the EPL ultrafine fiber of the present invention, the presence of CF bond can be confirmed by, for example, infrared absorption spectrum measurement or elemental analysis. It will be shown in Examples described later.
本発明の極細繊維は、２種類以上の繊維を混繊して使用してもよい。混繊して繊維集合体として使用する場合は、混繊する繊維の種類は特に限定されるものではなく、適宜選択することができるが、繊維集合体中にＥＰＬを主成分として含んでいることがより好適である。得られる繊維集合体中のＥＰＬの構成比率は特に制限されるものではないが、５０重量％以上であることが好ましく、８０重量％以上であることが更に好ましい。混繊する繊維の種類は特に限定されるものではなく、使用する用途を鑑みて、適宜選択できるが、ポリフッ化ビニリデンやナイロン６、ナイロン６，６、ポリウレタン、ポリエチレングリコール、ポリビニルアルコール、ポリエチレンオキサイド、天然コラーゲン、ポリ乳酸、キトサンなどを例示することができる。 The ultrafine fibers of the present invention may be used by mixing two or more types of fibers. When the fibers are mixed and used as a fiber aggregate, the type of fibers to be mixed is not particularly limited and can be appropriately selected, but the fiber aggregate contains EPL as a main component. Is more suitable. The composition ratio of EPL in the obtained fiber aggregate is not particularly limited, but is preferably 50% by weight or more, and more preferably 80% by weight or more. The type of fiber to be mixed is not particularly limited and may be appropriately selected in consideration of the intended use, but polyvinylidene fluoride, nylon 6, nylon 6,6, polyurethane, polyethylene glycol, polyvinyl alcohol, polyethylene oxide, etc. Examples include natural collagen, polylactic acid, and chitosan.
本発明の極細繊維は、極細繊維を集積して繊維集合体を形成することができる。繊維集合体の形態は特に限定されないが、シート状やブロック状、球状などのあらゆる形態にすることができる。また、繊維集合体は、本発明の極細繊維のみから構成されていてもよく、また、それ以外の素材と複合されていてもよい。他素材との複合繊維集合体としては、本発明の極細繊維と他素材からなる極細繊維の混繊繊維集合体や、本発明の極細繊維とＥＰＬを含むもしくは含まない、やや繊維径が大きい繊維の混繊繊維集合体、本発明の極細繊維の繊維集合体とフィルム状物等との複合体など、あらゆる形態をとりえる。 The ultrafine fibers of the present invention can accumulate ultrafine fibers to form a fiber aggregate. The form of the fiber aggregate is not particularly limited, but any form such as a sheet shape, a block shape, or a spherical shape can be used. Further, the fiber aggregate may be composed of only the ultrafine fibers of the present invention, or may be composited with other materials. As the composite fiber aggregate with other materials, a mixed fiber aggregate of the ultrafine fibers of the present invention and ultrafine fibers made of another material, or a fiber containing or not containing the ultrafine fibers and EPL of the present invention and having a slightly large fiber diameter. It can take any form such as a mixed fiber aggregate of the above, a composite of a fiber aggregate of the ultrafine fibers of the present invention and a film-like material, and the like.
本発明の極細繊維の中には、本発明の効果を妨げない範囲において、機能剤を添加してもよく、抗菌剤や消臭剤、架橋剤、生体親和性材料、医薬成分、酵素、蛍光材料、親水化剤、撥水化剤、界面活性剤などの機能剤を例示することができる。また、極細繊維は、効果を妨げない範囲で機能付与のために二次加工を施されていてもよく、極細繊維に特定の官能基や架橋剤を導入する化学処理、滅菌処理、親水化や疎水化のコーティング処理、カチオン・アニオンコンプレックス形成能を活かしたカチオン性ＥＰＬ極細繊維へのアニオンコーティングなどを例示できる。 Functional agents may be added to the ultrafine fibers of the present invention as long as the effects of the present invention are not impaired, and antibacterial agents, deodorants, cross-linking agents, biocompatible materials, pharmaceutical components, enzymes, and fluorescence may be added. Functional agents such as materials, hydrophilic agents, water repellent agents, and surfactants can be exemplified. In addition, the ultrafine fibers may be subjected to secondary processing to impart functions as long as the effects are not impaired, and chemical treatments, sterilization treatments, hydrophilic treatments, etc., in which specific functional groups or cross-linking agents are introduced into the ultrafine fibers are used. Examples thereof include a hydrophobizing coating treatment and an anion coating on cationic EPL ultrafine fibers utilizing the ability to form a cationic / anionic complex.
本発明の極細繊維及び繊維集合体は、水溶性のものと不溶性のものを作製することができる。不溶性の極細繊維及び繊維集合体は、ＥＰＬに化学修飾等を施して水不溶性にしたものを用いて、電界紡糸することで得られる。また、架橋剤を含ませたＥＰＬ溶液を電界紡糸することでも得ることができる。水溶性の極細繊維および繊維集合体は、ＥＰＬ及びその塩などを電界紡糸すること等で得ることができる。本発明で得られる極細繊維及び繊維集合体が水溶性の場合は、得られた当該繊維に不溶化処理を施して使用することも可能である。不溶化処理としては、熱、グルタルアルデヒドによる架橋等の化学的及び物理的架橋、クエン酸やヒアルロン酸などのアニオンと交互積層法（ＬｂＬ）等のポリイオンコンプレックスなどを例示することができる。 The ultrafine fibers and fiber aggregates of the present invention can be made water-soluble and insoluble. Insoluble ultrafine fibers and fiber aggregates can be obtained by electrospinning EPLs that have been chemically modified to make them water-insoluble. It can also be obtained by electrospinning an EPL solution containing a cross-linking agent. Water-soluble ultrafine fibers and fiber aggregates can be obtained by electrospinning EPL and salts thereof. When the ultrafine fibers and fiber aggregates obtained in the present invention are water-soluble, the obtained fibers can be insolubilized before use. Examples of the insolubilization treatment include chemical and physical cross-linking such as heat and cross-linking with glutaraldehyde, and polyion complexes such as alternating lamination method (LbL) with anions such as citric acid and hyaluronic acid.
本発明の極細繊維及び極細繊維集合体が水溶性の場合、潮解性の特徴を有する。ＥＰＬの化学修飾の導入量や架橋の程度により、潮解性の制御が可能であり、医療用包装材や食品用包装材、抗菌コーティングなど用途に応じて、潮解性の程度を適宜選択し、使用することができる。 When the ultrafine fibers and the ultrafine fiber aggregates of the present invention are water-soluble, they have a deliquescent characteristic. Deliquescent property can be controlled by the amount of chemical modification introduced in EPL and the degree of cross-linking, and the degree of deliquescent property is appropriately selected and used according to the application such as medical packaging materials, food packaging materials, and antibacterial coatings. can do.
本発明の極細繊維は、原料に用いたＥＰＬと比較して極細繊維にすることで抗菌性の効果が高まることから、原料に用いたＥＰＬと同様に食品保存剤、化粧品、医薬、医療材料、抗菌素材、包装材料、防腐剤、止血材などの原料に用いたＥＰＬと同様の用途に使用することができる。さらに本発明の極細繊維は、カチオン性に加え高分子量であることを利用して、塗料、接着剤、紙力増強剤、化粧品、医薬、抗体等の固定など種々の用途に使用することができる。また、極細繊維にすることで、従来のＥＰＬに比べて抗菌効果も高く、より少ない使用量であっても従来と同等の効果を得ることができる。 Since the ultrafine fiber of the present invention has an enhanced antibacterial effect by making it an ultrafine fiber as compared with the EPL used as a raw material, food preservatives, cosmetics, pharmaceuticals, medical materials, like the EPL used as a raw material, It can be used for the same purposes as EPL used as a raw material for antibacterial materials, packaging materials, preservatives, hemostatic materials and the like. Further, the ultrafine fiber of the present invention can be used for various purposes such as fixing paints, adhesives, paper strength enhancers, cosmetics, pharmaceuticals, antibodies, etc. by utilizing the high molecular weight in addition to the cationic property. .. Further, by using ultrafine fibers, the antibacterial effect is higher than that of the conventional EPL, and the same effect as the conventional one can be obtained even with a smaller amount of use.
また、本発明の極細繊維は、種々のポリアニオンとポリイオンコンプレックスを形成することが可能である。ポリアニオンを巧みに利用することで、生分解性で安全性の高いポリカチオンであるポリリジンをより多岐な分野で利用できる。 In addition, the ultrafine fibers of the present invention can form polyion complexes with various polyanions. By skillfully using polyanions, polylysine, which is a biodegradable and highly safe polycation, can be used in a wider range of fields.
（ε−ポリリジン極細繊維の製造方法）
本発明の極細繊維を得る方法は、特に限定されるものではなく、公知の方法を用いることができる。例えば、この極細繊維を得る方法としては、海島繊維溶解法、湿式紡糸法、分散法、析出法、フォーススピニング法、電界紡糸法等が挙げられ、いずれの方法も採用することができる。本発明において極細繊維は、好ましくは、電界紡糸法により作製される。電界紡糸法で得られた極細繊維は、均一な径の繊維が形成されやすく、高品質な繊維集合体が得られ、また、高い比表面積と空隙率を有することから、抗菌性等のＥＰＬの特徴を効果的に発揮することができる。
(Manufacturing method of ε-polylysine ultrafine fiber)
The method for obtaining the ultrafine fibers of the present invention is not particularly limited, and a known method can be used. For example, examples of the method for obtaining the ultrafine fibers include a sea-island fiber dissolution method, a wet spinning method, a dispersion method, a precipitation method, a force spinning method, an electric field spinning method, and the like, and any of these methods can be adopted. In the present invention, the ultrafine fibers are preferably produced by an electrospinning method. The ultrafine fibers obtained by the electrospinning method can easily form fibers having a uniform diameter, obtain high-quality fiber aggregates, and have a high specific surface area and porosity. The features can be effectively exhibited.
電界紡糸法は、静電紡糸法、エレクトロスピニング法、またはエレクトロスプレー法と呼ばれる繊維の紡糸方法である。電界紡糸の方式は特に限定されず、一般的に知られている方式、例えば、１本もしくは複数のニードルを使用するニードル方式、ニードル先端に気流を噴き付けることでニードル１本あたりの生産性を向上させるエアブロー方式、１つのスピナレットに複数の溶液吐出孔を設けた多孔スピナレット方式、溶液槽に半浸漬させた円柱状や螺旋ワイヤ状の回転電極を用いるフリーサーフェス方式、ワイヤ電極に紡糸溶液を塗付しながら電界紡糸するワイヤ電極方式、供給エアによってポリマー溶液表面に発生したバブルを起点に電界紡糸するエレクトロバブル方式などが挙げられ、求める極細繊維の品質、生産性、または操業性を鑑みて、適宜選択することができる。 The electrospinning method is a fiber spinning method called an electrostatic spinning method, an electrospinning method, or an electrospray method. The method of electric field spinning is not particularly limited, and a generally known method, for example, a needle method using one or more needles, or a needle method in which an air flow is blown to the tip of a needle increases the productivity per needle. Air blow method to improve, porous spinneret method with multiple solution discharge holes in one spinneret, free surface method using columnar or spiral wire-shaped rotating electrodes semi-immersed in a solution tank, spinning solution applied to wire electrodes Examples include a wire electrode method in which electric field spinning is performed while attaching, and an electro bubble method in which electric field spinning is performed starting from a bubble generated on the surface of a polymer solution by supply air. In consideration of the required quality, productivity, or operability of ultrafine fibers. It can be selected as appropriate.
電界紡糸法は上記記述を含む、周知の手段で行うことができる。具体的には、紡糸溶液を充填したノズルとコレクター（基板）の間に電圧を印加した状態で、ノズルから紡糸溶液を吐出させて、コレクター上に繊維を回収する。電界紡糸を行う条件は特に限定されず、紡糸溶液の種類や得られる極細繊維の用途によって適宜調整すればよい。紡糸雰囲気温湿度は管理されていることが好ましく、その範囲としては２０〜３０℃、２０〜４５％の範囲が例示できる。この温湿度範囲であれば、年間を通して比較的容易に管理することが可能で、雰囲気温湿度の変化による電界紡糸挙動の変化や、得られる極細繊維物性の変化を生じ難くなる。また、湿度が高い場合においても、同様の効果を有する極細繊維を作製することができるが、その際は、捕集された極細繊維が潮解しやすいので、貧溶媒中への捕集や、架橋等による不溶化処理を行うことが好ましい。 The electrospinning method can be performed by well-known means including the above description. Specifically, the spinning solution is discharged from the nozzle in a state where a voltage is applied between the nozzle filled with the spinning solution and the collector (substrate), and the fibers are collected on the collector. The conditions for electrospinning are not particularly limited, and may be appropriately adjusted depending on the type of spinning solution and the use of the obtained ultrafine fibers. It is preferable that the temperature and humidity of the spinning atmosphere are controlled, and the range thereof can be exemplified in the range of 20 to 30 ° C. and 20 to 45%. Within this temperature and humidity range, it can be managed relatively easily throughout the year, and changes in the electrospinning behavior due to changes in the atmospheric temperature and humidity and changes in the physical properties of the obtained ultrafine fibers are less likely to occur. Further, even when the humidity is high, ultrafine fibers having the same effect can be produced, but in that case, the collected ultrafine fibers are easily deliquescent, so that they can be collected in a poor solvent or crosslinked. It is preferable to carry out an insolubilization treatment such as.
電界紡糸法で、本発明の極細繊維を製造する際の繊維捕集方式は、特に限定されず、公知の捕集方式を採用することができる。例えば、繊維捕集方式として、ロールツーロール方式のコレクターを使用すれば、長尺の繊維シートを採取することができ、高速回転可能なドラムコレクターやディスクコレクターを使用すれば、一方向にＥＰＬ繊維が配列した配列繊維シートが採取することができる。繊維が配列した配列繊維シートを採取する方法としては、平行分割電極を使用する方法も報告されており、これをコレクターとして使用することもできる。また、貧溶媒中に捕集することもできる。 The fiber collecting method for producing the ultrafine fibers of the present invention by the electric field spinning method is not particularly limited, and a known collecting method can be adopted. For example, if a roll-to-roll type collector is used as the fiber collection method, a long fiber sheet can be collected, and if a high-speed rotating drum collector or disc collector is used, EPL fibers are unidirectionally used. The arranged fiber sheet in which is arranged can be collected. As a method of collecting an arrayed fiber sheet in which fibers are arranged, a method of using a parallel split electrode has also been reported, and this can also be used as a collector. It can also be collected in a poor solvent.
電界紡糸法で、本発明の極細繊維および繊維構造体を製造する際の捕集体は、特に限定されず、前記のコレクター上に直接捕集してもよく、溶液中に捕集してもよく、コレクター上に配した、不織布、織布、ネット、もしくは微多孔フィルムなどの少なくとも１種類の基材の上に捕集してもよい。不織布、織布、ネット、もしくは微多孔フィルムなどの基材に捕集する場合、基材の構成は特に限定されず、１種類からなる単層品であってもよく、２種類以上からなる多層品であってもよく、これらは機能やその効果に応じて、適宜選択することができる。溶液中に捕集する場合、溶液は得られた極細繊維が不溶な溶媒であれば、特に限定されない。 The collector for producing the ultrafine fibers and the fiber structure of the present invention by the electrospinning method is not particularly limited, and may be collected directly on the collector or in a solution. , May be collected on at least one substrate such as non-woven fabric, woven fabric, net, or microporous film placed on the collector. When collecting on a base material such as a non-woven fabric, a woven cloth, a net, or a microporous film, the composition of the base material is not particularly limited, and a single layer product consisting of one type may be used, or a multi-layer product consisting of two or more types. It may be a product, and these can be appropriately selected according to the function and its effect. When collecting in a solution, the solution is not particularly limited as long as the obtained ultrafine fibers are an insoluble solvent.
電界紡糸法で、本発明の極細繊維および繊維構造体を製造する際の、ＥＰＬを溶解するための溶媒は、特に限定される物ではなく、水やエタノール、メチルアルコール、トリフルオロ酢酸、ヘキサフルオロイソプロパノール、３，３，３−トリフルオロプロピオン酸、トリフルオロメタンスルホン酸、ペンタフルオロプロピオン酸等の、ポリリジンを溶解可能な溶媒を例示することができる。また、これら溶媒は単独で用いてもよく、複数を任意の割合で混合した混合溶媒として用いてもよい。ポリリジンを前記溶媒に溶解して得られる紡糸溶液の濃度は、特に限定される物ではなく、電界紡糸過程の安定性や得られる極細繊維の特性を鑑みて、適宜設定することができるが、５〜７０重量％の範囲を例示することができる。 The solvent for dissolving EPL in producing the ultrafine fibers and fiber structures of the present invention by the electrospinning method is not particularly limited, and water, ethanol, methyl alcohol, trifluoroacetic acid, and hexafluoro Examples of solvents capable of dissolving polylysine, such as isopropanol, 3,3,3-trifluoropropionic acid, trifluoromethanesulfonic acid, and pentafluoropropionic acid, can be exemplified. Further, these solvents may be used alone or as a mixed solvent in which a plurality of these solvents are mixed at an arbitrary ratio. The concentration of the spinning solution obtained by dissolving polylysine in the solvent is not particularly limited, and can be appropriately set in consideration of the stability of the electrospinning process and the characteristics of the obtained ultrafine fibers. The range of ~ 70% by weight can be exemplified.
特に、溶媒としてフッ素を含む有機溶媒、すなわち、トリフルオロ酢酸、ヘキサフルオロイソプロパノール、３，３，３−トリフルオロプロピオン酸、トリフルオロメタンスルホン酸、ペンタフルオロプロピオン酸等を用いることが好ましい。 In particular, it is preferable to use an organic solvent containing fluorine as a solvent, that is, trifluoroacetic acid, hexafluoroisopropanol, 3,3,3-trifluoropropionic acid, trifluoromethanesulfonic acid, pentafluoropropionic acid and the like.
下記の実施例は、例示を目的としたものに過ぎない。本発明の範囲は、本実施例に限定されない。なお、実施例中に示した物性値の測定方法または定義を以下に示す。
＜平均繊維径＞
日立株式会社製の走査型電子顕微鏡ＳＵ８０２０を使用して、極細繊維シートを観察し、画像解析ソフトを用いて極細繊維５０本の直径を測定した。繊維５０本の繊維径の平均値を平均繊維径とした。
＜フッ素原子の観察＞
本発明の極細繊維を４０℃、６時間真空乾燥し、極細繊維中の残存溶媒を取り除いた。真空乾燥処理後の極細繊維を、株式会社堀場製作所製のエネルギー分散型Ｘ線分析装置Ｘ−ｍａｘ８０ ＥＸ−３７０を使用して観察し、極細繊維２０本の元素分析を行った。繊維２０本のフッ素の質量％の平均値をフッ素原子の量とした。
The examples below are for illustration purposes only. The scope of the present invention is not limited to this embodiment. The measurement method or definition of the physical property values shown in the examples is shown below.
<Average fiber diameter>
The ultrafine fiber sheet was observed using a scanning electron microscope SU8020 manufactured by Hitachi, Ltd., and the diameters of 50 ultrafine fibers were measured using image analysis software. The average value of the fiber diameters of 50 fibers was taken as the average fiber diameter.
<Observation of fluorine atoms>
The ultrafine fibers of the present invention were vacuum dried at 40 ° C. for 6 hours to remove residual solvent in the ultrafine fibers. The ultrafine fibers after the vacuum drying treatment were observed using an energy dispersive X-ray analyzer X-max80 EX-370 manufactured by HORIBA, Ltd., and elemental analysis of 20 ultrafine fibers was performed. The average value of the mass% of fluorine of 20 fibers was taken as the amount of fluorine atoms.
[実施例１]
ＪＮＣ株式会社製のＥＰＬ塩酸塩５０重量％、トリフルオロ酢酸５０重量％からなる紡糸溶液を調製した。次いで、シリンジポンプにより内径０．４８ｍｍのノズルに紡糸溶液を０．５ｍｌ／ｍｉｎで供給するとともに、ノズルに２５ｋＶの電圧を印加し、ＥＰＬ極細繊維を静電紡糸した。ノズルと接地されたコレクター間の距離は１５ｃｍとした。ＥＰＬ極細繊維の平均繊維径は、２３０ｎｍであった。フッ素原子の量の平均値は、１．６質量％であった。
[Example 1]
A spinning solution composed of 50% by weight of EPL hydrochloride and 50% by weight of trifluoroacetic acid manufactured by JNC Corporation was prepared. Next, a spinning solution was supplied at 0.5 ml / min to a nozzle having an inner diameter of 0.48 mm by a syringe pump, and a voltage of 25 kV was applied to the nozzle to electrostatically spin EPL ultrafine fibers. The distance between the nozzle and the grounded collector was 15 cm. The average fiber diameter of the EPL ultrafine fibers was 230 nm. The average value of the amount of fluorine atoms was 1.6% by mass.
[実施例２]
ＪＮＣ株式会社製のＥＰＬ塩酸塩２０重量％、トリフルオロ酢酸８０重量％からなる紡糸溶液を調製した。次いで、シリンジポンプにより内径０．４８ｍｍのノズルに紡糸溶液を０．５ｍｌ／ｍｉｎで供給するとともに、ノズルに３０ｋＶの電圧を印加し、ＥＰＬ極細繊維を静電紡糸した。ノズルと接地されたコレクター間の距離は１５ｃｍとした。ＥＰＬ極細繊維の平均繊維径は、５０ｎｍであった。フッ素原子の量の平均値は、０．６質量％であった。
[Example 2]
A spinning solution composed of 20% by weight of EPL hydrochloride and 80% by weight of trifluoroacetic acid manufactured by JNC Corporation was prepared. Next, a spinning solution was supplied at 0.5 ml / min to a nozzle having an inner diameter of 0.48 mm by a syringe pump, and a voltage of 30 kV was applied to the nozzle to electrostatically spin EPL ultrafine fibers. The distance between the nozzle and the grounded collector was 15 cm. The average fiber diameter of the EPL ultrafine fibers was 50 nm. The average value of the amount of fluorine atoms was 0.6% by mass.
[実施例３]
ＪＮＣ株式会社製のＥＰＬフリー体４０重量％、トリフルオロ酢酸６０重量％からなる紡糸溶液を調製した。次いで、シリンジポンプにより内径０．４８ｍｍのノズルに紡糸溶液を０．５ｍｌ／ｍｉｎで供給するとともに、ノズルに２５ｋＶの電圧を印加し、ＥＰＬ極細繊維を静電紡糸した。ノズルと接地されたコレクター間の距離は１５ｃｍとした。ＥＰＬ極細繊維の平均繊維径は、４００ｎｍであった。フッ素原子の量の平均値は、０．８質量％であった。
[Example 3]
A spinning solution composed of 40% by weight of an EPL-free body and 60% by weight of trifluoroacetic acid manufactured by JNC Corporation was prepared. Next, a spinning solution was supplied at 0.5 ml / min to a nozzle having an inner diameter of 0.48 mm by a syringe pump, and a voltage of 25 kV was applied to the nozzle to electrostatically spin EPL ultrafine fibers. The distance between the nozzle and the grounded collector was 15 cm. The average fiber diameter of the EPL ultrafine fibers was 400 nm. The average value of the amount of fluorine atoms was 0.8% by mass.
[実施例４]
ＡＬＤＲＩＣＨ社製のナイロン６，６が１０重量％、蟻酸５４重量％、トリフルオロ酢酸３６重量％からなる紡糸溶液を調製した。この溶液に、ＥＰＬ塩酸塩をナイロン６，６に対して５０重量部加えた。次いで、シリンジポンプにより内径０．２２ｍｍのノズルに紡糸溶液を０．６ｍＬ／ｈｒで供給するとともに、ノズルに３５ｋＶの電圧を印加し、静電紡糸した。ノズルと接地されたコレクター間の距離は１５ｃｍとした。ＥＰＬ塩酸塩を含有したナイロン６，６極細繊維の平均繊維径は、２５０ｎｍであった。フッ素原子の量の平均値は、０．４質量％であった。得られた極細繊維は、実施例１〜３と比較すると繊維径のばらつきが大きいものの、満足できる繊維形態であった。
[Example 4]
A spinning solution containing 10% by weight of nylons 6 and 6 manufactured by ALDRICH, 54% by weight of formic acid, and 36% by weight of trifluoroacetic acid was prepared. To this solution, 50 parts by weight of EPL hydrochloride was added to nylons 6 and 6. Next, the spinning solution was supplied at 0.6 mL / hr to a nozzle having an inner diameter of 0.22 mm by a syringe pump, and a voltage of 35 kV was applied to the nozzle for electrostatic spinning. The distance between the nozzle and the grounded collector was 15 cm. The average fiber diameter of nylon 6,6 ultrafine fibers containing EPL hydrochloride was 250 nm. The average value of the amount of fluorine atoms was 0.4% by mass. The obtained ultrafine fibers had a satisfactory fiber morphology, although the fiber diameters varied widely as compared with Examples 1 to 3.
[実施例５]
ＪＮＣ株式会社製のＥＰＬフリー体１２重量％、トリフルオロ酢酸８８重量％からなる紡糸溶液を調製した。次いで、シリンジポンプにより内径０．２２ｍｍのノズルに紡糸溶液を０．０１６ｍｌ／ｍｉｎで供給するとともに、ノズルに３０ｋＶの電圧を印加し、ＥＰＬ極細繊維を静電紡糸した。ノズルと接地されたコレクター間の距離は１５ｃｍとした。ＥＰＬ極細繊維の平均繊維径は、５００ｎｍであった。
[Example 5]
A spinning solution composed of 12% by weight of an EPL-free body and 88% by weight of trifluoroacetic acid manufactured by JNC Corporation was prepared. Next, a spinning solution was supplied at 0.016 ml / min to a nozzle having an inner diameter of 0.22 mm by a syringe pump, and a voltage of 30 kV was applied to the nozzle to electrostatically spin EPL ultrafine fibers. The distance between the nozzle and the grounded collector was 15 cm. The average fiber diameter of the EPL ultrafine fibers was 500 nm.
[比較例１]
ＡＬＤＲＩＣＨ社製のナイロン６，６が１０重量％、蟻酸５４重量％、トリフルオロ酢酸３６重量％からなる紡糸溶液を調製した。この溶液に、ＥＰＬ塩酸塩をナイロン６，６に対して５重量部加えた。次いで、シリンジポンプにより内径０．２２ｍｍのノズルに紡糸溶液を０．６ｍＬ／ｈｒで供給するとともに、ノズルに３５ｋＶの電圧を印加し、ＥＰＬ塩酸塩を含有したナイロン６，６極細繊維を静電紡糸した。ノズルと接地されたコレクター間の距離は１５ｃｍとした。ナイロン６，６極細繊維の平均繊維径は、２００ｎｍであった。極細繊維に対して５重量％ＥＰＬの添加では、抗菌性などのＥＰＬの効果を十分に活かすことはできなかった。
[Comparative Example 1]
A spinning solution containing 10% by weight of nylons 6 and 6 manufactured by ALDRICH, 54% by weight of formic acid, and 36% by weight of trifluoroacetic acid was prepared. To this solution, 5 parts by weight of EPL hydrochloride was added to nylons 6 and 6. Next, a spinning solution was supplied at 0.6 mL / hr to a nozzle having an inner diameter of 0.22 mm by a syringe pump, and a voltage of 35 kV was applied to the nozzle to electrostatically spin nylon 6 and 6 ultrafine fibers containing EPL hydrochloride. did. The distance between the nozzle and the grounded collector was 15 cm. The average fiber diameter of the nylon 6 and 6 ultrafine fibers was 200 nm. In addition of 5% by weight EPL to the ultrafine fibers, the effects of EPL such as antibacterial properties could not be fully utilized.
本発明の極細繊維及び繊維集合体は、従来のＥＰＬが付着した繊維と比較し、ポリリジンを主成分として構成されている。そのため、従来のＥＰＬを付着した繊維と比べて、抗菌性をはじめとするポリリジンの特性を効果的に利用することが可能である。さらに、本発明の極細繊維及び繊維集合体は、ポリカチオンの極細繊維及び繊維集合体であるため、様々なポリアニオンとポリイオンコンプレックスを形成でき、ポリアニオンを巧みに利用することで、医療機器の梱包及び包装材、食品包装材、抗菌コーティング、止血材などの多岐にわたる用途で好適に用いることができる。 The ultrafine fibers and fiber aggregates of the present invention are composed mainly of polylysine as compared with conventional fibers to which EPL is attached. Therefore, it is possible to effectively utilize the characteristics of polylysine, including antibacterial properties, as compared with conventional fibers to which EPL is attached. Furthermore, since the ultrafine fibers and fiber aggregates of the present invention are ultrafine fibers and fiber aggregates of polycations, they can form polyion complexes with various polyanions, and by skillfully using polyanions, they can be used for packaging medical devices and. It can be suitably used in a wide range of applications such as packaging materials, food packaging materials, antibacterial coatings, and hemostatic materials.
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