JP2019123955A - Gelatin solution, spinning dope made of the gelatin solution, method for producing fiber assembly using the spinning dope, and method for producing film and composite body using the gelatin solution - Google Patents
Gelatin solution, spinning dope made of the gelatin solution, method for producing fiber assembly using the spinning dope, and method for producing film and composite body using the gelatin solution Download PDFInfo
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Abstract
Description
本発明はゼラチン溶液と該ゼラチン溶液からなる紡糸液、および、該紡糸液を用いた繊維集合体の製造方法と該ゼラチン溶液を用いたフィルムならびに複合体の製造方法に関する。 The present invention relates to a spinning solution comprising a gelatin solution and the gelatin solution, a method of producing a fiber assembly using the spinning solution, and a method of producing a film and a complex using the gelatin solution.
ゼラチンを溶媒に溶解してなるゼラチン溶液は、様々な産業用途に有用な材料を調製可能な溶液である。例えば、ゼラチン溶液を紡糸液として用いて紡糸することでゼラチン繊維を備える繊維集合体を調製でき、ゼラチン溶液をシート状に展開した後、溶媒を除去することでゼラチンフィルムを調製でき、ゼラチン溶液を被覆対象物に付与した後、溶媒を除去することで被覆対象物の表面にゼラチン被膜を備える複合体を調製できるなど、ゼラチン溶液を用いて様々な産業用途に有用な材料を調製できる。
しかしながら、特開２００１−０８９９２９号公報（特許文献１）や特開２００５−１６３２０４号公報（特許文献２）などにも開示されている通り、ゼラチン溶液はゲル化し易いなど安定性に劣るという問題を有していた。特に、２５℃などの室温条件下において、よりゲル化し易いなど安定性に劣るという問題を有していた。
A gelatin solution obtained by dissolving gelatin in a solvent is a solution capable of preparing materials useful for various industrial applications. For example, a fiber assembly provided with gelatin fibers can be prepared by spinning using a gelatin solution as a spinning solution, a gelatin solution can be prepared by removing the solvent after developing the gelatin solution into a sheet, and a gelatin solution can be prepared. Gelatin solutions can be used to prepare useful materials for various industrial applications, such as preparing a composite having a gelatin coating on the surface of the object to be coated by removing the solvent after application to the object to be coated.
However, as disclosed in Japanese Patent Application Laid-Open Nos. 2001-089929 (Patent Document 1), 2005-163204 (Patent Document 2), etc., the gelatin solution is apt to gel and has a problem such as poor stability. I had it. In particular, it has a problem that it is inferior in stability such as easy gelation under room temperature conditions such as 25 ° C.
そして、安定性に劣るゼラチン溶液を用いた場合には、様々な産業用途に有用な材料を調製するのが困難であった。特に、該ゼラチン溶液からなる紡糸液において、次の問題が生じるものであった。 And when gelatin solutions having poor stability were used, it was difficult to prepare materials useful for various industrial applications. In particular, the following problems occur in a spinning solution comprising the gelatin solution.
平均繊維径や繊維径のＣＶ値が小さい繊維からなる繊維集合体（例えば、不織布など）は、分離性能、液体保持性能、払拭性能、隠蔽性能、絶縁性能、或いは柔軟性など、様々な性能に優れることが知られている。
ゼラチン繊維を備える繊維集合体の製造方法として、ゼラチンを溶媒に溶解してなる紡糸液を用いる方法、例えば、静電気力を作用させて紡糸液を細径化させると共に繊維化し、紡糸された繊維を捕集して繊維集合体を製造する静電紡糸法や、随伴気流を作用させて紡糸液を細径化させると共に繊維化し、紡糸された繊維を捕集して繊維集合体を製造する方法（例えば、特開２０１１−０１２３７２号公報など）などが知られている。
本願出願人は、ゼラチン繊維からなる繊維集合体を、平均繊維径や繊維径のＣＶ値が小さい繊維からなる態様で提供するため、ゼラチンを溶媒に溶解してなる紡糸液を調製し、該紡糸液を用いて繊維集合体を製造することを試みた。
しかし、調製した紡糸液はゲル化するなど安定性に劣るという問題を有していた。
そして、このように安定性に劣る紡糸液を用いて繊維集合体を製造すると、紡糸時にノズル先からの紡糸液の吐出が安定しない、あるいは、ノズル先から紡糸液が吐出されない結果、繊維化がなされず繊維集合体が製造できないことがあった。あるいは、繊維集合体を製造できたとしても、製造した繊維集合体にショットなどの非繊維物が多く存在する、および／または、製造した繊維集合体における平均繊維径や繊維径のＣＶ値が意図せず大きくなり、望む態様の繊維集合体を提供できないものであった。
A fiber assembly (for example, non-woven fabric etc.) consisting of fibers with small average fiber diameter and CV value of fiber diameter has various performances such as separation performance, liquid retention performance, wiping performance, concealment performance, insulation performance, or flexibility. It is known to be excellent.
As a method of producing a fiber assembly comprising gelatin fibers, a method using a spinning solution obtained by dissolving gelatin in a solvent, for example, allowing an electrostatic force to act to reduce the diameter of the spinning solution and fiberize it Electrostatic spinning method of collecting fiber assemblies by collecting them, a method of making the spinning solution into smaller diameter and fiberizing by making the accompanying air flow act and collecting spun fibers to produce fiber assemblies ( For example, JP-A-2011-012372 etc. are known.
The applicant has prepared a spinning solution comprising gelatin dissolved in a solvent, in order to provide a fiber assembly consisting of gelatin fibers in a mode comprising fibers having a small average fiber diameter or a CV value of the fiber diameter. An attempt was made to produce a fiber assembly using the solution.
However, the prepared spinning solution has a problem of poor stability such as gelation.
And if a fiber assembly is manufactured using a spinning solution having poor stability as described above, discharge of the spinning solution from the nozzle tip is not stable at the time of spinning, or as a result of the spinning solution not being discharged from the nozzle tip, fiberization occurs. In some cases, fiber assembly could not be produced. Alternatively, even if the fiber assembly can be produced, a large number of non-fibers such as shots are present in the produced fiber assembly, and / or the CV value of the average fiber diameter and the fiber diameter in the produced fiber assembly is intended It was not possible to provide a fiber assembly in the desired manner.
また、安定性に劣るゼラチン溶液を用いて、ゼラチンフィルムや被覆対象物の表面にゼラチン被膜を備える複合体を製造した場合、製造したフィルムや複合体に、凹凸のある部分や剛性などの各種物性が局所的に異なる部分などの不均一な部分が存在して、望む態様のフィルムや複合体を提供できないものであった。
In addition, when a gelatin film or a composite having a gelatin coating on the surface of a coated object is produced using a gelatin solution having poor stability, various physical properties such as uneven portions and rigidity in the produced film or composite are produced. However, nonuniform portions such as locally different portions are present, and it is impossible to provide a film or a composite in the desired manner.
本願発明は、安定性に優れるゼラチン溶液と該ゼラチン溶液からなる紡糸液、および、望む態様の繊維集合体やフィルムあるいは複合体を製造する方法の提供を目的とする。 An object of the present invention is to provide a gelatin solution excellent in stability, a spinning solution comprising the gelatin solution, and a method for producing a fiber assembly, film or composite of a desired embodiment.
本発明は、
「〔１〕尿素系化合物とゼラチンを含有する、ゼラチン溶液。
〔２〕請求項１に記載のゼラチン溶液からなる、紡糸液。
〔３〕請求項２に記載の紡糸液を細径化させると共に繊維化して捕集する工程を備えた、繊維集合体の製造方法。
〔４〕請求項１に記載のゼラチン溶液をシート状に展開した後、前記シート状に展開したゼラチン溶液から溶媒を除去する工程を備えた、ゼラチンフィルムの製造方法。
〔５〕請求項１に記載のゼラチン溶液を被覆対象物に付与した後、前記被覆対象物に付与したゼラチン溶液から溶媒を除去する工程を備えた、被覆対象物の表面にゼラチン被膜を備える複合体の製造方法。」
である。
The present invention
[1] A gelatin solution containing a urea compound and gelatin.
[2] A spinning solution comprising the gelatin solution according to claim 1.
[3] A method for producing a fiber assembly, comprising the steps of reducing the diameter of the spinning solution according to claim 2 and forming it into fibers for collection.
[4] A method for producing a gelatin film, comprising the steps of: developing the gelatin solution according to claim 1 into a sheet; and removing the solvent from the gelatin solution developed into the sheet.
[5] A composite comprising a gelatin coating on the surface of a coated object, comprising the step of removing the solvent from the gelatin solution applied to the coated object after applying the gelatin solution according to claim 1 to the coated object How to make the body. "
It is.
本願出願人は検討を続けた結果、ゼラチン溶液に尿素系化合物を配合することによって、ゼラチン溶液がゲル化するのを防止できるなどゼラチン溶液の安定性を向上できることを見出した。
そのため、本発明にかかるゼラチン溶液ならびにゼラチン溶液からなる紡糸液は安定性に優れる。
そして、紡糸液を細径化させると共に繊維化して捕集する工程を備えた繊維集合体の製造方法において、本発明にかかる安定性に優れた紡糸液を用いることで、ノズル先からの紡糸液の吐出が安定した状態で紡糸を行うことができるため、ショットなどの非繊維物が多く存在するのを防止して、および／または、平均繊維径や繊維径のＣＶ値が意図せず大きくなるのを防止して、望む態様の繊維集合体を製造することができる。
As a result of continuing investigations, the applicant of the present invention has found that the stability of a gelatin solution can be improved, for example, by preventing the gelatin solution from gelling by blending a urea compound in the gelatin solution.
Therefore, the gelatin solution and the spinning solution comprising the gelatin solution according to the present invention are excellent in stability.
Then, in the method for producing a fiber assembly, including the steps of reducing the diameter of the spinning solution and forming and collecting the fiber, the spinning solution from the nozzle tip is used by using the spinning solution having excellent stability according to the present invention. Spinning can be carried out in a stable state, so that a large amount of non-fiber matter such as shot can be prevented and / or the CV value of the average fiber diameter or the fiber diameter unintentionally becomes large Can be produced to produce the fiber assembly of the desired embodiment.
また、本発明にかかるゼラチン溶液を用いることで、凹凸のある部分や剛性などの各種物性が局所的に異なる部分などの不均一な部分が存在するのを防止して、望む態様のフィルムや複合体を製造することができる。 In addition, by using the gelatin solution according to the present invention, it is possible to prevent the presence of nonuniform portions such as uneven portions such as uneven portions and locally different portions of various physical properties such as rigidity, etc. Body can be manufactured.
本発明は、尿素系化合物とゼラチンを含有するゼラチン溶液ならびに該ゼラチン溶液からなる紡糸液（以降、ゼラチン溶液や紡糸液と称することがある）にかかるものであり、例えば以下の構成など各種構成を適宜選択できる。 The present invention relates to a gelatin solution containing a urea compound and gelatin, and a spinning solution (hereinafter sometimes referred to as a gelatin solution or spinning solution) composed of the gelatin solution. It can be selected appropriately.
本発明でいう尿素系化合物とは、その化学構造に尿素骨格（Ｎ−Ｃ（Ｏ）−Ｎ又はＮ−Ｃ（Ｓ）−Ｎ）を有する化合物であり、例えば、尿素、チオ尿素、ヒドロキシ尿素、ジメチロール尿素、ジアセチル尿素、エチレン尿素、フェニル尿素、トリフェニル尿素、テトラフェニル尿素、Ｎ−ベンゾイル尿素、Ｎ，Ｎ′−ジベンゾイル尿素、リン酸グアニル尿素、Ｎ，Ｎ′−ジメチルアセチル尿素、ベンゼンスルホニル尿素、ｐ−トルエンスルホニル尿素、炭素数１〜６のアルキル基を有するアルキル尿素（例えば、メチル尿素、ジメチル尿素、トリメチル尿素、テトラメチル尿素、テトラエチル尿素、エチル尿素、ジエチル尿素など）、ホルミル尿素などを、単体あるいは複数種類の混合物として使用できる。なお、これら尿素の塩（例えば、硝酸塩、塩酸塩など）であっても良い。 The urea compound as referred to in the present invention is a compound having a urea skeleton (N-C (O) -N or N-C (S) -N) in its chemical structure, for example, urea, thiourea, hydroxyurea , Dimethylolurea, diacetylurea, ethyleneurea, phenylurea, triphenylurea, tetraphenylurea, N-benzoylurea, N, N'-dibenzoylurea, guanylurea phosphate, N, N'-dimethylacetylurea, benzenesulfonyl Urea, p-toluenesulfonylurea, alkylurea having an alkyl group having 1 to 6 carbon atoms (eg, methylurea, dimethylurea, trimethylurea, tetramethylurea, tetraethylurea, ethylurea, diethylurea, etc.), formylurea, etc. Can be used alone or in combination of two or more. In addition, salts (for example, nitrate, hydrochloride, etc.) of these ureas may be used.
特に、後述するようにゼラチン溶液や細径化した紡糸液から、溶媒を除去する工程（例えば、加熱工程や、水などに浸漬することで溶媒を除去する工程）において、溶媒と共に除去可能な尿素系化合物を使用するのが好ましい。このような尿素系化合物を含有するゼラチン溶液や紡糸液を用いることで、最終的に尿素系化合物が存在していない材料（尿素系化合物が存在していない繊維集合体やフィルムあるいは複合体など）、あるいは、尿素系化合物の存在量の少ない材料（尿素系化合物の存在量の少ない繊維集合体やフィルムあるいは複合体など）を提供することができる。このような除去可能な尿素系化合物として、尿素、ジメチル尿素、フェニル尿素などを使用することができる。
また、尿素、ジメチル尿素、フェニル尿素などの分子量が低い（低分子化合物あるいはモノマーの）尿素系化合物を使用するのが好ましい。このような尿素系化合物を含有するゼラチン溶液や紡糸液を用いることで、よりゼラチン溶液や紡糸液に含有させる尿素系化合物の質量を少なくでき、最終的に尿素系化合物が存在していない材料（尿素系化合物が存在していない繊維集合体やフィルムあるいは複合体など）、あるいは、尿素系化合物の存在量の少ない材料（尿素系化合物の存在量の少ない繊維集合体やフィルムあるいは複合体など）を提供することができる。
In particular, urea that can be removed together with the solvent in the step of removing the solvent from the gelatin solution or the spinning solution having a reduced diameter as described later (for example, the heating step or the step of removing the solvent by immersion in water). It is preferred to use a system compound. By using a gelatin solution or a spinning solution containing such a urea-based compound, a material (a fiber aggregate, a film, a composite, etc. in which the urea-based compound does not exist) in which the urea-based compound does not finally exist Alternatively, it is possible to provide a material having a small amount of urea compound (such as a fiber assembly, a film or a complex having a small amount of urea compound). Urea, dimethylurea, phenylurea and the like can be used as such removable urea compounds.
In addition, it is preferable to use a low molecular weight (low molecular weight compound or monomer) urea compound such as urea, dimethylurea or phenylurea. By using a gelatin solution or a spinning solution containing such a urea-based compound, the mass of the urea-based compound to be contained in the gelatin solution or the spinning solution can be further reduced, and finally, a material in which the urea-based compound does not exist ( Fiber aggregates or films or composites in which no urea compound is present, or materials having a small amount of urea compounds (fiber aggregates or films or complexes in a small amount of urea compound) Can be provided.
本発明でいうゼラチンとは、コラーゲンを水や熱などの作用によって変性させたものであり、本発明ではゼラチンの誘導体も含む概念である。
ゼラチン溶液や紡糸液に含まれるゼラチンの質量は、求める材料を提供できるようゼラチン溶液の使用条件などに合わせ適宜選択するものである。具体的には、溶媒の質量を１００部としたときに、０．００１〜１００質量部であることができ、０．０１〜７５質量部であることができ、０．１〜５０質量部であることができる。
The gelatin referred to in the present invention is a substance obtained by denaturing collagen by the action of water, heat and the like, and the present invention is a concept including derivatives of gelatin.
The mass of gelatin contained in the gelatin solution or the spinning solution is appropriately selected in accordance with the conditions of use of the gelatin solution and the like so as to provide the desired material. Specifically, when the mass of the solvent is 100 parts, it can be 0.001 to 100 parts by mass, can be 0.01 to 75 parts by mass, and 0.1 to 50 parts by mass Can be.
本発明にかかるゼラチン溶液や紡糸液を構成する溶媒の種類は、少なくとも尿素系化合物とゼラチンを共に溶解可能な溶媒であるならば、適宜選択できるものであるが、例えば、水（蒸留水、イオン交換水など）、あるいはエタノール、１−プロパノール、２−プロパノール、グリセリンなどのアルコール類、あるいはジメチルホルムアミド、ジメチルアセトアミドなどのアミド類などを、単体あるいは複数種類の混合溶媒として使用できる。 The type of the solvent constituting the gelatin solution and the spinning solution according to the present invention can be appropriately selected as long as it is a solvent capable of dissolving at least both the urea compound and the gelatin, for example, water (distilled water, ion Exchanged water and the like), or alcohols such as ethanol, 1-propanol, 2-propanol, and glycerin, or amides such as dimethylformamide and dimethylacetamide can be used as a single or a plurality of mixed solvents.
ゼラチン溶液や紡糸液に含まれる尿素系化合物の質量は、ゼラチン溶液や紡糸液に含まれるゼラチンの質量に合わせ、求める材料を提供できるよう適宜選択するものである。しかし、ゼラチン溶液や紡糸液に含まれる尿素系化合物の質量があまりにも少ない場合には、ゼラチン溶液や紡糸液の安定性を向上する効果が十分発揮されない恐れがあり、ゼラチン溶液や紡糸液に含まれる尿素系化合物の質量があまりにも多い場合には、材料を製造することが困難となる恐れがある。
そのため、ゼラチン溶液や紡糸液に含まれる尿素系化合物の質量は適宜調整するが、ゼラチン溶液や紡糸液に含まれるゼラチンの質量を１００部としたときに、１〜１００質量部であるのが好ましく、５〜７０質量部であるのがより好ましく、１０〜５０質量部であるのが最も好ましい。
The mass of the urea-based compound contained in the gelatin solution or the spinning solution is appropriately selected according to the mass of gelatin contained in the gelatin solution or the spinning solution so as to provide the desired material. However, if the mass of the urea-based compound contained in the gelatin solution or the spinning solution is too small, the effect of improving the stability of the gelatin solution or the spinning solution may not be sufficiently exhibited, and it is contained in the gelatin solution or the spinning solution. If the mass of the urea compound to be reduced is too large, it may be difficult to manufacture the material.
Therefore, although the mass of the urea compound contained in the gelatin solution or the spinning solution is appropriately adjusted, it is preferably 1 to 100 mass parts when the mass of gelatin contained in the gelatin solution or the spinning solution is 100 parts. The amount is more preferably 5 to 70 parts by mass, and most preferably 10 to 50 parts by mass.
本発明のゼラチン溶液や紡糸液が安定性に優れている理由は完全に明らかになっていないが、ゼラチンにおける高分子鎖間の水素結合を生じる水酸基やアミノ基、カルボキシル基などの化学構造部分に対し、尿素系化合物のアミド構造部分が親和性を有していることで、溶媒中でゼラチンの自己架橋などの安定性の低下をもたらす望まない反応（ゲル化など）が進行し難くなるためだと考えられる。
この効果は分子量の低い（分子構造が小さいことでゼラチンにおける高分子鎖間の水素結合を生じる水酸基やアミノ基、カルボキシル基などの化学構造部分とより親和性が高いと考えられる）尿素などの尿素系化合物を採用することで、効果的に発揮される。
The reason why the gelatin solution or spinning solution of the present invention is excellent in stability is not completely clear, but in the chemical structure moiety such as hydroxyl group, amino group and carboxyl group which causes hydrogen bonding between polymer chains in gelatin On the other hand, when the amide structure part of the urea compound has an affinity, an undesired reaction (such as gelation) which leads to a decrease in stability such as self-crosslinking of gelatin in a solvent is difficult to progress. it is conceivable that.
This effect is urea such as urea, which has a low molecular weight (it is considered to have a higher affinity for chemical structures such as hydroxyl groups, amino groups, and carboxyl groups that cause hydrogen bonding between polymer chains in gelatin due to its small molecular structure) By adopting a compound of the type, it is effectively exhibited.
本発明にかかるゼラチン溶液や紡糸液は、必要に応じて、他の有機樹脂や各種添加剤を含有していても良い。
他の有機樹脂の種類は適宜選択できるが、例えば、ポリオレフィン系樹脂（例えば、ポリエチレン、ポリプロピレン、ポリメチルペンテン、炭化水素の一部をシアノ基またはフッ素或いは塩素といったハロゲンで置換した構造のポリオレフィン系樹脂など）、スチレン系樹脂、ポリビニルアルコール系樹脂、ポリエーテル系樹脂（例えば、ポリエーテルエーテルケトン、ポリアセタール、変性ポリフェニレンエーテル、芳香族ポリエーテルケトンなど）、ポリエステル系樹脂（例えば、ポリエチレンテレフタレート、ポリトリメチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンナフタレート、ポリカーボネート、ポリアリレート、全芳香族ポリエステル樹脂など）、ポリイミド系樹脂、ポリアミドイミド樹脂、ポリアミド系樹脂（例えば、芳香族ポリアミド樹脂、芳香族ポリエーテルアミド樹脂、ナイロン樹脂など）、二トリル基を有する樹脂（例えば、ポリアクリロニトリルなど）、ウレタン系樹脂、エポキシ系樹脂、ポリスルホン系樹脂（例えば、ポリスルホン、ポリエーテルスルホンなど）、フッ素系樹脂（例えば、ポリテトラフルオロエチレン、ポリフッ化ビニリデンなど）、セルロース系樹脂、ポリベンゾイミダゾール樹脂、アクリル系樹脂（例えば、アクリル酸エステルあるいはメタクリル酸エステルなどを共重合したポリアクリロニトリル系樹脂、アクリロニトリルと塩化ビニルまたは塩化ビニリデンを共重合したモダアクリル系樹脂など）など、公知の有機樹脂を単体あるいは複数で含有できる。
ゼラチン溶液や紡糸液に含有されている他の有機樹脂の質量は、求める材料を提供できるよう紡糸条件など材料の調製条件などに合わせ適宜選択できる。
The gelatin solution and the spinning solution according to the present invention may contain other organic resins and various additives as required.
Although the type of other organic resin can be selected appropriately, for example, polyolefin resin (for example, polyethylene, polypropylene, polymethylpentene, polyolefin resin having a structure in which a part of hydrocarbon is substituted with cyano group or halogen such as fluorine or chlorine) Etc.), styrene resins, polyvinyl alcohol resins, polyether resins (eg, polyether ether ketone, polyacetal, modified polyphenylene ether, aromatic polyether ketone etc.), polyester resins (eg, polyethylene terephthalate, polytrimethylene) Terephthalates, polybutylene terephthalates, polyethylene naphthalates, polybutylene naphthalates, polycarbonates, polyarylates, wholly aromatic polyester resins, etc.), polyimide resins, polyureas Doimide resin, polyamide resin (for example, aromatic polyamide resin, aromatic polyetheramide resin, nylon resin etc.), resin having ditolyl group (for example, polyacrylonitrile etc.), urethane resin, epoxy resin, polysulfone resin Resin (eg, polysulfone, polyether sulfone, etc.), fluorocarbon resin (eg, polytetrafluoroethylene, polyvinylidene fluoride, etc.), cellulose resin, polybenzimidazole resin, acrylic resin (eg, acrylic ester or methacrylic acid) A known organic resin such as polyacrylonitrile resin obtained by copolymerizing ester or the like, modacrylic resin obtained by copolymerizing acrylonitrile and vinyl chloride or vinylidene chloride, etc., etc. can be contained singly or in combination.
The mass of the other organic resin contained in the gelatin solution or the spinning solution can be appropriately selected in accordance with the preparation conditions of the material such as the spinning conditions so as to provide the desired material.
また、各種添加剤の種類は適宜選択できるが、例えば、架橋剤、難燃剤、香料、顔料、抗菌剤、抗黴材、光触媒粒子、乳化剤、分散剤、増粘剤、消泡剤、例えばアルミナやシリカなどの無機粒子や無機フィラー、活性炭やチャコールブラック、紡糸安定化剤などを添加できる。紡糸安定化剤の種類は適宜選択できるが、例えば、塩化カルシウムや塩化リチウムなどの金属塩や、特開２０１２―４６８４４号公報に開示されているような有機酸と窒素化合物からなる塩などを、単体あるいは複数種類の混合物として使用できる。
また、ゼラチン溶液や紡糸液に含有されている各種添加剤の質量は、求める材料を提供できるよう紡糸条件など材料の調製条件などに合わせ適宜選択するものである。具体的には、ゼラチン溶液や紡糸液の質量を１００部としたときに、０．０１〜３０質量部存在することができ、０．１〜２０質量部存在することができ、１〜１０質量部存在することができる。
Further, the type of various additives can be appropriately selected, but, for example, a crosslinking agent, a flame retardant, a fragrance, a pigment, an antibacterial agent, an anti-glaze material, photocatalyst particles, an emulsifier, a dispersant, a thickener, an antifoamer such as alumina And inorganic particles such as silica, inorganic fillers, activated carbon and charcoal black, spinning stabilizers and the like can be added. The kind of the spinning stabilizer can be appropriately selected, and for example, metal salts such as calcium chloride and lithium chloride, salts comprising an organic acid and a nitrogen compound as disclosed in JP 2012-46844 A, etc. It can be used alone or in combination of two or more.
In addition, the mass of various additives contained in the gelatin solution and the spinning solution is appropriately selected in accordance with the preparation conditions of the material such as the spinning conditions so as to provide the desired material. Specifically, when the mass of the gelatin solution or the spinning solution is 100 parts, it can be present in an amount of 0.01 to 30 parts by mass, can be present in an amount of 0.1 to 20 parts by mass, and is 1 to 10 parts Some can exist.
架橋剤の種類は適宜選択できるが、ホルムアルデヒドやグルタルアルデヒドなどのアルデヒド類、ブチルグリシジルエーテルやエチレングリコールジグリシジルエーテルなどのエポキシ化合物などを使用できる。架橋剤はゼラチン溶液に直接添加してもよいし、ゼラチンの繊維集合体あるいはフィルムあるいは複合体を架橋剤溶液に含浸することで、架橋剤の添加を行ってもよい。 Although the kind of crosslinking agent can be selected suitably, aldehydes, such as formaldehyde and glutaraldehyde, epoxy compounds, such as butyl glycidyl ether and ethylene glycol diglycidyl ether, etc. can be used. The crosslinking agent may be added directly to the gelatin solution, or the crosslinking agent may be added by impregnating a fiber assembly or film of gelatin or a complex into the crosslinking agent solution.
ゼラチン溶液や紡糸液の温度や粘度は、求める材料を提供できるよう紡糸条件など材料の調製条件に合わせ適宜選択するものである。具体的には、ゼラチン溶液や紡糸液の温度は０〜１００℃であることができ、１０〜８０℃であることができ、２０〜６０℃であることができる。また、ゼラチン溶液や紡糸液の粘度は２５℃において１０〜３００００ｍＰａ・ｓであることができ、１００〜２００００ｍＰａ・ｓであることができ、１０００〜１００００ｍＰａ・ｓであることができる。 The temperature and viscosity of the gelatin solution and the spinning solution are appropriately selected in accordance with the preparation conditions of the material such as the spinning conditions so as to provide the desired material. Specifically, the temperature of the gelatin solution or the spinning solution can be 0 to 100 ° C., can be 10 to 80 ° C., and can be 20 to 60 ° C. The viscosity of the gelatin solution or the spinning solution can be 10 to 30,000 mPa · s at 25 ° C., can be 100 to 20,000 mPa · s, and can be 1,000 to 10,000 mPa · s.
次いで、本発明にかかる紡糸液を用いた、繊維集合体の製造方法について例示し説明する。なお、すでに説明した項目と構成を同じくする点については説明を省略する。 Next, a method for producing a fiber assembly using the spinning solution according to the present invention will be illustrated and described. Description of the same items as the items already described will be omitted.
繊維集合体の製造方法は適宜選択できるが、例えば、静電紡糸法、特開２００９−２８７１３８号公報に開示されているようなガスの作用により紡糸する方法、特開２０１１−３２５９３号公報に開示されているような電界の作用に加えてガスの剪断力を作用させて紡糸する方法、遠心紡糸法などを用いることができる。そして、これらの製造方法を用いて紡糸液を細径化させるとともに繊維化して、例えばネットあるいはドラムやベルトコンベアなどの捕集体上に捕集することで、捕集体上に繊維ウェブを形成できる。
これらの中でも静電紡糸法や、特開２００９−２８７１３８号公報に開示されているようなガスの剪断作用により紡糸する方法を用いることで、平均繊維径が２μｍ以下の極細繊維を紡糸しやすく、繊維径が揃っており、しかも連続した極細繊維からなる繊維集合体を製造しやすいため好適である。
The method for producing the fiber assembly can be appropriately selected, but for example, a method of spinning by the action of a gas as disclosed in the electrostatic spinning method, JP 2009-287138 A, JP 2011-32593 JP In addition to the action of the electric field as described above, it is possible to use a method of spinning by applying a shearing force of gas, a centrifugal spinning method or the like. Then, the spinning solution is reduced in diameter and formed into fibers using these manufacturing methods, and the fiber web can be formed on the collector, for example, by collecting it on a collector such as a net or a drum or a belt conveyor.
Among these, it is easy to spin an ultrafine fiber having an average fiber diameter of 2 μm or less by using an electrostatic spinning method or a method of spinning by a gas shearing action as disclosed in JP 2009-287138 A, The fiber diameter is uniform, and it is preferable because it is easy to manufacture a fiber assembly consisting of continuous microfibers.
このようにして製造した繊維ウェブは、そのまま繊維集合体として使用することもできるが、繊維ウェブから溶媒や尿素系化合物を除去するため加熱装置へ供してもよい。加熱装置の種類は適宜選択でき、例えば、ロールにより加熱または加熱加圧する装置、オーブンドライヤー、遠赤外線ヒーター、乾熱乾燥機、熱風乾燥機、赤外線を照射し加熱できる装置などを用いることができる。加熱装置による繊維ウェブの加熱温度は適宜選択するが、溶媒や尿素系化合物を揮発あるいは分解し揮発させ除去可能であると共に、構成繊維などの構成成分が意図せず分解や変性しない温度であるように適宜調整する。
また、上述のようにして製造した繊維ウェブあるいは繊維集合体を、水などに浸漬することで、構成繊維中に残留している溶媒や尿素系化合物を溶出させることで除去してもよい。
更に、上述のようにして製造した繊維ウェブあるいは繊維集合体を、表面を平滑とするためカレンダー処理など加圧処理する工程へ供してもよい。
The fiber web thus produced may be used as it is as a fiber assembly, but may be subjected to a heating device to remove the solvent and the urea compound from the fiber web. The type of heating device can be appropriately selected, and for example, a device for heating or heating and pressing with a roll, an oven dryer, a far infrared heater, a dry heat dryer, a hot air dryer, a device capable of irradiating with infrared light and the like can be used. The heating temperature of the fiber web by the heating device is appropriately selected, but it is possible to volatilize or decompose and volatilize the solvent or the urea compound and to remove it, and to be a temperature at which the constituent components such as constituent fibers do not unintentionally decompose or Adjust as appropriate.
Alternatively, the fiber web or fiber assembly produced as described above may be removed by immersing in water or the like to elute the solvent or urea compound remaining in the constituent fibers.
Furthermore, the fiber web or fiber assembly produced as described above may be subjected to a pressure treatment such as calendering to smooth the surface.
このようにして製造した繊維集合体は、そのまま各種用途に使用してもよいが、樹脂膜と複合化する工程、あるいは、別の多孔体、フィルム、発泡体などの構成部材を積層して積層体を製造する工程、用途や使用態様に合わせて形状を打ち抜くなどして加工する工程などの各種二次工程を経て、様々な産業用資材として使用可能な繊維集合体を備えた材料を調製してもよい。 The fiber assembly produced in this way may be used as it is for various applications, but the step of forming a composite with a resin film, or lamination of another porous member, film, foam, etc. Through various secondary processes such as the process of manufacturing the body, and the process of punching and processing the shape according to the use and usage mode, a material provided with a fiber assembly usable as various industrial materials is prepared. May be
また、ゼラチンを備えるフィルムや複合体は、ゼラチン溶液を従来知られているフィルムや複合体の製造方法へ供することによって製造できる。
具体的には、本発明にかかるゼラチン溶液をシート状に展開した後、前記シート状に展開したゼラチン溶液から溶媒を除去する工程を備えた、フィルムの製造方法を採用できる。製造するフィルムの厚さは要望に合わせ適宜選択でき、通気性を有していないフィルムであっても通気性を有するフィルムであってもよい。あるいは、発泡フィルムであってもよい。
また、本発明にかかるゼラチン溶液を被覆対象物に付与した後、前記被覆対象物に付与したゼラチン溶液から溶媒を除去する工程を備えた、被覆対象物の表面にゼラチン被膜を備える複合体の製造方法を採用できる。被覆対象物の種類や、複合体におけるゼラチン被膜の厚さは要望に合わせ適宜選択できる。
なお、上述した繊維集合体から残留している溶媒や尿素系化合物を除去する方法と同様にして、フィルムや複合体から残留している溶媒や尿素系化合物を除去することができる。
製造したフィルムや複合体も同様に、そのまま各種用途に使用してもよいが、樹脂膜と複合化する工程、あるいは、別の多孔体、フィルム、発泡体などの構成部材を積層して積層体を製造する工程、用途や使用態様に合わせて形状を打ち抜くなどして加工する工程などの各種二次工程を経て、様々な産業用資材として使用可能なフィルムや複合体を備えた材料を調製してもよい。
In addition, a film or complex comprising gelatin can be produced by subjecting a gelatin solution to a conventionally known method for producing a film or complex.
Specifically, it is possible to adopt a method for producing a film, which comprises the step of developing the gelatin solution according to the present invention into a sheet and then removing the solvent from the gelatin solution developed into the sheet. The thickness of the film to be produced can be selected appropriately according to the needs, and it may be a film having no air permeability or a film having air permeability. Alternatively, it may be a foam film.
In addition, after the gelatin solution according to the present invention is applied to a coated object, a step of removing the solvent from the gelatin solution applied to the coated object is provided, producing a complex having a gelatin coating on the surface of the coated object. The method can be adopted. The type of the object to be coated and the thickness of the gelatin coating in the complex can be appropriately selected according to the request.
The solvent and the urea compound remaining from the film or the composite can be removed in the same manner as the method for removing the solvent and the urea compound remaining from the fiber assembly described above.
Similarly, the produced film or composite may be used as it is in various applications as it is, but it is a step of forming a composite with a resin film, or a laminate by laminating other structural members such as a porous body, a film and a foam. Through various secondary processes such as the process of manufacturing shapes, and the process of punching and processing the shapes according to the application and usage mode, to prepare materials provided with films and composites that can be used as various industrial materials May be
以下、実施例によって本発明を具体的に説明するが、これらは本発明の範囲を限定するものではない。 Hereinafter, the present invention will be specifically described by way of examples, but these do not limit the scope of the present invention.
（比較例１）
イオン交換水７０質量部とゼラチン（ＷＡＫＯ社製）３０質量部を混合した後、混合液を６０℃まで加熱することでイオン交換水にゼラチンを溶解させ、６０℃のゼラチン溶液Ａを調製した。
(Comparative example 1)
After 70 parts by mass of ion exchange water and 30 parts by mass of gelatin (manufactured by WAKO) were mixed, gelatin was dissolved in ion exchange water by heating the mixture to 60 ° C. to prepare gelatin solution A at 60 ° C.
（比較例２）
６０℃のゼラチン溶液Ａへ、ゼラチン溶液中のゼラチン１００質量部に対し塩化カルシウム（ＷＡＫＯ社製）を１０質量部となるように混合して溶解させ、６０℃のゼラチン溶液Ｂを調製した。
(Comparative example 2)
Calcium chloride (manufactured by WAKO Co., Ltd.) was mixed and dissolved in gelatin solution A at 60 ° C. to 10 parts by mass with respect to 100 parts by mass of gelatin in the gelatin solution to prepare gelatin solution B at 60 ° C.
（実施例１）
６０℃のゼラチン溶液Ａへ、ゼラチン溶液中のゼラチン１００質量部に対し塩化カルシウムを１０質量部、および、尿素１０質量部となるように混合して溶解させ、６０℃のゼラチン溶液Ｃを調製した。
Example 1
10 parts by mass of calcium chloride and 10 parts by mass of urea were mixed and dissolved in gelatin solution A at 60 ° C. to 100 parts by mass of gelatin in the gelatin solution to prepare gelatin solution C at 60 ° C. .
（実施例２）
溶解させる尿素の質量を５０質量部に変更したこと以外は、実施例１と同様にして６０℃のゼラチン溶液Ｄを調製した。
(Example 2)
A gelatin solution D at 60 ° C. was prepared in the same manner as in Example 1 except that the mass of urea to be dissolved was changed to 50 parts by mass.
（実施例３）
溶解させる尿素系化合物を、フェニル尿素５０質量部に変更したこと以外は、実施例２と同様にして６０℃のゼラチン溶液Ｅを調製した。
(Example 3)
A gelatin solution E at 60 ° C. was prepared in the same manner as in Example 2 except that the urea compound to be dissolved was changed to 50 parts by mass of phenylurea.
（実施例４）
溶解させる尿素系化合物を、ジメチル尿素５０質量部に変更したこと以外は、実施例２と同様にして６０℃のゼラチン溶液Ｆを調製した。
(Example 4)
A gelatin solution F at 60 ° C. was prepared in the same manner as in Example 2, except that the urea compound to be dissolved was changed to 50 parts by mass of dimethylurea.
（実施例５）
６０℃のゼラチン溶液Ａへ、ゼラチン溶液中のゼラチン１００質量部に対し塩化カルシウムを５質量部、および、尿素１００質量部となるように混合して溶解させ、６０℃のゼラチン溶液Ｇを調製した。
(Example 5)
5 parts by mass of calcium chloride and 100 parts by mass of urea were mixed and dissolved in gelatin solution A at 60 ° C. to 100 parts by mass of gelatin in the gelatin solution to prepare gelatin solution G at 60 ° C. .
上述のようにして調製した各ゼラチン溶液を以下の測定方法へ供することで、各ゼラチン溶液の安定性を評価した。
（ゼラチン溶液の安定性の確認）
各ゼラチン溶液を２５℃まで冷却した。そして、２５℃の各ゼラチン溶液がゲル化しているか否か目視で確認した。
確認の結果、２５℃に冷却した比較例のゼラチン溶液はいずれもゲル化していたが、２５℃に冷却した実施例のゼラチン溶液はいずれもゲル化していなかった。
The stability of each gelatin solution was evaluated by applying each gelatin solution prepared as described above to the following measurement method.
(Confirmation of stability of gelatin solution)
Each gelatin solution was cooled to 25 ° C. Then, it was visually confirmed whether or not each gelatin solution at 25 ° C. had gelled.
As a result of the confirmation, the gelatin solutions of the comparative examples cooled to 25 ° C. were all gelled, but none of the gelatin solutions of the example cooled to 25 ° C. were gelled.
上述のようにして調製した各ゼラチン溶液を２５℃まで冷却した。そして、２５℃の各ゼラチン溶液を紡糸液として、以下条件の静電紡糸装置へ供することで不織布の製造を試みた。
（紡糸液、および、該紡糸液を用いた不織布の製造方法）
内径が０．４４ｍｍの金属製のノズルに、アース処理されたパワーサプライを接続した。ノズル先端部の開口と対面するように、アース処理された捕集体（アルミホイル）を設けた。この時、ノズル先端部と捕集体との最短距離が、１０ｃｍとなるように調整した。ノズルをパワーサプライにより５−１５ｋＶとなるように印加して、ノズルと捕集体の間に電界を形成した。
ノズルの開口から紡糸液を吐出量が０．５ｃｃ／時間となるようにして吐出させ、紡糸液を電界に導いて、紡糸液をノズル先端部の開口から捕集体へと飛翔させると共に細径化させ、繊維化して捕集体上に捕集し繊維ウェブを調製することを試みた。なお、本工程における紡糸環境は、温度２５℃、湿度４０％ＲＨに調整した。
このようにして繊維ウェブが得られた場合、得られた繊維ウェブを電気炉（ＴＡＢＡＩ社製ＰＨＨ２００）へ供し１４０℃で３０分間加熱処理することで、繊維ウェブを構成する繊維中に残留している水を揮発させて（ならびに、繊維ウェブに尿素系化合物が残留している場合には、該尿素系化合物も揮発させて）除去し、不織布を製造することを試みた。
Each gelatin solution prepared as described above was cooled to 25 ° C. Then, production of non-woven fabric was attempted by applying each gelatin solution at 25 ° C. as a spinning solution to an electrostatic spinning device under the following conditions.
(Spinning solution and method for producing non-woven fabric using the spinning solution)
The grounded power supply was connected to a metal nozzle with an inner diameter of 0.44 mm. An earth-treated collecting body (aluminum foil) was provided to face the opening of the nozzle tip. At this time, the shortest distance between the nozzle tip and the collection body was adjusted to be 10 cm. The nozzle was applied by a power supply to 5-15 kV to form an electric field between the nozzle and the collector.
The spinning solution is discharged from the opening of the nozzle so that the amount of discharge is 0.5 cc / hour, and the spinning solution is guided to an electric field to fly the spinning solution from the opening at the tip of the nozzle to the collection body and reduce in diameter. It was tried to make a fiber web by collecting it on a collecting body and forming it into fibers. The spinning environment in this step was adjusted to a temperature of 25 ° C. and a humidity of 40% RH.
When a fiber web is thus obtained, the obtained fiber web is subjected to an electric furnace (PHH 200 manufactured by TABAI) and heat treated at 140 ° C. for 30 minutes to remain in the fibers constituting the fiber web. It tried to produce non-woven fabric by volatilizing the existing water (as well as volatilizing the urea-based compound if the urea-based compound remained in the fiber web).
（比較例３−４）
２５℃のゼラチン溶液Ａ−Ｂはゲル化していたためノズルから吐出できず、不織布を製造できなかった。そのため、２５℃のゼラチン溶液Ａ−Ｂは紡糸液として使用できなかった。
(Comparative Example 3-4)
Since the gelatin solution A-B at 25 ° C. was gelled, it could not be discharged from the nozzle, and a non-woven fabric could not be manufactured. Therefore, the gelatin solution A-B at 25 ° C. could not be used as a spinning solution.
（実施例６−１０）
２５℃のゼラチン溶液Ｃ−Ｇはいずれもゲル化していなかったためノズルから吐出でき、安定した状態で紡糸が行えたため不織布を製造することができた。そのため、２５℃のゼラチン溶液Ｃ−Ｇは紡糸液として使用できるものであった。そして、製造したゼラチン不織布には、いずれも、ショットなどの非繊維物の存在が少なく、平均繊維径（３００ｎｍ）および繊維径のＣＶ値（０．２）が小さいものであった。
(Examples 6-10)
Since none of the gelatin solutions C-G at 25 ° C. were gelled, they could be discharged from the nozzles and spinning could be performed in a stable state, so that non-woven fabrics could be produced. Therefore, the gelatin solution C-G at 25 ° C. can be used as a spinning solution. And in all the manufactured gelatin nonwoven fabrics, presence of non-fibers, such as a shot, was small, and CV value (0.2) of an average fiber diameter (300 nm) and a fiber diameter was small.
以上から、本発明にかかるゼラチン溶液および該ゼラチン溶液からなる紡糸液は安定性に優れているものであり、本発明にかかる紡糸液を用いることで、望む態様の繊維集合体を製造できる。 From the above, the gelatin solution according to the present invention and the spinning solution comprising the gelatin solution are excellent in stability, and by using the spinning solution according to the present invention, a fiber assembly of a desired embodiment can be produced.
（実施例６）
実施例２のゼラチン溶液をＰＥＴフィルム上にコーター（スリット幅：１ｍｍ）を用いてシート状に展開することで付与した。その後、ガラス板上に展開されたゼラチン溶液をガラス板ごとオーブン（加熱温度：８０℃）へ供することで、シート状に展開したゼラチン溶液から水を除去することで、ＰＥＴフィルム表面にゼラチン被膜を備える複合体（ゼラチン被膜の厚さ：８０μｍ）を製造した。そして、ＰＥＴフィルムからゼラチン被膜を剥離することで、ゼラチンフィルム（厚さ：８０μｍ）を製造した。
このようにして製造した複合体におけるゼラチン被膜の主面、および、フィルムの主面は、凹凸が少なく外観のよいものであった。
(Example 6)
The gelatin solution of Example 2 was applied onto a PET film by spreading it into a sheet using a coater (slit width: 1 mm). Thereafter, the gelatin solution developed on a glass plate is subjected to an oven (heating temperature: 80 ° C.) together with the glass plate to remove water from the gelatin solution developed in the form of a sheet, whereby the gelatin film is formed on the PET film surface. A composite (gelatin film thickness: 80 μm) was prepared. And the gelatin film (thickness: 80 micrometers) was manufactured by peeling a gelatin film from PET film.
The main surface of the gelatin coating in the composite thus produced and the main surface of the film had few irregularities and had a good appearance.
以上から、本発明にかかるゼラチン溶液を用いることで、凹凸のある部分や剛性などの各種物性が局所的に異なる部分などの不均一な部分が存在するのを防止して、望む態様のフィルムや複合体を製造することができる。 From the above, by using the gelatin solution according to the present invention, it is possible to prevent the presence of nonuniform portions such as a portion having unevenness and a portion locally having various physical properties such as rigidity, etc. Complexes can be produced.
本発明のゼラチン溶液と該ゼラチン溶液からなる紡糸液、および、該紡糸液を用いた繊維集合体の製造方法とゼラチン溶液を用いたフィルムならびに複合体の製造方法によって、例えば、マスクや貼付薬用基材などの衛生材料、止血材、創傷被覆材、癒着防止材、人工硬膜、細胞培養基材、再生医療用材料などの様々な産業用資材として使用可能な材料を提供できる。 A spinning solution comprising the gelatin solution of the present invention and the gelatin solution, and a method of producing a fiber assembly using the spinning solution and a film using the gelatin solution and a method of producing a composite, for example, for masks and patches Materials that can be used as various industrial materials such as sanitary materials such as wood, hemostatic materials, wound covering materials, adhesion preventing materials, artificial dura mater, cell culture substrates, materials for regenerative medicine and the like can be provided.
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