JP2010185146A - Structural coloring fiber assembly, and method for producing the same - Google Patents
Structural coloring fiber assembly, and method for producing the same Download PDFInfo
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本発明は、家電、家具、車、建材（壁、天井など）、衣類、スポーツ用品、包装材（包装紙、リボン、テープなど）、インテリア材（カーテン、アートフラワー材料など）などに使用できる、透過光によって発色する繊維集合体、及びその製造方法に関する。 The present invention can be used for home appliances, furniture, cars, building materials (walls, ceilings, etc.), clothing, sports equipment, packaging materials (wrapping paper, ribbons, tapes, etc.), interior materials (curtains, art flower materials, etc.), The present invention relates to a fiber aggregate that develops color by transmitted light and a method for producing the same.
例えば、モルフォチョウや熱帯魚は色素を有していないにも拘らず、鮮やかに発色している。これは体表面の微細構造によって、特定の波長の光を反射することで生じている。このような発色は構造発色と言われている。 For example, morpho butterflies and tropical fish are vividly colored despite having no pigment. This is caused by reflecting light of a specific wavelength due to the fine structure of the body surface. Such coloring is called structural coloring.
このような構造発色を人工的に作る研究がなされている。例えば、特許文献１には、「エレクトロスプレーデポジション法により形成された、平均繊維径が１００ｎｍ〜１μｍの透明繊維の堆積物又は平均繊維径が１００ｎｍ〜１μｍの透明繊維と平均粒子径が１００ｎｍ〜１μｍの透明粒子との堆積物からなる光の反射・干渉機能によって可視光領域の波長の着色光を発する構造発色性材料」（請求項１）が提案されている。しかしながら、この構造発色性材料は光の反射・干渉機能を発揮させるために、実際には基体が必要である（請求項２、実施例など）ため、包装材やインテリア材など、意匠性として透過光を必要とする場合には、利用することができなかった。 Researches have been made to artificially produce such structural colors. For example, Patent Document 1 states that “a deposit of transparent fibers having an average fiber diameter of 100 nm to 1 μm formed by an electrospray deposition method or transparent fibers having an average fiber diameter of 100 nm to 1 μm and an average particle diameter of 100 nm to A “structural color-developing material that emits colored light having a wavelength in the visible light region by a light reflection / interference function composed of a deposit with 1 μm transparent particles” has been proposed. However, since this structural color-developing material actually requires a substrate in order to exhibit the light reflection / interference function (Claim 2, Example, etc.), it is transparent as a design property for packaging materials and interior materials. When light was needed, it could not be used.
また、特許文献２には、「繊維の集合体で構成された材料であって、前記繊維はセラミックスからなり、かつ、平均繊維径が５０ｎｍ以上１０００ｎｍ以下であり、可視領域の波長の着色光を発する構造発色材料」（請求項１）が提案されている。この構造発色材料は可視光の透過によって発色するものである（［０００８］、実施例など）。しかしながら、この構造発色材料は実施例１において、波長約４９０ｎｍの透過率が約３．１％であることを開示している（図３）ように、発色強度が弱く、実用的ではなかった。 Patent Document 2 states that “a material composed of an aggregate of fibers, wherein the fibers are made of ceramics, have an average fiber diameter of 50 nm to 1000 nm, and emit colored light having a wavelength in the visible region. "Structural coloring materials that emit" (Claim 1) have been proposed. This structural coloring material is colored by transmission of visible light ([0008], Examples, etc.). However, as disclosed in Example 1 that the transmittance at a wavelength of about 490 nm is about 3.1% in FIG. 1 (FIG. 3), this structural color-developing material has a low color intensity and is not practical.
本発明の課題は、従来技術のこれらの問題点を解決し、透過光を利用して発色させることができ、且つ、充分な発色強度を示す新規の構造発色繊維集合体、及びその製造方法を提供することにある。 An object of the present invention is to solve these problems of the prior art, and to develop a novel structural color fiber assembly capable of color development using transmitted light and exhibiting sufficient color development intensity, and a method for producing the same. It is to provide.
本発明は、
［１］平均繊維径が０．７〜１．６μｍであり、繊維表面に繊維軸方向に伸びる複数の溝を有する繊維から実質的になる構造発色繊維集合体、
［２］繊維が一方向に配向している、［１］の構造発色繊維集合体、
［３］ポリマーと前記ポリマーに対する良溶媒及び貧溶媒とを含む紡糸原液を静電紡糸法により紡糸した繊維を直接集積させることを特徴とする、［１］又は［２］の構造発色繊維集合体の製造方法
に関する。
The present invention
[1] A structural color fiber assembly having an average fiber diameter of 0.7 to 1.6 μm and substantially comprising fibers having a plurality of grooves extending in the fiber axis direction on the fiber surface;
[2] The structural color fiber assembly according to [1], wherein the fibers are oriented in one direction,
[3] A structurally colored fiber assembly according to [1] or [2], wherein fibers obtained by spinning a spinning stock solution containing a polymer and a good solvent and a poor solvent for the polymer by an electrostatic spinning method are directly accumulated. It relates to the manufacturing method.
本発明の構造発色繊維集合体は、平均繊維径が０．７〜１．６μｍであり、且つ、繊維表面に溝を有することにより、透過光により充分に発色することができる。
また、本発明の好適態様である、繊維が一方向に配向している構造発色繊維集合体では、繊維が一方向に配向していることによって、入射角度によって発色が異なる。
The structural color fiber assembly of the present invention has an average fiber diameter of 0.7 to 1.6 μm and has a groove on the fiber surface, so that it can sufficiently color by transmitted light.
Further, in the structural color fiber assembly in which the fibers are oriented in one direction, which is a preferred embodiment of the present invention, the color development varies depending on the incident angle because the fibers are oriented in one direction.
本発明の構造発色繊維集合体は、平均繊維径が０．７〜１．６μｍであり、繊維表面に繊維軸方向に伸びる複数の溝を有する繊維（以下、構造発色繊維と称する）から実質的になる。
本明細書において、「構造発色繊維から実質的になる」とは、構造発色繊維集合体を形成する構成繊維の主体が構造発色繊維であって、且つ、構造発色繊維集合体が所望の構造発色を示す限り、特に限定されるものではないが、例えば、構造発色繊維集合体の構成繊維の６０％以上、好ましくは８０％以上、より好ましくは１００％を占めることを意味する。
The structural color fiber assembly of the present invention has an average fiber diameter of 0.7 to 1.6 μm and is substantially composed of fibers having a plurality of grooves extending in the fiber axis direction on the fiber surface (hereinafter referred to as structural color fibers). become.
In this specification, “consisting essentially of structural coloring fibers” means that the main constituent fibers forming the structural coloring fiber aggregate are structural coloring fibers, and the structural coloring fiber aggregate has a desired structural coloring. Although it is not particularly limited, it means that, for example, 60% or more, preferably 80% or more, more preferably 100% of the constituent fibers of the structural color fiber assembly.
本明細書における用語「平均繊維径」とは、４０点における繊維径の算術平均値を意味する。また、「繊維径」とは、顕微鏡写真を元に計測した値を意味する。なお、構造発色繊維は、繊維表面に溝を有するため、写真上、凹凸が観察されるが、写真における最外周部間の長さを繊維径とする。 The term “average fiber diameter” in this specification means an arithmetic average value of fiber diameters at 40 points. The “fiber diameter” means a value measured based on a micrograph. In addition, since the structural color fiber has grooves on the fiber surface, irregularities are observed on the photograph, but the length between the outermost peripheral parts in the photograph is the fiber diameter.
本発明の構造発色繊維集合体を構成する構造発色繊維の平均繊維径は、０．７〜１．６μｍである。後述する実施例のデータから、本発明の構造発色繊維集合体は、透過スペクトルに関して平均繊維径の約５１〜５４％の波長にピークをもち、発色する。可視光の波長は３８０〜８００ｎｍ程度であるため、平均繊維径は０．７μｍ（＝０．３８／０．５４）〜１．６μｍ（＝０．８／０．５１）であれば、発色する。 The average fiber diameter of the structural color fibers constituting the structural color fiber assembly of the present invention is 0.7 to 1.6 μm. From the data of Examples described later, the structural color fiber assembly of the present invention has a peak at a wavelength of about 51 to 54% of the average fiber diameter with respect to the transmission spectrum, and develops color. Since the wavelength of visible light is about 380 to 800 nm, color development occurs when the average fiber diameter is 0.7 μm (= 0.38 / 0.54) to 1.6 μm (= 0.8 / 0.51). .
構造発色繊維の材料としては、前記特定範囲の平均繊維径を与えることができ、且つ、繊維表面に繊維軸方向に伸びる複数の溝を形成することができるポリマー材料である限り、特に限定されるものではなく、例えば、ポリフッ化ビニリデン、ポリフッ化ビニリデン−ヘキサフルオロプロピレン共重合体などのフッ素化ポリマー；ポリエチレン、ポリプロピレンなどのオレフィン系ポリマー；ナイロン６などのナイロン系ポリマー；ポリエチレンテレフタレートなどのポリエステル系ポリマー；ポリアクリロニトリル、ポリアクリロニトリル−メタクリレート共重合体、ポリメタクリル酸メチル、ポリアクリルアミドなどのアクリル系ポリマー；ポリ塩化ビニル、ポリビニルアルコール、セルロース、ポリビニルピロリドン、ポリエチレンオキサイド、ポリプロピレンオキサイド、ポリスチレン、ポリ乳酸、ポリウレタン、これらの共重合体や混合物なども使用可能である。 The material of the structural coloring fiber is particularly limited as long as it is a polymer material that can give an average fiber diameter in the specific range and can form a plurality of grooves extending in the fiber axis direction on the fiber surface. For example, fluorinated polymers such as polyvinylidene fluoride and polyvinylidene fluoride-hexafluoropropylene copolymer; olefin polymers such as polyethylene and polypropylene; nylon polymers such as nylon 6; polyester polymers such as polyethylene terephthalate Acrylic polymers such as polyacrylonitrile, polyacrylonitrile-methacrylate copolymer, polymethyl methacrylate, polyacrylamide; polyvinyl chloride, polyvinyl alcohol, cellulose, polyvinyl pyrrolidone, polyethylene Side, polypropylene oxide, polystyrene, polylactic acid, polyurethane, and copolymers thereof and mixtures may also be used.
構造発色繊維の繊維表面の溝は、繊維軸方向に伸びていれば良く、幅、深さ等は特に限定しない。また、繊維軸に平行である必要はない。 The groove on the fiber surface of the structural color fiber is not particularly limited as long as it extends in the fiber axis direction. Moreover, it is not necessary to be parallel to the fiber axis.
本発明の構造発色繊維集合体では、構造発色繊維が一方向に配向していると、入射角度によって発色が異なる。
本明細書において「一方向に配向している」とは、下記の測定及び算出により決定される「繊維配向の標準偏差値」が３０以下であることを意味する。前記「繊維配向の標準偏差値」の測定・算出方法は、例えば、特開２００４−１８３１３１号公報に記載されており、具体的には、繊維集合体の電子顕微鏡写真上に直線を引いた場合に形成される、繊維と前記直線とのなす角度（同じ回転方向にて測定）を１００点について測定し、その測定の結果得られる角度の標準偏差値を「繊維配向の標準偏差値」とする。
In the structural color fiber assembly of the present invention, when the structural color fibers are oriented in one direction, the color development varies depending on the incident angle.
In this specification, “oriented in one direction” means that the “standard deviation value of fiber orientation” determined by the following measurement and calculation is 30 or less. The measurement / calculation method of the “standard deviation value of fiber orientation” is described in, for example, Japanese Patent Application Laid-Open No. 2004-183131. Specifically, when a straight line is drawn on an electron micrograph of a fiber assembly The angle formed by the fiber and the straight line (measured in the same rotational direction) is measured for 100 points, and the standard deviation value of the angle obtained as a result of the measurement is defined as the “standard deviation value of fiber orientation”. .
このような一方向に配向した構造発色繊維集合体は、例えば、特開２００４−１８３１３１号公報に記載されているように、繊維の集積体を２００ｍ／ｍｉｎ．以上の速さで移動させることにより製造できる。 Such a structure-colored fiber assembly oriented in one direction is, for example, described in Japanese Patent Application Laid-Open No. 2004-183131, in which an aggregate of fibers is 200 m / min. It can be manufactured by moving at the above speed.
本発明の構造発色繊維集合体は、これに限定されるものではないが、本発明の製造方法により製造することができる。
本発明の製造方法では、ポリマーと前記ポリマーに対する良溶媒及び貧溶媒とを含む紡糸原液を用いること以外は、周知の静電紡糸法に従って、静電紡糸法により紡糸した繊維を直接集積させる。例えば、特開２００５−１９４６７５号公報、特開２００３−０７３９６４号公報、特開２００６−１１２０２３号公報等に記載されているように、１つ又は２つ以上のノズルから紡糸原液を吐出するとともに、電界を作用させ、繊維化した後にシリンダ、コンベア等に集積する方法によって実施できる。
The structural color fiber assembly of the present invention is not limited to this, but can be produced by the production method of the present invention.
In the production method of the present invention, fibers spun by an electrospinning method are directly accumulated according to a well-known electrospinning method, except that a spinning solution containing a polymer and a good solvent and a poor solvent for the polymer is used. For example, as described in JP-A-2005-194675, JP-A-2003-073964, JP-A-2006-112023 and the like, the spinning dope is discharged from one or two or more nozzles, It can be carried out by a method in which an electric field is applied and the fibers are made into fibers and then accumulated on a cylinder, a conveyor or the like.
本発明の製造方法で用いる良溶媒は、構造発色繊維の材料として使用するポリマーを溶解することができる溶媒であれば良く、特に限定されるものではない。より具体的には、ポリマーとしてポリアクリルアミドを用いる場合には、良溶媒として、例えば、水を用いることができる。 The good solvent used in the production method of the present invention is not particularly limited as long as it is a solvent that can dissolve the polymer used as the material of the structural color fiber. More specifically, when polyacrylamide is used as the polymer, for example, water can be used as the good solvent.
本発明の製造方法で用いる貧溶媒は、良溶媒よりもポリマーの溶解性が悪く、良溶媒と混和し、かつ良溶媒よりも沸点の高い溶媒であれば良く、特に限定されるものではない。貧溶媒は良溶媒よりも沸点が高いことによって、良溶媒が揮発しても残存し、貧溶媒が揮発する際に繊維の体積を収縮させ、繊維表面に皺を発生させやすい。
ポリマーとしてポリアクリルアミドを使用し、良溶媒として水（沸点：１００℃）を用いる場合には、貧溶媒として、例えば、ジメチルホルムアミド（ＤＭＦ、沸点：１５２℃）、ジメチルアセトアミド（沸点：１６５℃）、Ｎ−メチルピロリドン（沸点：２０２℃）を用いることができる。
The poor solvent used in the production method of the present invention is not particularly limited as long as it has a lower polymer solubility than the good solvent, is miscible with the good solvent, and has a higher boiling point than the good solvent. Since the poor solvent has a boiling point higher than that of the good solvent, it remains even if the good solvent volatilizes, and when the poor solvent volatilizes, the volume of the fiber is contracted and wrinkles are easily generated on the fiber surface.
When polyacrylamide is used as the polymer and water (boiling point: 100 ° C.) is used as the good solvent, examples of the poor solvent include dimethylformamide (DMF, boiling point: 152 ° C.), dimethylacetamide (boiling point: 165 ° C.), N-methylpyrrolidone (boiling point: 202 ° C.) can be used.
本発明の製造方法により、本発明の構造発色繊維集合体を製造できる理由について、本発明者は、次のように推測している。なお、本発明は、以下の推測に限定されるものではない。
まず、紡糸原液が紡糸されると、まず、良溶媒が揮発し、主としてポリマーと貧溶媒から構成されることになる。この主としてポリマーと貧溶媒からなる繊維は貧溶媒であるが故に繊維表面が固化しやすい。
この繊維表面が固化した状態で飛翔を続け、繊維内部に残っている貧溶媒が揮発する際に繊維の体積が小さくなるように収縮するが、既に繊維表面が固化しているため、繊維表面に皺が発生する。
この繊維が飛翔している時には電界の作用を受けているため、収縮の際に、電界方向、つまり、繊維軸方向に延伸力が働き、繊維表面に繊維軸方向に伸びる複数の溝が形成される。
The inventor presumes the reason why the structural color fiber assembly of the present invention can be manufactured by the manufacturing method of the present invention as follows. Note that the present invention is not limited to the following estimation.
First, when the spinning dope is spun, first, the good solvent is volatilized and is mainly composed of a polymer and a poor solvent. Since the fiber mainly composed of a polymer and a poor solvent is a poor solvent, the fiber surface is easily solidified.
When the fiber surface is solidified, it continues to fly, and when the poor solvent remaining inside the fiber volatilizes, it shrinks so that the volume of the fiber becomes small, but since the fiber surface is already solidified, Habits occur.
When this fiber is flying, it receives the action of an electric field, so that when it contracts, stretching force acts in the direction of the electric field, that is, in the fiber axis direction, and a plurality of grooves extending in the fiber axis direction are formed on the fiber surface. The
本発明の製造方法では、良溶媒と貧溶媒との沸点差は１０℃以上あるのが好ましい。貧溶媒による繊維表面固化効果が得られやすいためである。また、貧溶媒の沸点が高すぎると、繊維の飛翔中に揮発しないため、２１０℃以下であるのが好ましい。 In the production method of the present invention, the difference in boiling point between the good solvent and the poor solvent is preferably 10 ° C. or more. It is because the fiber surface solidification effect by a poor solvent is easy to be obtained. Further, if the boiling point of the poor solvent is too high, it does not volatilize during the flight of the fiber, so that the temperature is preferably 210 ° C. or lower.
貧溶媒の混合溶媒中における重量比率は良溶媒と貧溶媒との組み合わせによって異なるため、特に限定するものではないが、１〜５０ｗｔ％であるのが好ましい。例えば、ポリアクリルアミドを水（良溶媒）とＤＭＦ（貧溶媒）に溶解させる場合、貧溶媒であるＤＭＦは混合溶媒中、３０〜４５ｗｔ％であるのが好ましい。 Since the weight ratio of the poor solvent in the mixed solvent varies depending on the combination of the good solvent and the poor solvent, it is not particularly limited, but is preferably 1 to 50 wt%. For example, when polyacrylamide is dissolved in water (good solvent) and DMF (poor solvent), the poor solvent DMF is preferably 30 to 45 wt% in the mixed solvent.
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。 EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but these do not limit the scope of the present invention.
《実施例１》
攪拌機、温度計、還流冷却管、及び窒素ガス導入管を付した１リットル四つ口フラスコに水５０７．４ｇ、５０％アクリルアミド水溶液１８４．３ｇ、５％メタリルスルホン酸ナトリウム水溶液２．９ｇを仕込み、３０％硫酸水溶液でｐＨ２．５に調整した。次いで、窒素ガス雰囲気下、６０℃に昇温し、５％２，２’−アゾビス（２−メチルプロピオンアミジン）二塩酸塩（和光純薬工業株式会社製、Ｖ−５０）水溶液３．５ｇを加え、８５℃まで昇温した。昇温から１時間後に更に５％２，２’−アゾビス（２−メチルプロピオンアミジン）二塩酸塩（和光純薬工業株式会社製、Ｖ−５０）水溶液４．７ｇを加え、その１時間３０分後に水２２０．１ｇを加え反応を停止した。固形分１０．２％、ｐＨ３．４、粘度（２５℃、ブルックフィールド回転粘度計使用）２，３００ｍＰａ・ｓのポリアクリルアミド水溶液を得た。
重量平均分子量をＧＰＣ−ＭＡＬＬＳで測定したところ、５０万であった。
このポリアクリルアミド水溶液はそのまま、若しくは水を減圧下で留去し高濃度化してから使用した。
Example 1
A 1-liter four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube was charged with 507.4 g of water, 184.3 g of 50% acrylamide aqueous solution, and 2.9 g of 5% sodium methallylsulfonate solution. The pH was adjusted to 2.5 with a 30% aqueous sulfuric acid solution. Next, the temperature was raised to 60 ° C. in a nitrogen gas atmosphere, and 3.5 g of 5% 2,2′-azobis (2-methylpropionamidine) dihydrochloride (W-50 Pure Chemical Industries, Ltd., V-50) aqueous solution was added. In addition, the temperature was raised to 85 ° C. 1 hour after the temperature rise, 4.7 g of 5% 2,2′-azobis (2-methylpropionamidine) dihydrochloride (Wako Pure Chemical Industries, Ltd., V-50) aqueous solution was added, and the time was 1 hour 30 minutes. Later, 220.1 g of water was added to stop the reaction. A polyacrylamide aqueous solution having a solid content of 10.2%, a pH of 3.4, and a viscosity (25 ° C., using Brookfield rotary viscometer) of 2,300 mPa · s was obtained.
It was 500,000 when the weight average molecular weight was measured by GPC-MALLS.
The polyacrylamide aqueous solution was used as it was or after the water was distilled off under reduced pressure to increase the concentration.
１０ｗｔ％に調整したポリアクリルアミド（重量平均分子量５０万）水溶液に、貧溶媒としてＤＭＦ（沸点：１５２℃）を加え、ポリマー濃度が６ｗｔ％となるように紡糸原液を調製した。ＤＭＦの混合溶媒中における重量比率［｛ＤＭＦ／（水＋ＤＭＦ）｝×１００（％）］は４２．５ｗｔ％であった。
特開２００５−１９４６７５号公報に開示の静電紡糸装置と同じ装置にて、吐出量０．５ｇ／ｈｒ、ノズルとドラムの距離１０ｃｍ、ドラムの周速：１ｍ／ｍｉｎ．、印加電圧＋１３ｋＶ、紡糸雰囲気の温湿度２５℃／１５％ＲＨの条件で静電紡糸を行い、目付１ｇ／ｍ２の構造発色繊維集合体シートを作製した。
DMF (boiling point: 152 ° C.) was added as a poor solvent to a polyacrylamide (weight average molecular weight 500,000) aqueous solution adjusted to 10 wt% to prepare a spinning dope so that the polymer concentration was 6 wt%. The weight ratio [{DMF / (water + DMF)} × 100 (%)] in the mixed solvent of DMF was 42.5 wt%.
In the same apparatus as the electrostatic spinning apparatus disclosed in JP-A-2005-194675, the discharge rate is 0.5 g / hr, the distance between the nozzle and the drum is 10 cm, and the peripheral speed of the drum is 1 m / min. Electrostatic spinning was performed under the conditions of applied voltage +13 kV and temperature and humidity of the spinning atmosphere of 25 ° C./15% RH to produce a structural color fiber assembly sheet having a basis weight of 1 g / m 2 .
平均繊維径は７７０ｎｍであり、走査型電子顕微鏡（ＳＥＭ）により繊維表面の観察を行ったところ、繊維の表面には繊維軸方向に伸びる溝が多数形成されていた。
構造発色繊維集合体シートの透過スペクトルを測定（島津製作所製、分光光度計ＵＶ−３１００Ｓを使用、試料を２ｃｍ×６ｃｍとなるように枠に貼り付け、光の入射角９０°で測定）したところ、波長４１０ｎｍにピークを持ち、ピークトップの透過率は２４％であった。構造発色繊維集合体シートの透過光は、強い青色の構造色を示した。
The average fiber diameter was 770 nm. When the fiber surface was observed with a scanning electron microscope (SEM), many grooves extending in the fiber axis direction were formed on the fiber surface.
When the transmission spectrum of the structural color fiber assembly sheet was measured (manufactured by Shimadzu Corporation, using a spectrophotometer UV-3100S, the sample was attached to a frame so as to be 2 cm × 6 cm, and measured at an incident angle of light of 90 °) And had a peak at a wavelength of 410 nm, and the transmittance at the peak top was 24%. The transmitted light of the structural color fiber assembly sheet showed a strong blue structural color.
《実施例２》
ポリマー濃度が６．５ｗｔ％となるようにＤＭＦを加えたこと以外は、実施例１と同様にして目付１ｇ／ｍ２の構造発色繊維集合体シートを作製した。ＤＭＦの混合溶媒中における重量比率は３７．５ｗｔ％であった。
Example 2
A structural color fiber assembly sheet having a basis weight of 1 g / m 2 was produced in the same manner as in Example 1 except that DMF was added so that the polymer concentration was 6.5 wt%. The weight ratio of DMF in the mixed solvent was 37.5 wt%.
平均繊維径は６５０ｎｍであり、ＳＥＭにより繊維表面の観察を行ったところ、繊維の表面には繊維軸方向に伸びる溝が多数形成されていた。
構造発色繊維集合体シートの透過スペクトルを測定したところ、波長３５０ｎｍにピークを持ち、ピークトップの透過率は２０％であった。構造発色繊維集合体シートの透過光は、強い紫色の構造色を示した。
The average fiber diameter was 650 nm, and the fiber surface was observed by SEM. As a result, many grooves extending in the fiber axis direction were formed on the fiber surface.
When the transmission spectrum of the structural color fiber assembly sheet was measured, it had a peak at a wavelength of 350 nm, and the transmittance at the peak top was 20%. The transmitted light of the structural color fiber assembly sheet showed a strong purple structural color.
《実施例３》
ＤＭＦに代えて、ポリマー濃度が６．５ｗｔ％となるようにジメチルアセトアミド（沸点：１６５℃）を加えたこと以外は、実施例２と同様にして目付１ｇ／ｍ２の構造発色繊維集合体シートを作製した。ジメチルアセトアミドの混合溶媒中における重量比率は３７．５ｗｔ％であった。
Example 3
A structural color fiber assembly sheet having a basis weight of 1 g / m 2 in the same manner as in Example 2 except that dimethylacetamide (boiling point: 165 ° C.) was added so that the polymer concentration was 6.5 wt% instead of DMF. Was made. The weight ratio of dimethylacetamide in the mixed solvent was 37.5 wt%.
平均繊維径は６６０ｎｍであり、ＳＥＭにより繊維表面の観察を行ったところ、繊維の表面には繊維軸方向に伸びる溝が多数形成されていた。
構造発色繊維集合体シートの透過スペクトルを測定したところ、波長３４５ｎｍにピークを持ち、ピークトップの透過率は２１％であった。構造発色繊維集合体シートの透過光は、強い紫色の構造色を示した。
The average fiber diameter was 660 nm, and when the fiber surface was observed by SEM, many grooves extending in the fiber axis direction were formed on the fiber surface.
When the transmission spectrum of the structural color fiber assembly sheet was measured, it had a peak at a wavelength of 345 nm and the transmittance at the peak top was 21%. The transmitted light of the structural color fiber assembly sheet showed a strong purple structural color.
《実施例４》
実施例１で合成したポリアクリルアミド（重量平均分子量５０万）に代えて、以下の手順に従って合成したポリアクリルアミド（重量平均分子量３６０万）の１０ｗｔ％水溶液を用いたこと以外は、実施例１と同様にして、目付１ｇ／ｍ２の構造発色繊維集合体シートを作製した。
Example 4
Instead of the polyacrylamide synthesized in Example 1 (weight average molecular weight 500,000), a 10 wt% aqueous solution of polyacrylamide (weight average molecular weight 3.6 million) synthesized according to the following procedure was used, as in Example 1. Thus, a structural color fiber assembly sheet having a basis weight of 1 g / m 2 was produced.
攪拌機、温度計、還流冷却管、及び窒素ガス導入管を付した１リットル四つ口フラスコに水５１２．１ｇ、５０％アクリルアミド水溶液１８４．３ｇ、１％メチレンビスアクリルアミド水溶液５．０ｇ、５％メタリルスルホン酸ナトリウム水溶液９．９ｇを仕込み、３０％硫酸水溶液でｐＨ２．５に調整した。次いで、窒素ガス雰囲気下、６０℃に昇温し、５％過硫酸アンモニウム水溶液３．０ｇを加え、８５℃まで昇温した。昇温から１時間後に更に５％過硫酸アンモニウム水溶液４．０ｇを加え、その２時間後に水２１４．７ｇを加え反応を停止した。固形分１０．５％、ｐＨ３．５、粘度（２５℃、ブルックフィールド回転粘度計使用）１，４００ｍＰａ・ｓのポリマー溶液を得た。
重量平均分子量をＧＰＣ−ＭＡＬＬＳで測定したところ、３６０万であった。
In a 1 liter four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube, water 512.1 g, 50% acrylamide aqueous solution 184.3 g, 1% methylenebisacrylamide aqueous solution 5.0 g, 5% meta 9.9 g of sodium rilsulfonate aqueous solution was charged and adjusted to pH 2.5 with 30% sulfuric acid aqueous solution. Next, the temperature was raised to 60 ° C. in a nitrogen gas atmosphere, 3.0 g of 5% ammonium persulfate aqueous solution was added, and the temperature was raised to 85 ° C. One hour after the temperature rise, 4.0 g of 5% ammonium persulfate aqueous solution was further added, and after 2 hours, 214.7 g of water was added to stop the reaction. A polymer solution having a solid content of 10.5%, a pH of 3.5, and a viscosity (at 25 ° C., using a Brookfield rotational viscometer) of 1,400 mPa · s was obtained.
When the weight average molecular weight was measured by GPC-MALLS, it was 3.6 million.
得られた構造発色繊維集合体シートの平均繊維径は７２０ｎｍであり、ＳＥＭにより繊維表面の観察を行ったところ、図１に示すように、繊維の表面には繊維軸方向に伸びる溝が多数形成されていた。
構造発色繊維集合体シートの透過スペクトルを測定したところ、波長３８０ｎｍにピークを持ち、ピークトップの透過率は３１％であった。構造発色繊維集合体シートの透過光は、強い紫色の構造色を示した。
The resulting structural color fiber assembly sheet has an average fiber diameter of 720 nm, and the surface of the fiber was observed by SEM. As shown in FIG. 1, a number of grooves extending in the fiber axis direction were formed on the surface of the fiber. It had been.
When the transmission spectrum of the structural color fiber assembly sheet was measured, it had a peak at a wavelength of 380 nm and the transmittance at the peak top was 31%. The transmitted light of the structural color fiber assembly sheet showed a strong purple structural color.
《実施例５》
実施例１で合成したポリアクリルアミド（重量平均分子量５０万）の１３ｗｔ％水溶液に、貧溶媒としてＤＭＦを加え、ポリマー濃度が８ｗｔ％となるように紡糸原液を調製した。ＤＭＦの混合溶媒中における重量比率は４１．９ｗｔ％であった。
特開２００５−１９４６７５号公報に開示の静電紡糸装置と同じ装置にて、吐出量０．５ｇ／ｈｒ、ノズルとドラムの距離１２ｃｍ、ドラムの周速：１ｍ／ｍｉｎ．、印加電圧＋１３ｋＶ、紡糸雰囲気の温湿度２５℃／１５％ＲＨの条件で静電紡糸を行い、目付１ｇ／ｍ２の構造発色繊維集合体シートを作製した。
Example 5
DMF was added as a poor solvent to the 13 wt% aqueous solution of polyacrylamide (weight average molecular weight 500,000) synthesized in Example 1 to prepare a spinning dope so that the polymer concentration was 8 wt%. The weight ratio of DMF in the mixed solvent was 41.9 wt%.
In the same apparatus as the electrostatic spinning apparatus disclosed in JP-A-2005-194675, the discharge amount is 0.5 g / hr, the distance between the nozzle and the drum is 12 cm, and the peripheral speed of the drum is 1 m / min. Electrostatic spinning was performed under the conditions of applied voltage +13 kV and temperature and humidity of the spinning atmosphere of 25 ° C./15% RH to produce a structural color fiber assembly sheet having a basis weight of 1 g / m 2 .
平均繊維径は９８０ｎｍであり、ＳＥＭにより繊維表面の観察を行ったところ、繊維の表面には繊維軸方向に伸びる溝が多数形成されていた。
構造発色繊維集合体シートの透過スペクトルを測定したところ、波長５００ｎｍにピークを持ち、ピークトップの透過率は２２％であった。構造発色繊維集合体シートの透過光は、強い緑色の構造色を示した。
The average fiber diameter was 980 nm, and the fiber surface was observed by SEM. As a result, many grooves extending in the fiber axis direction were formed on the fiber surface.
When the transmission spectrum of the structural color fiber assembly sheet was measured, it had a peak at a wavelength of 500 nm, and the transmittance at the peak top was 22%. The transmitted light of the structural color fiber assembly sheet showed a strong green structural color.
《実施例６》
実施例１で合成したポリアクリルアミド（重量平均分子量５０万）の１５ｗｔ％水溶液に、貧溶媒としてＤＭＦを加え、ポリマー濃度が９．５ｗｔ％となるように紡糸原液を調製した。ＤＭＦの混合溶媒中における重量比率は４０．５ｗｔ％であった。
特開２００５−１９４６７５号公報に開示の静電紡糸装置と同じ装置にて、吐出量０．５ｇ／ｈｒ、ノズルとドラムの距離１３ｃｍ、ドラムの周速：１ｍ／ｍｉｎ．、印加電圧＋１３ｋＶ、紡糸雰囲気の温湿度２５℃／１５％ＲＨの条件で静電紡糸を行い、目付１ｇ／ｍ２の構造発色繊維集合体シートを作製した。
Example 6
DMF was added as a poor solvent to a 15 wt% aqueous solution of polyacrylamide (weight average molecular weight 500,000) synthesized in Example 1 to prepare a spinning dope so that the polymer concentration was 9.5 wt%. The weight ratio of DMF in the mixed solvent was 40.5 wt%.
In the same apparatus as the electrostatic spinning apparatus disclosed in JP-A-2005-194675, the discharge amount is 0.5 g / hr, the distance between the nozzle and the drum is 13 cm, and the peripheral speed of the drum is 1 m / min. Electrostatic spinning was performed under the conditions of applied voltage +13 kV and temperature and humidity of the spinning atmosphere of 25 ° C./15% RH to produce a structural color fiber assembly sheet having a basis weight of 1 g / m 2 .
平均繊維径は１１５０ｎｍであり、ＳＥＭにより繊維表面の観察を行ったところ、図２に示すように、繊維の表面には繊維軸方向に伸びる溝が多数形成されていた。
構造発色繊維集合体シートの透過スペクトルを測定したところ、波長５７０ｎｍにピークを持ち、ピークトップの透過率は２３％であった。構造発色繊維集合体シートの透過光は、強い黄色の構造色を示した。
The average fiber diameter was 1150 nm, and the surface of the fiber was observed by SEM. As shown in FIG. 2, many grooves extending in the fiber axis direction were formed on the surface of the fiber.
When the transmission spectrum of the structural color fiber assembly sheet was measured, it had a peak at a wavelength of 570 nm, and the transmittance at the peak top was 23%. The transmitted light of the structural color fiber assembly sheet showed a strong yellow structural color.
《実施例７》
ドラムの周速を１０００ｍ／ｍｉｎとしたこと以外は、実施例１と同様に静電紡糸を行い、繊維が１方向に配向した構造発色繊維集合体シートを作製した。
Example 7
Except that the peripheral speed of the drum was set to 1000 m / min, electrostatic spinning was performed in the same manner as in Example 1 to produce a structural color fiber assembly sheet in which the fibers were oriented in one direction.
平均繊維径は７５０ｎｍであり、ＳＥＭにより繊維表面の観察を行ったところ、繊維の表面には繊維軸方向に伸びる溝が多数形成されていた。
この構造発色繊維集合体シートを構成する繊維の長軸方向に対する光の入射角を９０°、６０°、４５°、３０°と変化させて、構造発色繊維集合体シートの透過スペクトルを測定したところ、透過光のピーク波長はそれぞれ４００、４３０、４９０、５６０ｎｍであった。また、光の入射角を変えるにしたがって、構造色は青−緑−黄色に変化した。
The average fiber diameter was 750 nm, and when the fiber surface was observed by SEM, many grooves extending in the fiber axis direction were formed on the fiber surface.
The transmission spectrum of the structural color fiber assembly sheet was measured by changing the incident angle of light with respect to the major axis direction of the fibers constituting the structural color fiber assembly sheet to 90 °, 60 °, 45 °, and 30 °. The peak wavelengths of transmitted light were 400, 430, 490, and 560 nm, respectively. The structural color changed to blue-green-yellow as the incident angle of light was changed.
《比較例１》
実施例１で合成したポリアクリルアミド（重量平均分子量５０万）の１０ｗｔ％水溶液を用いて、特開２００５−１９４６７５号公報に開示の静電紡糸装置と同じ装置にて、吐出量０．５ｇ／ｈｒ、ノズルとドラムの距離１０ｃｍ、ドラムの周速：１ｍ／ｍｉｎ．、印加電圧＋１３ｋＶ、紡糸雰囲気の温湿度２５℃／１５％ＲＨの条件で静電紡糸を行い、目付１ｇ／ｍ２の繊維集合体シートを作製した。
<< Comparative Example 1 >>
Using a 10 wt% aqueous solution of polyacrylamide (weight average molecular weight 500,000) synthesized in Example 1, the same apparatus as the electrostatic spinning apparatus disclosed in Japanese Patent Application Laid-Open No. 2005-194675 has a discharge rate of 0.5 g / hr. The distance between the nozzle and the drum is 10 cm, the peripheral speed of the drum is 1 m / min. Electrospinning was performed under the conditions of applied voltage +13 kV and temperature and humidity of the spinning atmosphere of 25 ° C./15% RH to produce a fiber assembly sheet having a basis weight of 1 g / m 2 .
平均繊維径は１５０ｎｍであり、ＳＥＭにより繊維表面の観察を行ったところ、繊維表面に溝は観察されなかった。
繊維集合体シートの透過スペクトルを測定したところ、可視部にピークは見られず、構造色は観察されなかった。
The average fiber diameter was 150 nm, and when the fiber surface was observed by SEM, no groove was observed on the fiber surface.
When the transmission spectrum of the fiber assembly sheet was measured, no peak was observed in the visible portion, and no structural color was observed.
《比較例２》
ポリマー濃度が７．５ｗｔ％となるようにＤＭＦを加えたこと以外は、実施例１と同様にして繊維集合体シートを作製した。ＤＭＦの混合溶媒中における重量比率は２７ｗｔ％であった。
<< Comparative Example 2 >>
A fiber assembly sheet was produced in the same manner as in Example 1 except that DMF was added so that the polymer concentration was 7.5 wt%. The weight ratio of DMF in the mixed solvent was 27 wt%.
平均繊維径は４００ｎｍであり、ＳＥＭにより繊維表面の観察を行ったところ、繊維の表面には繊維軸方向に伸びる溝が多数形成されていた。
繊維集合体シートの透過スペクトルを測定したところ、可視部にピークは見られず、構造色は観察されなかった。
The average fiber diameter was 400 nm, and the fiber surface was observed by SEM. As a result, many grooves extending in the fiber axis direction were formed on the fiber surface.
When the transmission spectrum of the fiber assembly sheet was measured, no peak was observed in the visible portion, and no structural color was observed.
《比較例３》
実施例１で合成したポリアクリルアミド（重量平均分子量５０万）の１０ｗｔ％水溶液に、ポリマー濃度が５．５ｗｔ％となるようにＤＭＦを加えたところ、液が白濁し、静電紡糸法により繊維化することができなかった。ＤＭＦの混合溶媒中における重量比率は４７．６ｗｔ％であった。
<< Comparative Example 3 >>
When DMF was added to a 10 wt% aqueous solution of polyacrylamide (weight average molecular weight 500,000) synthesized in Example 1 so that the polymer concentration became 5.5 wt%, the liquid became cloudy and was made into fibers by an electrospinning method. I couldn't. The weight ratio of DMF in the mixed solvent was 47.6 wt%.
《比較例４》
実施例４で合成したポリアクリルアミド（重量平均分子量３６０万）の１０ｗｔ％水溶液に、貧溶媒としてエタノール（沸点：７８℃）を加え、ポリマー濃度が６ｗｔ％となるように紡糸原液を調製した。エタノールの混合溶媒中における重量比率は４２．５ｗｔ％であった。
実施例１と同じ条件で静電紡糸を行ったが、紡糸原液が固化されないままドラムに捕集され、繊維を作製することができなかった。
<< Comparative Example 4 >>
Ethanol (boiling point: 78 ° C.) was added as a poor solvent to a 10 wt% aqueous solution of polyacrylamide (weight average molecular weight 3.6 million) synthesized in Example 4 to prepare a spinning dope so that the polymer concentration was 6 wt%. The weight ratio of ethanol in the mixed solvent was 42.5 wt%.
Electrospinning was carried out under the same conditions as in Example 1, but the spinning solution was collected on the drum without solidification, and fibers could not be produced.
《比較例５》
実施例１で作製した構造発色繊維集合体シートを温度６０℃に加熱した湯浴上で３０秒間保持し、水蒸気処理を行った。
水蒸気処理後の繊維集合体シート構成繊維の繊維径は８４０ｎｍであり、ＳＥＭにより繊維表面の観察を行ったところ、繊維表面に溝は観察されなかった。また、繊維集合体シートの透過スペクトルを測定したところ、可視部にピークは観察されなかった。
<< Comparative Example 5 >>
The structural color fiber assembly sheet produced in Example 1 was kept on a hot water bath heated to 60 ° C. for 30 seconds and subjected to steam treatment.
The fiber diameter of the fiber assembly sheet-constituting fiber after the steam treatment was 840 nm, and when the fiber surface was observed by SEM, no groove was observed on the fiber surface. Moreover, when the transmission spectrum of the fiber assembly sheet was measured, no peak was observed in the visible part.
本発明の構造発色繊維集合体は、例えば、家電、家具、車、建材（壁、天井など）、衣類、スポーツ用品、包装材（包装紙、リボン、テープなど）、インテリア材（カーテン、アートフラワー材料など）などの用途に利用することができる。 The structural coloring fiber assembly of the present invention includes, for example, home appliances, furniture, cars, building materials (walls, ceilings, etc.), clothing, sports equipment, packaging materials (wrapping paper, ribbons, tapes, etc.), interior materials (curtains, art flowers, etc.) It can be used for applications such as materials.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102517801A (en) * | 2011-12-07 | 2012-06-27 | 苏州大学 | Method for preparing fiber film with structural color |
| CN107938163A (en) * | 2017-12-19 | 2018-04-20 | 苏州中科纳福材料科技有限公司 | The preparation method of magnetic induced self-assembled structures color fibre film |
| CN111074367A (en) * | 2019-12-30 | 2020-04-28 | 江苏杜为新材料科技有限公司 | Preparation method of structural color-producing silk |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107938175B (en) * | 2017-11-28 | 2020-05-15 | 北京理工大学 | Preparation method and application of high-orientation flexible luminous polarization composite fiber film |
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| JPS62170510A (en) * | 1986-01-22 | 1987-07-27 | Toray Ind Inc | Fiber having interference color |
| JPH03167306A (en) * | 1989-11-22 | 1991-07-19 | I C I Japan Kk | Extra fine fibrous substance |
| JPH08234007A (en) * | 1995-02-28 | 1996-09-13 | Res Dev Corp Of Japan | Opal-like deffractive color developing film |
| JP2003342828A (en) * | 2002-05-24 | 2003-12-03 | Nissan Motor Co Ltd | Article having light-reflecting function and method for producing the same |
| WO2004088024A1 (en) * | 2003-03-31 | 2004-10-14 | Teijin Limited | Nonwoven fabric and process for producing the same |
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|---|---|---|---|---|
| JPS62170510A (en) * | 1986-01-22 | 1987-07-27 | Toray Ind Inc | Fiber having interference color |
| JPH03167306A (en) * | 1989-11-22 | 1991-07-19 | I C I Japan Kk | Extra fine fibrous substance |
| JPH08234007A (en) * | 1995-02-28 | 1996-09-13 | Res Dev Corp Of Japan | Opal-like deffractive color developing film |
| JP2003342828A (en) * | 2002-05-24 | 2003-12-03 | Nissan Motor Co Ltd | Article having light-reflecting function and method for producing the same |
| WO2004088024A1 (en) * | 2003-03-31 | 2004-10-14 | Teijin Limited | Nonwoven fabric and process for producing the same |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102517801A (en) * | 2011-12-07 | 2012-06-27 | 苏州大学 | Method for preparing fiber film with structural color |
| CN107938163A (en) * | 2017-12-19 | 2018-04-20 | 苏州中科纳福材料科技有限公司 | The preparation method of magnetic induced self-assembled structures color fibre film |
| CN111074367A (en) * | 2019-12-30 | 2020-04-28 | 江苏杜为新材料科技有限公司 | Preparation method of structural color-producing silk |
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