JP6980238B2 - Light absorption heat generation complex for heat insulation - Google Patents
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本発明は、バナジウムを含有し、近赤外線などの光を吸収して発熱および保温する光吸収発熱保温用複合体と、その製造方法に関する。 The present invention relates to a light-absorbing heat-retaining composite containing vanadium and absorbing light such as near-infrared rays to generate heat and retain heat, and a method for producing the same.
スポーツなどの特殊用途を除く日用品では、天然素材製品の方が人工素材製品より高い価値があると認識される場合が多い。ストール、マフラー、日傘、および衣類などでは、天然素材を用いた色彩豊かな製品の需要が近年高まっており、これらの製品開発が行なわれている。さらに高付加価値のある天然素材製品を実現するため、特に冬季に身に着ける天然繊維製品には、天然素材が備える特性に加えて、温熱機能などの性質を付与した製品の開発が望まれている。 For daily necessities other than special uses such as sports, natural material products are often recognized as having higher value than artificial material products. For stoles, mufflers, parasols, clothing, etc., the demand for colorful products using natural materials has been increasing in recent years, and these products are being developed. In order to realize products made of natural materials with higher added value, it is desired to develop products with properties such as thermal function in addition to the properties of natural materials, especially for natural fiber products worn in winter. There is.
光エネルギーを熱に変換する機能を備える機能性セラミックのミクロ粒子を、繊維の芯部分に錬り込んだ蓄熱保温素材が知られている（非特許文献１）。しかしながら、この蓄熱保温素材と天然素材の交織や混紡では、天然素材部分の光照射による発熱が低いため、蓄熱保温機能が十分に発現できない。また、天然素材に機能性粒子を付加させるためにバインダーを用いると、天然素材の特長である風合いを損ねてしまうおそれがある。 A heat storage heat insulating material in which microparticles of functional ceramic having a function of converting light energy into heat is kneaded into a core portion of a fiber is known (Non-Patent Document 1). However, in this mixed weaving or blending of the heat storage heat insulating material and the natural material, the heat generation due to the light irradiation of the natural material portion is low, so that the heat storage heat insulating function cannot be sufficiently exhibited. In addition, if a binder is used to add functional particles to the natural material, the texture that is a feature of the natural material may be impaired.
また、大量の繊維を染色するとき、チーズ染色方法がよく用いられている。チーズ染色方法は、多孔体製の円筒の外表面に繊維を多重に巻き、円筒の内表面に染色液を流し、その後円筒の外表面に染色液を流し、これらを繰り返して繊維を染色する方法である。チーズ染色方法に、ＺｒＣまたはＶＯ２などの機能性固体微粒子が分散している染色液を用いると、円筒の内表面および外側の繊維に機能性固体微粒子が捕捉されてしまう。このため、内側の繊維に機能性固体微粒子が付着されない。したがって、染色液に溶ける機能性物質の出現が望まれている。 Also, when dyeing a large amount of fibers, the cheese dyeing method is often used. The cheese dyeing method is a method in which fibers are wound multiple times on the outer surface of a porous cylinder, a dyeing solution is poured on the inner surface of the cylinder, and then a dyeing solution is poured on the outer surface of the cylinder, and these are repeated to dye the fibers. Is. When a dyeing solution in which functional solid fine particles such as ZrC or VO 2 are dispersed is used as a cheese dyeing method, the functional solid fine particles are captured by the inner surface and outer fibers of the cylinder. Therefore, the functional solid fine particles do not adhere to the inner fibers. Therefore, the emergence of functional substances that are soluble in stains is desired.
本発明のある態様は、上記の事情に鑑みてなされたものであり、繊維との相互作用などによって繊維に付着するバナジウムを含有する光吸収発熱保温用複合体を提供することを目的とする。また、本発明の他の態様は、バナジウムが官能基に化学結合している樹脂を備える光吸収発熱保温用複合体を提供することを目的とする。 One aspect of the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a light-absorbing heat-retaining complex containing vanadium that adheres to fibers by interaction with the fibers. Another aspect of the present invention is to provide a light-absorbing heat-retaining composite comprising a resin in which vanadium is chemically bonded to a functional group.
本発明のある態様の光吸収発熱保温用複合体は、天然繊維と、天然繊維に付着しているバナジウムと、化学染料とを有し、光を吸収して発熱機能および保温機能を発揮する。この光吸収発熱保温用複合体の製造方法は、濃度１０ｍＭ以上でバナジウムイオンを含む液体に、天然繊維を浸す浸漬工程と、化学染料で天然繊維を染色する染色工程を有する。 The light-absorbing heat-retaining composite of one aspect of the present invention has a natural fiber, vanadium adhering to the natural fiber, and a chemical dye, and absorbs light to exert a heat-generating function and a heat-retaining function. The method for producing the light-absorbing heat-retaining composite includes a dipping step of immersing the natural fiber in a liquid containing vanadium ions at a concentration of 10 mM or more, and a dyeing step of dyeing the natural fiber with a chemical dye.
本発明の他の態様の光吸収発熱保温用複合体は、官能基を備え、親水性溶媒に溶ける樹脂と、官能基に化学結合しているバナジウムとを有し、光を吸収して発熱および保温する。この光吸収発熱保温用複合体の製造方法は、親水性溶媒に溶けるバナジウム塩と、樹脂を親水性溶媒に溶かした溶液とを混合する混合工程を有する。 The light-absorbing, heat-generating and heat-retaining complex of another aspect of the present invention has a resin having a functional group and is soluble in a hydrophilic solvent, and vanadium chemically bonded to the functional group, and absorbs light to generate heat and heat. Keep warm. This method for producing a light-absorbing heat-retaining composite includes a mixing step of mixing a vanadium salt dissolved in a hydrophilic solvent and a solution in which a resin is dissolved in a hydrophilic solvent.
本発明のある態様の光吸収発熱保温用複合体によれば、天然素材の風合いを活かした光吸収発熱保温性能を備える天然繊維製品が得られる。また、本発明の他の態様の光吸収発熱保温用複合体によれば、光を吸収して発熱および保温する樹脂製品が得られる。 According to the light-absorbing heat-retaining composite of a certain aspect of the present invention, a natural fiber product having light-absorbing heat-retaining performance utilizing the texture of a natural material can be obtained. Further, according to the light absorption heat generation heat insulating composite of another aspect of the present invention, a resin product that absorbs light to generate heat and keep heat can be obtained.
以下、本発明の光吸収発熱保温用複合体および光吸収発熱保温用複合体の製造方法について、実施形態と実施例に基づいて説明する。なお、重複説明は適宜省略する。また、２つの数値の間に「〜」を記載して数値範囲を表す場合には、この２つの数値も数値範囲に含まれる。 Hereinafter, a method for producing the light-absorbing heat-retaining composite and the light-absorbing heat-retaining composite of the present invention will be described based on embodiments and examples. The duplicate explanation will be omitted as appropriate. Further, when "~" is described between two numerical values to indicate a numerical range, these two numerical values are also included in the numerical range.
本発明の第一実施形態に係る光吸収発熱保温用複合体は、光を吸収して発熱機能および保温機能を発揮する。光としては太陽光が挙げられる。本実施形態の光吸収発熱保温用複合体は、天然繊維と、静電気力による結合によってこの天然繊維に付着しているバナジウムとを備えている。本実施形態の光吸収発熱保温用複合体が光を吸収して発熱機能を発揮するとは、光照射１０分後の光吸収発熱保温用複合体の温度が、光照射１０分後のバナジウムを備えていない天然繊維の温度と比べて、５℃以上高いことをいう。
The light-absorbing heat-retaining complex according to the first embodiment of the present invention absorbs light and exhibits a heat-generating function and a heat-retaining function. Examples of light include sunlight. The light-absorbing heat-retaining composite of the present embodiment includes natural fibers and vanadium attached to the natural fibers by binding due to electrostatic force. The fact that the light-absorbing heat-retaining composite of the present embodiment absorbs light and exerts a heat-generating function means that the temperature of the light-absorbing heat-retaining
また、光吸収発熱保温用複合体が光を吸収して保温機能を発揮するとは、光照射１０分後に光照射を停止し、停止から１分後の光吸収発熱保温用複合体の温度が、光照射１０分後に光照射を停止し、停止から１分後のバナジウムを備えていない天然繊維の温度と比べて、１．０℃以上高いことをいう。本実施形態の光吸収発熱保温用複合体は、特に波長１０００ｎｍ付近の近赤外線を吸収して発熱する。バナジウムが近赤外線を吸収しやすいからだと考えられる。天然繊維としては、羊毛、絹、カシミヤ、麻、および木綿、ならびにレーヨンまたはキュプラのように、天然繊維を原料とした再生繊維等が挙げられる。 Further, when the light absorption heat generation heat retention complex absorbs light and exerts a heat retention function, the light irradiation is stopped 10 minutes after the light irradiation, and the temperature of the light absorption heat generation heat retention complex 1 minute after the stop is determined. It means that the light irradiation is stopped 10 minutes after the light irradiation, and the temperature is 1.0 ° C. or more higher than the temperature of the natural fiber without vanadium 1 minute after the stop. The light-absorbing heat-retaining complex of the present embodiment particularly absorbs near-infrared rays having a wavelength of around 1000 nm and generates heat. This is probably because vanadium easily absorbs near-infrared rays. Examples of natural fibers include wool, silk, cashmere, hemp, and cotton, and recycled fibers made from natural fibers such as rayon or cupra.
バナジウムは天然繊維に付着している。バナジウムは、イオン結合のような静電気力による結合によって、天然繊維に付着していると考えられる。バナジウムが天然繊維に付着しているため、光吸収発熱保温用複合体の機能、すなわち光を吸収して発熱および保温する機能を発揮する。本実施形態の光吸収発熱保温用複合体は、化学染料をさらに備えている。本実施形態の光吸収発熱保温用複合体は、化学染料を含有していても、光を吸収して発熱および保温する機能を有する。 Vanadium is attached to natural fibers. Vanadium is considered to be attached to natural fibers by binding due to electrostatic force such as ionic bonding. Since vanadium is attached to the natural fiber, it exhibits the function of the light-absorbing heat-retaining complex, that is, the function of absorbing light to generate heat and heat-retaining. The light-absorbing heat-retaining complex of the present embodiment further comprises a chemical dye. The light-absorbing heat-retaining composite of the present embodiment has a function of absorbing light to generate heat and heat-retaining even if it contains a chemical dye.
また、本実施形態の光吸収発熱保温用複合体の化学染料を天然染料に代えた場合、植物色素の没食子酸によって染色された黒色の複合体および緑色の複合体以外では、光耐久性が低く、繊維製品として成立しない。このように、本実施形態の光吸収発熱保温用複合体によれば、光を吸収して発熱機能および保温機能を発揮し、カラーバリエーションが豊富な天然繊維製品が得られる。化学染料としては、直接染料、酸性染料、塩基性染料、建染染料、反応染料、もしくは分散染料等の人工染料、または顔料を溶いたもの等が挙げられる。 Further, when the chemical dye of the light-absorbing heat-retaining complex of the present embodiment is replaced with a natural dye, the light durability is low except for the black complex and the green complex dyed with the gall-acid of the plant pigment. , Not established as a textile product. As described above, according to the light-absorbing heat-retaining composite of the present embodiment, a natural fiber product that absorbs light and exhibits a heat-generating function and a heat-retaining function and has abundant color variations can be obtained. Examples of the chemical dye include a direct dye, an acidic dye, a basic dye, a bat dye, a reactive dye, an artificial dye such as a disperse dye, or a dye in which a pigment is dissolved.
本実施形態の光吸収発熱保温用複合体は、濃度１０ｍＭ以上でバナジウムイオンを含む液体に、天然繊維を浸す浸漬工程と、化学染料で天然繊維を染色する染色工程を経て製造される。濃度５ｍＭ以下でバナジウムイオンを含む液体を用いると、得られた複合体が発熱機能を発揮しないからである。より具体的には、浸漬工程では、例えば、硫酸バナジル、シュウ酸バナジル、または五酸化バナジウム等のバナジウム塩の濃度１０ｍＭ以上の溶液に天然繊維を浸し、撹拌しながら必要に応じて加熱処理する。浸漬工程の後、ソーピング、すなわちセッケン水溶液で加熱処理し、流水ですすいで乾燥させる。こうしてバナジウムが天然繊維に付着する。 The light-absorbing heat-retaining composite of the present embodiment is produced through a dipping step of immersing the natural fiber in a liquid containing vanadium ions at a concentration of 10 mM or more and a dyeing step of dyeing the natural fiber with a chemical dye. This is because when a liquid containing vanadium ions at a concentration of 5 mM or less is used, the obtained complex does not exhibit a heat generating function. More specifically, in the dipping step, the natural fiber is immersed in a solution of vanadyl salt having a concentration of 10 mM or more, such as vanadyl sulfate, vanadyl oxalate, or vanadium pentoxide, and heat-treated as necessary while stirring. After the dipping step, it is heat-treated with soap, that is, an aqueous soap solution, rinsed with running water, and dried. Vanadium thus adheres to the natural fibers.
染色工程では、化学染料を用いた一般的な天然繊維の染色が行われる。例えば、化学染料の溶液に天然繊維を浸し、撹拌しながら必要に応じて加熱処理する。染色工程の後、ソーピングし、流水ですすいで乾燥させる。こうして、化学染料が天然繊維に定着する。浸漬工程と染色工程の順番、すなわち、先媒染であるか後媒染であるかは、どちらでもよい。さらに、浸漬工程と染色工程を一緒に、すなわち同時媒染を行ってもよい。なお、本願発明者は、化学染料を用いずに、濃度１００ｍＭ以上のバナジウムイオンを含む水溶液を用いて、繊維を緑色に染色した。しかしながら、この緑色の繊維は、光耐久性が極めて低く、光を照射すると濃緑色に変色してしまう。このため、この緑色の繊維は製品として成立しない。 In the dyeing step, general natural fibers are dyed using chemical dyes. For example, natural fibers are dipped in a solution of a chemical dye and heat-treated as necessary with stirring. After the dyeing process, it is soaped, rinsed with running water and dried. In this way, the chemical dye is fixed to the natural fiber. The order of the dipping step and the dyeing step, that is, whether it is pre-mordanting or post-mordanting, may be either. Further, the dipping step and the dyeing step may be performed together, that is, simultaneous mordanting. The inventor of the present application dyed the fibers green using an aqueous solution containing vanadium ions having a concentration of 100 mM or more without using a chemical dye. However, these green fibers have extremely low light durability and turn dark green when irradiated with light. Therefore, this green fiber cannot be established as a product.
本発明の第二実施形態に係る光吸収発熱保温用複合体は、光を吸収して発熱および保温する。本実施形態の光吸収発熱保温用複合体は、官能基を備え、親水性溶媒に溶ける樹脂と、官能基に化学結合しているバナジウムとを備えている。化学結合としては、イオン結合のような静電気力による結合などが挙げられる。親水性溶媒に溶ける樹脂としては、デンプンもしくはゼラチンなどの天然由来高分子、カルボキシメチルセルロース（ＣＭＣ）もしくはメチルセルロース（ＭＣ）などの半合成樹脂、またはレゾール型フェノール樹脂、メチロール化ユリア（尿素）樹脂、メチロール化メラミン樹脂、ポリビニルアルコール（ＰＶＡ）、ポリアクリル酸系ポリマー、ポリアクリルアミド（ＰＡＭ）、もしくはポリエチレンオキシド（ＰＥＯ）などの合成樹脂などが挙げられる。 The light absorption heat generation heat insulating complex according to the second embodiment of the present invention absorbs light to generate heat and keep warm. The light-absorbing heat-retaining complex of the present embodiment includes a resin that has a functional group and is soluble in a hydrophilic solvent, and vanadium that is chemically bonded to the functional group. Examples of the chemical bond include a bond due to an electrostatic force such as an ionic bond. Examples of the resin soluble in a hydrophilic solvent include naturally derived polymers such as starch or gelatin, semi-synthetic resins such as carboxymethyl cellulose (CMC) or methyl cellulose (MC), resol-type phenol resins, methylolated urea (urea) resins, and methylols. Examples thereof include synthetic resins such as melamine resin, polyvinyl alcohol (PVA), polyacrylic acid polymer, polyacrylamide (PAM), and polyethylene oxide (PEO).
本実施形態の光吸収発熱保温用複合体は、近赤外光を含む太陽光を吸収して発熱および保温するので、ビニールハウスのシート等に利用できる。本実施形態の光吸収発熱保温用複合体は、親水性溶媒に溶けるバナジウム塩と、樹脂を親水性溶媒に溶かした溶液とを混合する混合工程を経て製造される。より具体的には、混合工程では、例えば、硫酸バナジル、シュウ酸バナジル、または五酸化バナジウム等の親水性溶媒に溶けるバナジウム塩を、樹脂を親水性溶媒に溶かした溶液に添加して攪拌し、必要に応じて加熱する。なお、樹脂を親水性溶媒に溶かした溶液に染料を加えて、樹脂を着色してもよい。 Since the light-absorbing heat-retaining composite of the present embodiment absorbs sunlight including near-infrared light to generate heat and retain heat, it can be used for a greenhouse sheet or the like. The light-absorbing heat-retaining composite of the present embodiment is produced through a mixing step of mixing a vanadium salt dissolved in a hydrophilic solvent and a solution in which a resin is dissolved in a hydrophilic solvent. More specifically, in the mixing step, a vanadium salt soluble in a hydrophilic solvent such as vanadyl sulfate, vanadyl oxalate, or vanadium pentoxide is added to a solution in which the resin is dissolved in a hydrophilic solvent and stirred. Heat as needed. The resin may be colored by adding a dye to a solution of the resin in a hydrophilic solvent.
そして、攪拌と加熱をやめて室温で静置して気泡を取り除くと、本実施形態の光吸収発熱保温用複合体が得られる。親水性溶媒としては水などが挙げられる。従来の光発熱材料のＺｒＣまたはＶＯ２は、親水性溶媒に溶けないため、親水性溶媒に溶ける樹脂に高分散させることが難しい。これに対して、硫酸バナジル等の親水性溶媒に容易に溶けてイオン化する物質は、バナジウムを含有するイオンが、親水性溶媒に溶ける樹脂の官能基と静電気力による結合をすることができる。 Then, when the stirring and heating are stopped and the mixture is allowed to stand at room temperature to remove air bubbles, the light-absorbing heat-retaining composite of the present embodiment is obtained. Examples of the hydrophilic solvent include water and the like. Since the conventional photoheating material ZrC or VO 2 is insoluble in a hydrophilic solvent, it is difficult to disperse it in a resin soluble in a hydrophilic solvent. On the other hand, in a substance that is easily dissolved and ionized in a hydrophilic solvent such as vanadyl sulfate, vanadium-containing ions can be bonded to the functional group of the resin that is soluble in the hydrophilic solvent by electrostatic force.
このため、バナジウムが高分散でこの樹脂に付着する。したがって、本実施形態の光吸収発熱保温用複合体は、光を吸収すると、従来の複合体よりかなり高く発熱する。また、イオン結合性の官能基を有する樹脂に、親水性溶媒に溶かしたバナジウム塩溶液を接触させて、本実施形態の光吸収発熱保温用複合体を得てもよい。イオン結合性の官能基としては、カルボキシル基、スルホン酸基、ヒドロキシル基、ハロゲン基、またはアミド基などが挙げられる。なお、従来の光発熱材料のＺｒＣまたはＶＯ２の無機粒子は、これらの官能基に結合させることは困難である。 Therefore, vanadium adheres to this resin with high dispersion. Therefore, when the light-absorbing heat-retaining complex of the present embodiment absorbs light, it generates heat considerably higher than that of the conventional complex. Further, the light-absorbing heat-retaining composite of the present embodiment may be obtained by contacting a resin having an ionic-bonding functional group with a vanadium salt solution dissolved in a hydrophilic solvent. Examples of the ionic bonding functional group include a carboxyl group, a sulfonic acid group, a hydroxyl group, a halogen group, an amide group and the like. Inorganic particles of ZrC or VO 2 of the conventional photoheating material are difficult to bond to these functional groups.
〔天然繊維を含む複合体〕
Ａ：実験
１．バナジウム媒染（実施例と比較例）と鉄媒染（比較例）
蒸留水に硫酸バナジルＶＯＳＯ４（関東化学株式会社）を溶解し、濃度が１．０×１０−３ｍｏｌ／Ｌ（比較例）、５．０×１０−３ｍｏｌ／Ｌ（比較例）、１．０×１０−２ｍｏｌ／Ｌ、５．０×１０−２ｍｏｌ／Ｌ、１．０×１０−１ｍｏｌ／Ｌ、および５．０×１０−１ｍｏｌ／Ｌの６種類の水溶液を調製した。また、蒸留水に硫酸第一鉄ＦｅＳＯ４（関東化学株式会社）を溶解して、濃度が１．０×１０−１ｍｏｌ／Ｌの水溶液を調製した。
[Complex containing natural fibers]
A: Experiment 1. Vanadium mordanting (Example and Comparative Example) and Iron Mordanting (Comparative Example)
Vanazyl sulfate VOSO 4 (Kanto Kagaku Co., Ltd.) was dissolved in distilled water, and the concentrations were 1.0 × 10 -3 mol / L (comparative example), 5.0 × 10 -3 mol / L (comparative example), 1 Prepare 6 kinds of aqueous solutions of 0.0 × 10 -2 mol / L, 5.0 × 10 -2 mol / L, 1.0 × 10 -1 mol / L, and 5.0 × 10 -1 mol / L. did. Further, ferrous sulfate FeSO 4 (Kanto Chemical Co., Inc.) was dissolved in distilled water to prepare an aqueous solution having a concentration of 1.0 × 10 -1 mol / L.
小型の回転式ポット染色試験機ＭＩＮＩ ＣＯＬＯＵＲ（テクサム技研株式会社）（以下、単に「回転式ポット染色試験機」ということがある）を用いて、上記の各媒染剤水溶液にウール布帛１０ｇ（ＪＩＳ染色堅ろう度試験用添付白布１−１号、財団法人日本規格協会）を浴比１：２０となるように浸漬し、１００℃で１時間処理した。そして、回転式ポット染色試験機を用いて、２．０ｇ／Ｌのマルセル石鹸溶液で処理後の布帛を、浴比１：２０、５０℃、２０分間ソーピングし、その後、５分間流水で洗って乾燥させた。こうして、バナジウム媒染ウール布帛と鉄媒染ウール布帛を得た。 Using a small rotary pot dyeing tester MINI COLOR (Texam Giken Co., Ltd.) (hereinafter, may be simply referred to as "rotary pot dyeing tester"), 10 g of wool cloth (JIS dyeing hard wax) was added to each of the above-mentioned medium dyeing agents aqueous solutions. The white cloth No. 1-1 for the degree test, Japanese Standards Association) was immersed in a bath ratio of 1:20 and treated at 100 ° C. for 1 hour. Then, using a rotary pot dyeing tester, the fabric treated with 2.0 g / L Marcel soap solution was soaped at a bath ratio of 1:20, 50 ° C. for 20 minutes, and then washed with running water for 5 minutes. It was dried. In this way, a vanadium-mordanted wool cloth and an iron-mordanted wool cloth were obtained.
２．染色
（１）天然染料での染色
天然染料として植物由来ポリフェノール（タンニン）の構成成分である没食子酸ＧＡ（関東化学株式会社）と蒸留水を用いて２．５ｗｔ％水溶液を調製した。回転式ポット染色試験機を用いて、この染料水溶液にウール布帛、バナジウム媒染ウール布帛、または鉄媒染ウール布帛を５０％ｏ．ｗ．ｆ、浴比１：２０となるように浸漬し、１００℃で１時間染色した。そして、回転式ポット染色試験機を用いて、２．０ｇ／Ｌのマルセル石鹸溶液で染色後の各ウール布帛を、浴比１：２０、５０℃、２０分間ソーピングし、その後、５分間流水で洗って乾燥させた。こうして、黒色バナジウム先媒染ウール布帛と黒色鉄先媒染ウール布帛を得た。
2. 2. Dyeing (1) Dyeing with a natural dye A 2.5 wt% aqueous solution was prepared using gallic acid GA (Kanto Chemical Co., Inc.), which is a component of plant-derived polyphenol (tannin), and distilled water as a natural dye. Using a rotary pot dyeing tester, 50% o. Wool cloth, vanadium mordant wool cloth, or iron mordant wool cloth was added to this dye solution. w. The cells were immersed at f and a bath ratio of 1:20 and stained at 100 ° C. for 1 hour. Then, using a rotary pot dyeing tester, each wool fabric dyed with a 2.0 g / L Marcel soap solution was soaped at a bath ratio of 1:20, 50 ° C. for 20 minutes, and then under running water for 5 minutes. Washed and dried. In this way, a black vanadium pre-mordanted wool cloth and a black iron pre-mordanted wool cloth were obtained.
（２）先媒染化学染料での染色
また、回転式ポット染色試験機を用いて、赤色染料Ｒｅｄ ＧＲＮ、緑色染料Ｇｒｅｅｎ ５ＧＷ、または青色染料Ｃｙａｎｉｎｅ ５Ｒ（いずれもＫａｙａｎｏｌ Ｍｉｌｌｉｎｇ）で、５．０×１０−２ｍｏｌ／ＬのＶＯＳＯ４水溶液で媒染したバナジウム媒染ウール布帛を、濃度２．０％ｏ．ｗ．ｆ．で染色した。他の染色条件はＧＡでの染色条件と同じであった。染色後、ＧＡでの染色と同条件でソーピング、水洗、および乾燥を行った。こうして、化学赤色バナジウム先媒染ウール布帛、化学緑色バナジウム先媒染ウール布帛、および化学青色バナジウム先媒染ウール布帛を得た。
(2) Dyeing with pre-mordanting chemical dyes Also, using a rotary pot dyeing tester, 5.0 × 10 with red dye Red GRN, green dye Green 5GW, or blue dye Chainine 5R (all are Kayanol Milling). A vanadium mordanted wool cloth mordanted with -2 mol / L VOSO 4 aqueous solution was mixed with a concentration of 2.0% o. w. f. Stained with. Other staining conditions were the same as those for GA. After staining, soaping, washing with water, and drying were performed under the same conditions as for staining with GA. Thus, a chemically red vanadium pre-mordanted wool fabric, a chemically green vanadium pre-mordanted wool fabric, and a chemically blue vanadium pre-mordanted wool fabric were obtained.
（３）同時媒染化学染料での染色
また、ＶＯＳＯ４（５．０×１０−２ｍｏｌ／Ｌの）とＲｅｄ ＧＲＮ（２．０％ｏ．ｗ．ｆ）を溶解させた水溶液を用いて、ＧＡでの染色と同じ条件でウール布帛を染色した。染色後、ＧＡでの染色と同条件でソーピング、水洗、および乾燥を行った。こうして、化学赤色バナジウム同時媒染ウール布帛を得た。
(3) staining with simultaneous mordant chemical dye addition, VOSO 4 (of 5.0 × 10 -2 mol / L) and using an aqueous solution prepared by dissolving Red GRN (2.0% o.w.f), The wool fabric was dyed under the same conditions as the dyeing with GA. After staining, soaping, washing with water, and drying were performed under the same conditions as for staining with GA. In this way, a chemically red vanadium co-mordanted wool fabric was obtained.
（４）媒染なし化学染料
また、回転式ポット染色試験機を用いて、表１に示す配合染料（Ｋａｙａｎｏｌ Ｍｉｌｌｉｎｇ、日本化薬株式会社）と、１．０％ｏ．ｗ．ｆの均染剤（ニューボンＥ−１ Ｋ、日華化学株式会社）および１．０ｇ／ＬのｐＨ調整剤（オプチシド ＶＳ）の助剤で、ウール布帛を浴比１：２０で黒色に染色して比較例の化学黒色ウール布帛を作製した。なお、染色工程では、３０分間かけて２０℃から９０℃まで昇温し、９０℃に達した時点で酸を加えて３５分間保持した。その後、冷却して１５分間流水で洗浄した。
(4) Chemical dyes without mordanting In addition, using a rotary pot dyeing tester, the compound dyes shown in Table 1 (Kayanal Milling, Nippon Kayaku Co., Ltd.) and 1.0% o. w. Wool fabric is dyed black with a bath ratio of 1:20 with an auxiliary agent of f leveling agent (Newbon E-1K, NICCA CHEMICAL CO., LTD.) And 1.0 g / L pH adjuster (Opticid VS). The chemical black wool fabric of the comparative example was prepared. In the dyeing step, the temperature was raised from 20 ° C. to 90 ° C. over 30 minutes, and when the temperature reached 90 ° C., an acid was added and the temperature was maintained for 35 minutes. Then, it was cooled and washed with running water for 15 minutes.
３．色彩評価
分光測色計（ＳＤ−６０００、日本電色工業株式会社）を用いて、測定径φ６．４ｍｍ、光源Ｄ６５、１０°視野、正反射光を含むモードで媒染後および／または染色後のウール布帛の色彩を測定し、数値化した。そして、色彩管理ソフト（Ｃｏｌｏｒ Ｍａｔｅ Ｐｒｏ、日本電色工業株式会社）のＬ＊ａ＊ｂ＊表色系および色差（ΔＥ００）で媒染後および／または染色後のウール布帛の色彩を評価した。
3. 3. Color evaluation Using a spectrophotometer (SD-6000, Nippon Denshoku Kogyo Co., Ltd.), after mordanting and / or after dyeing in a mode including measurement diameter φ6.4 mm, light source D 65, 10 ° field, and positively reflected light. The color of the wool cloth was measured and quantified. Then, the color of the wool cloth after mordanting and / or dyeing was evaluated by L * a * b * color system and color difference (ΔE00) of the color management software (Color Mate Pro, Nippon Denshoku Kogyo Co., Ltd.).
４．光吸収発熱保温性能試験
ボーケン法（ＢＱＥ−Ａ法）を用いて、媒染後および／または染色後のウール布帛の光吸収発熱保温性能試験を行った。すなわち、裏面中央部に熱電対温度センサーを設けた発泡スチロール製試料台に、１５ｃｍ四方の各種ウール布帛を並列に置き、３０ｃｍ離れた位置から写真用レフランプ（ＰＲＦ−５００ＷＢ／Ｄ、パナソニック株式会社、またはＰＲＦ−５００ＷＤ、岩崎電気株式会社）で１０分間照射した。その後、レフランプを消し、１０分間続けて温度の測定を行った。
4. Light Absorption Heat Insulation Performance Test Using the Boken method (BQE-A method), a light absorption heat insulation performance test of wool fabric after mordanting and / or dyeing was performed. That is, various wool cloths of 15 cm square are placed in parallel on a foamed styrene sample table provided with a thermocouple temperature sensor in the center of the back surface, and a photographic reflex lamp (PRF-500WB / D, Panasonic Corporation, or Panasonic Co., Ltd.) is placed 30 cm away. It was irradiated with PRF-500WD, Iwasaki Electric Co., Ltd. for 10 minutes. After that, the ref lamp was turned off and the temperature was continuously measured for 10 minutes.
また、特定の波長領域をカットするフィルターを用いて、上記と同様にして光吸収発熱保温性能試験を行った。すなわち、濃度１．０×１０−１ｍｏｌ／Ｌの硫酸バナジル水溶液、硫酸第一鉄水溶液、および炭化ジルコニウム（関東化学株式会社）でそれぞれ先媒染した１５ｃｍ四方のウール布帛の上方１ｃｍ地点に、サイズ５ｃｍ×５ｃｍ×３ｍｍの３種類の色ガラスフィルター（東芝硝子株式会社製の赤外線フィルターＩＲＡ−１０、紫外線フィルターＵＶ−２９、および紫外線フィルターＹ−４６）を配置した。 In addition, a light absorption heat generation heat retention performance test was conducted in the same manner as above using a filter that cuts a specific wavelength region. That is, the size is located 1 cm above the 15 cm square wool cloth pre-injected with an aqueous solution of vanazine sulfate having a concentration of 1.0 × 10 -1 mol / L, an aqueous solution of ferrous sulfate, and zirconium carbide (Kanto Kagaku Co., Ltd.). Three types of 5 cm × 5 cm × 3 mm colored glass filters (infrared filter IRA-10 manufactured by Toshiba Glass Co., Ltd., ultraviolet filter UV-29, and ultraviolet filter Y-46) were arranged.
ＢＱＥ−Ａ法と同様に、試験環境は温度２０℃、湿度６５％であった。写真用レフランプ（ＰＲＦ−５００ＷＤ）の出力波長特性は、減光フィルター（０３ＦＮＱ０２３／ＯＤ ２．０、ＭＥＬＬＥＳ ＧＲＩＯＴ社）を通して、受光器（ＰＨＯＴＯＮＩＣ ＭＵＬＴＩ−ＣＨＡＮＮＥＬ ＡＮＡＬＹＺＥＲ、浜松ホトニクス株式会社）を用いて測定した。 Similar to the BQE-A method, the test environment was a temperature of 20 ° C. and a humidity of 65%. The output wavelength characteristics of the photographic reflex lamp (PRF-500WD) were measured using a light receiver (PHOTONIC MULTI-CHANNEL ANALYZER, Hamamatsu Photonics Co., Ltd.) through a neutral density filter (03FNQ023 / OD 2.0, MELLES GRIOT). ..
５．透過率・反射率測定
紫外可視近赤外分光光度計（ＵＶ−ＶＩＳ ＮＩＲ ＳＰＥＣＴＲＯＰＨＯＴＯＭＥＴＥＲ ＳｏｌｉｄＳｐｅｃ−３７００、株式会社島津製作所）を用いて、媒染後および／または染色後のウール布帛の光透過率と光反射率を測定して、ウール布帛の光吸収性を評価した。なお、スリット幅は３２ｎｍ、測定波長範囲は２００〜２５００ｎｍとした。検出器の切替波長は８７０ｎｍおよび１６５０ｎｍ、グレーティングの切替波長は７８０ｎｍとした。
5. Transmittance / Reflectance Measurement Using an ultraviolet-visible near-infrared spectrophotometer (UV-VIS NIR SPECTROPHOTOMETER SolidSpec-3700, Shimadzu Corporation), the light transmittance and light reflection of the wool fabric after medium dyeing and / or dyeing. The rate was measured to evaluate the light absorption of the wool fabric. The slit width was 32 nm, and the measurement wavelength range was 200 to 2500 nm. The switching wavelength of the detector was 870 nm and 1650 nm, and the switching wavelength of the grating was 780 nm.
Ｂ：結果
１．バナジウム媒染ウール布帛と鉄媒染ウール布帛の光吸収発熱保温状態
濃度１．０×１０−１ｍｏｌ／Ｌでのバナジウム媒染ウール布帛（▲：Ｖ）と鉄媒染ウール布帛（□：Ｆｅ）の光吸収発熱保温性能試験の結果を図１に示す。なお、光照射開始時が経過時間０分である（図２、図３、および図６〜図１０も同様）。媒染後に光吸収発熱保温性能を示すことの指標は、媒染後と媒染前の温度差が、光照射１０分後で５℃以上、その後の光照射停止１分後で１．０℃以上である。
B: Result 1. Light absorption of vanadium mordant wool cloth and iron mordant wool cloth Heat retention state Light absorption of vanadium mordant wool cloth (▲: V) and iron mordant wool cloth (□: Fe) at a concentration of 1.0 × 10 -1 mol / L The results of the heat generation heat retention performance test are shown in FIG. The elapsed time is 0 minutes at the start of light irradiation (the same applies to FIGS. 2, 3, and 6 to 10). The index of showing the light absorption heat generation heat retention performance after mordanting is that the temperature difference between after mordanting and before mordanting is 5 ° C or more 10 minutes after light irradiation and 1.0 ° C or more 1 minute after the light irradiation is stopped. ..
鉄は、ログウッドとの組み合わせによる黒色染色に用いられる媒染剤である。鉄媒染ウール布帛と、媒染してないウール布帛（●：ｂｌａｎｋ）の温度差は、光照射１０分後で１．４℃、光照射停止１分後で０．８℃であった。一方、バナジウム媒染ウール布帛と、媒染してないウール布帛の温度差は、光照射１０分後で１４．９℃、光照射停止１分後で５．９℃であった。鉄媒染ウール布帛は光吸収発熱保温性能を示さなかった。これに対して、バナジウム媒染ウール布帛は、非常に高い光吸収発熱保温性能を示した。 Iron is a medium dyeing agent used for black dyeing in combination with logwood. The temperature difference between the iron mordant-dyed wool cloth and the non-mordanted wool cloth (●: blank) was 1.4 ° C. 10 minutes after light irradiation and 0.8 ° C. 1 minute after light irradiation was stopped. On the other hand, the temperature difference between the vanadium-mordanted wool fabric and the non-mordanted wool fabric was 14.9 ° C. 10 minutes after light irradiation and 5.9 ° C. 1 minute after light irradiation was stopped. The iron mordant wool fabric did not show light absorption, heat generation and heat retention performance. On the other hand, the vanadium mordant wool fabric showed extremely high light absorption, heat generation and heat retention performance.
２．バナジウム媒染剤濃度と光吸収発熱保温状態
図２は、バナジウム媒染剤濃度を変化させたとき（１．０×１０−３ｍｏｌ／Ｌ（■）〜５．０×１０−１ｍｏｌ／Ｌ（◇）の６種類）のバナジウム媒染ウール布帛および媒染していないウール布帛（〇：０ｍｏｌ／Ｌ）の光吸収発熱保温状態を示している。バナジウム媒染剤の濃度が５．０×１０−３ｍｏｌ／Ｌ以下では、光吸収発熱保温性能を示さなかった。
2. 2. Vanadium mordant concentration and light absorption heat retention state Figure 2 shows when the vanadium mordant concentration was changed (1.0 × 10 -3 mol / L (■) to 5.0 × 10 -1 mol / L (◇). It shows the light absorption heat generation heat retention state of the vanadium mordant wool cloth (6 types) and the non-mordanted wool cloth (〇: 0 mol / L). When the concentration of the vanadium mediator was 5.0 × 10 -3 mol / L or less, the light absorption heat generation heat retention performance was not shown.
一方、バナジウム媒染剤の濃度が１．０×１０−２ｍｏｌ／Ｌ以上では、バナジウム媒染剤の濃度が上昇するにつれて、光吸収発熱保温性能が徐々に向上することがわかった。なお、植物染料の発色バリエーションを増やす目的で、媒染剤ＶＯＳＯ４を繊維に導入することが知られている（「植物染料五倍子染色におけるバナジウム先媒染の最適条件」、繊維製品消費科学、２０１４年）。しかし、媒染剤自体の着色を抑えるために、ＶＯＳＯ４濃度は５ｍＭ以下に抑えられている。 On the other hand, it was found that when the concentration of the vanadium medium dyeing agent was 1.0 × 10 −2 mol / L or more, the light absorption heat generation heat retention performance gradually improved as the concentration of the vanadium medium dyeing agent increased. It is known to introduce the mordant VOSO 4 into fibers for the purpose of increasing the color variation of plant dyes (“Optimal conditions for vanadium pre-mordanting in plant dye quintuple dyeing”, Textile Product Consumption Science, 2014). However, in order to suppress coloring of the mordant itself, VOSO 4 concentration is suppressed to below 5 mM.
光照射１０分後の染色バナジウム先媒染ウール布帛と染色ウール布帛（バナジウム媒染なし）の温度差が１０．０℃以上となるためには、濃度１．０×１０−２ｍｏｌ／Ｌ以上の媒染剤で媒染することが必要であることがわかった。なお、高濃度１．０×１０−１ｍｏｌ／Ｌのバナジウム媒染剤で処理したバナジウム先媒染ウール布帛の皮膚一次刺激性は、蒸留水およびワセリン程度の低刺激性であることが確認されている。 In order for the temperature difference between the dyed vanadium pre-mordanted wool fabric and the dyed wool fabric (without vanadium mordant) to be 10.0 ° C or more 10 minutes after light irradiation, a mordant with a concentration of 1.0 × 10-2 mol / L or more It turned out that mordanting was necessary. It has been confirmed that the primary skin irritation of the vanadium pre-mordanted wool fabric treated with a high-concentration 1.0 × 10 -1 mol / L vanadium mordant is as low as that of distilled water and petrolatum.
３．光源波長が光吸収発熱保温状態に及ぼす影響
バナジウム媒染ウール布帛（□：Ｖ）、鉄媒染ウール布帛（▲：Ｆｅ）、ジルコニウム媒染ウール布帛（◇：Ｚｒ）、およびウール布帛（●：ｎｏ ｍｏｒｄａｎｔ）の発熱保温性に影響を及ぼす特性波長を調べた。媒染剤ＶＯＳＯ４、ＺｒＣ、およびＦｅＳＯ４の濃度は、いずれも１．０×１０−１ｍｏｌ／Ｌとした。３種類の波長カットフィルターを用いたときと、波長カットフィルターを用いなかったときの光吸収発熱保温性能試験の結果を図３に示す。
3. 3. Effect of light source wavelength on light absorption, heat generation and heat retention state Vanadium mordant wool cloth (□: V), iron mordant wool cloth (▲: Fe), zircon mordant wool cloth (◇: Zr), and wool cloth (●: no mordant) The characteristic wavelength that affects the heat retention of heat was investigated. The concentrations of the mediators VOSO 4 , ZrC, and FeSO 4 were all 1.0 × 10 -1 mol / L. FIG. 3 shows the results of the light absorption heat generation heat insulation performance test when the three types of wavelength cut filters were used and when the wavelength cut filter was not used.
赤外線フィルターＩＲＡ−１０は波長３２０ｎｍ以下および８００ｎｍ〜４８００ｎｍをカットする（図３（ｄ））。紫外線フィルターＵＶ−２９は波長２４０ｎｍ以下をカットする（図３（ｂ））。紫外線フィルターＹ−４６は波長４３０ｎｍ以下をカットする（図３（ｃ））。図３（ｂ）と図３（ｃ）では、波長カットフィルターを用いなかった図３（ａ）と変わらない傾向が見られた。これは、紫外線の光吸収発熱保温性能に対する寄与が小さいことを示している。一方、赤外線カットフィルターを用いると光吸収発熱保温性が劣った（図３（ｄ））。これより、バナジウムの赤外線領域波長の光吸収が、光吸収発熱保温性能に影響を及ぼしていることがわかった。 The infrared filter IRA-10 cuts wavelengths of 320 nm or less and 800 nm to 4800 nm (FIG. 3 (d)). The ultraviolet filter UV-29 cuts wavelengths of 240 nm or less (FIG. 3 (b)). The ultraviolet filter Y-46 cuts wavelengths of 430 nm or less (FIG. 3 (c)). In FIGS. 3 (b) and 3 (c), the same tendency as in FIG. 3 (a) in which the wavelength cut filter was not used was observed. This indicates that the contribution of ultraviolet rays to the light absorption, heat generation and heat retention performance is small. On the other hand, when the infrared cut filter was used, the light absorption heat generation and heat retention were inferior (FIG. 3 (d)). From this, it was found that the light absorption of vanadium in the infrared region wavelength affects the light absorption heat generation heat retention performance.
また、炭化ジルコニウムを含有する媒染剤で媒染したジルコニウム媒染ウール布帛の発熱保温性も、バナジウム媒染ウール布帛の発熱保温性と同様の傾向を示した。これより、ジルコニウムとバナジウムは、赤外線領域波長の光を吸収して、似たようなメカニズムによって媒染ウール布帛が発熱保温性を示すと推察される。バナジウムとジルコニウムの飽和到達温度を比較すると、バナジウムの方が約１０℃高い。これは、水に溶けるバナジウム塩から供給されるバナジウムが、媒染により、静電気力による結合で天然繊維に付着しやすいからだと考えられる。 Further, the heat-retaining property of the zirconium-mordanted wool cloth mordant-dyed with a zirconium carbide-containing mordant showed the same tendency as the heat-retaining property of the vanadium mordant wool cloth. From this, it is inferred that zirconium and vanadium absorb light with wavelengths in the infrared region, and the mordant wool fabric exhibits heat retention by a similar mechanism. Comparing the saturation reaching temperatures of vanadium and zirconium, vanadium is about 10 ° C higher. It is considered that this is because vanadium supplied from a water-soluble vanadium salt easily adheres to natural fibers due to binding by electrostatic force due to mordanting.
４．バナジウム媒染ウール布帛の光透過率と光反射率
バナジウム媒染ウール布帛の光透過率と光反射率の測定結果を図４に示す。媒染剤濃度を高くしていくと、光透過率（図４（ａ））および光反射率（図４（ｂ））はともに低くなっていく。１００％から光透過率と光反射率の和を引いた数値がバナジウム媒染ウール布帛の光吸収率である。可視領域光波長３８０ｎｍ〜７８０ｎｍにおけるバナジウム媒染ウール布帛の光吸収は、バナジウム媒染ウール布帛の色に関する吸収である、このため、波長３８０ｎｍ〜７８０ｎｍを除いた領域におけるバナジウム媒染ウール布帛の光透過率と光反射率の低さは、バナジウム媒染ウール布帛の光吸収率の高さといえる。波長３００ｎｍ〜３８０ｎｍおよび波長７８０ｎｍ〜１９００ｎｍでは、媒染剤濃度を高くしていくとバナジウム媒染ウール布帛の光吸収率が高くなることが図４からわかった。
4. Light transmittance and light reflectance of vanadium-coated wool fabric FIG. 4 shows the measurement results of light transmittance and light reflectance of vanadium-coated wool fabric. As the concentration of the mediator increases, both the light transmittance (FIG. 4 (a)) and the light reflectance (FIG. 4 (b)) decrease. The value obtained by subtracting the sum of the light transmittance and the light reflectance from 100% is the light absorption rate of the vanadium mordant wool fabric. The light absorption of the vanadium-coated wool fabric in the visible region light wavelength of 380 nm to 780 nm is the absorption with respect to the color of the vanadium-borne wool fabric. The low reflectance can be said to be the high light absorption rate of the vanadium-borne wool fabric. It was found from FIG. 4 that at wavelengths of 300 nm to 380 nm and wavelengths of 780 nm to 1900 nm, the light absorption rate of the vanadium mordant wool fabric increased as the mordant concentration increased.
バナジウム媒染剤濃度に対するバナジウム媒染ウール布帛の特定波長における光透過率（□：Ｔ）および光反射率（●：Ｒ）を図５に示す。紫外線領域の波長２００ｎｍと、近赤外線領域の長波長側の波長２０００ｎｍにおいては、バナジウム媒染剤濃度を高くしてもバナジウム媒染ウール布帛の光吸収率に変化が見られなかった（図５（ａ）と図５（ｄ））。これは、これらの波長が光吸収発熱保温性能にあまり寄与しないことを意味している。 FIG. 5 shows the light transmittance (□: T) and the light reflectance (●: R) at a specific wavelength of the vanadium mordant wool fabric with respect to the vanadium mordant concentration. At a wavelength of 200 nm in the ultraviolet region and a wavelength of 2000 nm on the long wavelength side in the near infrared region, no change was observed in the light absorption rate of the vanadium mordant wool fabric even if the vanadium mordant concentration was increased (FIG. 5 (a)). FIG. 5 (d)). This means that these wavelengths do not contribute much to the light absorption, heat generation and heat retention performance.
一方、図５（ｂ）および図５（ｃ）では、バナジウム媒染剤濃度を高くしていくと、バナジウム媒染ウール布帛の光透過率および光反射率がともに下がり、媒染剤の濃度が５．０×１０−２ｍｏｌ／Ｌ以上で、バナジウム媒染ウール布帛の光吸収率が最も高く飽和している。図５（ｂ）は、可視光領域の波長５００ｎｍの光照射であり、バナジウム媒染後に緑色の度合いが深まっていることを示している。図５（ｃ）は、近赤外線領域の波長１０００ｎｍの光照射である。バナジウム媒染剤の濃度が５．０×１０−２ｍｏｌ／Ｌ以上で１０００ｎｍの光吸収率が飽和していることは、バナジウム媒染ウール布帛の光吸収発熱保温性能が、このバナジウム媒染剤濃度で飽和していると推察される。 On the other hand, in FIGS. 5 (b) and 5 (c), as the concentration of the vanadium mordant is increased, both the light transmittance and the light reflectance of the vanadium mordant wool cloth decrease, and the concentration of the mordant is 5.0 × 10. At -2 mol / L or more, the light transmittance of the vanadium mordant wool fabric is the highest and saturated. FIG. 5B shows light irradiation with a wavelength of 500 nm in the visible light region, and shows that the degree of green color is deepened after vanadium mordanting. FIG. 5 (c) shows light irradiation having a wavelength of 1000 nm in the near infrared region. The fact that the light absorption rate at 1000 nm is saturated when the concentration of the vanadium mordant is 5.0 × 10-2 mol / L or more means that the light absorption heat retention performance of the vanadium mordant wool fabric is saturated at this vanadium mordant concentration. It is presumed that there is.
これらの結果から、天然繊維であるウール布帛をバナジウム媒染して、バナジウムを付着させたバナジウム媒染ウール布帛は、１０００ｎｍ等の近赤外線領域の中で特に短波長側の光を吸収し、高い発熱保温性を示すことが明らかとなった。地球表面にそそぐ太陽エネルギースペクトルは５００ｎｍ付近を極大として長波長側は減衰する。太陽光は近赤外領域においても短波長側のエネルギー強度が高いことから、バナジウム媒染ウール布帛は、太陽光による光吸収発熱保温に関して有利であると考えられる。 From these results, the vanadium mordant wool cloth, which is a natural fiber wool mordant dyed with vanadium and adhered with vanadium, absorbs light on the short wavelength side especially in the near infrared region such as 1000 nm, and has high heat generation and heat retention. It became clear that it showed sex. The solar energy spectrum pouring into the earth's surface is attenuated on the long wavelength side with the maximum around 500 nm. Since sunlight has a high energy intensity on the short wavelength side even in the near-infrared region, vanadium mordant wool fabric is considered to be advantageous in terms of light absorption, heat generation and heat retention by sunlight.
５．黒色バナジウム先媒染ウール布帛の光吸収発熱保温状態
濃度１．０×１０−１ｍｏｌ／Ｌのバナジウム媒染剤で媒染したバナジウム媒染ウール布帛を、ポリフェノール構成成分である没食子酸ＧＡで染色した黒色バナジウム先媒染ウール布帛（▲：Ｖ→ＧＡ）の光吸収発熱保温状態を図６示す。また、媒染せずにウール布帛を没食子酸で染色した黒色ウール布帛（□：ＧＡ）と、媒染も染色もしていないウール布帛（●：ｂｌａｎｋ）の光吸収発熱保温状態も図６に示す。黒色バナジウム先媒染ウール布帛と媒染も染色もしていないウール布帛の温度差は、光照射１０分後で１４．５℃、光照射停止１分後で５．８℃であった。黒色バナジウム先媒染ウール布帛の光吸収発熱保温性能が没食子酸での黒色染色前後で同等であることから（図１参照）、バナジウム媒染ウール布帛の黒色度の光吸収発熱保温性能への寄与は小さいと考えられる。
5. Light absorption heat retention state of black vanadium mordant wool cloth Black vanadium mordant dyed with vanadium mordant wool cloth dyed with vanadium mordant with concentration 1.0 × 10 -1 mol / L with gallic acid GA, which is a polyphenol component. FIG. 6 shows the light absorption heat generation heat retention state of the wool cloth (▲: V → GA). FIG. 6 also shows the light absorption heat generation and heat retention state of the black wool cloth (□: GA) in which the wool cloth is dyed with mortal acid without mordanting and the wool cloth (●: blank) which is neither mordanted nor dyed. The temperature difference between the black vanadium premordanted wool fabric and the unmordanted and undyed wool fabric was 14.5 ° C. 10 minutes after light irradiation and 5.8 ° C. 1 minute after light irradiation was stopped. Since the light absorption heat retention performance of the black vanadium mordant wool fabric is the same before and after black dyeing with galvanic acid (see Fig. 1), the contribution of the blackness of the vanadium mordant wool fabric to the light absorption heat generation heat retention performance is small. it is conceivable that.
６．化学黒色ウール布帛の光吸収発熱保温状態
バナジウム媒染剤で媒染したバナジウム媒染ウール布帛を没食子酸で染色した黒色バナジウム先媒染ウール布帛と、媒染していないウール布帛を化学染料の黒色染料ＴＬＢ（Ｋａｙａｎｏｌ Ｍｉｌｌｉｎｇ）、またはＴＬＢおよび緑色染料Ｇｒｅｅｎ ５ＧＷ（以下、単に５ＧＷと記載することがある）（Ｋａｙａｎｏｌ Ｍｉｌｌｉｎｇ）の混合物で染色した化学黒色ウール布帛の明度Ｌ＊値と、クロマティクネス指数ａ＊値およびｂ＊値と、色差値ΔＥ００を表２に示す。なお、ΔＥ００は黒色バナジウム先媒染ウール布帛を基準とした。
6. Light absorption heat retention state of chemical black wool cloth Black vanadium pre-mordanted wool cloth dyed with vanadium mordant dyed vanadium mordant wool cloth with mordanting acid and unmordanted wool cloth are dyed with chemical dye black dye TLB (Kayanor Milling). , Or a mixture of TLB and the green dye Green 5GW (hereinafter, may be simply referred to as 5GW) (Kayanol Milling), and the lightness L * value and the chromaticity index a * value and b * value of the chemical black wool fabric. And the color difference value ΔE00 is shown in Table 2. In addition, ΔE00 was based on the black vanadium pre-mordanted wool fabric.
表２に示すように、濃度２．４５％ｏ．ｗ．ｆのＴＬＢと濃度１．７５ｏ．ｗ．ｆ％の５ＧＷを含有する染色剤（以下、「ＴＬＢ２．４５％ｏ．ｗ．ｆ＋５ＧＷ１．７５ｏ．ｗ．ｆ％」と記載することがある。他の染色剤についても同様の記載をすることがある）で染色した化学黒色ウール布帛の色差値ΔＥ００は、基準と一致した。また、他の染色剤での染色では、ΔＥ００が全て３．０未満であった。これらのΔＥ００は、Ａ級許容差と呼ばれる色の離間比較においてほとんど色差を認識することができないレベルである。黒色バナジウム先媒染ウール布帛のｂ＊値はプラスであり、化学黒色ウール布帛のｂ＊値はすべて０に近いマイナスであった。これらの結果から、基準色となる黒色バナジウム先媒染ウール布帛は黄色系の黒色であり、化学黒色ウール布帛は青味を若干帯びた黒色であることがわかる。しかし、これらの色差は目視でほとんど認識できない。 As shown in Table 2, the concentration is 2.45% o. w. TLB of f and concentration 1.75 o. w. A dyeing agent containing 5 GW of f% (hereinafter, may be described as "TLB 2.45% o.w.f + 5GW 1.75 o.w.f%". The same description may be applied to other dyeing agents. The color difference value ΔE00 of the chemically black wool fabric dyed with) was in agreement with the standard. In addition, in the dyeing with other dyeing agents, ΔE00 was all less than 3.0. These ΔE00 are levels at which color differences can hardly be recognized in a color separation comparison called a class A tolerance. B * values of the black vanadium destination mordant wool fabric is positive, b * values of chemical black wool fabric was negative close to all zeros. From these results, it can be seen that the black vanadium yarn-dyed wool fabric, which is the standard color, is yellowish black, and the chemically black wool fabric is slightly bluish black. However, these color differences are hardly recognizable visually.
６種類の化学黒色ウール布帛の平均（□：ｂｌａｃｋ）、濃度が５．０×１０−２ｍｏｌ／Ｌのバナジウム媒染剤で媒染したバナジウム媒染ウール布帛を、ＴＬＢ２．４５％ｏ．ｗ．ｆ＋５ＧＷ１．７５％ｏ．ｗ．ｆの化学染料で染色した化学黒色バナジウム先媒染ウール布帛（▲：Ｖ→ｂｌａｃｋ）、および媒染も染色もしていないウール布帛（●：ｂｌａｎｋ）の光吸収発熱保温状態を図７示す。なお、６種類の化学黒色ウール布帛のプロットはほぼ重なっていた。図７に示すように、化学黒色ウール布帛と媒染も染色もしていないウール布帛の温度差は、光照射１０分後で２．５℃、光照射停止１分後で１．４℃であった。したがって、化学染料で天然繊維のウール布帛を黒色染色すると、従来の発熱保温素材の指標程度の効果は得られるが、それほど高い効果は期待できない。 A vanadium mordant wool cloth dyed with a vanadium mordant having an average (□: black) and a concentration of 5.0 × 10 −2 mol / L of 6 kinds of chemical black wool cloths was prepared with TLB 2.45% o. w. f + 5GW 1.75% o. w. FIG. 7 shows the light absorption heat generation heat retention state of the chemically black vanadium pre-mordanted wool cloth (▲: V → black) dyed with the chemical dye of f, and the wool cloth (●: blank) which is neither mordant nor dyed. The plots of the six types of chemical black wool fabrics almost overlapped. As shown in FIG. 7, the temperature difference between the chemically black wool fabric and the undyed or undyed wool fabric was 2.5 ° C. 10 minutes after light irradiation and 1.4 ° C. 1 minute after light irradiation was stopped. .. Therefore, when the wool fabric of natural fiber is dyed black with a chemical dye, the effect of the index of the conventional heat-generating and heat-retaining material can be obtained, but such a high effect cannot be expected.
７．化学赤色ウール布帛、化学緑色ウール布帛、化学青色ウール布帛の光吸収発熱保温状態
媒染していないウール布帛を赤色の化学染料で染色した化学赤色ウール布帛（□：ｒｅｄ）、濃度が５．０×１０−２ｍｏｌ／Ｌのバナジウム媒染剤で媒染したバナジウム媒染ウール布帛を、赤色の化学染料で染色した化学赤色バナジウム先媒染ウール布帛（▲：Ｖ→ｒｅｄ）、濃度が５．０×１０−２ｍｏｌ／Ｌのバナジウム媒染剤と赤色の化学染料を含む染色剤で同時媒染した化学赤色バナジウム同時媒染ウール布帛（◇：Ｖ＋ｒｅｄ）、および媒染も染色もしていないウール布帛（●：ｂｌａｎｋ）の光吸収発熱保温状態を図８示す。なお、同時媒染は、媒染および染色の工程の省力化のために検討した。
7. Light absorption heat retention state of chemical red wool cloth, chemical green wool cloth, chemical blue wool cloth Chemical red wool cloth (□: red) in which unmordanted wool cloth is dyed with red chemical dye, concentration 5.0 × 10 vanadium mordant wool fabric was mordanted vanadium mordant -2 mol / L, red stained chemically red vanadium destination mordanted wool fabric with chemical dye (▲: V → red), concentration of 5.0 × 10 -2 mol Light absorption heat retention of chemical red vanadium co-mordanting wool cloth (◇: V + red) co-mordanted with / L vanadium mordant and dyeing agent containing red chemical dye, and unmordanted and undyed wool cloth (●: blank) The state is shown in FIG. Simultaneous mordanting was examined to save labor in the mordanting and dyeing processes.
同様に、媒染していないウール布帛を緑色の化学染料で染色した化学緑色ウール布帛（□：ｇｒｅｅｎ）、濃度が５．０×１０−２ｍｏｌ／Ｌのバナジウム媒染剤で媒染したバナジウム媒染ウール布帛を、緑色の化学染料で染色した化学緑色バナジウム先媒染ウール布帛（▲：Ｖ→ｇｒｅｅｎ）、および媒染も染色もしていないウール布帛（●：ｂｌａｎｋ）の光吸収発熱保温状態を図９示す。 Similarly, a chemical green wool cloth (□: green) obtained by dyeing unmordanted wool cloth with a green chemical dye, and a vanadium mordant wool cloth dyed with a vanadium mordant having a concentration of 5.0 × 10-2 mol / L. FIG. 9 shows the light absorption heat generation and heat retention state of the chemical green vanadium premordanting wool cloth (▲: V → green) dyed with a green chemical dye, and the wool cloth (●: blank) which is neither mordant nor dyed.
また同様に、媒染していないウール布帛を青色の化学染料で染色した化学青色ウール布帛（□：ｂｌｕｅ）、濃度が５．０×１０−２ｍｏｌ／Ｌのバナジウム媒染剤で媒染したバナジウム媒染ウール布帛を、青色の化学染料で染色した化学青色バナジウム先媒染ウール布帛（▲：Ｖ→ｂｌｕｅ）、および媒染も染色もしていないウール布帛（●：ｂｌａｎｋ）の光吸収発熱保温状態を図１０示す。 Similarly, a chemical blue wool cloth (□: blue) obtained by dyeing an unmordanted wool cloth with a blue chemical dye, and a vanadium mordant wool cloth dyed with a vanadium mordant having a concentration of 5.0 × 10-2 mol / L. FIG. 10 shows the light absorption heat generation heat retention state of the chemical blue vanadium premordanting wool cloth (▲: V → blue) dyed with a blue chemical dye and the wool cloth (●: blank) which is neither mordant nor dyed.
図８から図１０に示すように、バナジウム媒染ウール布帛を３原色の化学染料で染色しても、化学赤色バナジウム先媒染ウール布帛、化学緑色バナジウム先媒染ウール布帛、および化学青色バナジウム先媒染ウール布帛と、媒染も染色もしていないウール布帛の温度差の平均値は、光照射１０分後で１６．５℃、光照射停止１分後で６．４℃であった。すなわち、化学赤色バナジウム先媒染ウール布帛、化学緑色バナジウム先媒染ウール布帛、および化学青色バナジウム先媒染ウール布帛は、高い光吸収発熱保温性能を示した。また、化学赤色バナジウム同時媒染ウール布帛も、同様の高い光吸収発熱保温性能を示した。硫酸バナジル水溶液と化学染料の混合溶液による染色を行っても発熱保温効果が得られることは、染色工程の一元化による染色コスト低減につながる。 As shown in FIGS. 8 to 10, even if the vanadium mordant wool cloth is dyed with the three primary colors of chemical dyes, the chemical red vanadium mordant wool cloth, the chemical green vanadium mordant wool cloth, and the chemical blue vanadium mordant wool cloth are used. The average value of the temperature difference of the wool fabric that was neither mordanted nor dyed was 16.5 ° C. 10 minutes after light irradiation and 6.4 ° C. 1 minute after the light irradiation was stopped. That is, the chemically red vanadium pre-mordanted wool fabric, the chemically green vanadium pre-mordanted wool fabric, and the chemically blue vanadium pre-mordanted wool fabric showed high light absorption, heat generation and heat retention performance. In addition, the chemically red vanadium simultaneous mordant wool fabric also showed the same high light absorption, heat generation and heat retention performance. The fact that the heat-retaining effect can be obtained even when dyeing with a mixed solution of vanadyl sulfate aqueous solution and chemical dye leads to reduction of dyeing cost by unifying the dyeing process.
化学赤色バナジウム先媒染ウール布帛、化学緑色バナジウム先媒染ウール布帛、および化学青色バナジウム先媒染ウール布帛と、バナジウム媒染剤と赤色の化学染料を含む染色剤で同時媒染した化学赤色バナジウム同時媒染ウール布帛（表中に「ｍｉｘｅｄ」の記載あり）のＬ＊値、ａ＊値、およびｂ＊値を表３に示す。 Chemical red vanadium pre-mordanting wool cloth, chemical green vanadium pre-mordanting wool cloth, and chemical blue vanadium pre-mordanting wool cloth, and chemical red vanadium co-mordanting wool cloth co-mordanted with a dye containing a vanadium medium dye and a red chemical dye (Table). Table 3 shows the L * value, a * value, and b * value of (with the description of "mixed" in it).
化学赤色バナジウム同時媒染ウール布帛は、化学赤色バナジウム先媒染ウール布帛と比べて、染色コストの低減化が可能であるが、Ｌ＊値が若干下がり、黄色味を示すｂ＊値も低下している。これより、同時媒染では、明度の低い紫系に染色されており、布帛の色彩と色相の調色が必要となってくると考えられる。明度の低い紫系に染色されるのは、媒染剤のバナジウム高濃度によるバナジウム由来の着色が要因であると考えられる。 The chemical red vanadium co-mordanting wool fabric can reduce the dyeing cost as compared with the chemical red vanadium pre-mordanting wool fabric, but the L * value is slightly lower and the b * value indicating yellowness is also lower. .. From this, it is considered that the simultaneous mordanting is dyed in a purple system with low lightness, and it is necessary to adjust the color and hue of the fabric. It is considered that the reason why the purple color is dyed with low lightness is the coloration derived from vanadium due to the high concentration of vanadium in the mediator.
本発明によれば、化学染料による染色を用いることで繊維のカラーバリエーションが豊富になり、黒色に限定されずに耐光性の高い染料の選択肢が増加する。従来の炭化ジルコニウムを用いた繊維の染色方法では、染料が練り込みできる樹脂系繊維に限定され、また色彩も灰色から黒系に限定されていた。また、天然染料による染色では、黒色または緑色以外の繊維は耐光性が低い。一方、本発明では、天然素材への媒染によって、様々な色相や色彩に対応可能である。 According to the present invention, by using dyeing with a chemical dye, the color variation of the fiber is abundant, and the choice of dye having high light resistance is increased without being limited to black. The conventional method for dyeing fibers using zirconium carbide is limited to resin fibers that can be kneaded with dyes, and the color is also limited to gray to black. In addition, when dyed with natural dyes, fibers other than black or green have low light resistance. On the other hand, in the present invention, various hues and colors can be dealt with by mordanting a natural material.
以上より、ウール布帛にバナジウムを付着することによって、高い光吸収発熱保温性能が得られることが明らかになった。バナジウムの付着はウール布帛のみならずシルクやナイロンにも可能で、さらに改質することでセルロース系素材にも適用できる。したがって、様々な天然素材に光吸収発熱保温機能を持たせることができると考えられる。バナジウム先媒染繊維は、化学染料で様々な色相や色彩に染色しても光吸収発熱保温性能が発揮される。特殊な波長カットフィルターを用いて光照射した光吸収発熱保温性能試験の結果、その効果は近赤外線領域におけるバナジウムの光吸収によるものであり、紫外線領域におけるバナジウムの光吸収の寄与は小さいと考えられる。 From the above, it was clarified that high light absorption, heat generation and heat retention performance can be obtained by adhering vanadium to the wool fabric. Vanadium can be attached not only to wool fabrics but also to silk and nylon, and by further modification, it can be applied to cellulosic materials. Therefore, it is considered that various natural materials can be provided with a light absorption heat generation heat retention function. Vanadium pre-mordanting fibers exhibit light absorption, heat generation and heat retention performance even when dyed in various hues and colors with chemical dyes. As a result of the light absorption heat generation heat retention performance test irradiating with light using a special wavelength cut filter, the effect is due to the light absorption of vanadium in the near infrared region, and it is considered that the contribution of vanadium light absorption in the ultraviolet region is small. ..
炭化ジルコニウムも２０００ｎｍ以下の近赤外線領域に吸収を持つことが知られている。バナジウムも同様の作用で光吸収発熱保温性を示すものと推察される。バナジウムは、特に１０００ｎｍ等の２０００ｎｍ付近よりも短波長側における近赤外線領域の光吸収が発熱保温性効果に寄与していると考えられる。バナジウムは、天然素材への導入が可能である点、少量で効果が非常に高い点、およびカラーバリエーションを任意に選べる点で、媒染物質として優れている。 Zirconium carbide is also known to have absorption in the near infrared region of 2000 nm or less. It is presumed that vanadium also exhibits light absorption, heat generation, and heat retention by the same action. For vanadium, it is considered that the light absorption in the near-infrared region on the shorter wavelength side than the vicinity of 2000 nm such as 1000 nm contributes to the heat insulating effect. Vanadium is excellent as a mordant in that it can be introduced into natural materials, it is very effective with a small amount, and the color variation can be arbitrarily selected.
〔樹脂を含む複合体〕
親水性溶媒に溶ける樹脂としてポリビニルアルコール（ＰＶＡ）を用い、光吸収発熱保温用複合体であるバナジウム含有ＰＶＡフィルムを作製した。ＰＶＡは無色透明のため、染料と複合化することで様々な色のバナジウム含有ポリビニルアルコールフィルムを作製することができる。純水２００ｍＬにＰＶＡ（ｎ＝１５００〜１８００、和光純薬工業株式会社）１０ｇを加えて溶かした。硫酸バナジル・ｎ水和物（鹿特級、関東化学株式会社）０．４ｇをさらに加え（ＶＯＳＯ４濃度０．１９％）、沸騰しない温度の５０〜８０℃に保ちながら１時間攪拌した。
[Complex containing resin]
Polyvinyl alcohol (PVA) was used as a resin soluble in a hydrophilic solvent to prepare a vanadium-containing PVA film which is a composite for heat absorption and heat insulation. Since PVA is colorless and transparent, vanadium-containing polyvinyl alcohol films of various colors can be produced by combining with a dye. To 200 mL of pure water, 10 g of PVA (n = 1500-1800, Wako Pure Chemical Industries, Ltd.) was added and dissolved. Further, 0.4 g of vanadyl sulfate n-hydrate (Deer Special Grade, Kanto Chemical Co., Inc.) was further added (VOSO 4 concentration 0.19%), and the mixture was stirred for 1 hour while maintaining a non-boiling temperature of 50 to 80 ° C.
加熱と攪拌をやめ、室温で１時間静置して気泡を取り除いた。樹脂溶液の上部に形成された樹脂固形分を取り除いた。水平な金属板上に水溶液を静かにキャストし、樹脂溶液を薄く伸ばした。乾燥機で４０℃、２０時間、キャストした樹脂溶液を加熱および乾燥した後、放冷して樹脂フィルムを形成した。金属板から樹脂フィルムを剥がし取り、バナジウム含有ＰＶＡフィルムを得た。得られたバナジウム含有ＰＶＡフィルムは、従来の光発熱材料のＺｒＣまたはＶＯ２の無機粒子が分散されているＰＶＡフィルムと異なり、高い透明性を備えていた。無機粒子が分散されているＰＶＡフィルムは、無機粒子が光を散乱して、艶消し効果が発現するためだと考えられる。 The heating and stirring were stopped, and the mixture was allowed to stand at room temperature for 1 hour to remove air bubbles. The resin solid content formed on the upper part of the resin solution was removed. The aqueous solution was gently cast on a horizontal metal plate and the resin solution was spread thinly. The cast resin solution was heated and dried in a dryer at 40 ° C. for 20 hours, and then allowed to cool to form a resin film. The resin film was peeled off from the metal plate to obtain a vanadium-containing PVA film. Vanadium-containing PVA film obtained is different from the PVA film ZrC or VO 2 of the inorganic particles of the conventional light heat generating material is dispersed, it was equipped with high transparency. It is considered that the PVA film in which the inorganic particles are dispersed is due to the inorganic particles scattering light and exhibiting a matting effect.
以下のようにして、ＰＶＡフィルムとバナジウム含有ＰＶＡフィルムの各試料の光吸収発熱保温性能試験を行った。発砲スチロール製試料台の上に、一辺が５ｃｍの正方形板状の各試料を置き、試料から３０ｃｍの距離に写真用レフランプ（パナソニック、ＰＲＦ−５００ＷＢ／Ｄ）を設置して光を照射した。実験室の温度は２０℃で、相対湿度は６５％であった。光照射中、一定時間毎に赤外線サーモグラフィで温度を測定した。その後、レフランプを消灯した状態でも、一定時間毎に温度を測定した。試料の表面温度は、非接触小型放射温度計（ＮＥＣ Ａｖｉｏ赤外線テクノロジー（株）、赤外線サーモグラフィ ＩｎｆＲｅＣ Ｔｈｅｒｍｏ ＧＥＡＲ Ｇ１００）を用いて、放射率Ｅ＝０．９４で測定した。試料面から約４５°の方向で、７０ｃｍの距離に放射温度計を設置して温度測定した。 The light absorption heat generation heat retention performance test of each sample of the PVA film and the vanadium-containing PVA film was carried out as follows. Each of the square plate-shaped samples having a side of 5 cm was placed on a foamed styrene sample table, and a photographic reflamp (Panasonic, PRF-500WB / D) was installed at a distance of 30 cm from the sample to irradiate the light. The laboratory temperature was 20 ° C. and the relative humidity was 65%. During light irradiation, the temperature was measured by infrared thermography at regular intervals. After that, even when the ref lamp was turned off, the temperature was measured at regular intervals. The surface temperature of the sample was measured at an emissivity of E = 0.94 using a small non-contact radiation thermometer (NEC Avio Infrared Technology Co., Ltd., Infrared Thermography InfReC Thermo GEAR G100). A radiation thermometer was installed at a distance of 70 cm in a direction of about 45 ° from the sample surface to measure the temperature.
レフランプ点灯から２７０秒後、ＰＶＡフィルムおよびバナジウム含有ＰＶＡフィルムの表面到達温度は、それぞれ３９．４℃および４３．６℃であった。また、レフランプ消灯から６０秒後、ＰＶＡフィルムおよびバナジウム含有ＰＶＡフィルムの表面到達温度は、それぞれ３０．８℃および３５．６℃であった。このように、バナジウム含有ＰＶＡフィルムは、光を吸収して、大きく発熱および保温した。なお、ウール布帛の比熱と比べてＰＶＡフィルムの比熱が小さいので、バナジウム含有ＰＶＡフィルムは、バナジウム媒染ウール布帛よりも、光を吸収して発熱および保温する程度が低かった。 After 270 seconds from turning on the ref lamp, the surface temperature of the PVA film and the vanadium-containing PVA film reached 39.4 ° C and 43.6 ° C, respectively. Further, 60 seconds after the ref lamp was turned off, the surface temperature reached of the PVA film and the vanadium-containing PVA film was 30.8 ° C. and 35.6 ° C., respectively. As described above, the vanadium-containing PVA film absorbed light and greatly generated heat and kept warm. Since the specific heat of the PVA film is smaller than that of the wool cloth, the vanadium-containing PVA film absorbs light to generate heat and retains heat less than the vanadium mordant wool cloth.
同様の方法で、バナジウム含有ＰＶＡフィルムと、ＶＯＳＯ４粒子が分散されているポリ塩化ビニルフィルム（ＶＯＳＯ４分散ＰＶＣフィルム）が、光を吸収して発熱および保温する程度を比べた。なお、ＶＯＳＯ４分散ＰＶＣは、濃度１．６％となるようにポリ塩化ビニル溶液にＶＯＳＯ４を混合し、減圧脱泡しながら硬化させて得た。レフランプ点灯から２７０秒後、ＶＯＳＯ４分散ＰＶＣフィルムおよびバナジウム含有ＰＶＡフィルムの表面到達温度は、それぞれ４０．６℃および４３．０℃であった。 In the same manner, the degree to which the vanadium-containing PVA film and the polyvinyl chloride film in which VOSO 4 particles were dispersed (VOSO 4 dispersed PVC film) absorbed light to generate heat and retain heat was compared. Incidentally, VOSO 4 dispersed PVC is mixed VOSO 4 polyvinyl chloride solution to a concentration of 1.6% was obtained by curing with vacuum degassing. After 270 seconds from turning on the ref lamp, the surface reaching temperatures of the VOSO 4- dispersed PVC film and the vanadium-containing PVA film were 40.6 ° C and 43.0 ° C, respectively.
また、レフランプ消灯から６０秒後、ＶＯＳＯ４分散ＰＶＣフィルムおよびバナジウム含有ＰＶＡフィルムの表面到達温度は、それぞれ３２．１℃および３５．４℃であった。ＶＯＳＯ４分散ＰＶＣフィルムは、バナジウム含有ＰＶＡフィルムよりバナジウム濃度が高かったにも関わらず、バナジウム含有ＰＶＡフィルムより保温の程度が低かった。このように、機能性粒子が樹脂中に分散している複合体よりも、本実施例のような樹脂の官能基にバナジウムが化学結合している複合体の方が、透明性と、光を吸収して発熱および保温する程度が高かった。 Further, 60 seconds after the ref lamp was turned off, the surface reaching temperatures of the VOSO 4- dispersed PVC film and the vanadium-containing PVA film were 32.1 ° C and 35.4 ° C, respectively. Although the VOSO 4- dispersed PVC film had a higher vanadium concentration than the vanadium-containing PVA film, the degree of heat retention was lower than that of the vanadium-containing PVA film. As described above, the complex in which vanadium is chemically bonded to the functional group of the resin as in this example has more transparency and light than the complex in which the functional particles are dispersed in the resin. The degree of absorption, heat generation and heat retention was high.
本発明の光吸収発熱保温用複合体またはその製造方法は、発色機能および／または光を熱エネルギーに変換する機能を有するので、温熱機能付きのビニールハウス用ビニールシート、色素増感太陽電池、化粧品、ヘアカラー、繊維の染色、漆の塗膜、ＣＤ−ＲやＤＶＤ−Ｒの記録層の色素、コピー機のトナー用色素、ボールペンのインク、インクジェットプリンタの染料インクなどに利用できる。 Since the light-absorbing heat-retaining composite of the present invention or a method for producing the same has a color-developing function and / or a function of converting light into heat energy, a vinyl sheet for a vinyl house with a heat function, a dye-sensitized solar cell, and a cosmetic product. It can be used for hair coloring, dyeing of fibers, lacquer coating, dyes for recording layers of CD-R and DVD-R, dyes for toners of copiers, inks for ball pens, dye inks for inkjet printers, and the like.
Claims (4)
前記樹脂が、デンプン、ゼラチン、カルボキシメチルセルロース、メチルセルロース、レゾール型フェノール樹脂、メチロール化ユリア樹脂、メチロール化メラミン樹脂、ポリビニルアルコール、ポリアクリル酸系ポリマー、およびポリエチレンオキシドの少なくとも一種である光吸収発熱保温用複合体。 Oite to claim 1,
Wherein the resin is a starch, gelatin, carboxymethyl cellulose, methyl cellulose, resol type phenolic resins, methylolated urea resin, methylolated melamine resin, polyvinyl alcohol, polyacrylic acid polymer, the light absorbing heat generating warmth is at least one contact and polyethylene oxide Complex for .
前記親水性溶媒が水である光吸収発熱保温用複合体。 In claim 1 or 2 ,
A light-absorbing heat-retaining complex in which the hydrophilic solvent is water.
前記光が近赤外光である光吸収発熱保温用複合体。 In any of claims 1 to 3 ,
A light-absorbing heat-retaining complex in which the light is near-infrared light.
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