JP2005224312A - Heating sheet - Google Patents
Heating sheet Download PDFInfo
- Publication number
- JP2005224312A JP2005224312A JP2004034145A JP2004034145A JP2005224312A JP 2005224312 A JP2005224312 A JP 2005224312A JP 2004034145 A JP2004034145 A JP 2004034145A JP 2004034145 A JP2004034145 A JP 2004034145A JP 2005224312 A JP2005224312 A JP 2005224312A
- Authority
- JP
- Japan
- Prior art keywords
- sheet
- exothermic
- heat
- heat generating
- molded body
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Abstract
Description
本発明は、空気中の酸素と被酸化性金属との酸化反応に伴う発熱を利用した発熱シート及びこれを用いたシート状発熱成形体に関する。 The present invention relates to a heat generating sheet using heat generated by an oxidation reaction between oxygen in air and an oxidizable metal, and a sheet-like heat-generating molded body using the heat generating sheet.
空気中の酸素と被酸化性金属との酸化反応に伴う発熱を利用した発熱シートに関し、本出願人は、下記特許文献１に記載の薄型の発熱シートについて先に提案している。この発熱シートは、厚さが極めて薄いにもかかわらず発熱体として優れた発熱特性を有しているとともに、生産性に優れている。また、従来の粉体を用いた発熱体と比較してシートからの構成成分の脱落が少ないことを特徴としている。 The present applicant has previously proposed a thin heat generating sheet described in Patent Document 1 below, which relates to a heat generating sheet using heat generated by an oxidation reaction between oxygen in the air and an oxidizable metal. The heat generating sheet has excellent heat generation characteristics as a heat generating element despite its extremely small thickness, and is excellent in productivity. Further, it is characterized in that the constituent components are less dropped from the sheet as compared with a heating element using a conventional powder.
ところで、斯かる発熱シートは、用途によっては、使用時に即座に高い温度が発現することが望まれる場合がある。 By the way, depending on the application, it may be desired that such a heat generating sheet immediately develop a high temperature.
本発明は、薄くて、使用時に即座に発熱を感じられる等の発熱特性特に優れる発熱シート及びこれ用いたシート状発熱成形体に関する。 The present invention relates to a heat-generating sheet that is thin and particularly excellent in heat-generating properties such as immediate heat generation during use, and a sheet-like heat-generating molded body using the same.
本発明は、被酸化性金属、活性炭及び繊維状物を含む発熱中間シートに、電解質及び水を含ませた発熱シートであって、前記活性炭の平均粒径が１〜２０μｍであり、前記発熱中間シートの坪量１００ｇ／ｍ2当たりの透気度が３〜３０秒／６．４ｃｍ2・３００ｍｌ）である発熱シートを提供するものである。 The present invention is a heat generation sheet in which an electrolyte and water are included in an exothermic intermediate sheet containing an oxidizable metal, activated carbon and a fibrous material, wherein the activated carbon has an average particle size of 1 to 20 μm, and the exothermic intermediate An exothermic sheet having an air permeability of 3 to 30 seconds / 6.4 cm 2 · 300 ml per 100 g / m 2 basis weight of the sheet is provided.
また、本発明は、前記本発明の発熱シートの少なくとも片面に通気性シートが配されているシート状発熱成形体を提供するものである。 The present invention also provides a sheet-like exothermic molded body in which a breathable sheet is disposed on at least one side of the heat generating sheet of the present invention.
本発明によれば、薄くて発熱特性に優れた発熱シート及びこれを用いたシート状発熱成形体が提供される。 ADVANTAGE OF THE INVENTION According to this invention, the heat_generation | fever sheet | seat which was thin and excellent in heat_generation | fever characteristics and a sheet-like heat_generation | fever molded object using the same are provided.
以下本発明を、その好ましい実施形態に基づき図面を参照しながら説明する。 The present invention will be described below based on preferred embodiments with reference to the drawings.
図１は、本発明のシート状発熱成形体の一実施形態を示すものである。図１において、符号１はシート状発熱成形体を示している。 FIG. 1 shows an embodiment of the sheet-like exothermic molded body of the present invention. In FIG. 1, the code | symbol 1 has shown the sheet-like exothermic molded object.
図１に示すように、シート状発熱成形体１は、被酸化性金属、活性炭及び繊維状物を含む発熱シート（以下、後述する電解質成分が含まれていない場合を発熱中間シート、電解質成分と水が含まれている場合を発熱シートという。）２の両面に通気性シート３が積層されている。
As shown in FIG. 1, a sheet-like exothermic molded body 1 includes a heat-generating sheet containing an oxidizable metal, activated carbon, and a fibrous material (hereinafter referred to as a heat-generating intermediate sheet, an electrolyte component when an electrolyte component described later is not included). The case where water is contained is referred to as a heat generating sheet.)
シート状発熱成形体１は、その坪量が５０〜３０００ｇ／ｍ2であることが好ましく、１００〜１５００ｇ／ｍ2であることがより好ましい。該坪量が５０ｇ／ｍ2以上であると被酸化性金属等の中でも比重の大きな材を使用する場合等においても、特に安定したシートを形成することができる点で好ましい。また、該坪量が３０００ｇ／ｍ2を以下であると軽くて使用感に優れる上に、生産性や操業性等の点でも好ましい。 Sheet heating the molded body 1, preferably has a basis weight of 50~3000g / m 2, and more preferably 100 to 1500 g / m 2. When the basis weight is 50 g / m 2 or more, even when using a material having a large specific gravity among oxidizable metals and the like, it is preferable in that a stable sheet can be formed. Further, when the basis weight is 3000 g / m 2 or less, it is light and excellent in feeling of use, and is also preferable in terms of productivity and operability.
シート状発熱成形体１は、発熱到達温度が３０〜１００℃であることが好ましく、３５〜９０℃であることがより好ましい。ここで、発熱到達温度は、シート状発熱成形体を構成する発熱シートから５０ｍｍ×５０ｍｍの試験片を切り出した後、該シート状発熱成形体を構成する通気シートと非透湿シートとを両側に袋状に貼り合わせて包装した後、容積４．２リットル、相対湿度１％以下の環境下で密封系内に５リットル／ｍｉｎの乾燥空気を供給可能な試験機を準備し、その内部に前記透湿シート側を上面として静置して発熱させたときの発熱シートの下側の温度を熱電対で測定した値である。シート状発熱成形体１の発熱到達温度は、商品用途によって急激な発熱が必要な場合や比較的低温で長時間の持続が必要な商品等、前述の配合組成ならびに、通気シートの透湿度（ＪＩＳ Ｚ２０８で測定される透湿度、以下、本明細書において、単に透湿度という。）の組み合わせにより任意に設計ができる。 The sheet-like exothermic molded body 1 preferably has an exothermic temperature of 30 to 100 ° C, and more preferably 35 to 90 ° C. Here, the heat generation attainable temperature is determined by cutting a 50 mm × 50 mm test piece from the heat generating sheet constituting the sheet-like exothermic molded body and then placing the air-permeable sheet and non-moisture permeable sheet constituting the sheet-like exothermic molded body on both sides. After bonding and packaging in a bag shape, a tester capable of supplying dry air of 5 liters / min into a sealed system in an environment of a volume of 4.2 liters and a relative humidity of 1% or less is prepared. It is the value which measured with the thermocouple the temperature of the lower side of the heat generating sheet when it stood still with the moisture permeable sheet side as the upper surface to generate heat. The heat generation temperature of the sheet-like exothermic molded body 1 is the above-described blending composition and the moisture permeability of the ventilation sheet (JIS), such as products that require rapid heat generation depending on the product application or products that need to be maintained at a relatively low temperature for a long time. The design can be arbitrarily made by a combination of moisture permeability measured by Z208, hereinafter referred to simply as moisture permeability.
シート状発熱成形体１は、水蒸気発生量が、０．１〜１００ｍｇ／(ｃｍ2・１０ｍｉｎ)であることが好ましく、１〜５０ｍｇ／(ｃｍ2・１０ｍｉｎ)であることがより好ましい。本明細書において、水蒸気発生量というときは、例えば、以下のように測定される値をいう。 The sheet-like exothermic molded body 1 preferably has a water vapor generation amount of 0.1 to 100 mg / (cm 2 · 10 min), and more preferably 1 to 50 mg / (cm 2 · 10 min). In the present specification, the term “water vapor generation amount” refers to, for example, a value measured as follows.
容積４．２リットル、湿度１ＲＨ％以下とし、密閉系内に５リットル／ｍｉｎの乾燥空気を供給可能な試験機を準備し、その内部に水蒸気が蒸散可能なようにシートを静置して発熱させる。そして、前記密閉系内に排出される空気の湿度を湿度計で想定し、下記式（１）を用いて発熱開始後に発生する水蒸気量を求め、単位時間当たりの水蒸気量とした。そして、１０分間の累積値を蒸気発生量として求めた。ここで、ｅは水蒸気圧（Ｐａ）、ｅｓは飽和水蒸気圧（Ｐａ：ＪＩＳ Ｚ８８０６より引用）、Ｔは温度（℃：乾球温度）、ｓはサンプリング周期（秒）である。
相対湿度Ｕ（％ＲＨ）＝（ｅ／ｅｓ）×100
絶対湿度Ｄ（ｇ／ｍ3）＝（0.794×10-2×ｅ）／（１＋0.00366Ｔ）
＝（0.794×10-2×Ｕ×ｅｓ）／〔100×（１＋0.00366Ｔ）〕
単位空気容積Ｐ（リットル）＝（2.1×ｓ）／60
単位時間当たりの水蒸気量Ａ（ｇ）＝（Ｐ×Ｄ）／1000・・・（１）
Prepare a tester with a volume of 4.2 liters and a humidity of 1 RH% or less and capable of supplying 5 liters / min of dry air in a closed system. Let And the humidity of the air discharged | emitted in the said closed system was assumed with the hygrometer, the amount of water vapor | steam generated after the start of heat_generation | fever was calculated | required using following formula (1), and it was set as the amount of water vapor | steam per unit time. And the cumulative value for 10 minutes was calculated | required as a steam generation amount. Here, e is a water vapor pressure (Pa), es is a saturated water vapor pressure (Pa: quoted from JIS Z8806), T is a temperature (° C .: dry bulb temperature), and s is a sampling period (seconds).
Relative humidity U (% RH) = (e / es) × 100
Absolute humidity D (g / m 3 ) = (0.794 × 10 −2 × e) / (1 + 0.00366T)
= (0.794 × 10 -2 × U × es) / [100 × (1 + 0.00366T)]
Unit air volume P (liter) = (2.1 x s) / 60
Amount of water vapor per unit time A (g) = (P × D) / 1000 (1)
シート状発熱成形体１の水蒸気発生量は、発熱到達時間と同様に商品用途によって急激な発熱が必要な場合や比較的低温で長時間の持続が必要な商品等、前述の配合組成並びに通気シートの組み合わせにより任意に設計ができる。 The amount of water vapor generated in the sheet-like exothermic molded body 1 is the same as that of the above-described blending composition and breathable sheet, such as when the heat generation requires sudden heat generation as well as the heat generation arrival time, or products that require a relatively long time at a relatively low temperature. Any combination can be designed.
前記発熱中間シート２に含まれる前記被酸化性金属には、従来からこの種の発熱成形体に通常用いられている被酸化性金属を特に制限無く用いることができる。該被酸化性金属の形態は、取り扱い性、成形性等の観点から粉体、繊維状の形態を有するものを用いることが好ましい。 As the oxidizable metal contained in the exothermic intermediate sheet 2, an oxidizable metal conventionally used in this type of exothermic molded body can be used without particular limitation. As the form of the oxidizable metal, it is preferable to use a form having a powdery or fibrous form from the viewpoint of handleability and moldability.
粉体の形態を有する被酸化性金属としては、例えば、鉄粉、アルミニウム粉、亜鉛粉、マンガン粉、マグネシウム粉、カルシウム粉等が挙げられ、これらの中でも取り扱い性、安全性、製造コストの点から鉄粉が好ましく用いられる。該被酸化性金属には、後述の繊維状物への定着性、反応のコントロールが良好なことから粒径（以下、粒径というときには、粉体の形態における最大長さ、又は動的光散乱法、レーザー回折法等により測定される平均粒径をいう。）が０．１〜３００μｍのものを用いることが好ましく、粒径が０．１〜１５０μｍものを５０重量％以上含有するものを用いることがより好ましい。 Examples of the oxidizable metal having a powder form include iron powder, aluminum powder, zinc powder, manganese powder, magnesium powder, and calcium powder. Among these, handling property, safety, and manufacturing cost are included. Iron powder is preferably used. The oxidizable metal has a particle size (hereinafter referred to as the particle size, the maximum length in the form of powder, or dynamic light scattering because the fixability to a fibrous material and control of the reaction are good. The average particle diameter measured by a method, a laser diffraction method, etc.) is preferably 0.1 to 300 μm, and the one having a particle diameter of 0.1 to 150 μm containing 50% by weight or more is used. It is more preferable.
また、繊維状の形態を有する被酸化性金属としては、スチール繊維、アルミ繊維、マグネシウム繊維等が挙げられる。これらのなかでも取り扱い性、安全性、製造コストの点からスチール繊維、アルミ繊維等が好ましく用いられる。繊維状の形態を有する被酸化性金属は、成形性や得られるシートの機械的強度、表面の平滑性、発熱性能の点から繊維長０．１〜５０ｍｍ、太さ１〜１０００μｍのものを用いることが好ましい。 Examples of the oxidizable metal having a fibrous form include steel fibers, aluminum fibers, and magnesium fibers. Among these, steel fibers, aluminum fibers, and the like are preferably used from the viewpoints of handleability, safety, and manufacturing cost. As the oxidizable metal having a fibrous form, a fiber having a fiber length of 0.1 to 50 mm and a thickness of 1 to 1000 μm is used in terms of formability, mechanical strength of the obtained sheet, surface smoothness, and heat generation performance. It is preferable.
前記発熱中間シート２中の前記被酸化性金属の配合量は、１０〜９５重量％であることが好ましく、３０〜８０重量％であることがより好ましい。該配合量が１０重量％以上であると、得られるシート状発熱成形体１の発熱温度を、人が指先等で触って熱く感じる程度以上に上昇させることができ、発熱シート２を構成する後述の繊維状物、接着成分（凝集剤等）の量を抑えることができるため、成形体の通気性が十分なものとなり、その結果成形体内部まで十分に反応が起こり発熱温度を十分に上昇させることができる。また、発熱時間を十分な長さにできるほか、活性炭による水分供給も十分なものとすることができ、被酸化性金属の脱落も生じ難い。また、成形体を構成する後述の繊維状物、接着性分をある程度の量に維持することができるため、曲げ強度や引張強度等の機械的強度を十分なものとすることができる。ここで、発熱中間シート２中の被酸化性金属の配合量は、ＪＩＳ Ｐ８１２８に準じる灰分試験や、熱重量測定器で求めることができる。他に例えば、鉄の場合は外部磁場を印加すると磁化が生じる性質を利用して振動試料型磁化測定試験等により定量することができる。 The blending amount of the oxidizable metal in the exothermic intermediate sheet 2 is preferably 10 to 95% by weight, and more preferably 30 to 80% by weight. When the blending amount is 10% by weight or more, the exothermic temperature of the obtained sheet-like exothermic molded body 1 can be increased to a level that a person feels hot by touching with a fingertip or the like. The amount of fibrous materials and adhesive components (flocculant, etc.) can be suppressed, so that the molded body has sufficient air permeability, and as a result, the reaction sufficiently occurs inside the molded body to sufficiently raise the heat generation temperature. be able to. Further, the heat generation time can be made sufficiently long, the water supply by activated carbon can be made sufficient, and the oxidizable metal does not easily fall off. In addition, since the fibrous material and adhesiveness described later constituting the molded body can be maintained at a certain amount, mechanical strength such as bending strength and tensile strength can be made sufficient. Here, the compounding amount of the oxidizable metal in the exothermic intermediate sheet 2 can be determined by an ash test according to JIS P8128 or a thermogravimetric measuring instrument. In addition, for example, in the case of iron, it can be quantified by a vibration sample type magnetization measurement test or the like using the property that magnetization occurs when an external magnetic field is applied.
前記活性炭は、水分保持剤として働く他に、被酸化性金属への酸素保持／供給剤としての機能も有している。該活性炭としては、例えば、椰子殻炭、木炭粉、暦青炭、泥炭、亜炭が挙げられる。該活性炭には、本発明における発熱特性を得る上で被酸化性金属との有効な接触状態を形成できる点から平均粒径が１〜２０μｍ、特に２〜１８μｍであり、比表面積が３００〜２０００ｍ2／ｇ、特に５００〜１５００ｍ2／ｇである粉体状のものを用いることが好ましい。活性炭の平均粒径の測定法には、レーザー回折／散乱式測定方法、光散乱式測定法、レーザー回折式測定法、遠心沈降式測定法などがあるが、その中でも、試料の因子が少なく幅広い測定範囲を持つことから、レーザー回折／散乱式測定方法を用いるのが好ましい。また、比表面積は、ＢＥＴ法により測定される。活性炭には、粒径が１〜２０μｍものを５０重量％以上含有するものを用いることが好ましい。活性炭には、上述のような粉体状以外の形態のものを用いることもでき、例えば、活性炭繊維等の繊維状の形態のものを用いることもできる。 In addition to functioning as a moisture retention agent, the activated carbon also has a function as an oxygen retention / supply agent for oxidizable metals. Examples of the activated carbon include coconut shell charcoal, charcoal powder, calendar bituminous coal, peat, and lignite. The activated carbon has an average particle diameter of 1 to 20 μm, particularly 2 to 18 μm, and a specific surface area of 300 to 2000 m from the viewpoint that an effective contact state with an oxidizable metal can be formed in obtaining heat generation characteristics in the present invention. It is preferable to use a powdery material having a density of 2 / g, particularly 500 to 1500 m 2 / g. Methods for measuring the average particle size of activated carbon include laser diffraction / scattering measurement methods, light scattering measurement methods, laser diffraction measurement methods, and centrifugal sedimentation measurement methods. It is preferable to use a laser diffraction / scattering measurement method because it has a measurement range. The specific surface area is measured by the BET method. It is preferable to use activated carbon containing 50% by weight or more of particles having a particle size of 1 to 20 μm. The activated carbon may be in a form other than the powder form as described above, for example, a fibrous form such as activated carbon fiber may be used.
発熱中間シート２中の前記活性炭の配合量は、０．５〜６０重量％であることが好ましく、１〜５０重量％であることがより好ましい。該配合量が０．５重量％以上であると、被酸化性金属が酸化反応により人体温度以上に温度上昇する程度に反応を持続させるために必要な水分をシート状発熱成形体１中に蓄積できる。また、シート状発熱成形体１の通気性が十分に確保されるため、酸素供給が十分に得られて発熱効率が高い発熱成形体となる。該配合量が６０重量％以下であると、得られる発熱量に対するシート状発熱成形体１の熱容量を小さく抑えることができるため、発熱温度上昇が大きくなり、人が温かいと体感できる温度上昇が得られる。また、活性炭の脱落の発生や発熱シート２を構成する後述の繊維状物、接着成分の減少が抑えられるため、曲げ強度や引張強度等の機械的強度も十分に得られる。 The amount of the activated carbon in the exothermic intermediate sheet 2 is preferably 0.5 to 60% by weight, and more preferably 1 to 50% by weight. When the blending amount is 0.5% by weight or more, moisture necessary for the oxidizable metal to continue the reaction to such an extent that the temperature rises above the human body temperature due to the oxidation reaction is accumulated in the sheet-like exothermic molded body 1. it can. Further, since the air permeability of the sheet-like exothermic molded body 1 is sufficiently ensured, the oxygen supply is sufficiently obtained and the exothermic molded body has high heat generation efficiency. When the blending amount is 60% by weight or less, the heat capacity of the sheet-like exothermic molded body 1 with respect to the obtained calorific value can be kept small, so that the exothermic temperature rises greatly, and a temperature rise that can be experienced when a person is warm is obtained. It is done. Moreover, since generation | occurrence | production of fallen of activated carbon and the reduction | decrease of the fibrous material and the adhesive component mentioned later which comprise the heat_generation | fever sheet | seat 2 are suppressed, mechanical strength, such as bending strength and tensile strength, is fully obtained.
前記繊維状物としては、例えば、天然繊維状物としては植物繊維（コットン、カボック、木材パルプ、非木材パルプ、落花生たんぱく繊維、とうもろこしたんぱく繊維、大豆たんぱく繊維、マンナン繊維、ゴム繊維、麻、マニラ麻、サイザル麻、ニュージーランド麻、羅布麻、椰子、いぐさ、麦わら等）、動物繊維（羊毛、やぎ毛、モヘア、カシミア、アルカパ、アンゴラ、キャメル、ビキューナ、シルク、羽毛、ダウン、フェザー、アルギン繊維、キチン繊維、ガゼイン繊維等）、鉱物繊維（石綿等）が挙げられ、合成繊維状物としては、例えば、半合成繊維（アセテート、トリアセテート、酸化アセテート、プロミックス、塩化ゴム、塩酸ゴム等）、金属繊維、炭素繊維、ガラス繊維等が挙げられる。また、高密度ポリエチレン、中密度ポリエチレン、低密度ポリエチレン、ポリプロピレン等のポリオレフィン、ポリエステル、ポリ塩化ビニリデン、デンプン、ポリビニルアルコール若しくはポリ酢酸ビニル又はこれらの共重合体若しくは変性体等の単繊維、又はこれらの樹脂成分を鞘部に有する芯鞘構造の複合繊維を用いることができる。そしてこれらの中でも、繊維どうしの接着強度が高く、繊維どうしの融着による三次元の網目構造を作り易すく、パルプ繊維の発火点よりも融点が低い点からポリオレフィン、変性ポリエステルが好ましく用いられる。また、枝分かれを有するポリオレフィン等の合成繊維も被酸化性金属や活性炭との定着性が良好なことから好ましく用いられる。これらの繊維は、単独で又は二種以上を組み合わせて用いることができる。また、これらの繊維は、その回収再利用品を用いることもできる。そして、これらの中でも、前記被酸化性金属、前記活性炭の定着性、得られるシート状発熱成形体の柔軟性、空隙の存在からくる酸素透過性、製造コスト等の点から、木材パルプ、コットンが好ましく用いられる。 Examples of the fibrous material include, for example, vegetable fibers (cotton, kabok, wood pulp, non-wood pulp, peanut protein fiber, corn protein fiber, soy protein fiber, mannan fiber, rubber fiber, hemp, and Manila hemp. , Sisal, New Zealand hemp, Rafu hemp, eggplant, rush, straw, etc.), animal fiber (wool, goat hair, mohair, cashmere, alkapa, Angola, camel, vicuña, silk, feathers, down, feather, algin fiber, chitin Fiber, casein fiber, etc.) and mineral fiber (asbestos, etc.). Examples of synthetic fibers include semi-synthetic fibers (acetate, triacetate, oxide acetate, promix, chlorinated rubber, hydrochloric acid rubber, etc.), metal fibers , Carbon fiber, glass fiber and the like. Also, polyolefins such as high density polyethylene, medium density polyethylene, low density polyethylene, polypropylene, etc., polyester, polyvinylidene chloride, starch, polyvinyl alcohol or polyvinyl acetate, single fibers such as copolymers or modified products thereof, or these A core-sheath composite fiber having a resin component in the sheath can be used. Among these, polyolefins and modified polyesters are preferably used because they have high adhesive strength between fibers, are easy to form a three-dimensional network structure by fusion of fibers, and have a melting point lower than the ignition point of pulp fibers. Synthetic fibers such as polyolefin having branches are also preferably used because of their good fixability to oxidizable metals and activated carbon. These fibers can be used alone or in combination of two or more. In addition, these fibers can be used in the form of collected and reused. Among these, wood pulp and cotton are used in terms of the oxidizable metal, the fixing property of the activated carbon, the flexibility of the obtained sheet-like exothermic molded product, the oxygen permeability resulting from the presence of voids, the production cost, and the like. Preferably used.
前記繊維状物は、そのＣＳＦ（Ｃａｎａｄｉａｎ Ｓｔａｎｄａｒｄ Ｆｒｅｅｎｅｓｓ）が、６００ｍｌ以下であることが好ましく、４５０ｍｌ以下であることがより好ましい。６００ｍｌ以下であると繊維状物と前記被酸化性金属や活性炭等の成分との定着性も十分に良好であり、所定の配合量を保持でき発熱性能を十分に発揮させることができる。また、均一な厚みのシートが得られ、繊維状物と該成分との定着が良好となり、該成分の脱落がし難く、該成分と該繊維状物との絡み合いや水素結合に由来する結合強度を持たせることができる。また、曲げ強度や引張強度等の機械的強度も十分なものとすることができ、加工性も良好である。 The fibrous material preferably has a CSF (Canadian Standard Freeness) of 600 ml or less, and more preferably 450 ml or less. When the amount is 600 ml or less, the fixing property between the fibrous material and the components such as the oxidizable metal and activated carbon is sufficiently good, and the predetermined blending amount can be maintained and the heat generation performance can be sufficiently exhibited. In addition, a sheet having a uniform thickness is obtained, the fixing between the fibrous material and the component is good, the component is difficult to fall off, and the bond strength derived from the entanglement between the component and the fibrous material or hydrogen bonding Can be given. Further, the mechanical strength such as bending strength and tensile strength can be sufficient, and the workability is also good.
前記繊維状物のＣＳＦは、低い程好ましいが、通常のパルプ繊維のみの抄紙では、繊維状物以外の成分比率が低い場合、ＣＳＦが１００ｍｌ以上であると濾水性が十分に良好であり、脱水も十分に行うことができ均一な厚みの発熱シートが得られ、乾燥時にブリスター破れが生じず成形性も良好となる。本発明においては、繊維状物以外の成分比率が高いことから、濾水性も良好で均一な厚みの発熱シートを得ることができる。また、ＣＳＦが低い程、フィブリルが多くなるため、繊維状物と該繊維状物以外の成分との定着性が良好となり、高いシート強度を得ることができる。
繊維状物のＣＳＦの調整は、叩解処理などによって行うことができる。ＣＳＦの低い繊維と高い繊維とを混ぜ合わせ、ＣＳＦの調整を行っても良い。
The lower the CSF of the fibrous material, the better. However, in the case of normal pulp fiber-only papermaking, when the component ratio other than the fibrous material is low, the drainage is sufficiently good when the CSF is 100 ml or more, and dehydration. Can be sufficiently performed, and a heat-generating sheet having a uniform thickness is obtained, and blister breakage does not occur during drying, and the moldability is improved. In the present invention, since the ratio of components other than the fibrous material is high, it is possible to obtain a heat generating sheet with good drainage and uniform thickness. Further, since the CSF is lower as the CSF is lower, the fixability between the fibrous material and components other than the fibrous material is improved, and a high sheet strength can be obtained.
Adjustment of the CSF of the fibrous material can be performed by a beating process or the like. CSF may be adjusted by mixing low and high CSF fibers.
前記繊維状物は、そのゼータ電位がマイナス（負）であることが好ましい。ここで、ゼータ電位とは、荷電粒子界面と溶液間のずり面におけるみかけの電位をいい、流動電位法、電気泳動法等により測定される。そのゼータ電位がマイナスであると、繊維状物への前記被酸化性金属や活性炭等の成分の定着が良好であり、所定の配合量を保持できて発熱性能が優れたものとなるほか、排水に多量の該成分が混じることを抑えることができ、生産性、環境保全にも悪影響を及ぼすことがない。 The fibrous material preferably has a negative (negative) zeta potential. Here, the zeta potential is an apparent potential at the shear plane between the charged particle interface and the solution, and is measured by a streaming potential method, an electrophoresis method or the like. When the zeta potential is negative, the components such as the oxidizable metal and activated carbon are well fixed to the fibrous material, and the predetermined blending amount can be maintained and the heat generation performance is excellent. It is possible to prevent a large amount of the component from being mixed with the product, and it does not adversely affect productivity and environmental conservation.
該繊維状物には、平均繊維長が０．１〜５０ｍｍのものを用いることが好ましく、０．２〜２０ｍｍのものを用いることがより好ましい。該平均繊維長を斯かる範囲とすることで、得られる発熱シートの曲げ強度や引張強度等の機械的強度が十分に確保できるほか、繊維層が密になりすぎず発熱シートの通気性が良好となり、酸素供給が良好で発熱性に優れるものとなる。また、発熱シート中に該繊維状物を均一に分散できるため、一様な機械的強度が得られるほか、均一な肉厚の発熱シートが得られる。また、繊維間隔が広くなりすぎず、繊維による前記被酸化性金属や活性炭等の成分の保持能力が維持されて該成分が脱落し難くなる。 The fibrous material preferably has an average fiber length of 0.1 to 50 mm, and more preferably 0.2 to 20 mm. By setting the average fiber length in such a range, the mechanical strength such as bending strength and tensile strength of the resulting heat generating sheet can be sufficiently secured, and the air permeability of the heat generating sheet is good without the fiber layer becoming too dense. Thus, the oxygen supply is good and the heat generation is excellent. Further, since the fibrous material can be uniformly dispersed in the heat generating sheet, uniform mechanical strength can be obtained, and a heat generating sheet having a uniform thickness can be obtained. In addition, the fiber spacing does not become too wide, and the retention capability of the components such as the oxidizable metal and activated carbon by the fibers is maintained, so that the components are difficult to fall off.
発熱中間シート２中の前記繊維状物の配合量は、２〜５０重量％であることが好ましく、５〜４０重量％であることがより好ましい。該配合量が２重量％以上であると、被酸化性金属や活性炭等の成分の脱落を十分に防止できるほか、発熱シートを十分なものにすることができる。該配合量が５０重量％以下であると、発熱成形体の発熱量に対する熱容量を抑えることができ、温度上昇を十分なものとすることができるほか、得られるシート状発熱成形体１中の該成分の比率をある程度以上に確保できるため、所望の発熱性能を十分に得ることができるので好ましい。 The blending amount of the fibrous material in the exothermic intermediate sheet 2 is preferably 2 to 50% by weight, and more preferably 5 to 40% by weight. When the blending amount is 2% by weight or more, it is possible to sufficiently prevent the components such as the oxidizable metal and activated carbon from falling off and to make the heat generating sheet sufficient. When the blending amount is 50% by weight or less, the heat capacity with respect to the heat generation amount of the exothermic molded body can be suppressed, the temperature rise can be made sufficient, and the obtained exothermic molded body 1 in the sheet-like exothermic molded body 1 can be obtained. Since the ratio of the components can be secured to a certain level or more, the desired heat generation performance can be sufficiently obtained, which is preferable.
前記発熱中間シート２中の前記被酸化性金属と前記活性炭との含有量の比は、好ましくは被酸化性金属：活性炭＝４５：１〜０．３：１（重量比率）、より好ましくは被酸化性金属：活性炭＝２０：１〜１：１であり、発熱中間シート中の前記被酸化性金属と保水材の合計含有率が５０〜９８重量％、より好ましくは６０〜９５重量％であることが好ましい。これらの成分の含有比が前記範囲であると、被酸化性金属の酸化効率が高く、シート状発熱成形体の発熱性能を効果的に向上させることができる。 The ratio of the content of the oxidizable metal and the activated carbon in the exothermic intermediate sheet 2 is preferably oxidizable metal: activated carbon = 45: 1 to 0.3: 1 (weight ratio), more preferably coated. Oxidizing metal: activated carbon = 20: 1 to 1: 1, and the total content of the oxidizable metal and the water retaining material in the exothermic intermediate sheet is 50 to 98% by weight, more preferably 60 to 95% by weight. It is preferable. When the content ratio of these components is within the above range, the oxidation efficiency of the oxidizable metal is high, and the heat generation performance of the sheet-like heat-emitting molded body can be effectively improved.
発熱中間シート２には、後述するように凝集剤が添加されていることが好ましい。
また、発熱シート２には、必要に応じ、サイズ剤、着色剤、紙力増強剤、歩留向上剤、填料、増粘剤、ｐＨコントロール剤、嵩高剤等の抄紙の際に通常用いられる添加物を特に制限無く添加することができる。該添加物の添加量は、添加する添加物に応じて適宜設定することができる。
It is preferable that a flocculant is added to the exothermic intermediate sheet 2 as described later.
In addition, the heat generating sheet 2 includes additives usually used for paper making such as a sizing agent, a colorant, a paper strength enhancer, a yield improver, a filler, a thickener, a pH control agent, and a bulking agent. The product can be added without any particular limitation. The addition amount of the additive can be appropriately set according to the additive to be added.
前記発熱中間シート２の一枚の厚みは、０．０８〜１．２ｍｍであることが好ましく、０．１〜０．６ｍｍであることがより好ましい。該厚みが０．０８ｍｍ以上であると、発熱性能、機械的強度、被酸化性金属や活性炭等の成分の定着が良好となり、安定した均一の肉厚、組成分布が得られるほか、ピンホールの発生等によるシートの破壊等が発生し難くなり、生産性及び加工性が良好となる。該厚みが１．２ｍｍ以下であると、シートの折曲強度を確保でき、脆性破壊を簡単に起こし難くなるほか、柔軟性も良好であり、特に肘、膝、顔等の身体部位の屈伸する部位に装着した場合、装着性が悪く違和感なく使用できる。また、生産性においても、紙層形成時間や乾燥時間の遅延が起こり難く、操業性も良好となる他、発熱性能が良好で、曲げ等の加工性にも優れる。
発熱中間シートは複数枚重ねて使用することができる。複数枚重ねることにより、必要とされる発熱性能を容易に実現できるようになると同時に、発熱体厚さが厚くても、フレキシブル性が高く、使用感の優れた発熱体を得ることができる。
The thickness of one exothermic intermediate sheet 2 is preferably 0.08 to 1.2 mm, and more preferably 0.1 to 0.6 mm. When the thickness is 0.08 mm or more, heat generation performance, mechanical strength, oxidizable metal, activated carbon, and other components are well fixed, and a stable and uniform thickness and composition distribution can be obtained. It becomes difficult for the sheet to be broken due to the occurrence, and the productivity and workability are improved. When the thickness is 1.2 mm or less, the bending strength of the sheet can be secured, and brittle fracture is not easily caused, and the flexibility is also good, particularly bending and stretching of body parts such as elbows, knees, and faces. When attached to a site, the wearability is poor and it can be used without a sense of incongruity. In terms of productivity, paper layer formation time and drying time are hardly delayed, operability is good, heat generation performance is good, and workability such as bending is also excellent.
A plurality of exothermic intermediate sheets can be used in piles. By superimposing a plurality of sheets, the required heat generation performance can be easily realized, and at the same time, even if the heat generation element is thick, a heat generation element with high flexibility and excellent usability can be obtained.
発熱中間シート２は、坪量１００ｇ／ｍ2当たりの透気度が３〜３０秒／６．４ｃｍ2・３００ｍｌであり、４〜２０秒／６．４ｃｍ2・３００ｍｌであることが好ましい。該透気度を斯かる範囲とすることによって、本発明における発熱特性を得る上の発熱反応が良好に進行するほか、後述するように電解液を添加する際にも、より均一に電解液を含ませることができる。本明細書において、透気度というときはＪＩＳ Ｐ８１１７で測定される透湿度をいう。 The exothermic intermediate sheet 2 has an air permeability per basis weight of 100 g / m 2 of 3 to 30 seconds / 6.4 cm 2 · 300 ml, and preferably 4 to 20 seconds / 6.4 cm 2 · 300 ml. By setting the air permeability within such a range, the exothermic reaction for obtaining exothermic characteristics in the present invention proceeds well, and the electrolyte solution can be more evenly added when the electrolyte solution is added as described later. Can be included. In this specification, the term “air permeability” refers to moisture permeability measured by JIS P8117.
発熱中間シート２は、一枚の坪量が１０〜１０００ｇ／ｍ2であることが好ましく、５０〜６００ｇ／ｍ2であることがより好ましい。該坪量が１０ｇ／ｍ2以上であると被酸化性金属等の中でも比重の大きなものを使用する場合等において、特に安定したシートを形成することができる。該坪量が１０００ｇ／ｍ2以下であると軽量で使用感が良好となり、生産性や操業性等も良好である。 Heating the intermediate sheet 2 is preferably one having a basis weight of 10 to 1000 g / m 2, and more preferably 50~600g / m 2. When the basis weight is 10 g / m 2 or more, a particularly stable sheet can be formed when an oxidizable metal having a large specific gravity is used. When the basis weight is 1000 g / m 2 or less, it is lightweight and has a good feeling of use, and productivity and operability are also good.
発熱中間シート２の裂断長は、１００〜４０００ｍであることが好ましく、２００〜３０００ｍであることがより好ましい。該裂断長が斯かる範囲内であると使用時ならびに生産・操業時での取り扱いが容易となるとともに、適度な通気性を有すために発熱シート中の被酸化性金属の酸化を有意に促進することができる。ここで、裂断長は、発熱中間シートから長さ１５０ｍｍ×幅１５ｍｍの試験片を切り出した後、ＪＩＳ Ｐ８１１３に準じ、該試験片をチャック間隔１００ｍｍで引っ張り試験機に装着し、引っ張り速度２０ｍｍ／ｍｉｎで引っ張り試験を行い、下記計算式により算出される値である。
裂断長〔ｍ〕＝（1/9.8)×（引張強さ〔Ｎ/ｍ〕）×106／（試験片坪量〔g/m2〕）
The breaking length of the exothermic intermediate sheet 2 is preferably 100 to 4000 m, and more preferably 200 to 3000 m. When the breaking length is within such a range, handling during use and production / operation is facilitated, and in order to have appropriate air permeability, oxidation of the oxidizable metal in the heat generating sheet is significantly increased. Can be promoted. Here, the tearing length is determined by cutting a test piece of length 150 mm ×
Breaking length [m] = (1 / 9.8) × (Tensile strength [N / m]) × 10 6 / (Test piece basis weight [g / m 2 ])
発熱シート２に含まれる前記電解質には、従来からこの種の発熱成形体に通常用いられている電解質を特に制限なく用いることができる。該電解質としては、例えば、アルカリ金属、アルカリ土類金属若しくは重金属の硫酸塩、炭酸塩、塩化物又は水酸化物等が挙げられる。そしてこれらの中でも、導電性、化学的安定性、生産コストに優れる点から塩化ナトリウム、塩化カリウム、塩化カルシウム、塩化マグネシウム、塩化鉄（第１、第２）等の各種塩化物が好ましく用いられる。これらの電解質は、単独で又は二種以上を組み合わせて用いることもできる。 As the electrolyte contained in the heat generating sheet 2, an electrolyte that has been conventionally used for this type of exothermic molded body can be used without particular limitation. Examples of the electrolyte include alkali metal, alkaline earth metal or heavy metal sulfates, carbonates, chlorides or hydroxides. Among these, various chlorides such as sodium chloride, potassium chloride, calcium chloride, magnesium chloride, and iron chloride (first and second) are preferably used from the viewpoint of excellent conductivity, chemical stability, and production cost. These electrolytes can be used alone or in combination of two or more.
発熱シート２中の前記電解質の配合量は、発熱シート２中の水重量比で０．５〜３０重量％であることが好ましく、１〜２５重量％であることがより好ましい。該配合量が０．５重量％以上であると、得られるシート状発熱成形体１の酸化反応を十分に進行させることができるため好ましい。該配合量が３０重量％以下であると電解質の析出も起こりが難く、シート状発熱成形体１の通気性が良好であり、発熱機能に必要な電解質を確保することができ、十分な水が被酸化性金属等に供給され、発熱性能に優れ、シート状発熱成形体１に均一に電解質を配合することができるので好ましい。 The amount of the electrolyte in the heat generating sheet 2 is preferably 0.5 to 30% by weight, more preferably 1 to 25% by weight in terms of the weight ratio of water in the heat generating sheet 2. The blending amount of 0.5% by weight or more is preferable because the oxidation reaction of the obtained sheet-like exothermic molded body 1 can sufficiently proceed. When the blending amount is 30% by weight or less, precipitation of the electrolyte hardly occurs, the air permeability of the sheet-like exothermic molded body 1 is good, the electrolyte necessary for the heat generating function can be secured, and sufficient water is provided. It is preferable because it is supplied to an oxidizable metal or the like, has excellent heat generation performance, and can uniformly mix an electrolyte with the sheet-like exothermic molded body 1.
発熱シート２は、含水率（重量含水率、以下同じ。）が５〜８０％であることが好ましく、１０〜６０％であることがより好ましい。該含水率が５％以上であると酸化反応を持続するために必要な水分が十分に確保でき、酸化反応が途中で終了してしまうことを抑えることができるほか、シート状発熱成形体１に均一に水分を供給することができるため、均一な発熱性能を得ることができる。該含水率が８０％以下であると得られるシート状発熱成形体１の発熱量に対する熱容量を低く抑えることができ、発熱温度を十分に上昇させることができるほか、シート状発熱成形体１の通気性が十分に得られるため、発熱性能に優れるとともに、保形性や機械的強度も十分に得られる。 The heat generating sheet 2 preferably has a moisture content (weight moisture content, hereinafter the same) of 5 to 80%, and more preferably 10 to 60%. When the water content is 5% or more, it is possible to sufficiently secure moisture necessary for continuing the oxidation reaction, and to prevent the oxidation reaction from being terminated in the middle. Since moisture can be supplied uniformly, uniform heat generation performance can be obtained. When the water content is 80% or less, the heat capacity of the sheet-like exothermic molded body 1 obtained can be kept low, the heat generation temperature can be sufficiently increased, and the air flow of the sheet-like exothermic molded body 1 can be increased. Therefore, the heat generation performance is excellent, and the shape retention and mechanical strength are sufficiently obtained.
発熱シート２の一枚の坪量は、１０〜２０００ｇ／ｍ2であり、５０〜１５００ｇ／ｍ2であることが好ましく、１００〜１０００ｇ／ｍ2であることがより好ましい。該坪量が１０ｇ／ｍ2以上であると被酸化性金属等の中でも比重の大きなものを使用する場合等において、特に安定したシートを形成することができる。該坪量が２０００ｇ／ｍ2以下であると軽量で使用感が良好となり、生産性や操業性等も良好である。 Single basis weight of the heat generating sheet 2 is 10 to 2000 g / m 2, is preferably 50 to 1500 g / m 2, and more preferably 100 to 1000 g / m 2. When the basis weight is 10 g / m 2 or more, a particularly stable sheet can be formed when an oxidizable metal having a large specific gravity is used. When the basis weight is 2000 g / m 2 or less, it is lightweight and has a good feeling of use, and productivity and operability are also good.
発熱シート２は、発熱到達温度が３０〜１００℃であることが好ましく、３５〜９０℃であることがより好ましい。発熱シート２の発熱到達温度は、例えば、後述する実施例の測定方法により測定される。商品用途に応じ、前述の配合組成の組み合わせにより任意に設計ができる。 The exothermic sheet 2 preferably has an exothermic temperature of 30 to 100 ° C, and more preferably 35 to 90 ° C. The heat generation arrival temperature of the heat generating sheet 2 is measured by, for example, a measuring method of an example described later. Depending on the product application, it can be arbitrarily designed by a combination of the above-mentioned blending compositions.
発熱シート２は、人が暖かいと体感できる温度に５分以内、好ましくは４分以内に到達することができる。 The heat generating sheet 2 can reach a temperature at which a person can feel when it is warm within 5 minutes, preferably within 4 minutes.
発熱シート２は、水蒸気発生量が、０.１〜１００ｍｇ／(ｃｍ2・１０ｍｉｎ)であることが好ましく、１〜５０ｍｇ／(ｃｍ2・１０ｍｉｎ)であることがより好ましい。発熱シート２の水蒸気発生量は、発熱到達時間と同様に商品用途に応じ、前述の配合組成の組み合わせにより任意に設計ができる。 The heat generating sheet 2 preferably has a water vapor generation amount of 0.1 to 100 mg / (cm 2 · 10 min), and more preferably 1 to 50 mg / (cm 2 · 10 min). The amount of water vapor generated in the exothermic sheet 2 can be arbitrarily designed according to the combination of the above-described blending compositions, depending on the product use as well as the heat generation arrival time.
前記通気性シート３は、透湿度が５００ｇ／(ｍ2・２４ｈ)以上であり、８００〜１００００ｇ／(ｍ2・２４ｈ)であることが好ましく、１０００〜８０００ｇ／(ｍ2・２４ｈ)であることがより好ましい。透湿度がこのような範囲にあると酸素の供給がスムーズになり、すばやい発熱と水蒸気の発生を可能とする。通気性シート３は、その全面に通気性を有していてもよく、部分的に通気性を有していてもよい。
The
通気性シート３は、坪量が１０〜２００ｇ／ｍ2であることが好ましく、２０〜１００ｇ／ｍ2であることがより好ましい。通気性シート３の坪量がこのような範囲であると、薄くて、フレキシブル性を損なわず、発熱シート２の柔らかさを損なわないものとなるほか、すばやい発熱を発現することができ、且つ、水蒸気の発生も期待することができる。
The
通気性シート３としては、ポリエチレン、ポリプロピレン等のポリオレフィンやポリエステル、ポリアミド、ポリウレタン、ポリスチレン、ポリエチレン−酢酸ビニル共重合体等の樹脂からなるシートに機械的に孔を形成させたもの、前記樹脂と無機フィラーの混合シートを延伸により界面剥離させ微孔を設けたもの、また、その結晶構造の界面剥離を利用し、微孔を形成させたもの、発泡成形による連続気泡を利用し微孔を連通させたものなどが挙げられる。また、ポリオレフィン等の合成パルプ、木材パルプ、レーヨン、アセテート等の半合成繊維、ビニロン繊維、ポリエステル繊維等から形成された不織布、織布、合成紙、紙等が挙げられる。通気性シート３は複数枚を重ねて用いることもできる。
The
次に、シート状発熱成形体１の製造方法について説明する。
シート状発熱成形体１の製造に際しては、先ず、前記被酸化性金属、前記活性炭、前記繊維状物、及び水を含む原料組成物（スラリー）を調製し、該原料組成物から前記発熱中間シート２を抄紙により成形することが好ましい。
Next, the manufacturing method of the sheet-like exothermic molded object 1 is demonstrated.
In producing the sheet-like exothermic molded body 1, first, a raw material composition (slurry) containing the oxidizable metal, the activated carbon, the fibrous material, and water is prepared, and the exothermic intermediate sheet is prepared from the raw material composition. 2 is preferably formed by papermaking.
該原料組成物には、前記凝集剤を添加することが好ましい。
該凝集剤としては、硫酸バンド、ポリ塩化アルミニウム、塩化第二鉄、ポリ硫酸第二鉄、硫酸第一鉄等の金属塩からなる無機凝集剤；ポリアクリルアミド系、ポリアクリル酸ナトリウム系、ポリアクリルアミドのマンニッヒ変性物、ポリ（メタ）アクリル酸アミノアルキルエステル系、カルボキシメチルセルロースナトリウム系、キトサン系、デンプン系、ポリアミドエピクロヒドリン系等の高分子凝集剤；ジメチルジアリルアンモニウムクロライド系若しくはエチレンイミン系のアルキレンジクロライドとポリアルキレンポリアミンの縮合物、ジシアンジアミド・ホルマリン縮合物等の有機凝結剤；モンモリロナイト、ベントナイト等の粘土鉱物；コロイダルシリカ等の二酸化珪素若しくはその水和物；タルク等の含水ケイ酸マグネシウム等が挙げられる。そして、これら凝集剤の中でもシートの表面性、地合い形成、成形性の向上、被酸化性金属や活性炭等の材の定着率、紙力向上の点からアニオン性のコロイダルシリカやベントナイト等とカチオン性のデンプンやポリアクリルアミド等の併用やアニオン性のカルボキシメチルセルロースナトリウム塩やポリアクリルアミドとカチオン性のポリアミドエピクロルヒドリン系やポリアクリルアミド等のカチオン性とアニオン性の薬剤の併用が特に好ましい。上述の組み合わせ以外でも、これらの凝集剤は単独で又は二種以上を併用することもできる。
The flocculant is preferably added to the raw material composition.
Examples of the flocculant include inorganic flocculants composed of metal salts such as sulfate band, polyaluminum chloride, ferric chloride, polyferric sulfate, and ferrous sulfate; polyacrylamide, sodium polyacrylate, polyacrylamide Mannich modified products, poly (meth) acrylic acid aminoalkyl ester-based, carboxymethylcellulose sodium-based, chitosan-based, starch-based, polyamide epichlorohydrin-based polymer flocculants; dimethyldiallylammonium chloride-based or ethyleneimine-based Organic coagulants such as condensates of alkylene dichloride and polyalkylene polyamines, dicyandiamide / formalin condensates; clay minerals such as montmorillonite and bentonite; silicon dioxide such as colloidal silica or hydrates thereof; hydrous magnesium silicate such as talc And the like. Of these flocculants, anionic colloidal silica, bentonite, and the like are cationic in terms of sheet surface properties, texture formation, improved formability, fixing rate of materials such as oxidizable metals and activated carbon, and paper strength. Of these, starch, polyacrylamide, and the like, and anionic carboxymethylcellulose sodium salt, polyacrylamide and cationic polyamide epichlorohydrin, and cationic and anionic agents such as polyacrylamide are particularly preferred. Besides these combinations, these flocculants may be used alone or in combination of two or more.
前記凝集剤の添加量は、原料組成物の固形分に対して、０．０１〜５重量％であることが好ましく、０．０５〜１重量％であることがより好ましい。０．０１重量％以上であると、凝集効果に優れ、抄紙時の被酸化性金属や活性炭等の成分の脱落も抑えることができ原料組成物が均一となり、肉厚及び組成の均一な発熱シートを得ることができる点で優れている。該添加量が５重量％以下であると、乾燥時の乾燥ロールに貼り付き、破れ、焼け、焦げ等の発生を抑えることができ、生産性に優れ、原料組成物の電位バランスを良好に保ち、抄紙時の白水への該成分の脱落量も抑えることができる点で優れている。また、発熱シートの酸化反応が進行し、発熱特性や強度等の保存安定性に優れる。 The amount of the flocculant added is preferably 0.01 to 5% by weight, more preferably 0.05 to 1% by weight, based on the solid content of the raw material composition. When the content is 0.01% by weight or more, the coagulation effect is excellent, the falling off of components such as oxidizable metals and activated carbon during papermaking can be suppressed, the raw material composition becomes uniform, and the heat generating sheet has a uniform thickness and composition. It is excellent in that it can be obtained. When the added amount is 5% by weight or less, it is possible to suppress the occurrence of tearing, burning, scorching, etc., sticking to a drying roll during drying, excellent productivity, and maintaining a good potential balance of the raw material composition. This is excellent in that the amount of the component dropped into the white water during papermaking can be suppressed. Moreover, the oxidation reaction of the exothermic sheet proceeds, and the storage stability such as exothermic characteristics and strength is excellent.
前記原料組成物の濃度は、０．０５〜１０重量％が好ましく、０．１〜２重量％がより好ましい。該濃度が０．０５重量％以上であると大量の水を必要とせず、発熱シートの成形に長時間を要せず、均一な厚みの発熱シートを成形することができる点で好ましい。該濃度が１０重量％以下であると原料組成物の分散状態も良好であり、得られるシートの表面性にも優れ、均一な厚みのシートが得られる点で優れている。 The concentration of the raw material composition is preferably 0.05 to 10% by weight, and more preferably 0.1 to 2% by weight. A concentration of 0.05% by weight or more is preferable in that a large amount of water is not required, and it is not necessary to form a heat generating sheet for a long time, and a heat generating sheet having a uniform thickness can be formed. When the concentration is 10% by weight or less, the dispersion state of the raw material composition is good, the surface property of the obtained sheet is excellent, and the sheet having a uniform thickness is obtained.
次に、前記原料組成物を抄紙して前記発熱中間シートを成形する。
前記発熱中間シートの抄紙方法には、例えば、連続抄紙式である円網抄紙機、長網抄紙機、ヤンキー抄紙機、ツインワイヤー抄紙機などを用いた抄紙方法、バッチ方式の抄紙方法である手漉法等が挙げられる。更に、前記原料組成物と、該原料組成物と異なる組成の組成物とを用いた複層抄き合わせによって発熱中間シートを成形することもできる。また、前記原料組成物を抄紙して得られた発熱中間シートどうしを複層に貼り合わせたり、該発熱中間シートに該原料組成物と異なる組成を有する組成物から得られたシート状物を貼り合わせることによって発熱中間シートを成形することもできる。
Next, the raw material composition is made to form the exothermic intermediate sheet.
Examples of the paper making method for the heat generating intermediate sheet include a paper making method using a continuous paper making type circular paper making machine, a long paper making machine, a Yankee paper making machine, a twin wire paper making machine, and a batch type paper making method. For example, there is an acupuncture method. Furthermore, an exothermic intermediate sheet can also be formed by multilayer lamination using the raw material composition and a composition having a composition different from the raw material composition. Also, the exothermic intermediate sheets obtained by papermaking the raw material composition are laminated together in multiple layers, or a sheet-like material obtained from a composition having a composition different from the raw material composition is attached to the exothermic intermediate sheet. An exothermic intermediate sheet can also be formed by combining them.
前記発熱中間シートは、抄紙後における形態を保つ（保形性）点や、機械的強度を維持する点から、含水率（重量含水率、以下同じ。）が７０％以下となるまで脱水させることが好ましく、６０％以下となるまで脱水させることがより好ましい。抄紙後の発熱中間シートの脱水方法は、例えば、吸引による脱水のほか、加圧空気を吹き付けて脱水する方法、加圧ロールや加圧板で加圧して脱水する方法等が挙げられる。 The exothermic intermediate sheet is dehydrated until the moisture content (weight moisture content, the same shall apply hereinafter) is 70% or less from the viewpoint of maintaining the form after paper making (shape retention) and maintaining the mechanical strength. Is preferable, and it is more preferable to dehydrate it to 60% or less. Examples of the method for dehydrating the exothermic intermediate sheet after papermaking include dewatering by suction, a method of dehydrating by blowing pressurized air, a method of dehydrating by pressing with a pressure roll or a pressure plate, and the like.
前記被酸化性金属（通常雰囲気下において加熱反応性を有する）を含有する発熱中間シートを、積極的に乾燥させて水分を分離することにより、製造工程中における被酸化性金属の酸化抑制、長期の保存安定性に優れた発熱中間シートを得ることが可能となる。さらに、乾燥後の前記繊維状物への被酸化性金属の担持力を高めてその脱落を抑える点に加え、熱溶融成分、熱架橋成分の添加による機械的強度の向上が期待できる点から、前記発熱中間シートの抄紙後で前記電解質の電解液を含有させる前に該発熱中間シートを乾燥させることが好ましい。 The exothermic intermediate sheet containing the oxidizable metal (having heat reactivity in a normal atmosphere) is actively dried to separate the moisture, thereby suppressing oxidation of the oxidizable metal during the manufacturing process, long-term It is possible to obtain an exothermic intermediate sheet having excellent storage stability. Furthermore, in addition to the point of increasing the supporting force of the oxidizable metal to the fibrous material after drying and suppressing its falling off, from the point of expectation of improvement in mechanical strength due to the addition of a hot melt component and a thermal crosslinking component, It is preferable that the exothermic intermediate sheet is dried after the exothermic intermediate sheet is formed and before the electrolytic electrolyte solution is contained.
前記発熱中間シートは、加熱乾燥によって乾燥することが好ましい。この場合、加熱乾燥温度は、６０〜３００℃であることが好ましく、８０〜２５０℃であることがより好ましい。発熱中間シートの加熱乾燥温度を斯かる温度範囲とすることで、乾燥時間を短くできるため、水分の乾燥に伴う被酸化性金属の酸化反応を抑えることができ、得られる発熱シートの発熱性の低下を防ぐことができる。また同時に、被酸化性金属が酸化する事によるシートの変色を防止することができる。さらに活性炭等の性能劣化を抑えることができるため、発熱シートの発熱効果を維持することができるほか、発熱中間シート内部で急激に水分が気化して発熱シートの構造が破壊されたりすることを防ぐことができる。 The exothermic intermediate sheet is preferably dried by heat drying. In this case, the heat drying temperature is preferably 60 to 300 ° C, more preferably 80 to 250 ° C. By setting the heating and drying temperature of the exothermic intermediate sheet to such a temperature range, the drying time can be shortened, so that the oxidation reaction of the oxidizable metal accompanying the drying of moisture can be suppressed, and the exothermic property of the resulting exothermic sheet can be reduced. Decline can be prevented. At the same time, discoloration of the sheet due to oxidation of the oxidizable metal can be prevented. Furthermore, since the performance deterioration of activated carbon, etc. can be suppressed, the heat generation effect of the heat generation sheet can be maintained, and the structure of the heat generation sheet can be prevented from being suddenly vaporized inside the heat generation intermediate sheet. be able to.
乾燥後における発熱中間シートの含水率は、２０％以下であることが好ましく、１０％以下であることがより好ましい。含水率が２０％以下であると長期保存安定性に優れ、例えば巻きロール状態で一時保存しておく場合等においても該ロールの厚み方向で水分の移動が起こり難く、発熱性能、機械的強度に変化がなく、優れている。 The moisture content of the exothermic intermediate sheet after drying is preferably 20% or less, and more preferably 10% or less. When the moisture content is 20% or less, excellent long-term storage stability, for example, even when temporarily stored in a wound roll state, moisture does not easily move in the thickness direction of the roll, and heat generation performance and mechanical strength are improved. No change and excellent.
前記発熱中間シートの乾燥方法は、当該発熱中間シートの厚さ、乾燥前の発熱中間シートの処理方法、乾燥前の含水率、乾燥後の含水率等に応じて適宜選択することができる。該乾燥方法としては、例えば、加熱構造体（発熱体）との接触、加熱空気や蒸気（過熱蒸気）の吹き付け、真空乾燥、電磁波加熱、通電加熱等の乾燥方法が挙げられる。また、前述の脱水方法と組み合わせて同時に実施することもできる。 The drying method of the exothermic intermediate sheet can be appropriately selected according to the thickness of the exothermic intermediate sheet, the processing method of the exothermic intermediate sheet before drying, the moisture content before drying, the moisture content after drying, and the like. Examples of the drying method include drying methods such as contact with a heating structure (heating element), spraying of heated air or steam (superheated steam), vacuum drying, electromagnetic wave heating, and electric heating. Moreover, it can also implement simultaneously with the above-mentioned dehydration method.
前記発熱中間シート２の成形（脱水、乾燥）は、不活性ガス雰囲気下で行うことが好ましいが、上述のように発熱中間シートに酸化助剤となる電解質を含有していないので、必要に応じて通常の空気雰囲気下で成形を行うこともできる。このため、製造設備を簡略化することができる。得られた発熱中間シートは、薄くて破れにくいので、必要に応じ、ロール状に巻き取ることができる。 The exothermic intermediate sheet 2 is preferably formed (dehydrated and dried) in an inert gas atmosphere. However, as described above, the exothermic intermediate sheet does not contain an electrolyte that serves as an oxidizing aid. The molding can also be performed in a normal air atmosphere. For this reason, manufacturing equipment can be simplified. Since the obtained exothermic intermediate sheet is thin and difficult to tear, it can be rolled up as necessary.
乾燥した発熱中間シート２には、必要に応じて、クレープ処理、スリット加工、トリミングを施したり、ニードルパンチ加工を行うことにより孔あけを行うこともできる。また、前記原料組成物に熱可塑性樹脂成分や熱水解成分を含有させることにより、ヒートシール加工を施して貼り合わせ等を行い易くすることもできる。 The dried exothermic intermediate sheet 2 may be pierced by creping, slitting, trimming, or needle punching as necessary. Moreover, by making the raw material composition contain a thermoplastic resin component or a hot water decomposing component, it is possible to perform heat sealing and facilitate bonding.
次に、乾燥した発熱中間シート２に前記層構成となるように、通気性シート３を積層させて複層化する。複層化とともにエンボス加工等によって凹凸の賦形を行ってもよい。
Next, the air-
次に、前記発熱中間シート２に、前記電解質を含有させる。この電解質を含有させる工程は、窒素、アルゴン等の不活性ガス雰囲気下で行うことが好ましいが、電解質をその電解液の含浸により添加する場合には、添加直後の酸化反応がゆるやかなため、通常の空気雰囲気下で該電解質を含有させることもできる。 Next, the exothermic intermediate sheet 2 contains the electrolyte. The step of containing the electrolyte is preferably performed in an inert gas atmosphere such as nitrogen or argon. However, when the electrolyte is added by impregnation with the electrolytic solution, the oxidation reaction immediately after the addition is gentle, The electrolyte may be contained in an air atmosphere.
前記発熱中間シートへ前記電解質を含有させる方法は、抄紙後における該発熱中間シートの処理方法、含水率、形態、複層化したシートの層構成等に応じて適宜設定することができる。該電解質を含有させる方法としては、例えば、前記発熱中間シートに、前記電解質の所定濃度の電解液を含浸させる方法、前記電解質の所定粒径のものを固体のまま添加して発熱中間シートに含有させる方法等が挙げられる。発熱中間シートに電解質を均一に含有させることができる点や含水率の調整が同時に行える点からは、所定濃度の電解液を含浸させる方法が好ましい。 The method of adding the electrolyte to the exothermic intermediate sheet can be appropriately set according to the processing method of the exothermic intermediate sheet after paper making, the moisture content, the form, the layer structure of the multilayered sheet, and the like. Examples of the method of containing the electrolyte include a method of impregnating the exothermic intermediate sheet with an electrolyte solution having a predetermined concentration of the electrolyte, and adding the electrolyte having a predetermined particle size as a solid to be contained in the exothermic intermediate sheet. And the like. From the standpoint that the electrolyte can be uniformly contained in the exothermic intermediate sheet and that the moisture content can be adjusted at the same time, a method of impregnating an electrolyte solution of a predetermined concentration is preferable.
上述のように前記電解質をその電解液で前記発熱中間シートに含浸させる場合、その含浸方法は、発熱中間シートの厚み等の形態、含水率に応じて適宜選択することができる。該含浸方法には、所定濃度の該電解液を該発熱中間シートにスプレー塗工する方法、該電解液をシリンジ等で該発熱中間シートの一部分に注入し、前記繊維状物の毛管現象を利用して該発熱中間シート全体に浸透させる方法、刷毛等で塗工する方法、該電解液に浸漬する方法、グラビアコート法、リバースコート法、ドクターブレード法等が挙げられ、これらの中でも、電解質を均一に分布でき、簡便で、設備コストも比較的少なくて済む点からスプレー塗工する方法が好ましい。また、複雑な形状、層構成の商品においては生産性が向上する点や、最終仕上げを別工程とできることにより生産のフレキシブル性が良好となる点、設備が簡便となる点からは、所定濃度の電解液をシリンジ等で注入する方法が好ましい。この電解液を注入する方法は、前記複層化したシートを所定の収容体に収容した後に行うこともできる。 As described above, when the exothermic intermediate sheet is impregnated with the electrolyte, the impregnation method can be appropriately selected according to the form such as the thickness of the exothermic intermediate sheet and the water content. The impregnation method includes a method of spray-coating the electrolyte solution of a predetermined concentration onto the exothermic intermediate sheet, and injecting the electrolyte solution into a part of the exothermic intermediate sheet with a syringe or the like, and utilizing the capillary action of the fibrous material And a method of penetrating the whole exothermic intermediate sheet, a method of coating with a brush, a method of immersing in the electrolytic solution, a gravure coating method, a reverse coating method, a doctor blade method, etc., among these, A spray coating method is preferable because it can be uniformly distributed, is simple, and requires relatively little equipment cost. In addition, in the case of products with complicated shapes and layer configurations, the concentration of the specified concentration is improved from the viewpoint that productivity is improved, the final finishing can be performed as a separate process, the production flexibility is improved, and the equipment is simplified. A method of injecting the electrolytic solution with a syringe or the like is preferable. This method of injecting the electrolytic solution can also be performed after the multilayered sheet is accommodated in a predetermined container.
上述のように発熱中間シートに電解質を含有させた後、必要に応じて含水率を調整し、安定化させてシート状発熱成形体１とする。そして必要に応じ、トリミング等の処理を施し、所定の大きさに加工することができる。得られたシート状発熱成形体１は、未使用状態では酸素不透過性の包装材で包装されて提供される。 After the electrolyte is contained in the exothermic intermediate sheet as described above, the moisture content is adjusted and stabilized as necessary to obtain a sheet-like exothermic molded body 1. Then, if necessary, it can be trimmed and processed into a predetermined size. The obtained sheet-like exothermic molded body 1 is provided by being packaged with an oxygen-impermeable packaging material in an unused state.
以上説明したように、本実施形態のシート状発熱成形体１は、前記組成を有し所定の裂断長の発熱シートの表裏に、通気性シートがそれぞれ積層されているため、使用を開始して直ぐに高い発熱性が得られ、しかも柔軟性にも優れている。また、構成材料の脱離を抑えることができる。 As described above, the sheet-like exothermic molded body 1 of the present embodiment is used because the breathable sheets are laminated on the front and back of the heat generating sheet having the above composition and having a predetermined tear length. High exothermic properties can be obtained immediately, and flexibility is also excellent. Further, detachment of the constituent material can be suppressed.
本発明は、前記実施形態に制限されるものではなく、本発明の趣旨を逸脱しない範囲において適宜変更することができる。 The present invention is not limited to the above-described embodiment, and can be modified as appropriate without departing from the spirit of the present invention.
また、本発明のシート状発熱成形体は、前記実施形態のように発熱シート２の表裏に通気性シートが積層されていることが好ましいが、通気性シートが片面にのみ積層されていてもよい。 Further, in the sheet-like exothermic molded body of the present invention, it is preferable that a breathable sheet is laminated on the front and back of the exothermic sheet 2 as in the above embodiment, but the breathable sheet may be laminated only on one side. .
以下、本発明の発熱シート及びシート状発熱成形体を実施例によりさらに具体的に説明する。
下記実施例１及び２並びに比較例１のようにして、表１に示す固形分含有組成の発熱中間シートを作製した。さらに、得られた発熱中間シートから下記のようにして発熱シート及びシート状発熱成形体を作製した。そして、得られた発熱中間シート、発熱シート及びシート状発熱成形体について、表１に示す各特性を下記のように測定して調べた。
Hereinafter, the heat generating sheet and the sheet-shaped heat generating molded body of the present invention will be described more specifically with reference to examples.
In the following Examples 1 and 2 and Comparative Example 1, exothermic intermediate sheets having a solid content-containing composition shown in Table 1 were prepared. Further, a heat-generating sheet and a sheet-like heat-formed body were produced from the obtained heat-generating intermediate sheet as follows. And about the obtained exothermic intermediate sheet, exothermic sheet, and sheet-like exothermic molded object, each characteristic shown in Table 1 was measured and examined as follows.
〔実施例１〕
＜原料組成物配合＞
被酸化性金属：鉄粉、同和鉱業株式会社製、商品名「ＲＫＨ」：７．５ｇ
繊維状物：パルプ繊維（フレッチャー チャレンジ カナダ社製、商品名 ＮＢＫＰ「Ｍａｃｋｅｎｚｉ（ＣＳＦ２００ｍｌに調整）」）：１．５ｇ
活性炭：平均粒径１０μｍ、ＢＥＴ比表面積１３００ｍ2／ｇ、（二村化学工業株式会社製、商品名「太閤ＳＡ１０００」）、１．０ｇ
凝集剤：ポリアミドエピクロロヒドリン樹脂（星光ＰＭＣ株式会社製、商品名「ＷＳ５５２」）０．１４ｇ
カルボキシメチルセルロースナトリウム（第一工業薬品株式会社製、商品名「セロゲン ＷＳ―Ｃ」、０．０１７ｇ
水：工業用水１５００ｇ
[Example 1]
<Combination of raw material composition>
Oxidizable metal: Iron powder, manufactured by Dowa Mining Co., Ltd., trade name “RKH”: 7.5 g
Fibrous material: Pulp fiber (Fletcher Challenge Canada, trade name NBKP “Mackenzi (adjusted to CSF 200 ml)”): 1.5 g
Activated carbon: average particle diameter of 10 μm, BET specific surface area of 1300 m 2 / g, (manufactured by Nimura Chemical Co., Ltd., trade name “Dazai SA1000”), 1.0 g
Flocculant: Polyamide epichlorohydrin resin (manufactured by Seiko PMC, trade name “WS552”) 0.14 g
Sodium carboxymethylcellulose (Daiichi Kogyo Seiyaku Co., Ltd., trade name “Serogen WS-C”, 0.017 g
Water: Industrial water 1500g
＜電解液＞
電解質：精製塩（ＮａＣｌ）
水：工業用水
電解液濃度：５．０質量％
<Electrolyte>
Electrolyte: Purified salt (NaCl)
Water: Industrial water Electrolyte concentration: 5.0% by mass
＜抄紙条件＞
上記原料組成物を３００ｒｐｍで１分間の撹拌条件で撹拌した。そして、ＪＩＳ Ｐ８２０９に準じて熊谷理機工業（株）製、標準角型シートマシンならびに８０ｍｅｓｈ抄紙ネットを用いて抄紙を行った。そして、熊谷理機工業（株）製、ＫＲＫ回転型乾燥機を用いて、含水率が１質量％以下となるように乾燥を行って発熱中間シートを得た。得られた発熱中間シートの組成を熱重量測定装置（セイコーインスツルメンツ社製、ＴＧ／ＤＴＡ６２００）を用いて測定した結果は表１−１に示した。
<Paper making conditions>
The raw material composition was stirred at 300 rpm for 1 minute. Then, according to JIS P8209, paper was made using Kumagaya Riki Kogyo Co., Ltd. standard square sheet machine and 80 mesh papermaking net. Then, using a KRK rotary dryer manufactured by Kumagai Riki Kogyo Co., Ltd., drying was performed so that the water content was 1% by mass or less, thereby obtaining an exothermic intermediate sheet. The results of measuring the composition of the obtained exothermic intermediate sheet using a thermogravimetric measuring device (TG / DTA 6200, manufactured by Seiko Instruments Inc.) are shown in Table 1-1.
＜発熱シートの作製＞
得られた発熱中間シートを５０ｍｍ×５０ｍｍに切り取り、発熱中間シートの重量に対し電解液量が３７．５％となるように、シリンジを用いて前記電解液を注入し、毛管現象を利用してシート全体に浸透させて発熱シートを得た。
<Preparation of exothermic sheet>
The obtained exothermic intermediate sheet was cut into 50 mm × 50 mm, and the electrolyte solution was injected using a syringe so that the amount of the electrolyte solution was 37.5% with respect to the weight of the exothermic intermediate sheet. The exothermic sheet was obtained by infiltrating the entire sheet.
<シート状発熱成形体の作製>
上記の発熱シートの上下に、下記の通気性シートと及び下記非通気シートを積層し、発熱シートの周りをヒートシールによって接合してシート状発熱体を作製した。
通気シート：ポリエチレン開孔シート、透湿度５０００ｇ/（ｍ2・２４ｈ）、坪量３６ｇ/ｍ2
非通気シート：ＰＥフィルム、坪量２０ｇ／ｍ2
非通気シートの表面材：ＰＥＴ／ＰＥ芯鞘繊維エアースルー不織布、坪量２０ｇ／ｍ2
<Preparation of sheet-like exothermic molded body>
The following air-permeable sheet and the following non-air-permeable sheet were laminated on the upper and lower sides of the above heat generating sheet, and the periphery of the heat generating sheet was joined by heat sealing to produce a sheet-like heating element.
Breathable sheet: polyethylene perforated sheet, water vapor transmission rate 5000 g / (m 2 · 24 h), basis weight 36 g / m 2
Non-breathable sheet: PE film, basis weight 20 g / m 2
Non-ventilated sheet surface material: PET / PE core-sheath fiber air-through nonwoven fabric, basis weight 20 g / m 2
〔実施例２〕
実施例１で用いた通気性シートならびに非通気シートを積層しない以外は、実施例１と同様にしてシート状発熱体を得た。
[Example 2]
A sheet-like heating element was obtained in the same manner as in Example 1 except that the breathable sheet and the non-vented sheet used in Example 1 were not laminated.
〔比較例１〕
下記の活性炭を用いた以外は、実施例１と同様にして発熱中間シート、発熱シート及びシート状発熱体を作製した。
活性炭：平均粒径２５μｍ、ＢＥＴ比表面積１２００ｍ2／ｇ、（二村化学工業株式会社製、商品名「太閤Ｍ」）
[Comparative Example 1]
A heat generating intermediate sheet, a heat generating sheet, and a sheet-shaped heating element were produced in the same manner as in Example 1 except that the following activated carbon was used.
Activated carbon:
〔発熱特性の評価〕
発熱シート又は電解質を含ませたシート状発熱成形体（５０×５０ｃｍ）を、容積４．２リットル、湿度１ＲＨ％以下とし、密封系内に２３℃の乾燥空気を５リットル／ｍｉｎで供給可能な試験機を準備し、その内部に前記透湿シート側を上面として静置して発熱させた。そして、当該発熱シートの下側の温度を熱電対で測定して発熱温度とした。
本評価においては、得られた最大温度と、人の体温を基準とした３６℃までの到達時間を評価対象とした。
[Evaluation of heat generation characteristics]
A heat-generating sheet or a sheet-like exothermic molded body (50 × 50 cm) containing an electrolyte has a volume of 4.2 liters and a humidity of 1 RH% or less, and 23 ° C. dry air can be supplied into the sealed system at 5 liters / min. A tester was prepared, and the moisture permeable sheet side was left as an upper surface in the tester to generate heat. And the temperature under the said heat_generation | fever sheet | seat was measured with the thermocouple, and it was set as the heat_generation | fever temperature.
In this evaluation, the maximum temperature obtained and the arrival time up to 36 ° C. on the basis of the human body temperature were evaluated.
表２及び図２に示すように、実施例のシート状発熱成形体は、比較例のものに比べ、３６℃以上の温度に短時間で到達した。特に、実施例１の発熱成形体は、活性炭の粒子径が小さいために被酸化金属の周囲に満遍なく活性炭が配置され、その活性炭が酸素を吸着することにより、被酸化金属により多くの酸素が供給されて酸化反応が促進されるので、最大温度も高く、当該最大温度にも素早く到達することが判った。 As shown in Table 2 and FIG. 2, the sheet-like exothermic molded body of the example reached a temperature of 36 ° C. or higher in a short time as compared with the comparative example. In particular, in the exothermic molded body of Example 1, activated carbon is evenly disposed around the metal to be oxidized because the particle diameter of the activated carbon is small, and the activated carbon adsorbs oxygen to supply more oxygen to the metal to be oxidized. Since the oxidation reaction is promoted, the maximum temperature is high, and the maximum temperature is reached quickly.
本発明の発熱シートは、薄く柔軟性を有し、短時間で高い発熱が得られる特性を利用することによって、例えば、おしぼり、蒸気発生体、パック等の顔、身体の洗浄、除菌、保湿、メイク落とし等のスキンケア用途、洗浄・除菌、ワックス徐放、芳香、消臭等の諸機能剤と組み合わせ、フローリング、畳み等の建物の内外装品及びインテリア用品や、レンジ周り、換気扇等の調理器具等の手入れといったいわゆるハウスケア用途、車等の洗浄、ワックスかけ等のカーケア用途にも適用することができる。 The heat-generating sheet of the present invention is thin and flexible, and uses the characteristics that can generate high heat in a short time, for example, wet hands, steam generators, packs and other faces, body washing, disinfection, moisturizing , Skincare applications such as makeup remover, cleaning / disinfecting, wax sustained release, aroma, deodorizing etc. in combination with functional agents such as flooring, folding, etc. The present invention can also be applied to so-called house care applications such as care for cooking utensils, car care applications such as car washing and waxing.
１ シート状発熱成形体
２ 発熱シート
３ 通気性シート
DESCRIPTION OF SYMBOLS 1 Sheet-like exothermic molded body 2
Claims (4)
前記活性炭の平均粒径が１〜２０μｍであり、
前記発熱中間シートの坪量１００ｇ／ｍ2当たりの透気度が３〜３０秒／（６．４ｃｍ2・３００ｍｌ）である発熱シート。 An exothermic sheet containing an electrolyte and water in an exothermic intermediate sheet containing an oxidizable metal, activated carbon and fibrous material,
The activated carbon has an average particle size of 1 to 20 μm,
An exothermic sheet having an air permeability of 3 to 30 seconds / (6.4 cm 2 · 300 ml) per 100 g / m 2 basis weight of the exothermic intermediate sheet.
The sheet-like exothermic molded object by which the air permeable sheet is distribute | arranged to the at least single side | surface of the heat generating sheet in any one of Claims 1-3.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007018211A1 (en) * | 2005-08-09 | 2007-02-15 | Kao Corporation | Heating element and heating intermediate |
| JP2009142507A (en) * | 2007-12-14 | 2009-07-02 | Kao Corp | Steam generator |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007018211A1 (en) * | 2005-08-09 | 2007-02-15 | Kao Corporation | Heating element and heating intermediate |
| JP2009142507A (en) * | 2007-12-14 | 2009-07-02 | Kao Corp | Steam generator |
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