JP5053325B2 - Method for producing nonwoven fabric for disposable warmer - Google Patents
Method for producing nonwoven fabric for disposable warmer Download PDFInfo
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- JP5053325B2 JP5053325B2 JP2009131791A JP2009131791A JP5053325B2 JP 5053325 B2 JP5053325 B2 JP 5053325B2 JP 2009131791 A JP2009131791 A JP 2009131791A JP 2009131791 A JP2009131791 A JP 2009131791A JP 5053325 B2 JP5053325 B2 JP 5053325B2
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Description
本発明は、使い捨てカイロをはじめとした使い捨て保温具の包材に用いる不織布の製造方法に関し、特に柔軟で保温性の良好な同保温具用不織布の製造方法に関するものである。 The present invention relates to a method for producing a nonwoven fabric used for a packaging material of a disposable warmer such as a disposable body warmer, and particularly relates to a method for producing a nonwoven fabric for the warmer that is flexible and has good heat retaining properties.
使い捨てカイロをはじめとした使い捨て保温具は、一般的に空気中で発熱する組成物を、不織布あるいは紙にポリエチレン等のフィルムをラミネートした材料で包んだもので、フィルムを有孔、微孔フィルムまたラミネート後に孔あけして通気性を持たせたものである。フィルム単体では硬いものの、不織布を積層することにより、フィルム特有の貼りついた触感、ゴワゴワする肌触り等を防ぎ、布的触感を持たせると共に、繊維層の裂けにくさを付与するものである。しかしながら、従来の保温具の包材に用いる不織布は、破袋等の点で強力面を配慮しつつ、繊維触感を持ち、人体との接触面において、心地よい伝熱媒体となるが、強力面および使用時の毛羽立ちを考えると、保温のためには空気層を持たせて断熱する考えと相反する点も多く、人体に感知する温度を適温にするなど、発熱体の発熱を有効に活かす工夫は充分とは言い難く、発熱体の維持温度を高めに設計することが必要になるなど、熱効率が低いという問題があった。 Disposable warmers such as disposable warmers are generally made by wrapping a composition that generates heat in the air with a nonwoven fabric or paper laminated with a film of polyethylene or the like. A hole is made after lamination to give air permeability. Although the film itself is hard, by laminating the non-woven fabric, it prevents the sticking touch peculiar to the film, the tingling touch, etc., gives the cloth touch and gives the fiber layer hard to tear. However, the non-woven fabric used for the packaging material of the conventional heat insulator has a fiber tactile sensation in consideration of the strong surface in terms of bag breakage and the like, and becomes a comfortable heat transfer medium on the contact surface with the human body. Considering the fluffing during use, there are many points that conflict with the idea of heat insulation with an air layer for heat insulation, and there are some ideas to make effective use of the heat generated by the heating element, such as making the temperature perceived by the human body appropriate. It is difficult to say that it is sufficient, and there is a problem in that the thermal efficiency is low, for example, it is necessary to design the heating element at a higher maintenance temperature.
本発明の課題は、上記問題点を解消し、特に柔軟で繊維触感を持ちながら、発熱体の熱を有効に活かす、保温効率の良好な使い捨て保温具用不織布の製造方法を提供することである。 An object of the present invention is to provide a method for producing a nonwoven fabric for a disposable warmer having good heat retention efficiency, which solves the above-mentioned problems and effectively utilizes heat of a heating element while being particularly flexible and having a fiber feel. .
本発明者は、前記課題を解決するため、種々検討した結果、繊維触感および適性な強力を持ちながら、熱ロスが少なく、発熱体の熱を有効に活かすために、各種包材の熱伝導率に着目し、これに基づいて使い捨て保温具用不織布に適した保温効率の測定方法を開発し、さらに該保温効率が良好な不織布包材について種々検討した結果、下記の製法により製造した不織布が使い捨て保温具の保温効率を高める上で極めて有効であることを見出し、本発明に到達したものである。
すなわち、本願で特許請求される発明は下記のとおりである。
As a result of various investigations to solve the above problems, the present inventor has various fiber packaging materials and thermal conductivity of various packaging materials in order to effectively utilize the heat of the heating element while having a good tactile feel and suitable strength and little heat loss. Based on this, we developed a measurement method of heat insulation efficiency suitable for nonwoven fabrics for disposable warmers, and further examined various nonwoven fabric packaging materials with good heat insulation efficiency. It has been found that it is extremely effective in increasing the heat retention efficiency of the heat retainer, and has reached the present invention.
That is, the invention claimed in the present application is as follows.
（１）フィルムをラミネートした不織布を少なくとも一面に有する包材に空気中で発熱する組成物を封入し、かつ該包材に通気性をもたせた使い捨て保温具に用いる不織布の製造方法であって、該不織布の温度２０℃、湿度６５％雰囲気下の定常保温効率が６０％以上になるように、捲縮数１０〜４０個／インチの捲縮をもつ、ポリエステル系またはポリプロピレン系合成繊維を含むカードウェブを水流絡合装置（ノズル径０．０５〜０．５ｍｍ、ノズル間隔１〜１０ｍｍ、水圧１〜１５ＭＰａ）を用いて、表裏を水流交絡することによって接合することを特徴とする使い捨て保温具用不織布の製造方法。
（２）前記不織布が、揺動する水流絡合装置を用いて、表裏を水流交絡することにより接合することを特徴とする（１）に記載の使い捨て保温具用不織布の製造方法。
(1) A method for producing a nonwoven fabric for use in a disposable warmer in which a composition that generates heat in air is enclosed in a packaging material having a nonwoven fabric laminated with a film on at least one surface, and the packaging material is air permeable. A card containing polyester-based or polypropylene-based synthetic fibers having a crimp of 10 to 40 crimps / inch so that the temperature retention efficiency of the nonwoven fabric at 20 ° C. and a humidity of 65% is 60% or more. For a disposable warmer characterized in that the web is joined by hydroentangling the front and back surfaces using a hydroentanglement device (nozzle diameter 0.05 to 0.5 mm, nozzle interval 1 to 10 mm, water pressure 1 to 15 MPa). Nonwoven fabric manufacturing method.
(2) The method for producing a nonwoven fabric for disposable warmers according to (1), wherein the nonwoven fabric is joined by hydroentangling the front and back surfaces using a swinging hydroentanglement device.
本発明によれば、柔軟で繊維触感を持ちながら、発熱体の熱を有効に活かす、保温効率の良好な不織布を包材とした使い捨て保温具および包材用不織布を提供することができる。 According to the present invention, it is possible to provide a disposable warmer and a non-woven fabric for packaging material, which is made of a non-woven fabric with good heat retention efficiency and that effectively uses the heat of the heating element while having a soft and tactile feel.
本発明の使い捨て保温具は、フィルムをラミネートした不織布を少なくとも一面に有する包材に空気中で発熱する組成物を封入し、かつ該包材に通気性をもたせたものからなり、かつ該不織布は、疎水性合成繊維を含み、温度２０℃、湿度６５％雰囲気下の定常保温効率が６０％以上となるように流体絡合により接合されてなるものである。 The disposable heat insulating device of the present invention comprises a packaging material having a nonwoven fabric laminated with a film on at least one surface, and a composition that generates heat in the air, and the packaging material has air permeability. In addition, it includes a hydrophobic synthetic fiber, and is joined by fluid entanglement so that the steady heat retention efficiency in an atmosphere of temperature 20 ° C. and humidity 65% is 60% or more.
本発明において、不織布に使用する繊維としては、ポリプロピレン系繊維、ポリエチレンテレフタレート、ポリプロピレンテレフタレート、ポリブチレンテレフタレート等のポリエステル系繊維が疎水性、強度あるいは可撓性の観点から好適であり、また保温性の観点から、熱を伝えにくく、熱伝導性が低いので好ましい。 In the present invention, as fibers used for the nonwoven fabric, polypropylene fibers, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, and other polyester fibers are suitable from the viewpoint of hydrophobicity, strength, and flexibility, and have heat retention properties. From the viewpoint, it is preferable because it is difficult to conduct heat and the thermal conductivity is low.
また不織布の寸法安定性、剛性、耐熱性の点からはポリエステル系繊維、疎水性、柔軟性の点からはポリプロピレン系繊維が好ましい。必要に応じて、これらの複合繊維、混合繊維、さらにはセルロース系繊維、その他特殊機能を持つ繊維との混合も有効である。 Polyester fibers are preferable from the viewpoint of dimensional stability, rigidity, and heat resistance of the nonwoven fabric, and polypropylene fibers are preferable from the viewpoint of hydrophobicity and flexibility. If necessary, mixing with these composite fibers, mixed fibers, cellulosic fibers, and other fibers having special functions is also effective.
不織布は、抄紙法、カード機などによる短繊維不織布、スパンボンド方式等の長繊維不織布等、特に限定されるものではないが、適性強力の点から、長繊維不織布が好ましく、例えば、スパンボンド法により溶融紡糸された連続長繊維をウェブとし、これを水流等で繊維を交絡させる流体交絡により接合することにより形成される。 The nonwoven fabric is not particularly limited, such as a papermaking method, a short fiber nonwoven fabric by a card machine, a long fiber nonwoven fabric such as a spunbond method, etc., but a long fiber nonwoven fabric is preferable from the viewpoint of suitable strength, for example, a spunbond method. A continuous long fiber melt-spun by the above method is used as a web, and this is joined by fluid entanglement in which the fiber is entangled with a water flow or the like.
本発明に用いる不織布は、温度２０℃、湿度６５％雰囲気下の定常保温効率が６０％以上であることが必要である。本発明でいう保温効率は、モデル的に説明すると次の通りである。つまり、熱板と不織布試料を重ね、熱板から不織布を通して移動する熱量を測定するために、熱板が一定温度（４０℃）を維持するように、熱板に供給される熱量を測定し、これを数値化することで、保温効率を算出する。すなわち、本発明でいう定常保温効率は、一定温度（２０℃）に維持された熱板Ａ（５ｃｍ角）上に不織布試料片を置き、その上に前記一定温度よりも高い温度（４０℃）に維持された熱板Ｂを重ね、該試料片を通して伝わる熱量を熱板Ｂの温度を維持する熱量Ｃとして測定し、一方、前記試料片を置かない場合の維持熱量Ｄを測定し（後述の実施例では、Ｄ＝１４．０６Ｗ／２５ｃｍ２・２０℃）、下式により算出したもので、使い捨て保温具用不織布の実用上の保温性を表す。この数値が大きい程、不織布の保温性が高い。
定常保温効率（％）＝{（Ｄ−Ｃ）／Ｄ}×１００
The nonwoven fabric used in the present invention needs to have a constant heat retention efficiency of 60% or more in an atmosphere of a temperature of 20 ° C. and a humidity of 65%. The heat retention efficiency in the present invention is described as a model as follows. That is, to measure the amount of heat supplied to the hot plate so that the hot plate maintains a constant temperature (40 ° C.) in order to measure the amount of heat transferred from the hot plate through the non-woven fabric by stacking the hot plate and the non-woven fabric sample, The thermal insulation efficiency is calculated by quantifying this. That is, the steady-state heat-retaining efficiency as used in the present invention is a non-woven fabric sample piece placed on a hot plate A (5 cm square) maintained at a constant temperature (20 ° C.), and a temperature higher than the constant temperature (40 ° C.) thereon. The amount of heat transmitted through the sample piece is measured as the amount of heat C that maintains the temperature of the hot plate B, while the amount of maintenance heat D when the sample piece is not placed is measured (described later). In the examples, D = 14.06 W / 25 cm 2 · 20 ° C.), which is calculated by the following equation, and represents the practical heat retention of the nonwoven fabric for disposable warmers. The larger this value, the higher the heat retention of the nonwoven fabric.
Constant heat retention efficiency (%) = {(D−C) / D} × 100
なお、現在市販されている使い捨てカイロの包材用不織布の定常時保温効率は３５％前後であり、発熱体の熱量が散逸し、有効に活かされておらず、保温効率が良好とは言えないことがわかった。 In addition, the thermal insulation efficiency at the time of steady state of the nonwoven fabric for packaging materials of disposable warmers currently marketed is around 35%, the amount of heat of the heating element is dissipated, and it is not effectively utilized, and it cannot be said that the thermal insulation efficiency is good. I understood it.
本発明に用いる不織布の保温効率は６０％以上、特に好ましくは８２％以上である。
不織布の保温性を改良するには、例えば、同じ目付でも不織布の厚みを厚く、不織布表面層繊維の接触面積を少なくすることによって達成することができる。
The heat retention efficiency of the nonwoven fabric used in the present invention is 60% or more, particularly preferably 82% or more.
Improving the heat retention of the nonwoven fabric can be achieved, for example, by increasing the thickness of the nonwoven fabric with the same basis weight and reducing the contact area of the nonwoven fabric surface layer fibers.
さらに、流体絡合処理によって高圧流体で繊維同士を絡ませることで嵩高くすることも保温性の観点から好ましい。
流体絡合は通常水流を用い、ノズル径０．０５〜０．５ｍｍ、ノズル間隔を０．２〜１０ｍｍになるよう配置し、１〜１５ＭＰａの水流が好ましい。
Furthermore, it is also preferable from the viewpoint of heat retention to increase the bulk by entanglement of fibers with a high-pressure fluid by fluid entanglement treatment.
For fluid entanglement, a normal water flow is used, the nozzle diameter is 0.05 to 0.5 mm, the nozzle interval is 0.2 to 10 mm, and a water flow of 1 to 15 MPa is preferable.
繊維の断面形状として、Ｃ型、Ｙ型、Ｖ型等の異形断面糸を用いたり、捲縮繊維例えば、捲縮数が１０〜４０個／インチを持つ複合系繊維あるいは異形で捲縮を持たせた繊維等を活用したりすることが嵩高性、保温性の観点から好ましい。 The cross-sectional shape of the fiber is C-shaped, Y-shaped, V-shaped or other irregular cross-section yarn, or a crimped fiber, for example, a composite fiber having a number of crimps of 10 to 40 / inch or an irregular shape with crimp It is preferable from the viewpoints of bulkiness and heat retention to use the soaked fibers.
不織布構造体として、不織布の嵩高性が持つ空気層の保温効果や、素材自体の熱伝導特性からくる保温効果の、その両者の合わさった保温効果が、実用上の保温効果であり、本発明では、これを前述の測定法で求め、定常時保温効率として示している。 As a non-woven fabric structure, the warming effect of the air layer with the bulkiness of the non-woven fabric and the warming effect resulting from the heat conduction characteristics of the material itself, the combined warming effect, is a practical warming effect. This is obtained by the above-described measurement method, and is shown as the steady-state heat retention efficiency.
繊度は、強度、柔軟性等の点から、０．８〜５ｄｔｅｘが好ましいが、嵩高保持性を重視する場合は２〜８ｄｔｅｘが好ましい。適用される不織布の目付は使い方により設定するが、３０〜１００ｇ／ｍ２が実用強度、触感の点から好ましい。
これらの不織布は人体との接触面が細かな繊維であり、心地よい伝熱媒体となる。
The fineness is preferably 0.8 to 5 dtex from the viewpoint of strength, flexibility, etc., but 2 to 8 dtex is preferable when emphasis is placed on bulk retention. The basis weight of the nonwoven fabric to be applied is set depending on how it is used, but 30 to 100 g / m 2 is preferable from the viewpoint of practical strength and touch.
These non-woven fabrics are fibers having a fine contact surface with the human body and become a comfortable heat transfer medium.
不織布と貼り合わせるフィルムは、ＬＤ、ＬＬＤ、ＨＤまたメタロセン系触媒ＰＥ等の各種ポリエチレン、ポリプロピレン等のポリオレフィン系、ＥＶＡ及びエチレン、プロピレン、ブテン等の各種共重合ポリプロピレン等のポリオレフィン共重合系、ポリアミド系、ポリエステル系のものでもよく、透湿性を有した微多孔フィルムであってもよい。柔軟性、シール性、価格の点から、ポリエチレンあるいはその共重合系オレフィンフィルムが好ましい。また、繊維層との相性、また包材周辺のシール性の点から２〜３層のフィルムを組み合わせたものでもよい。 Films to be bonded to non-woven fabrics are LD, LLD, HD, various polyethylenes such as metallocene catalyst PE, polyolefins such as polypropylene, polyolefins such as EVA and various copolymerized polypropylenes such as ethylene, propylene and butene, polyamides Further, a polyester-based one or a microporous film having moisture permeability may be used. From the viewpoint of flexibility, sealing properties, and price, polyethylene or a copolymer olefin film thereof is preferable. Moreover, what combined the film of 2-3 layers from the point of the compatibility with a fiber layer and the sealing performance around a packaging material may be used.
不織布とフィルムとの貼り合わせは、ヒートシール、熱接合あるいはホットメルト剤等の接着剤で積層される方法でもよく、全面接合、柔軟性を保つために部分接合であってもよい。
使い捨て保温具として必要な通気孔はラミネート後孔あけ、あるいは予め有孔、微孔のフィルムを用いるのが一般的である。
The non-woven fabric and the film may be bonded to each other by heat sealing, heat bonding, or a method of laminating with an adhesive such as a hot melt agent, or may be full surface bonding or partial bonding to maintain flexibility.
In general, a vent hole required as a disposable heat insulating device is a hole after post-lamination or a perforated or microporous film is used in advance.
以下、実施例及び比較例によって本発明をさらに説明する。
なお、測定法、評価方法は下記の通りである。
(1) 不織布の目付
１０ｃｍ角試料で重量を測定、目付（ｇ／ｍ２）した。
(2) 不織布の強力および５％伸長時応力
ＪＩＳ Ｌ−１９０６に準じて測定した。
(3) 不織布の定常保温効率
Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples.
Measurement methods and evaluation methods are as follows.
(1) Fabric weight of nonwoven fabric The weight was measured with a 10 cm square sample, and the fabric weight (g / m 2 ) was measured.
(2) Strength of nonwoven fabric and stress at 5% elongation Measured according to JIS L-1906.
(3) Non-woven fabric warming efficiency
２０℃、湿度６５％の環境下で、恒温水槽から水循環され２０℃で維持されるように設定された熱板Ａ（５ｃｍ角）上に、同寸法の試料片を置き、更にその上に５ｃｍ角で４０℃の熱板Ｂ（６ｇ／ｃｍ２）を重ね、試料を通して伝わる熱量を熱板Ｂの温度を維持する熱量として測定し、試料の熱伝導度とした。試料を置かない場合の維持熱量１４．０６Ｗ／２５ｃｍ２・２０℃を保温効率０％とし、次の（１）式による値を定常保温効率（％）とした。 A sample piece of the same size is placed on a hot plate A (5 cm square) set to be circulated from a constant temperature water bath and maintained at 20 ° C. in an environment of 20 ° C. and humidity 65%, and further 5 cm above it. The heat plate B (6 g / cm 2 ) having a corner of 40 ° C. was overlapped, and the amount of heat transmitted through the sample was measured as the amount of heat for maintaining the temperature of the heat plate B, and was defined as the thermal conductivity of the sample. The heat retention efficiency of 14.06 W / 25 cm 2 · 20 ° C. when the sample was not placed was defined as the heat retention efficiency 0%, and the value of the following equation (1) was defined as the steady heat retention efficiency (%).
定常保温効率（％）＝{（１４．０６−試料の熱伝導度）／１４．０６}×１００…（１）
また、４０℃の熱板Ｂ上に置いた試料の反熱板面の試料表面温度も熱伝導性の目安とした。
Steady temperature retention efficiency (%) = {(14.06-thermal conductivity of sample) /14.06} × 100 (1)
Moreover, the sample surface temperature of the counter-heated plate surface of the sample placed on the hot plate B at 40 ° C. was also used as a measure of thermal conductivity.
［実施例１］
ポリエステル短繊維（２．０ｄｔｅｘ、５３mm長）８０％とレーヨン短繊維（１．２ｄｔｅｘ、５３mm長）２０％で形成したカードウェブを８０メッシュの金網に載せて、１５０ｒｐｍ搖動する水流絡合装置（ノズル径０．１５ｍｍ、ノズル間隔５ｍｍ×５列、水圧６ＭＰａ）に表裏３回通し、目付７０ｇ／ｍ２のスパンレース不織布を得た。この不織布の性能は表１に示す。
[Example 1]
A water web entanglement device (nozzle) on which a card web formed of 80% polyester short fibers (2.0 dtex, 53 mm length) and 20% rayon short fibers (1.2 dtex, 53 mm length) is placed on an 80 mesh wire mesh and is oscillated at 150 rpm. A spunlace nonwoven fabric having a basis weight of 70 g / m 2 was obtained by passing the front and back three times through a nozzle having a diameter of 0.15 mm, a nozzle interval of 5 mm × 5 rows, and a water pressure of 6 MPa. The performance of this nonwoven fabric is shown in Table 1.
得られた不織布の表面にＬＤＰＥとメタロセン触媒系ポリエチレン（シール面）とを半々積層した４０μフィルムをラミネートした後、通常通り、針ロールで窄孔（約６％）し、カイロ用包材とした。この不織布を上被層とし、下被層は無孔の同ラミネート品を用い、フィルム面を内側に、発熱組成物を充填し、周囲をヒートシールした使い捨てカイロを製作した。得られた使い捨てカイロは表面の繊維が活きた、滑らかで、一段とソフトな触感のカイロであった。 After laminating a 40 μ film in which LDPE and metallocene catalyst-based polyethylene (seal surface) were laminated in half on the surface of the obtained non-woven fabric, it was narrowed with a needle roll (about 6%) as usual to obtain a packaging material for warmers. . The nonwoven fabric was used as an upper layer, and the lower layer was made of the same non-laminated laminate. A disposable body warmer was prepared by filling the heat generation composition with the film surface inside and heat-sealing the periphery. The obtained disposable warmer was a warmer, smoother and softer toucher with active surface fibers.
[比較例１]
比較例として、現在、市販されている使い捨てカイロの不織布に使用されているポリエチレンテレフタレート繊維（２．０ｄｔｅｘ）の各織目柄（圧着面積率２２％）の不織布を製作し、性能比較を行った。不織布の性能を表１に示す。比較例１の不織布の定常保温効率は４０％未満であり、実施例に比べて、保温効率が低かった。
上記実施例によれば、水流交絡による不織布は、定常時の保温効率が良好であり、使い捨てカイロとして柔軟な繊維触感を有し、発熱体としての保温効率が良好であるといえる。
[Comparative Example 1]
As a comparative example, a nonwoven fabric of each woven pattern (compression bonding area ratio 22%) of polyethylene terephthalate fiber (2.0 dtex) used for the disposable warmer nonwoven fabric currently on the market was manufactured, and the performance was compared. . The performance of the nonwoven fabric is shown in Table 1. The non-woven fabric of Comparative Example 1 had a constant heat retention efficiency of less than 40%, and the heat retention efficiency was lower than that of the example.
According to the said Example, it can be said that the nonwoven fabric by hydroentanglement has the favorable thermal insulation efficiency at the time of steadyness, has a soft fiber tactile sense as a disposable body warmer, and the thermal insulation efficiency as a heat generating body is favorable.
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| JP5935327B2 (en) | 2012-01-11 | 2016-06-15 | 東洋紡株式会社 | Non-woven for Cairo |
| KR102256079B1 (en) * | 2016-03-30 | 2021-05-24 | 코오롱인더스트리 주식회사 | Non-woven Fabric for Primary Carpet Backing in Carpet Preparing Process, and Method for Manufacturing the Same |
| CN111031972A (en) | 2017-06-15 | 2020-04-17 | 菲利克株式会社 | Warm body and method for producing same |
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| JPS6124026U (en) * | 1984-07-17 | 1986-02-13 | 永之介 村木 | Bag for chemical heating element |
| JPH031856A (en) * | 1989-05-30 | 1991-01-08 | Asahi Chem Ind Co Ltd | Throwaway pocket warmer |
| JPH08150169A (en) * | 1994-09-28 | 1996-06-11 | Unitika Ltd | Sack for disposable pocket heater |
| JPH08260315A (en) * | 1995-03-22 | 1996-10-08 | Mitsubishi Paper Mills Ltd | Web processing apparatus |
| JP3815517B2 (en) * | 1996-02-09 | 2006-08-30 | チッソ株式会社 | Tow |
| JPH1189869A (en) * | 1997-09-24 | 1999-04-06 | Asahi Chem Ind Co Ltd | Throw-away body warmer |
| JPH11107149A (en) * | 1997-09-30 | 1999-04-20 | Asahi Chem Ind Co Ltd | Nonwoven fabric |
| JPH11200213A (en) * | 1998-01-19 | 1999-07-27 | Unitika Ltd | Nonwoven fabric and its production |
| JP2001159059A (en) * | 1999-11-30 | 2001-06-12 | Toyobo Co Ltd | Promix fiber-based nonwoven fabric |
| JP2001238906A (en) * | 1999-12-24 | 2001-09-04 | Lion Corp | Heating element composition, heating element and method for manufacturing the same |
| JP3774105B2 (en) * | 2000-05-10 | 2006-05-10 | 大和紡績株式会社 | Wrapping material and manufacturing method thereof, and packing bag |
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