JP4383260B2 - Method for producing reinforced carbonized cotton sheet or carbonized cotton sheet - Google Patents
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本発明は、強度の高い補強炭化綿シート又は炭化綿シートの製造方法に関する。 The present invention relates to a method for producing a reinforced carbonized cotton sheet or a carbonized cotton sheet having high strength.
本発明者は、木綿を炭化した炭化綿が広範な性質と特性を持つ事を突き止め、先に「水浄化用フィルター及び使用済みフィルターの活性化方法」（特願2002- 217687）、「ドリップの吸収除去方法及びそのためのドリップシート」（特願2002-148820）、「寝装具及び寝装具用炭化綿の製造方法」（特願2002- 150231 ）、「ガス吸蔵材料並びにガスの吸蔵及び排出方法」、（特願2002- 184146）、「水耕用植物保持材及び水耕植物栽培法」（特願2002- 184192）、「燃料蒸発ガス発散抑制装置及び排気ガス浄化装置並びにこれらに使用するフィルター」（特願2002-184244 ）、「抗菌性医用材料」（特願2002- 184266）、「炭化綿、圧電素子、圧力センサー、温度センサー、ガス吸蔵材料、ガスセンサー、シート状発熱体、電磁波遮蔽材、帯電防止用材および炭化綿の製造方法」（特願2002-214695）、「浄化、精製又は脱色用フィルターおよびその製造方法」（特願2002-217818）、「浄化用フィルター、ならびにその製造法および保存方法」（特願2003-324000）、「魚及び水棲動物の水槽浄化用フィルター、同浄化用フィルターの製造方法、浄化用フィルターの保存方法及び魚及び水棲動物の水槽の浄化方法」（特願2003-354461）、「空気清浄方法」（特願2004-091239）を提案した（先願の発明）。 The present inventor has found that carbonized cotton obtained by carbonizing cotton has a wide range of properties and characteristics. First, “Activation of water purification filter and used filter” (Japanese Patent Application No. 2002-217687), “Drip Absorption and removal method and drip sheet therefor (Japanese Patent Application No. 2002-148820), “Method for producing bedding and carbonized cotton for bedding” (Japanese Patent Application No. 2002-150231), “Gas storage material and gas storage and discharge method” , (Japanese Patent Application No. 2002-184146), “Hydroponic Plant Holding Material and Hydroponic Plant Cultivation Method” (Japanese Patent Application No. 2002-184192), “Fuel Evaporative Gas Emission Control Device and Exhaust Gas Purifying Device, and Filters Used in These” (Japanese Patent Application No. 2002-184244), “Antimicrobial Medical Materials” (Japanese Patent Application No. 2002-184266), “Carbonized cotton, piezoelectric elements, pressure sensors, temperature sensors, gas storage materials, gas sensors, sheet-like heating elements, electromagnetic shielding materials Of antistatic materials and carbonized cotton Law "(Japanese Patent Application No. 2002-214695)," Purification, Purification or Decolorization Filter and its Manufacturing Method "(Japanese Patent Application No. 2002-217818)," Purification Filter, and its Manufacturing Method and Preservation Method "(Japanese Patent Application No. 2003-324000) ), “Fish and aquatic animal water tank purification filter, production method of the purification filter, preservation method of purification filter and purification method of fish and aquatic animal water tank” (Japanese Patent Application 2003-354461), “Air purification method (Patent application 2004-091239) was proposed (the invention of the prior application).
いずれも炭化綿という新しい素材の特性を活かした、優れた方法であり、炭化しても木綿の柔らかさが保持されるのが大きな特徴である。しかし、炭化綿は原料である木綿と比べると、明らかにその強度は低下する。
例えば、木綿を炭化したもの及び木綿タオルを炭化したものを、それぞれ長手方向に長さ2am、幅2amの短冊状に切り出し、その引っ張り強度を測定すると、炭化綿タオルの場合には、90.6+5.1gf/ 2amであり、未炭化タオル（7,521+106gf/2am）の約1.2%であった。
原料である木綿の種類によって、若干の違いがあるが、ほぼこの程度の強度の低下が観察された。
Both are excellent methods that take advantage of the properties of a new material called carbonized cotton, and the great feature is that the softness of cotton is maintained even when carbonized. However, the strength of carbonized cotton is clearly lower than that of raw cotton.
For example, carbonized cotton and carbonized cotton towels are cut into strips with a length of 2am and a width of 2am in the longitudinal direction, respectively, and when the tensile strength is measured, in the case of carbonized cotton towels, 90.6 + 5.1 gf / 2am, about 1.2% of uncarbonized towels (7,521 + 106gf / 2am).
Although there is a slight difference depending on the type of cotton used as a raw material, this degree of strength reduction was observed.
従って、そのままでは長時間の使用や、圧力による劣化が生じ、シートとして利用する際には、何らかの工夫が必要であった。すなわち、粉体が飛散しないように不織布などで被う事などである。この事は、炭化綿を様々な用途で使用する場合に、その耐久性、および余分な加工が余儀無くされ、価格の高騰は免れなかった。 Therefore, if it is used as it is, it will be used for a long time or deteriorated due to pressure, and some ingenuity has been required when used as a sheet. That is, covering with a non-woven fabric or the like so that the powder does not scatter. This means that when carbonized cotton is used in various applications, its durability and extra processing have been forced, and the price has been escalated.
一方、炭化した繊維を利用した技術として、冷蔵庫用脱臭兼鮮度維持剤及びその収納ケース（例えば、特許文献１参照）、微小炭素繊維懸濁液および微小炭素繊維含有塗料（例えば、特許文献２参照）、植物資材による脱臭能、イオン交換能、触媒能を有する炭化物製造方法（例えば、特許文献３参照）が開示されている。
しかし、これらも全て強度に関わる問題は同じである。
However, these are all the same strength issues.
本発明の目的は、木綿シートを炭化しても十分な強度を備え、劣化しにくい炭化方法を提供することである。 An object of the present invention is to provide a carbonization method that has sufficient strength even when a cotton sheet is carbonized and is not easily deteriorated.
本発明者は、上記目的を達成すべく鋭意研究を重ねた結果、木綿糸に対して、炭化しても劣化しにくい織物を裏打ち（補強）する事により、上記の問題を解決できるとの知見を得た。
本発明は、この知見に基づいて、
１）木綿以外の強度ある生地織布又はメッシュに木綿糸を織込み炭化させた炭化木綿シートであって、生地の織布が耐熱性のあるガラス繊維、炭化後に強度があるアクリル系繊維、レーヨン若しくは絹、又は耐熱性ステンレス製のメッシュであることを特徴とする補強炭化綿シート
２）直交する経線（b）と緯線（a）との平組織りでなるメッシュ上で、木綿糸が、一定の経線（b１）に交差する一定の緯線（a1）から、その緯線（a１）に平行あるいは一定の角度で、幾つかの経線（b１〜bn）の上部を乗り越えて、別の緯線（an+１）に絡み、今度は逆方向に同じ様式で、経線（b1〜bn）の上部を乗り越えて、元の経線（b1）に戻り、その経線（b1）に交差する次の緯線（a２）に絡むという一連の動作で往復を繰り返しながら織り上げられた構造を備えていることを特徴とする上記１）記載の補強炭化綿シート、を提供する。
As a result of intensive studies to achieve the above object, the present inventor has found that the above problem can be solved by lining (reinforcing) a woven fabric that does not deteriorate even when carbonized with respect to cotton yarn. Got.
The present invention is based on this finding.
1) A strong fabric woven fabric other than cotton or a carbonized cotton sheet obtained by weaving cotton yarn into a mesh and carbonizing, and the fabric woven fabric is heat-resistant glass fiber, acrylic fiber having strength after carbonization, rayon or Reinforced carbonized cotton sheet 2 characterized by being a mesh made of silk or heat-resistant stainless steel 2) On a mesh composed of a plane structure of orthogonal meridians (b) and parallels (a), cotton yarn is fixed From a certain parallel (a1) intersecting the meridian (b1), over the top of several meridians (b1 to bn) at a parallel or constant angle to that latitude (a1), another latitude (an + 1) ), This time in the same way in the opposite direction, over the top of the meridian (b1 to bn), return to the original meridian (b1), and entangle the next latitude (a2) that intersects that meridian (b1) It has a structure that is woven while repeating reciprocation in a series of operations Above, wherein the is 1) reinforcement carbide Cotton sheet according to offer.
本発明は、また、
３）耐熱性のあるガラス繊維、炭化後に強度があるアクリル系繊維、レーヨン若しくは絹、又は耐熱性ステンレス製のメッシュからなる生地織布に木綿糸を織込み、生地を支持体として木綿をシート化してから炭化を行ない、炭化された生地の強度を利用した強度ある炭化綿シートを製造することを特徴とする炭化綿シートの製造方法
４）メッシュの片面又は両面に木綿糸を整列させることを特徴とする上記３）記載の炭化綿シートの製造方法
５）直交する経糸（b）と緯糸（a）との平組織りでなる生地の織布上で、木綿糸が、一定の経糸（b１）に交差する一定の緯糸（a1）から、その緯糸（a１）に平行あるいは一定の角度で、幾つかの経糸（b１〜bn）の上部を乗り越えて、別の緯糸（an+１）に絡み、今度は逆方向に同じ様式で、経糸（b1〜bn）の上部を乗り越えて、元の経糸（b1）に戻り、その経糸（b1）に交差する次の緯糸（a２）に絡むという、一連の動作で往復を繰り返しながら織り上げることを特徴とする上記３）又は４）に記載の炭化綿シートの製造方法
６）木綿シートを不活性ガス雰囲気あるいは、無酸素雰囲気で、木綿の完全な熱分解温度を越える３８０°Ｃ〜９００°Ｃで加熱炭化することを特徴とする上記３）〜５）のいずれかに記載の炭化綿シートの製造方法、を提供する。
The present invention also provides
3) Cotton yarn is woven into a fabric woven fabric made of heat-resistant glass fiber, acrylic fiber that is strong after carbonization, rayon or silk, or heat-resistant stainless steel mesh, and the cotton is made into a sheet using the fabric as a support. Carbonized cotton sheet is produced by producing carbonized cotton sheet having strength by utilizing the strength of carbonized fabric. 4) A method comprising aligning cotton yarn on one or both sides of a mesh. 3) The method for producing a carbonized cotton sheet as described in 3) 5) On a woven fabric made of a plain structure of warp yarns (b) and weft yarns (a) perpendicular to each other, the cotton yarn is transformed into a constant warp yarn (b1). From the intersecting constant weft (a1), cross over the upper part of several warps (b1 to bn) at a certain angle or parallel to the weft (a1) and entangle it with another weft (an + 1). Are in the same direction in the opposite direction and warp (b1 ~ bn 3) The above-mentioned 3 characterized in that weaving is repeated while reciprocating in a series of operations, overcoming the upper part of), returning to the original warp yarn (b1) and entangled with the next weft yarn (a2) intersecting with the warp yarn (b1). ) Or 4) The method for producing carbonized cotton sheet 6) Carbonizing the cotton sheet in an inert gas atmosphere or an oxygen-free atmosphere at 380 ° C to 900 ° C exceeding the complete thermal decomposition temperature of cotton. A method for producing a carbonized cotton sheet according to any one of 3) to 5) above .
本発明の炭化綿シートは、炭化綿の通常の炭化温度で炭化しない防燃繊維、あるいは炭化しても引っ張り強度の低下が少ないアクリル系繊維、絹あるいはレーヨンなどの織布を裏打ち（補強）として用い、木綿糸を繊維状に織り込む事で、引っ張り強度に優れた炭化綿を製造できるという優れた効果を有する。
また、本発明では、裏地の織布の一方の面のみに炭化綿を集中させて表裏を作る事が可能となるため、必要な面のみを露出させて、裏面を接着したり、固定することが可能となる。このことは炭化綿を自在に変型させ、必要な形状を持たせる事が可能となることを意味している。さらにこのことは、両面も必要に応じて織り込む事が可能であることを示している。
さらに、金属メッシュに織り込んだ炭化綿は、通気、通水性が良いので、気体、あるいは液体の浄化に直接フィルターとして用いることが可能となる。また、菌着床床として多彩な使い方が可能となるという優れた効力を有する。
The carbonized cotton sheet of the present invention has a flameproof fiber that does not carbonize at the normal carbonization temperature of carbonized cotton, or a woven fabric such as acrylic fiber, silk, or rayon that has little decrease in tensile strength even when carbonized. It has an excellent effect that carbonized cotton excellent in tensile strength can be produced by using cotton yarn in a fibrous form.
In the present invention, it is possible to concentrate the carbonized cotton on only one side of the woven fabric of the lining and make the front and back, so that only the necessary side is exposed and the back side is bonded or fixed Is possible. This means that the carbonized cotton can be freely transformed to have a necessary shape. This also indicates that both sides can be woven as needed.
Furthermore, carbonized cotton woven into a metal mesh has good ventilation and water permeability, and can be used directly as a filter for purifying gas or liquid. In addition, it has an excellent effect that it can be used in various ways as a fungus implantation bed.
本発明者は、鋭意検討した結果、本発明の炭化綿シートは、炭化綿単独で用いた時と比べ、抜群の強度を持つことを突き止めた。この炭化綿シートは先の発明の全てに、適用が可能である。
この炭化綿シートを作成するにあたって、利用する織布は、防燃焼性のガラス繊維や、炭化しても引っ張り強度が低下しにくいアクリル系繊維、絹あるいはレーヨンが特に有効であり、その素材の種類によらない。織布の糸の太さや織りの種類にも影響されない。
As a result of intensive studies, the present inventor has found that the carbonized cotton sheet of the present invention has outstanding strength as compared with the case of using carbonized cotton alone. This carbonized cotton sheet can be applied to all of the previous inventions.
In making this carbonized cotton sheet, the woven fabric to be used is particularly effective for the flameproof glass fiber, acrylic fiber that does not easily decrease its tensile strength even when carbonized, silk or rayon. It does not depend. It is not affected by the thread thickness of the woven fabric or the type of weaving.
織り込む木綿糸の種類は、どこの産地のものでも良いが、織布の糸の太さと織り込む木綿糸の太さには、炭化後の強度を高めるための相性がある。
すなわち、織布の糸が太い場合には、木綿糸の太さを揃え、また、織布の糸が細い場合には、木綿糸の太さを細くすることである。それぞれが逆の特性を持つ太さの場合には十分な強度が保証されない。
また、織布ではなく、メッシュを用いた場合にも同様の関係が存在する。ステンレス製のメッシュを用いる場合には、ステンレスの熱耐性が重要であり、SUS308以上であることが望ましい。
The type of cotton yarn to be woven may be from any place of origin, but the thickness of the woven fabric and the thickness of the cotton yarn to be woven have compatibility to increase the strength after carbonization.
That is, when the yarn of the woven fabric is thick, the thickness of the cotton yarn is made uniform, and when the yarn of the woven fabric is thin, the thickness of the cotton yarn is made thin. In the case of thicknesses having opposite characteristics, sufficient strength is not guaranteed.
A similar relationship also exists when a mesh is used instead of a woven fabric. When using a stainless steel mesh, the heat resistance of the stainless steel is important, and it is desirable that it is SUS308 or higher.
木綿糸を織り込む例を以下に示す。図１〜図３に、その模式図を示した。図１は平織り織布を示している。経糸集団はbで、緯糸集団はaで示しており、それぞれ理解を容易にするため、経糸はb1、b2、・・・、bn、bn+1と示し、同様に緯糸はa1、a2、・・・、an、an+1と示し、特定の点は座標で表わす事とする。 An example of weaving cotton yarn is shown below. The schematic diagram was shown in FIGS. FIG. 1 shows a plain weave fabric. The warp group is indicated by b and the weft group is indicated by a. For ease of understanding, the warp yarns are indicated as b 1 , b 2 ,..., B n , b n + 1, and the weft yarns are indicated as a. 1 , a 2 ,..., A n , a n + 1, and specific points are represented by coordinates.
図２に織り込み方の一例を示すが、仮に（b1、a1）をスタートポイントとすると、木綿糸はこの点からa2〜anを乗り越えて、an+1の緯糸まで織布の上面（この面を表と定義する）に渡す。ここで、経糸（bn+1）に沈み込んでいる緯糸（an+1）に絡め、ここから逆方向にスタートポイントの次の点である（b２、a２）まで、同様な方法で引き戻し、緯糸a2に絡める。
以下同様な方法でこの操作を繰り返しながら織り込んで行く。図３は図２を断面（下部の方向から見た図）を示している。糸の絡め方により、木綿糸の織り込み密度を自在に変える事が可能である。
Although an example how weaving in FIG 2, if the (b 1, a 1) and a start point, cotton yarn overcame a 2 ~a n From this point, the woven fabric until weft a n + 1 Pass to the top surface (this surface is defined as the front). Here, the same method is applied to the next point of the start point (b 2 , a 2 ) in the opposite direction from the tangled weft (a n + 1 ) submerged in the warp (b n + 1 ). pull back in, entangled in the weft a 2.
In the following, we will weave it by repeating this operation in the same way. FIG. 3 shows a cross section of FIG. 2 (viewed from the bottom). It is possible to freely change the weaving density of the cotton yarn depending on how the yarn is entangled.
本発明の浄化用フィルターの製造に際しては、木綿を低酸素あるいは不活性ガス雰囲気で、木綿の完全な熱分解温度を越える３８０°Ｃ〜９００°Ｃで加熱炭化する。
焼成に際しては、特に焼成炉の昇温速度が毎時２０〜２００°Ｃとし、焼成温度到達後、１０〜２０時間保持することが望ましい。
In the production of the purification filter of the present invention, cotton is heated and carbonized in a low oxygen or inert gas atmosphere at 380 ° C. to 900 ° C., which exceeds the complete thermal decomposition temperature of cotton.
In firing, it is desirable to set the heating rate of the firing furnace at 20 to 200 ° C. per hour and hold for 10 to 20 hours after reaching the firing temperature.
また、本発明の炭化綿を不活性ガス雰囲気で製造する場合、木綿を脱気した後、不活性ガスを毎分１〜１０リットルの流量で通過させながら焼成するのが有効である。不活性ガスとしては、窒素あるいはアルゴンを使用する。
さらに、本発明のフィルターとしての有効な繊維長を保持するために、焼成時の木綿の密度を０．０１ｇ／aｍ２以下とすることが望ましい。
ここに示したのは、一つの例であり、同様の思想で構築されるものは全て、本願に包含されるものである。
Moreover, when manufacturing the carbonized cotton of this invention in inert gas atmosphere, after degassing cotton, it is effective to bake, passing inert gas by the flow volume of 1-10 liters per minute. Nitrogen or argon is used as the inert gas.
Furthermore, in order to maintain an effective fiber length as the filter of the present invention, it is desirable that the density of the cotton during firing is 0.01 g / am 2 or less.
What is shown here is an example, and everything constructed with the same idea is included in the present application.
次に、本発明の実施例及び比較例について説明する。なお、以下に示す実施例は、本発明の理解を容易にするためのものであって、本発明はこれらの実施例に制限されるものではない。すなわち、本発明の技術思想に基づく、他の例又は変形は、当然本発明に包含されるものである。 Next, examples and comparative examples of the present invention will be described. In addition, the Example shown below is for making an understanding of this invention easy, and this invention is not restrict | limited to these Examples. That is, other examples or modifications based on the technical idea of the present invention are naturally included in the present invention.
（実施例１）
［強度のある生地織布に木綿を織り込んだ場合の引っ張り強度］
木綿の炭化したものでは、脱脂綿、タオル、シーツなどでも、その強度は元の木綿と比較すると大きく低下することが判った。
従って、様々な生地について炭化後の引っ張り強度を比較すると、ガラス繊維あるいはアクリル系繊維が、一番強度低下が小さい。また、絹、レーヨンが比較的強度低下が低かったため、これらを基布として木綿糸を織り込んで炭化し、その強度を比較した。
Example 1
[Tensile strength when cotton is woven into a strong fabric cloth]
In the case of carbonized cotton, it was found that the strength of absorbent cotton, towels, sheets, etc. was greatly reduced compared to the original cotton.
Therefore, when the tensile strength after carbonization is compared for various fabrics, the strength decrease is the smallest for glass fibers or acrylic fibers. Moreover, since the strength reduction of silk and rayon was relatively low, cotton yarns were woven and carbonized using these as base fabrics, and their strengths were compared.
ガラス繊維シーツ、アクリル系繊維シーツ、絹織物、レーヨンシーツに木綿糸を織り込み、炭化を無酸素雰囲気、400°C、20時間行なった。
炭化前および炭化後のそれぞれの生地を長手方向に長さ2am幅2amの短冊状に切り出し、その引っぱり強度を測定すると、平均でアクリル系繊維の場合には、炭化前は15,400+412.0gf/ 2amであり、炭化後は11,800+377.1gf/ 2amであった。
Cotton yarn was woven into glass fiber sheets, acrylic fiber sheets, silk fabrics, and rayon sheets, and carbonized in an oxygen-free atmosphere at 400 ° C for 20 hours.
Before carbonization and after carbonization, each dough was cut into strips with a length of 2am and a width of 2am in the longitudinal direction, and the tensile strength was measured.In the case of acrylic fiber on average, before carbonization, it was 15,400 + 412.0gf / 2am It was 11,800 + 377.1 gf / 2am after carbonization.
絹織物の場合には、炭化前で8,680.0+505.7gf/ 2amであり、炭化後では1,057+123gf/2amであった。また、レーヨンの場合には、炭化前では10,758+1776gf/ 2amであり、炭化後では471+88.0gf/ 2amであった。いずれも30回の試験結果の平均と標準誤差を示した。
これらの強度は、いずれも炭化綿の強度（90.6+5.1gf/2am）と比較すると大きく、十分様々な用途に用いる事が可能であることが判った。
また、織り込んだ木綿糸の強度は炭化綿と同じであるが、強度の高い基布に密着しているため、全体での引っ張り強度は基布に依存しており、表面での摩擦によっても十分その強度を保っていた。
In the case of silk fabric, it was 8,680.0 + 505.7 gf / 2am before carbonization, and 1,057 + 123gf / 2am after carbonization. In the case of rayon, it was 10,758 + 1776 gf / 2 am before carbonization, and 471 + 88.0 gf / 2 am after carbonization. All showed the average and standard error of 30 test results.
All of these strengths were larger than the strength of carbonized cotton (90.6 + 5.1 gf / 2am), and it was found that they could be used for various purposes.
In addition, the strength of the woven cotton yarn is the same as that of carbonized cotton, but since it is in close contact with the high-strength base fabric, the overall tensile strength depends on the base fabric, and the surface friction is sufficient. The strength was maintained.
（実施例２）
［織り込み炭化綿のアンモニウムイオン吸着例］
次に、実施例で炭化した、織り込み炭化綿のアンモニウムイオンの吸着について調べた。アクリル系繊維、絹、およびレーヨンについて、それぞれ木綿糸の炭化前重量を一定にし（0.5g）、炭化したものを、基布ごと5mg/Lアンモニア水溶液50mLに浸し、震盪機で経常的に150rpmで10分間震盪し、アンモニアを定量した。
炭化した木綿糸がアクリル系繊維を基布とした場合には、アンモニア濃度が1.2mg/Lとなり、絹では1.3mg/L、レーヨンでは1.17mg/Lとなった。いずれも炭化綿単独で用いた吸着とほぼ変わらない吸着力があることが判った。
上記については、ガラス繊維シーツ、アクリル系繊維シーツ、絹織物、レーヨンシーツに木綿糸を織り込んだ例を示したが、ステンレス製メッシュにおいても同等の効果が得られた。
(Example 2)
[Example of ammonium ion adsorption on woven carbonized cotton]
Next, adsorption of ammonium ions of the woven carbonized cotton carbonized in the examples was examined. For acrylic fiber, silk, and rayon, the weight of cotton yarn before carbonization is kept constant (0.5 g), and the carbonized material is immersed in 50 mL of 5 mg / L aqueous ammonia solution together with the base fabric. Shake for 10 minutes and quantify ammonia.
When the carbonized cotton yarn was based on acrylic fiber, the ammonia concentration was 1.2 mg / L, 1.3 mg / L for silk, and 1.17 mg / L for rayon. It was found that the adsorption power was almost the same as that used with carbonized cotton alone.
As for the above, an example in which cotton yarn was woven into glass fiber sheets, acrylic fiber sheets, silk fabrics, and rayon sheets was shown, but the same effect was also obtained with a stainless steel mesh.
本発明の炭化綿シートは、補強によって炭化綿の強度を高め、炭化綿の特性を利用した各種フィルターとして利用できる。 The carbonized cotton sheet of the present invention increases the strength of carbonized cotton by reinforcement and can be used as various filters utilizing the characteristics of carbonized cotton.
ａ１・・・ａｎ＋１ 緯糸
ｂ１・・・ｂｎ＋１ 経糸
a1 ... an + 1 weft b1 ... bn + 1 warp
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