JP5728113B1 - Adsorbent - Google Patents
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- JP5728113B1 JP5728113B1 JP2014151573A JP2014151573A JP5728113B1 JP 5728113 B1 JP5728113 B1 JP 5728113B1 JP 2014151573 A JP2014151573 A JP 2014151573A JP 2014151573 A JP2014151573 A JP 2014151573A JP 5728113 B1 JP5728113 B1 JP 5728113B1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
【課題】適度な弾力を有し、優れた成形性及び水分存在下における高い安定性を備える吸着材を提供する。【解決手段】活性炭繊維と、前記活性炭繊維に熱融着した熱可塑性樹脂繊維とを含む吸着材であって、前記熱可塑性樹脂繊維は、芯鞘構造を有する第１の芯鞘型繊維と、芯鞘構造を有する第２の芯鞘型繊維とを有し、前記第１の芯鞘型繊維は、鞘部がポリオレフィン樹脂Ａにより形成され、芯部が前記ポリオレフィン樹脂Ａよりも融点が高いポリオレフィン樹脂Ｂにより形成されており、前記第２の芯鞘型繊維は、鞘部が前記ポリオレフィン樹脂Ｂよりも融点の低いポリオレフィン樹脂Ｃにより形成され、芯部が前記ポリオレフィン樹脂Ｂよりも融点が高い熱可塑性樹脂Ｄにより形成されている、吸着材。【選択図】なしAn adsorbent having moderate elasticity, excellent moldability and high stability in the presence of moisture is provided. An adsorbent comprising an activated carbon fiber and a thermoplastic resin fiber thermally fused to the activated carbon fiber, wherein the thermoplastic resin fiber includes a first core-sheath fiber having a core-sheath structure; A second core-sheath fiber having a core-sheath structure, wherein the first core-sheath fiber has a sheath part formed of a polyolefin resin A, and the core part has a higher melting point than the polyolefin resin A. The second core-sheath fiber formed of the resin B is formed of a polyolefin resin C having a lower melting point than the polyolefin resin B, and the core has a higher melting point than the polyolefin resin B. An adsorbent formed of a plastic resin D. [Selection figure] None
Description
本発明は、活性炭繊維と、活性炭繊維に熱融着した熱可塑性樹脂繊維とを含む吸着材、当該吸着材からなる廃液処理材、及び当該吸着材からなる脱臭材に関する。 The present invention relates to an adsorbent comprising activated carbon fibers and thermoplastic resin fibers thermally fused to the activated carbon fibers, a waste liquid treatment material comprising the adsorbent, and a deodorizing material comprising the adsorbent.
活性炭は、吸着材として工業的に極めて有用である。例えば、粉末状または粒状の活性炭は、廃液や排ガスなどに含まれる不純物を除去する吸着材などとして広く用いられる。しかしながら、粉末状の活性炭は、被処理物からの分離の操作などが複雑であるという欠点を有する。また、粉末状の活性炭に被処理物（気体や液体などの流体）を通過させる際の圧力損失が大きいという欠点もある。一方、粒状の活性炭は、粒径をある程度大きくすれば、圧力損失を低減させることはできる。しかしながら、活性炭の粒径が大きくなると、吸着表面が減少して吸着速度が低下する等の問題がある。 Activated carbon is extremely useful industrially as an adsorbent. For example, powdered or granular activated carbon is widely used as an adsorbent for removing impurities contained in waste liquid or exhaust gas. However, powdered activated carbon has the disadvantage that the operation of separation from the object to be processed is complicated. In addition, there is a disadvantage that a pressure loss is large when an object to be treated (fluid such as gas or liquid) is passed through powdered activated carbon. On the other hand, the granular activated carbon can reduce pressure loss if the particle size is increased to some extent. However, when the particle size of the activated carbon increases, there are problems such as a decrease in the adsorption surface and a decrease in the adsorption rate.
繊維状の活性炭、すなわち、活性炭繊維は、粉末状または粒状の活性炭に比して、被処理物との分離が容易であり、また表面積が大きく、吸着速度が速い等の利点がある。しかしながら、従来、活性炭繊維は、フェルト状やクロス状等で市販されることが多く、このような活性炭繊維を吸着材として使用する場合、吸着塔の形状や大きさ等に応じて切断したりして形を整える必要がある。 Fibrous activated carbon, that is, activated carbon fiber, has advantages such as easy separation from an object to be treated, large surface area, and high adsorption rate compared to powdered or granular activated carbon. However, conventionally activated carbon fibers are often marketed in the form of felt or cloth, and when such activated carbon fibers are used as adsorbents, they are cut according to the shape and size of the adsorption tower. Need to be shaped.
そこで、例えば特許文献１には、活性炭繊維１０〜９０重量％と熱可塑性合成繊維９０〜１０重量％とからなる繊維束を熱処理して熱可塑性合成繊維を融着させた棒状繊維集束体からなることを特徴とする吸着材が開示されている。特許文献１に開示された吸着材は、取り扱いが容易で、そのままの形状で吸着塔等の充填筒内に充填するだけで使用することが可能である。さらに、当該吸着材は、吸着速度が速く、微生物を担持させた生物処理用の担体とすることもできる。このため、当該吸着材は、廃液処理材、脱臭材などとして好適に使用することができる。 Therefore, for example, Patent Document 1 includes a rod-shaped fiber bundle in which a fiber bundle composed of 10 to 90% by weight of activated carbon fiber and 90 to 10% by weight of thermoplastic synthetic fiber is heat-treated to fuse the thermoplastic synthetic fiber. An adsorbent characterized by the above is disclosed. The adsorbent disclosed in Patent Document 1 is easy to handle, and can be used by simply filling it into a packed cylinder such as an adsorption tower in the same shape. Furthermore, the adsorbent has a high adsorption rate and can be used as a biological treatment carrier carrying microorganisms. For this reason, the said adsorbent can be used conveniently as a waste-liquid processing material, a deodorizing material, etc.
上記のとおり、廃液処理材や脱臭材などとして使用される吸着材は、吸着塔などに充填して使用されることがある。このため、吸着塔などへの充填特性をより高める観点からは、吸着材には適度な弾力が求められる。また、特許文献１に開示されているように、吸着材の形状としては、断面形状が円形、楕円径、ドーナツ状、トリローバル状、十字形状、星形形状などの種々の形状が知られており、このような吸着材には優れた成形性が要求される。さらに、廃液処理材や脱臭材などとして使用される吸着材は、通常、長期間に亘り水と接触する環境で使用されるため、水分存在下での高い安定性も要求される。
このような状況下、本発明は、適度な弾力を有し、優れた成形性及び水分存在下における高い安定性を備える吸着材を提供することを主な目的とする。
As described above, an adsorbent used as a waste liquid treatment material, a deodorizing material, or the like may be used by being packed in an adsorption tower or the like. For this reason, the adsorbent is required to have an appropriate elasticity from the viewpoint of further enhancing the packing characteristics of the adsorption tower and the like. As disclosed in Patent Document 1, various shapes such as a cross-sectional shape such as a circle, an elliptical diameter, a donut shape, a trilobal shape, a cross shape, and a star shape are known as the shape of the adsorbent. Such an adsorbent is required to have excellent moldability. Furthermore, since adsorbents used as waste liquid treatment materials, deodorizing materials, and the like are usually used in an environment where they are in contact with water for a long period of time, high stability in the presence of moisture is also required.
Under such circumstances, the main object of the present invention is to provide an adsorbent having an appropriate elasticity and having excellent moldability and high stability in the presence of moisture.
本発明者は、上記のような課題を解決すべく鋭意検討を行った。その結果、活性炭繊維と、活性炭繊維に熱融着した熱可塑性樹脂繊維とを含む吸着材において、熱可塑性樹脂繊維として、それぞれ特定の樹脂により形成された芯鞘構造を有する第１の芯鞘型繊維と第２の芯鞘型繊維とを併用することにより、適度な弾力を有し、優れた成形性及び水分存在下における高い安定性が奏されることを見出した。本発明は、このような知見に基づき、さらに鋭意検討を重ねて完成された発明である。 The present inventor has intensively studied to solve the above problems. As a result, in the adsorbent containing the activated carbon fiber and the thermoplastic resin fiber thermally fused to the activated carbon fiber, the first core-sheath type having a core-sheath structure formed of a specific resin as the thermoplastic resin fiber, respectively. It has been found that by using the fiber and the second core-sheath fiber in combination, the fiber has an appropriate elasticity and has excellent moldability and high stability in the presence of moisture. The present invention is an invention which has been completed based on such findings and further earnest studies.
すなわち、本発明は、下記に掲げる態様の発明を提供する。
項１． 活性炭繊維と、前記活性炭繊維に熱融着した熱可塑性樹脂繊維とを含む吸着材であって、
前記熱可塑性樹脂繊維は、芯鞘構造を有する第１の芯鞘型繊維と、芯鞘構造を有する第２の芯鞘型繊維とを有し、
前記第１の芯鞘型繊維は、鞘部がポリオレフィン樹脂Ａにより形成され、芯部が前記ポリオレフィン樹脂Ａよりも融点が高いポリオレフィン樹脂Ｂにより形成されており、
前記第２の芯鞘型繊維は、鞘部が前記ポリオレフィン樹脂Ｂよりも融点の低いポリオレフィン樹脂Ｃにより形成され、芯部が前記ポリオレフィン樹脂Ｂよりも融点が高い熱可塑性樹脂Ｄにより形成されている、吸着材。
項２． 前記第１の芯鞘型繊維及び前記第２の芯鞘型繊維の全質量中における、ポリオレフィン樹脂の質量の合計割合が、３０〜８０％である、項１に記載の吸着材。
項３． 前記ポリオレフィン樹脂Ａの融点及び前記ポリオレフィン樹脂Ｃの融点と、前記ポリオレフィン樹脂Ｂの融点との差が、それぞれ、３０〜５５℃である、項１または２に記載の吸着材。
項４． 前記ポリオレフィン樹脂Ａの融点及び前記ポリオレフィン樹脂Ｃの融点と、前記熱可塑性樹脂Ｄの融点との差が、それぞれ、１２０〜１４５℃である、項１〜３のいずれかに記載の吸着材。
項５． 前記熱可塑性樹脂Ｄが、結晶性を有する、項１〜４のいずれかに記載の吸着材。
項６． 前記ポリオレフィン樹脂Ａ及び前記ポリオレフィン樹脂Ｃが、それぞれ、ポリエチレンである、項１〜５のいずれかに記載の吸着材。
項７． 前記ポリオレフィン樹脂Ｂが、ポリプロピレンである、項１〜６のいずれかに記載の吸着材。
項８． 前記熱可塑性樹脂Ｄが、ポリエステル樹脂である、項１〜７のいずれかに記載の吸着材。
項９． 前記熱可塑性樹脂Ｄが、ポリエチレンテレフタレートである、項１〜８のいずれかに記載の吸着材。
項１０． 前記第１の芯鞘型繊維と、前記第２の芯鞘型繊維との質量比が、１：１．５〜１：５の範囲にある、項１〜９のいずれかに記載の吸着材。
項１１． 前記活性炭繊維の割合が５〜９０質量％、前記熱可塑性樹脂繊維の割合が９５〜１０質量％である、項１〜１０のいずれかに記載の吸着材。
項１２． 項１〜１１のいずれかに記載の吸着材からなる、廃液処理材。
項１３． 項１〜１１のいずれかに記載の吸着材からなる、脱臭材。
That is, this invention provides the invention of the aspect hung up below.
Item 1. An adsorbent comprising activated carbon fibers and thermoplastic resin fibers thermally fused to the activated carbon fibers,
The thermoplastic resin fiber has a first core-sheath fiber having a core-sheath structure, and a second core-sheath fiber having a core-sheath structure,
The first core-sheath fiber has a sheath part formed of a polyolefin resin A, and a core part formed of a polyolefin resin B having a melting point higher than that of the polyolefin resin A.
The second core-sheath fiber has a sheath part formed of a polyolefin resin C having a melting point lower than that of the polyolefin resin B, and a core part formed of a thermoplastic resin D having a melting point higher than that of the polyolefin resin B. , Adsorbent.
Item 2. Item 2. The adsorbent according to Item 1, wherein the total proportion of the mass of the polyolefin resin in the total mass of the first core-sheath fiber and the second core-sheath fiber is 30 to 80%.
Item 3. Item 3. The adsorbent according to Item 1 or 2, wherein a difference between the melting point of the polyolefin resin A, the melting point of the polyolefin resin C, and the melting point of the polyolefin resin B is 30 to 55 ° C.
Item 4. Item 4. The adsorbent according to any one of Items 1 to 3, wherein differences between the melting point of the polyolefin resin A and the melting point of the polyolefin resin C and the melting point of the thermoplastic resin D are 120 to 145 ° C, respectively.
Item 5. Item 5. The adsorbent according to any one of Items 1 to 4, wherein the thermoplastic resin D has crystallinity.
Item 6. Item 6. The adsorbent according to any one of Items 1 to 5, wherein the polyolefin resin A and the polyolefin resin C are each polyethylene.
Item 7. Item 7. The adsorbent according to any one of Items 1 to 6, wherein the polyolefin resin B is polypropylene.
Item 8. Item 8. The adsorbent according to any one of Items 1 to 7, wherein the thermoplastic resin D is a polyester resin.
Item 9. Item 9. The adsorbent according to any one of Items 1 to 8, wherein the thermoplastic resin D is polyethylene terephthalate.
Item 10. Item 10. The adsorbent according to any one of Items 1 to 9, wherein a mass ratio between the first core-sheath fiber and the second core-sheath fiber is in a range of 1: 1.5 to 1: 5. .
Item 11. Item 11. The adsorbent according to any one of Items 1 to 10, wherein a ratio of the activated carbon fiber is 5 to 90% by mass and a ratio of the thermoplastic resin fiber is 95 to 10% by mass.
Item 12. Item 12. A waste liquid treatment material comprising the adsorbent according to any one of Items 1 to 11.
Item 13. Item 12. A deodorizing material comprising the adsorbent according to any one of Items 1 to 11.
本発明によれば、適度な弾力を有し、優れた成形性及び水分存在下における高い安定性を備える吸着材を提供することができる。当該吸着材は、微生物を担持させる生物処理担体として使用することができる。さらに、当該吸着材は、廃液処理材や脱臭材として好適に使用することができる。 ADVANTAGE OF THE INVENTION According to this invention, it has moderate elasticity and can provide the adsorbent provided with the outstanding moldability and the high stability in the presence of moisture. The adsorbent can be used as a biological treatment carrier for supporting microorganisms. Furthermore, the adsorbent can be suitably used as a waste liquid treatment material or a deodorizing material.
本発明の吸着材は、活性炭繊維と、当該活性炭繊維に熱融着した熱可塑性樹脂繊維とを含み、熱可塑性樹脂繊維が、芯鞘構造を有する第１の芯鞘型繊維と、芯鞘構造を有する第２の芯鞘型繊維とを有し、熱可塑性樹脂繊維は、芯鞘構造を有する第１の芯鞘型繊維と、芯鞘構造を有する第２の芯鞘型繊維とを有し、第１の芯鞘型繊維は、鞘部がポリオレフィン樹脂Ａにより形成され、芯部が前記ポリオレフィン樹脂Ａよりも融点が高いポリオレフィン樹脂Ｂにより形成されており、第２の芯鞘型繊維は、鞘部がポリオレフィン樹脂Ｂよりも融点の低いポリオレフィン樹脂Ｃにより形成され、芯部がポリオレフィン樹脂Ｂよりも融点が高い熱可塑性樹脂Ｄにより形成されていることを特徴とする。以下、本発明の吸着材、当該吸着材からなる廃液処理材及び脱臭材について詳述する。 The adsorbent of the present invention includes activated carbon fiber and a thermoplastic resin fiber thermally fused to the activated carbon fiber, wherein the thermoplastic resin fiber has a first sheath-core fiber having a sheath-core structure, and a sheath-core structure. The thermoplastic resin fiber has a first core-sheath fiber having a core-sheath structure and a second core-sheath fiber having a core-sheath structure. In the first core-sheath fiber, the sheath part is formed of polyolefin resin A, the core part is formed of polyolefin resin B having a melting point higher than that of the polyolefin resin A, and the second core-sheath fiber is The sheath is formed of a polyolefin resin C having a melting point lower than that of the polyolefin resin B, and the core is formed of a thermoplastic resin D having a melting point higher than that of the polyolefin resin B. Hereinafter, the adsorbent of the present invention, the waste liquid treatment material and the deodorizing material comprising the adsorbent will be described in detail.
本発明の吸着材において、活性炭繊維の種類としては、特に制限されず、例えば、ポリアクリロニトリル系、レーヨン系、フェノール樹脂系、石炭ピッチ系、石油ピッチ系などの繊維を不融化し、所望により炭化処理した後、水蒸気、二酸化炭素を含有する雰囲気中、所定温度で所定時間保持することによって賦活することにより製造される任意の活性炭繊維を用いることができる。活性炭繊維としては、これらの中でも、石炭ピッチ、石油ピッチを原料とした活性炭繊維が好ましい。活性炭繊維は、１種類単独で使用してもよいし、２種類以上を組み合わせて使用してもよい。 In the adsorbent of the present invention, the type of activated carbon fiber is not particularly limited. For example, fibers such as polyacrylonitrile, rayon, phenolic resin, coal pitch, and petroleum pitch are infusible, and carbonized as desired. After the treatment, any activated carbon fiber produced by activation by holding at a predetermined temperature for a predetermined time in an atmosphere containing water vapor and carbon dioxide can be used. Among these, the activated carbon fiber is preferably activated carbon fiber using coal pitch or petroleum pitch as a raw material. Activated carbon fiber may be used individually by 1 type, and may be used in combination of 2 or more types.
活性炭繊維の性状は、特に制限されないが、例えば、比表面積７００〜２５００ｍ2／ｇ程度、平均細孔径５〜３５Å程度であることが好ましい。また、活性炭繊維の直径としては、例えば５〜２０μｍ程度が挙げられる。 The properties of the activated carbon fiber are not particularly limited, but are preferably, for example, a specific surface area of about 700 to 2500 m 2 / g and an average pore diameter of about 5 to 35 mm. Moreover, as a diameter of activated carbon fiber, about 5-20 micrometers is mentioned, for example.
なお、活性炭繊維は、Ｍｇ、Ｍｎ、Ｆｅ、Ｙ、Ｐｔ、及びＧｄからなる群から選択された少なくとも１種の金属成分を含むことによって、特定のメソ細孔モード直径を有する活性炭繊維となり得る。例えば、含有する金属成分の種類に応じて次のような構造・特性を有する活性炭繊維となる。本初発明においては、これらの活性炭繊維を使用してもよい。 The activated carbon fiber can be activated carbon fiber having a specific mesopore mode diameter by including at least one metal component selected from the group consisting of Mg, Mn, Fe, Y, Pt, and Gd. For example, the activated carbon fiber has the following structure and characteristics depending on the type of the metal component contained. In the present invention, these activated carbon fibers may be used.
（ａ）Ｍｇを含む場合
７７．４Ｋにおける窒素吸着等温線よりＢＪＨ法で求めた細孔分布において細孔直径３０Å以上５０Å未満の範囲のメソ細孔容積が０．０２〜０．４０ｍｌ／ｇであり、全細孔容積に対する上記メソ細孔容積の割合が５〜４５％であり、かつ、メソ細孔モード直径が３０〜３６Åである活性炭繊維。
(A) When Mg is included The mesopore volume in the range of the pore diameter of 30 mm or more and less than 50 mm in the pore distribution determined by the BJH method from the nitrogen adsorption isotherm at 77.4 K is 0.02 to 0.40 ml / g. And activated carbon fibers having a ratio of the mesopore volume to the total pore volume of 5 to 45% and a mesopore mode diameter of 30 to 36 mm.
（ｂ）Ｍｎ、Ｙ、Ｐｔ、Ｇｄの少なくとも１種を含む場合
７７．４Ｋにおける窒素吸着等温線よりＢＪＨ法で求めた細孔分布において細孔直径３０Å以上５０Å未満の範囲のメソ細孔容積が０．０２〜０．４０ｍｌ／ｇであり、全細孔容積に対するメソ細孔容積の割合が５〜４５％であり、かつ、メソ細孔モード直径が３４〜４０Åである活性炭繊維。
(B) When containing at least one of Mn, Y, Pt, and Gd The mesopore volume in the range of pore diameters of 30 mm or more and less than 50 mm in the pore distribution determined by the BJH method from the nitrogen adsorption isotherm at 77.4K Activated carbon fibers having a mesopore volume ratio of 5 to 45% and a mesopore mode diameter of 34 to 40 mm with a ratio of 0.02 to 0.40 ml / g.
（ｃ）Ｆｅを含む場合
７７．４Ｋにおける窒素吸着等温線よりＢＪＨ法で求めた細孔分布において細孔直径３０Å以上５０Å未満の範囲のメソ細孔容積が０．０２〜０．４０ｍｌ／ｇであり、全細孔容積に対するメソ細孔容積の割合が５〜４５％であり、かつ、メソ細孔モード直径が４０Å〜４５Åである活性炭繊維。
(C) When Fe is included The mesopore volume in the pore diameter range of 30 mm or more and less than 50 mm in the pore distribution determined by the BJH method from the nitrogen adsorption isotherm at 77.4 K is 0.02 to 0.40 ml / g. An activated carbon fiber having a mesopore volume ratio of 5 to 45% with respect to the total pore volume and a mesopore mode diameter of 40 to 45 mm.
上記のような活性炭繊維は、公知の方法により製造することができ、例えば、特開２００４−１８２５１１号公報に記載された方法により製造することができる。また、活性炭繊維の市販品としては、例えば、アドール社製のＡ−７等が挙げられる。 The activated carbon fiber as described above can be produced by a known method, for example, by the method described in JP-A No. 2004-182511. Moreover, as a commercial item of activated carbon fiber, A-7 by Adol Co., etc. are mentioned, for example.
本発明の吸着材は、上記の活性炭繊維に加えて、活性炭繊維に熱融着した熱可塑性樹脂繊維を含む。また、本発明においては、熱可塑性樹脂繊維が、芯鞘構造を有する第１の芯鞘型繊維と、芯鞘構造を有する第２の芯鞘型繊維とを有している。なお、本発明の吸着材においては、第１の芯鞘型繊維及び第２の芯鞘型繊維の全ての部分が熱融着しているわけではなく、第１及び第２の芯鞘型繊維が部分的に活性炭繊維に熱融着している。また、第１及び第２の芯鞘型繊維も、互いに部分的に熱融着している。 The adsorbent of the present invention includes, in addition to the above activated carbon fiber, thermoplastic resin fiber thermally fused to the activated carbon fiber. In the present invention, the thermoplastic resin fiber includes a first core-sheath fiber having a core-sheath structure and a second core-sheath fiber having a core-sheath structure. In the adsorbent of the present invention, not all portions of the first core-sheath fiber and the second core-sheath fiber are thermally fused, but the first and second core-sheath fibers. Is partially heat-sealed to the activated carbon fiber. The first and second core-sheath fibers are also partially heat-sealed.
第１の芯鞘型繊維においては、鞘部がポリオレフィン樹脂Ａにより形成されており、芯部が当該ポリオレフィン樹脂Ａよりも融点の高いポリオレフィン樹脂Ｂにより形成されている。また、第２の芯鞘型繊維においては、鞘部が第１の芯鞘型繊維の芯部を形成するポリオレフィン樹脂Ｂよりも融点の低いポリオレフィン樹脂Ｃにより形成されており、芯部が第１の芯鞘型繊維の芯部を形成するポリオレフィン樹脂Ｂよりも融点の高い熱可塑性樹脂Ｄにより形成されている。 In the first core-sheath fiber, the sheath part is formed of the polyolefin resin A, and the core part is formed of the polyolefin resin B having a melting point higher than that of the polyolefin resin A. Further, in the second core-sheath fiber, the sheath part is formed of a polyolefin resin C having a melting point lower than that of the polyolefin resin B forming the core part of the first core-sheath fiber, and the core part is the first core part. It is formed of a thermoplastic resin D having a melting point higher than that of the polyolefin resin B that forms the core of the core-sheath fiber.
すなわち、本発明の吸着材において、第１の芯鞘型繊維の鞘部を形成するポリオレフィンＡ、当該繊維の芯部を形成するポリオレフィンＢ、第２の芯鞘型繊維の鞘部を形成するポリオレフィンＣ、及び当該繊維の芯部を形成する熱可塑性樹脂Ｄの融点は、以下の関係にある。なお、本発明において、各樹脂の融点は、示差走査熱量測定（ＤＳＣ）における吸熱ピーク温度を意味する。 That is, in the adsorbent of the present invention, polyolefin A that forms the sheath of the first core-sheath fiber, polyolefin B that forms the core of the fiber, and polyolefin that forms the sheath of the second core-sheath fiber C and the melting point of the thermoplastic resin D forming the core of the fiber have the following relationship. In the present invention, the melting point of each resin means an endothermic peak temperature in differential scanning calorimetry (DSC).
（各樹脂の融点の関係）
ポリオレフィン樹脂Ａ，Ｃの融点＜ポリオレフィン樹脂Ｂの融点＜熱可塑性樹脂Ｄの融点
(Relationship between melting points of each resin)
Melting point of polyolefin resins A and C <Melting point of polyolefin resin B <Melting point of thermoplastic resin D
上記のとおり、例えば廃液処理材や脱臭材などとして使用される吸着材は、通常、長期間に亘り水と接触する環境で使用されるため、水分存在下での高い安定性も要求される。活性炭繊維と熱可塑性樹脂繊維とを含む吸着材において、水分存在下における高い安定性を発揮するためには、バインダーとなる熱可塑性樹脂繊維を単一のポリオレフィン樹脂のみにより形成することが考えられる。しかしながら、ポリオレフィン樹脂は、結晶性が高く、融点に達すると速やかに溶融する。また、ある程度の太さをもった吸着材を製造する際、吸着材の表面部分と該表面部分より中心側にある部分（中央部分）とが均一な温度となるように熱を加えることは困難である。従って、吸着材の製造工程において、吸着材の表面部分に位置する熱可塑性樹脂繊維を適度に軟化させるために高温で加熱した場合、バインダーとなる熱可塑性樹脂繊維を単一のポリオレフィン樹脂のみにより形成すると、吸着材の表面部分に位置する熱可塑性樹脂繊維が溶融し、繊維形状が保てなくなる。そうすると、吸着材の強度が極端に低くなり、成形などの際に吸着材が切断されやすくなる。一方、吸着材の表面部分に位置するポリオレフィン樹脂が溶融しすぎないように低温で加熱した場合、吸着材の中央部分に位置するポリオレフィン樹脂がほとんど溶融しない。そうすると、得られる吸着材は、表面部分だけ硬くて中央部分が柔らかいものとなってしまい、弾力性に乏しいものとなる。 As described above, for example, an adsorbent used as a waste liquid treatment material, a deodorizing material, or the like is usually used in an environment where it is in contact with water for a long period of time. In order to exhibit high stability in the presence of moisture in an adsorbent containing activated carbon fibers and thermoplastic resin fibers, it is conceivable to form thermoplastic resin fibers serving as a binder only with a single polyolefin resin. However, the polyolefin resin has high crystallinity and melts rapidly when the melting point is reached. In addition, when manufacturing an adsorbent having a certain thickness, it is difficult to apply heat so that the surface portion of the adsorbent and the portion (center portion) closer to the center than the surface portion have a uniform temperature. It is. Therefore, in the manufacturing process of the adsorbent, when heated at a high temperature in order to moderately soften the thermoplastic resin fibers located on the surface of the adsorbent, the thermoplastic resin fibers used as a binder are formed only from a single polyolefin resin. Then, the thermoplastic resin fiber located on the surface portion of the adsorbent is melted and the fiber shape cannot be maintained. If it does so, the intensity | strength of an adsorbent will become extremely low and it will become easy to cut | disconnect an adsorbent in the case of shaping | molding. On the other hand, when the polyolefin resin located on the surface portion of the adsorbent is heated at a low temperature so as not to melt too much, the polyolefin resin located in the central portion of the adsorbent hardly melts. As a result, the adsorbent obtained is hard only at the surface portion and soft at the central portion, and is poor in elasticity.
このような問題を解消するために、バインダーとなる熱可塑性樹脂繊維として、芯部の融点が鞘部の融点よりも高いものを用いることが考えられる。具体例としては、熱可塑性樹脂繊維として、芯部がポリプロピレン、鞘部がポリエチレンにより形成された芯鞘型繊維を使用することが考えられる。しかしながら、分子量などによっても異なるが、ポリプロピレンの融点は１６０℃程度、ポリエチレンの融点は１３０℃程度であり、通常、両者の融点の差は小さい。従って、このような芯鞘型繊維を用いた場合にも、芯部の融点以上の温度で吸着材を加熱すると、特に吸着材の表面部分に位置する熱可塑性樹脂繊維の芯部まで溶融し、得られる吸着材としては、硬く、弾力に劣るものが得られる。一方、芯部の融点以下の温度で加熱すると、特に吸着材の中央部分に位置する熱可塑性樹脂繊維の鞘部が溶融するのに非常に時間がかかり、吸着材の生産性が大きく低下する。 In order to solve such a problem, it is conceivable to use a thermoplastic resin fiber serving as a binder having a melting point of the core higher than that of the sheath. As a specific example, it is conceivable to use a core-sheath fiber having a core part made of polypropylene and a sheath part made of polyethylene as the thermoplastic resin fiber. However, although it varies depending on the molecular weight and the like, the melting point of polypropylene is about 160 ° C. and the melting point of polyethylene is about 130 ° C. Usually, the difference between the melting points of both is small. Therefore, even when such a core-sheath fiber is used, when the adsorbent is heated at a temperature equal to or higher than the melting point of the core, it is melted to the core of the thermoplastic resin fiber particularly located on the surface portion of the adsorbent, The obtained adsorbent is hard and inferior in elasticity. On the other hand, when heated at a temperature below the melting point of the core, it takes a very long time for the sheath of the thermoplastic resin fiber located at the center of the adsorbent to melt, and the productivity of the adsorbent is greatly reduced.
そこで、本発明者等は、芯部がポリプロピレンよりも融点の高い樹脂（例えばポリエチレンテレフタレート）であり、鞘部がポリエチレンである芯鞘型複合繊維を用いることを検討した。しかしながら、このような繊維を用いた場合、得られる吸着材は柔らかくなりすぎ、弾力性に乏しくなるという問題が生じた。 Therefore, the present inventors examined using a core-sheath type composite fiber in which the core part is a resin having a melting point higher than that of polypropylene (for example, polyethylene terephthalate) and the sheath part is polyethylene. However, when such a fiber is used, the resulting adsorbent becomes too soft, resulting in poor elasticity.
このような状況下、本発明者等がさらに検討を重ねたところ、上記の第１の芯鞘型繊維と第２の芯鞘型繊維とを併用することにより、適度な弾力を有し、優れた成形性及び水分存在下における高い安定性を備える吸着材が得られることを見出した。より具体的な例としては、芯部がポリエチレンテレフタレートで鞘部がポリエチレンである芯鞘型複合繊維と、芯部がポリエチレンテレフタレートよりも柔らかい樹脂であるポリオレフィン樹脂（例えば、ポリプロピレン）であり、鞘部がポリエチレンである芯鞘型複合繊維とを併用したところ、意外にも、得られる吸着材は、芯部がポリプロピレンよりも融点の高い樹脂（例えばポリエチレンテレフタレート）であり、鞘部がポリエチレンである芯鞘型複合繊維を単独で用いた場合よりも硬くなり、しかも適度な弾力を有し、成形性に優れることを見出した。 Under such circumstances, the present inventors have further studied, and by using the first core-sheath fiber and the second core-sheath fiber together, it has an appropriate elasticity and is excellent. The present inventors have found that an adsorbent having high moldability and high stability in the presence of moisture can be obtained. More specific examples include a core-sheath type composite fiber having a core part of polyethylene terephthalate and a sheath part of polyethylene, and a polyolefin resin (for example, polypropylene) whose core part is softer than polyethylene terephthalate, and the sheath part. Surprisingly, the resulting adsorbent is a resin having a higher core melting point than polypropylene (for example, polyethylene terephthalate) and a sheath whose core is polyethylene. It has been found that the sheath type composite fiber is harder than when the sheath type composite fiber is used alone, has an appropriate elasticity, and is excellent in moldability.
本発明において、熱可塑性樹脂繊維として、上記の第１の芯鞘型繊維と第２の芯鞘型繊維とを併用することにより、適度な弾力を有し、優れた成形性及び水分存在下における高い安定性を備える吸着材が得られる機序の詳細は明らかではないが、例えば次のように考えることができる。すなわち、本発明の吸着材においては、第１の芯鞘型繊維の鞘部が融点の低いポリオレフィン樹脂Ａ、芯部が当該ポリオレフィン樹脂Ａよりも融点の高いポリオレフィン樹脂Ｂより形成されていることに加えて、第２の芯鞘型繊維の鞘部がポリオレフィン樹脂Ｂよりも融点の低いポリオレフィン樹脂Ｃより形成され、芯部がポリオレフィン樹脂Ｂよりも融点が高い熱可塑性樹脂Ｄにより形成されている。このため、第１及び第２の芯鞘型繊維の表面部分（鞘部分）が、共に、加熱により素早く溶融すると考えられる。これにより、吸着材の中央部分にまで溶融が進行しやすく、吸着材全体において均一性高く部分的な熱融着が生じるものと考えられる。さらに、第１及び第２の芯鞘型繊維の鞘部の溶融にやや遅れて、第１の芯鞘型繊維の芯部のポリオレフィン樹脂Ｂが軟化することにより、第１の芯鞘型繊維の形状が加熱時の成形に追従して変化しやすくなり、結果、芯部がポリプロピレンよりも融点の高い樹脂（例えばポリエチレンテレフタレート）であり、鞘部がポリエチレンである芯鞘型複合繊維を単独で用いた場合よりも、吸着材の冷却後の形状において応力の低減された形状になっていると考えられる。さらに、第２の芯鞘型繊維の芯部を形成する熱可塑性樹脂Ｄの融点が高いため、成形後の吸着材の形状は維持されやすいと考えられる。以上の相乗効果により、本発明の吸着材においては、加熱による優れた成形性と、冷却後に適度な弾力が発現しているものと考えられる。また、第１および第２の芯鞘型繊維の鞘部は、それぞれ、ポリオレフィン樹脂により形成されているため、いずれも表面が加水分解し難い化学構造を有する。このため、例えばポリエステルが表面に存在する熱可塑性樹脂を用いる場合に比して、水分存在下における高い安定性を備えている。 In the present invention, as the thermoplastic resin fiber, the first core-sheath type fiber and the second core-sheath type fiber are used in combination, thereby having an appropriate elasticity, excellent moldability and in the presence of moisture. The details of the mechanism by which an adsorbent with high stability is obtained are not clear, but can be considered as follows, for example. That is, in the adsorbent of the present invention, the sheath portion of the first core-sheath fiber is formed from the polyolefin resin A having a low melting point, and the core portion is formed from the polyolefin resin B having a melting point higher than that of the polyolefin resin A. In addition, the sheath portion of the second core-sheath fiber is formed of a polyolefin resin C having a melting point lower than that of the polyolefin resin B, and the core portion is formed of a thermoplastic resin D having a melting point higher than that of the polyolefin resin B. For this reason, it is considered that both the surface portions (sheath portions) of the first and second core-sheath fibers are rapidly melted by heating. Thereby, melting is likely to proceed to the central portion of the adsorbent, and it is considered that partial heat fusion occurs with high uniformity throughout the adsorbent. Furthermore, the polyolefin resin B in the core of the first core-sheath fiber softens slightly after the melting of the sheath of the first and second core-sheath fibers, so that the first core-sheath fiber of the first core-sheath fiber is softened. The shape is easy to change following molding during heating. As a result, a core-sheath type composite fiber whose core is a resin having a higher melting point than polypropylene (for example, polyethylene terephthalate) and whose sheath is polyethylene is used alone. The shape after the cooling of the adsorbent is considered to be a shape with reduced stress, compared to the case where the adsorbent was cooled. Furthermore, since the melting point of the thermoplastic resin D forming the core portion of the second core-sheath fiber is high, it is considered that the shape of the adsorbent after molding is easily maintained. Due to the above synergistic effect, it is considered that the adsorbent of the present invention exhibits excellent moldability by heating and appropriate elasticity after cooling. In addition, since the sheath portions of the first and second core-sheath fibers are each formed of a polyolefin resin, both have a chemical structure in which the surface is hardly hydrolyzed. For this reason, for example, compared with the case where the thermoplastic resin in which polyester exists on the surface is used, it has high stability in the presence of moisture.
本発明の吸着材の弾力性、成形性、及び水分存在下における安定性を向上させる観点から、第１の芯鞘型繊維の鞘部を形成するポリオレフィン樹脂Ａの融点としては、好ましくは１００〜１４０℃程度、より好ましくは１２０〜１４０℃程度、さらに好ましくは１２５〜１３５℃程度が挙げられる。同様の観点から、鞘部を形成するポリオレフィン樹脂Ａは、ポリエチレンであることが好ましい。 From the viewpoint of improving the elasticity, moldability, and stability in the presence of moisture of the adsorbent of the present invention, the melting point of the polyolefin resin A forming the sheath portion of the first core-sheath fiber is preferably 100 to About 140 degreeC, More preferably, about 120-140 degreeC, More preferably, about 125-135 degreeC is mentioned. From the same viewpoint, the polyolefin resin A forming the sheath is preferably polyethylene.
また、第１の芯鞘型繊維において、芯部を形成するポリオレフィン樹脂Ｂの融点としては、鞘部を形成する上記のポリオレフィン樹脂Ａよりも融点が高ければ特に制限されないが、上記の観点からは、好ましくは、１４５〜１８５℃程度、より好ましくは１５０〜１８０℃程度、さらに好ましくは１６０〜１７０℃程度が挙げられる。また、同様の観点から、第１の芯鞘型繊維の芯部を形成するポリオレフィン樹脂Ｂは、ポリプロピレンであることが好ましい。第１の芯鞘型繊維は、１種類単独で使用してもよいし、２種類以上を組み合わせて使用してもよい。 Further, in the first core-sheath fiber, the melting point of the polyolefin resin B forming the core part is not particularly limited as long as the melting point is higher than that of the polyolefin resin A forming the sheath part. Preferably, about 145-185 degreeC, More preferably, about 150-180 degreeC, More preferably, about 160-170 degreeC is mentioned. From the same viewpoint, the polyolefin resin B forming the core of the first core-sheath fiber is preferably polypropylene. A 1st core sheath type fiber may be used individually by 1 type, and may be used in combination of 2 or more type.
第２の芯鞘型繊維の鞘部を形成するポリオレフィン樹脂Ｃの融点としては、吸着材の弾力、成形性、及び水分存在下における安定性を向上させる観点から、好ましくは１００〜１４０℃程度、より好ましくは１２０〜１４０℃程度、さらに好ましくは１２５〜１３５℃程度が挙げられる。同様の観点から、鞘部を形成するポリオレフィン樹脂Ｃは、ポリエチレンであることが好ましい。 The melting point of the polyolefin resin C that forms the sheath portion of the second core-sheath fiber is preferably about 100 to 140 ° C. from the viewpoint of improving the elasticity of the adsorbent, moldability, and stability in the presence of moisture. More preferably, it is about 120-140 degreeC, More preferably, about 125-135 degreeC is mentioned. From the same viewpoint, the polyolefin resin C forming the sheath is preferably polyethylene.
また、第２の芯鞘型繊維において、吸着材の弾力、成形性を向上させる観点から、芯部を形成する熱可塑性樹脂Ｄの融点としては、好ましくは、１９０〜２７０℃程度、より好ましくは２４５〜２６５℃程度、さらに好ましくは２５０〜２６０℃程度が挙げられる。同様の観点から、熱可塑性樹脂Ｄは、結晶性を有することが好ましい。また、同様の観点から、芯部を形成する熱可塑性樹脂Ｄは、ポリエステルであることが好ましく、ポリエチレンテレフタレートであることがより好ましい。第２の芯鞘型繊維は、１種類単独で使用してもよいし、２種類以上を組み合わせて使用してもよい。 In the second core-sheath fiber, from the viewpoint of improving the elasticity and moldability of the adsorbent, the melting point of the thermoplastic resin D forming the core is preferably about 190 to 270 ° C., more preferably About 245-265 degreeC, More preferably, about 250-260 degreeC is mentioned. From the same viewpoint, the thermoplastic resin D preferably has crystallinity. Further, from the same viewpoint, the thermoplastic resin D forming the core is preferably polyester, and more preferably polyethylene terephthalate. A 2nd core sheath type fiber may be used individually by 1 type, and may be used in combination of 2 or more types.
第１の芯鞘型繊維の繊維径としては、例えば０．１〜２０ｄｔｅｘ程度、より好ましくは１〜１０ｄｔｅｘ程度が挙げられる。また、第１の芯鞘型繊維における鞘部と芯部との質量比（鞘部：芯部）としては、好ましくは１：４〜４：１程度、より好ましくは２：３〜３：２程度が挙げられる。 The fiber diameter of the first core-sheath fiber is, for example, about 0.1 to 20 dtex, more preferably about 1 to 10 dtex. Moreover, as mass ratio (sheath part: core part) of the sheath part and a core part in a 1st core sheath type fiber, Preferably it is about 1: 4-4: 1, More preferably, it is 2: 3-3: 2. Degree.
第２の芯鞘型繊維の繊維径としては、例えば０．１〜２０ｄｔｅｘ程度、より好ましくは１〜１０ｄｔｅｘ程度が挙げられる。また、第２の芯鞘型繊維における鞘部と芯部との質量比（鞘部：芯部）としては、好ましくは７：３〜３：７程度、より好ましくは１：１〜３：７程度が挙げられる。 Examples of the fiber diameter of the second core-sheath fiber include about 0.1 to 20 dtex, and more preferably about 1 to 10 dtex. The mass ratio of the sheath portion to the core portion (sheath portion: core portion) in the second core-sheath fiber is preferably about 7: 3 to 3: 7, more preferably 1: 1 to 3: 7. Degree.
本発明の吸着材の弾力、成形性、及び水分存在下における安定性を向上させる観点から、第１の芯鞘型繊維及び前記第２の芯鞘型繊維の全質量中における、ポリオレフィン樹脂の質量の合計割合としては、特に制限されないが、好ましくは３０〜８０％程度、より好ましくは３５〜７５％程度、さらに好ましくは４０〜６８％程度、特に好ましくは４０〜６３％程度が挙げられる。 From the viewpoint of improving the elasticity, moldability, and stability in the presence of moisture of the adsorbent of the present invention, the mass of the polyolefin resin in the total mass of the first core-sheath fiber and the second core-sheath fiber The total ratio is not particularly limited, but is preferably about 30 to 80%, more preferably about 35 to 75%, still more preferably about 40 to 68%, and particularly preferably about 40 to 63%.
また、本発明の吸着材において、吸着材の弾力、成形性を向上させる観点から、ポリオレフィン樹脂Ａの融点及びポリオレフィン樹脂Ｃの融点と、前記ポリオレフィン樹脂Ｂの融点との差としては、それぞれ、好ましくは３０〜５５℃程度、より好ましくは３０〜５０℃程度、さらに好ましくは２５〜４５℃程度が挙げられる。同様の観点から、本発明の吸着材において、ポリオレフィン樹脂Ａの融点及びポリオレフィン樹脂Ｃの融点と、前記熱可塑性樹脂Ｄの融点との差としては、それぞれ、好ましくは１２０〜１４５℃程、より好ましくは１２０〜１４０℃程度、さらに好ましくは１１５〜１３５℃程度が挙げられる。 Further, in the adsorbent of the present invention, from the viewpoint of improving the elasticity and moldability of the adsorbent, the difference between the melting point of the polyolefin resin A and the melting point of the polyolefin resin C and the melting point of the polyolefin resin B are preferably respectively. Is about 30 to 55 ° C, more preferably about 30 to 50 ° C, still more preferably about 25 to 45 ° C. From the same viewpoint, in the adsorbent of the present invention, the difference between the melting point of the polyolefin resin A and the melting point of the polyolefin resin C and the melting point of the thermoplastic resin D is preferably about 120 to 145 ° C., respectively. Is about 120 to 140 ° C, more preferably about 115 to 135 ° C.
以上の観点から、第１の芯鞘型繊維と第２の芯鞘型繊維との最も好ましい組み合わせとしては、第１の芯鞘型繊維は、鞘部がポリエチレンにより形成され、芯部がポリプロピレンにより形成されており、第２の芯鞘型繊維は、鞘部がポリエチレンにより形成され、芯部がポリエチレンテレフタレートにより形成されている構成が挙げられる。 From the above viewpoint, as the most preferable combination of the first core-sheath fiber and the second core-sheath fiber, the first core-sheath fiber is formed of polyethylene in the sheath and polypropylene in the core. The second core-sheath fiber that is formed has a configuration in which the sheath is formed of polyethylene and the core is formed of polyethylene terephthalate.
本発明の吸着材における第１の芯鞘型繊維と第２の芯鞘型繊維との質量比（第１の芯鞘型繊維の質量：第２の芯鞘型繊維の質量）としては、特に制限されないが、吸着材の弾力、成形性、及び水分存在下における安定性を向上させる観点からは、好ましく１：１．５〜１：５の範囲、より好ましくは１：２〜１：５の範囲、さらに好ましくは１：３．５〜１：４．５の範囲、特に好ましくは１：３．６〜１：４．２の範囲が挙げられる。 As a mass ratio of the first core-sheath fiber and the second core-sheath fiber in the adsorbent of the present invention (mass of first core-sheath fiber: mass of second core-sheath fiber), in particular, Although not limited, from the viewpoint of improving the elasticity, moldability, and stability in the presence of moisture of the adsorbent, it is preferably in the range of 1: 1.5 to 1: 5, more preferably 1: 2 to 1: 5. A range is more preferable, and a range of 1: 3.5 to 1: 4.5 is particularly preferable, and a range of 1: 3.6 to 1: 4.2 is particularly preferable.
本発明の吸着材において、活性炭繊維と熱可塑性樹脂繊維との割合は、特に制限されないが、吸着材の弾力、成形性、及び水分存在下における安定性を向上させる観点からは、活性炭繊維の割合が５〜９０質量％、熱可塑性樹脂繊維の割合が９５〜１０質量％であることが好ましく、活性炭繊維の割合が１０〜８５質量％、熱可塑性樹脂繊維の割合が９０〜１５質量％であることがより好ましく、活性炭繊維の割合が１５〜８０質量％、熱可塑性樹脂繊維の割合が８５〜２０質量％であることがさらに好ましく、活性炭繊維の割合が１０〜２０質量％、熱可塑性樹脂繊維の割合が９０〜８０質量％であることが特に好ましい。 In the adsorbent of the present invention, the ratio of the activated carbon fiber and the thermoplastic resin fiber is not particularly limited, but from the viewpoint of improving the elasticity, moldability, and stability in the presence of moisture of the adsorbent, the ratio of the activated carbon fiber 5 to 90 mass%, the ratio of thermoplastic resin fibers is preferably 95 to 10 mass%, the ratio of activated carbon fibers is 10 to 85 mass%, and the ratio of thermoplastic resin fibers is 90 to 15 mass%. More preferably, the ratio of the activated carbon fiber is 15 to 80% by mass, the ratio of the thermoplastic resin fiber is more preferably 85 to 20% by mass, the ratio of the activated carbon fiber is 10 to 20% by mass, and the thermoplastic resin fiber. Is particularly preferably 90 to 80% by mass.
本発明の吸着材の形状は、通常、棒状の繊維集束体である。吸着材の形状としては、最大直径が好ましくは２ｍｍ以上、より好ましくは３〜１５ｍｍであり、断面形状が円状、楕円状、ドーナツ状、トリローバル状（例えば図１）、十字形状（例えば図２）、星形状（例えば図３）、六葉断面（例えば図４）等のものが、吸着処理操作の際に取り扱いやすく、後述する生物処理担体としても適している点から好ましい。なお、吸着材における最大直径とは、球状、ドーナツ状の場合は直径、楕円状の場合は長軸の長さ、その他の形状の場合はその最大長さを意味する。 The shape of the adsorbent of the present invention is usually a rod-shaped fiber bundle. As the shape of the adsorbent, the maximum diameter is preferably 2 mm or more, more preferably 3 to 15 mm, and the cross-sectional shape is circular, oval, donut, trilobal (for example, FIG. 1), cross shape (for example, FIG. 2). ), Star shape (for example, FIG. 3), and six-leaf cross section (for example, FIG. 4) are preferable because they are easy to handle during the adsorption treatment operation and are suitable as a biological treatment carrier described later. The maximum diameter in the adsorbent means the diameter in the case of a spherical shape or a donut shape, the length of the major axis in the case of an elliptical shape, and the maximum length in the case of other shapes.
本発明の吸着材の長さとしては、特に制限されないが、製造のし易さ、取扱い易さなどの観点からは、好ましくは２ｍｍ以上、より好ましくは２〜５０ｍｍ、さらに好ましくは２〜２０ｍｍが挙げられる。また、本発明の吸着材を例えば吸着塔等の充填筒に充填して使用する場合、吸着材の長さと直径とをほぼ同じ長さとすることにより、充填に際して異方性が少なく、充填筒内に異常な空隙を生ずることなく充填できる。さらに、吸着材の長さを充填筒の長さとほぼ同じにすれば、吸着材を充填筒の断面方向に充填するだけでよい。 The length of the adsorbent of the present invention is not particularly limited, but is preferably 2 mm or more, more preferably 2 to 50 mm, and still more preferably 2 to 20 mm from the viewpoint of ease of manufacture, ease of handling, and the like. Can be mentioned. In addition, when the adsorbent of the present invention is used by being packed in a packed cylinder such as an adsorption tower, the length and diameter of the adsorbent are almost the same length, so that there is little anisotropy during packing, and the inside of the packed cylinder It can be filled without producing an abnormal gap. Furthermore, if the length of the adsorbent is made substantially the same as the length of the filling cylinder, the adsorbent need only be filled in the cross-sectional direction of the filling cylinder.
本発明の吸着材は、上記の活性炭繊維と上記の熱可塑性樹脂繊維（第１の芯鞘型繊維及び第２の芯鞘型繊維）とからなる繊維束を熱処理することにより、活性炭繊維に熱可塑性樹脂繊維を熱融着させた、棒状の繊維集束体である。熱処理によって、熱可塑性樹脂繊維の熱融着の程度を調整し、集束体内部の繊維を部分的に接合させることが好ましい。これにより、吸着材の内部に均一性の高い空隙を有し、圧縮によりその空隙を容易に縮小できる。このような吸着材は、充填筒への充填密度を上げても、圧力損失が少なくて偏流を起こし難い。 The adsorbent of the present invention heats the activated carbon fiber by heat-treating a fiber bundle composed of the activated carbon fiber and the thermoplastic resin fiber (first core-sheath fiber and second core-sheath fiber). This is a rod-shaped fiber bundle formed by heat-sealing plastic resin fibers. It is preferable that the degree of thermal fusion of the thermoplastic resin fibers is adjusted by heat treatment to partially bond the fibers inside the bundle. Thereby, there is a highly uniform void inside the adsorbent, and the void can be easily reduced by compression. Such an adsorbent is less likely to cause a drift due to a small pressure loss even if the packing density in the filling cylinder is increased.
本発明の吸着材においては、特定の第１の芯鞘型繊維と第２の芯鞘型繊維とを有する構成とすることにより、吸着材の弾力性を維持しながら、吸着材の軽量化も可能となる。具体的に、吸着材の見掛密度（ｇ／Ｌ）としては、７０〜１００（ｇ／Ｌ）が好ましく、８０〜９０（ｇ／Ｌ）がより好ましく、８２〜８８（ｇ／Ｌ）が特に好ましい。これにより、例えば、吸着材を吸着塔などに充填して使用する場合に吸着材の弾力性を維持しながら吸着塔の重量を軽量化でき、吸着塔を建築物の２階以上の階に設置しやすくなる等の効果を奏することが可能となる。ここで、吸着材の見掛密度の測定は、１Ｌのメスシリンダーを準備し、該メスシリンダーの重量Ｘ（ｇ）を測定した後、吸着材を該メスシリンダー内に１Ｌ充填して重量Ｙ（ｇ）を測定し、下記式により算出する。
見掛密度（ｇ／Ｌ）＝Ｙ−Ｘ
特に、吸着剤として、上記見掛密度とし、かつ、断面形状がトリローバル状、十字形状、星形状、六葉断面からなる群より選ばれた１種以上の形状のみからなる、好ましくは六葉断面のみからなるものとした場合、吸着材の弾力性を維持しながら、吸着材の軽量化も可能となるという効果をより一層向上させることができる。
In the adsorbent of the present invention, the weight of the adsorbent can be reduced while maintaining the elasticity of the adsorbent by adopting a configuration having the specific first core-sheath fiber and the second core-sheath fiber. It becomes possible. Specifically, the apparent density (g / L) of the adsorbent is preferably 70 to 100 (g / L), more preferably 80 to 90 (g / L), and 82 to 88 (g / L). Particularly preferred. This makes it possible to reduce the weight of the adsorption tower while maintaining the elasticity of the adsorbent, for example, when the adsorbent is packed in an adsorption tower, etc., and the adsorption tower is installed on the second floor or higher of the building It becomes possible to produce effects such as being easy to do. Here, the apparent density of the adsorbent is measured by preparing a 1 L graduated cylinder and measuring the weight X (g) of the graduated cylinder. g) is measured and calculated by the following formula.
Apparent density (g / L) = Y-X
In particular, the adsorbent has the above apparent density and the cross-sectional shape is composed of only one or more shapes selected from the group consisting of a trilobal shape, a cross shape, a star shape, and a six-leaf cross section, preferably a six-leaf cross section. When it consists only of, it can further improve the effect that the weight of the adsorbent can be reduced while maintaining the elasticity of the adsorbent.
次に、本発明の吸着材の製造方法の一例について詳述する。まず、活性炭繊維と、生糸状または捲縮を有する熱可塑性樹脂繊維（第１の芯鞘型繊維及び第２の芯鞘型繊維）とを、好ましくは２０〜１５０ｍｍに切断し、紡績用カード機で開繊、混合してスライバー状としたり、活性炭繊維と捲縮を有する熱可塑性樹脂繊維とを開繊、混合してトウ状で引取り、繊維束を得る。次に、この繊維束を熱処理して熱可塑性樹脂繊維を、活性炭繊維に熱融着（好ましくは部分的に熱融着）させて棒状の繊維集束体とする。熱処理の方法としては、熱風を吹きつける方法、高温雰囲気中を通過させる方法等を採用することができる。具体的な熱処理の方法としては、繊維集束体を円筒形や異形筒形の加熱体中に通して熱可塑性樹脂繊維を熱融着させる方法が挙げられる。熱処理の温度としては、適宜設定すればよいが、好ましくは１６０〜１８０℃程度、より好ましくは１６５〜１７５℃程度が挙げられる。次に、繊維集束体を圧縮して冷却することにより、棒状の繊維集束体を連続成形することができる。なお、本発明において、吸着材の成形性とは、繊維収束体を成形して所望の形状を有する吸着材とする際の成形のしやすさをいう。例えば、成形時において、吸着材中央部分の繊維同士の接点に熱融着部分が多く、かつ、ヒータ内を通過させた際の繊維集束体の切断が少ない場合には、成形性が良い。この棒状の繊維集束体を、所望の長さに切断することにより、本発明の吸着材が得られる。このように、本発明の吸着材は簡単な工程で安定して効率よく製造することができる。 Next, an example of the method for producing the adsorbent of the present invention will be described in detail. First, the activated carbon fiber and the thermoplastic resin fiber (first core-sheath fiber and second core-sheath fiber) having a raw silk shape or crimp are preferably cut into 20 to 150 mm, and a spinning card machine Is opened and mixed to form a sliver, or activated carbon fibers and crimped thermoplastic resin fibers are opened, mixed and taken up in a tow shape to obtain a fiber bundle. Next, this fiber bundle is heat-treated, and the thermoplastic resin fibers are heat-sealed (preferably partially heat-sealed) to the activated carbon fibers to form rod-shaped fiber bundles. As a heat treatment method, a method of blowing hot air, a method of passing through a high temperature atmosphere, or the like can be employed. As a specific heat treatment method, there is a method in which the fiber bundle is passed through a cylindrical or irregularly shaped heating body and the thermoplastic resin fibers are thermally fused. The temperature of the heat treatment may be set as appropriate, preferably about 160 to 180 ° C, more preferably about 165 to 175 ° C. Next, the rod-shaped fiber bundle can be continuously formed by compressing and cooling the fiber bundle. In the present invention, the moldability of the adsorbent refers to the ease of molding when the fiber converging body is molded into an adsorbent having a desired shape. For example, at the time of molding, if there are many heat-sealed portions at the contact points between the fibers in the central portion of the adsorbent material, and the fiber bundling body is less cut when passed through the heater, the moldability is good. The adsorbent of the present invention is obtained by cutting the rod-shaped fiber bundle into a desired length. Thus, the adsorbent of the present invention can be produced stably and efficiently by a simple process.
本発明の吸着材の製造方法において、短繊維状の活性炭繊維と熱可塑性樹脂繊維を用いる場合、これらの繊維長としては、開繊、混合する際の各繊維間の絡まりやすさなどの観点から、好ましくは１ｍｍ以上、より好ましくは２０〜１５０ｍｍが挙げられる。なお、繊維長が１ｍｍ未満であると、繊維同士の絡まり合いが少なく、使用時に成形体としての形状が維持し難くなったり、微粉化して炭塵を発生させる原因となりやすい。 In the production method of the adsorbent of the present invention, when using short-fiber activated carbon fibers and thermoplastic resin fibers, the lengths of these fibers are from the viewpoint of easy entanglement between the fibers when opening and mixing. , Preferably it is 1 mm or more, More preferably, 20-150 mm is mentioned. If the fiber length is less than 1 mm, the fibers are less entangled, making it difficult to maintain the shape as a molded body during use, or causing pulverization to generate carbon dust.
上述のとおり、本発明の吸着材は、活性炭繊維に対して、上記特定の２種類の熱可塑性樹脂繊維を熱融着させているため、適度な弾力を有し、優れた成形性及び水分存在下における高い安定性を備えている。また、当該吸着材は、微生物を担持させる生物処理担体として好適に使用することができる。さらに当該吸着材は、廃液処理材や脱臭材として好適に使用することができる。 As described above, the adsorbent of the present invention has an appropriate elasticity, excellent moldability, and presence of moisture because the two specific types of thermoplastic resin fibers are thermally fused to the activated carbon fibers. High stability underneath. Further, the adsorbent can be suitably used as a biological treatment carrier for supporting microorganisms. Further, the adsorbent can be suitably used as a waste liquid treatment material or a deodorizing material.
例えば、本発明の吸着材を廃液処理材として用いる場合において、吸着材に対して微生物を担持させる方法としては、次の２つの方法が例示できる。第１の方法としては、予め生物膜を形成させた吸着材を処理材として用いる方法である。吸着材に予め生物膜を形成させる方法としては、例えば吸着材を樹脂などからなる充填筒に充填した後、有機物分解菌、硝化菌等の微生物を含有した培養液や排水を通水する方法や、吸着材をそのまま培養液や排水の槽に投入した後、曝気あるいは撹拌する方法などがある。 For example, when the adsorbent of the present invention is used as a waste liquid treatment material, the following two methods can be exemplified as a method for supporting microorganisms on the adsorbent. As a first method, an adsorbent on which a biofilm is formed in advance is used as a treatment material. As a method of forming a biofilm in advance on the adsorbent, for example, after filling the adsorbent into a filling tube made of resin or the like, a method of passing a culture solution or wastewater containing microorganisms such as organic matter-decomposing bacteria or nitrifying bacteria, There is a method of aeration or agitation after the adsorbent is put into a culture solution or drainage tank as it is.
予め生物膜を形成させた吸着材を廃液処理材として用いる廃液処理方法の具体例としては、次の２つ方法が挙げられる。１つ目の方法は、吸着材を固定床として用いる方法である。この方法では、生物膜を形成した吸着材を充填筒に充填して処理槽に装着し、廃液を通液して吸着材表面の生物膜に接触させ、含有する有機物等を分解、処理する方法である。また、２つ目の方法は、吸着材を流動床として用いる方法である。この方法では、生物膜を形成した吸着材をそのまま被処理液の処理槽に投入し、曝気して廃液を吸着材表面の生物膜に接触させ、含有する有機物等を分解、処理する方法である。これらの方法では、生物膜を形成させる筒状体や槽を、廃液を処理する処理槽と共用してもよい。 The following two methods can be mentioned as specific examples of the waste liquid treatment method using an adsorbent having a biofilm formed in advance as a waste liquid treatment material. The first method uses an adsorbent as a fixed bed. In this method, a biofilm-formed adsorbent is filled into a filling cylinder and attached to a treatment tank, and a waste liquid is passed through to contact the biofilm on the adsorbent surface to decompose and treat the organic matter contained therein. It is. The second method is a method using an adsorbent as a fluidized bed. In this method, the adsorbent on which the biofilm is formed is directly put into the treatment tank of the liquid to be treated, aerated to bring the waste liquid into contact with the biofilm on the surface of the adsorbent, and decompose and treat the organic matter contained therein. . In these methods, a cylindrical body or a tank for forming a biofilm may be shared with a treatment tank for treating waste liquid.
吸着材に対して微生物を担持させる第２の方法としては、生物膜を形成させる前の吸着材を用いる方法が挙げられる。この方法においても、吸着材を固定床として用いる方法と流動床として用いる方法とがある。これらの方法においては、吸着材を充填筒に充填して処理槽に装着するか、吸着材を廃液の処理槽に充填し、処理槽に通液したり、処理槽を曝気または撹拌して吸着材表面に生物膜を形成させながら、廃液を生物膜に接触させ、含有する有機物等を分解、処理することができる。 As a second method for supporting microorganisms on the adsorbent, there is a method using an adsorbent before forming a biofilm. Also in this method, there are a method of using an adsorbent as a fixed bed and a method of using it as a fluidized bed. In these methods, the adsorbent is filled into a filling cylinder and attached to the treatment tank, or the adsorbent is filled into a waste liquid treatment tank and passed through the treatment tank, or the treatment tank is aerated or agitated for adsorption. While forming a biofilm on the surface of the material, the waste liquid can be brought into contact with the biofilm to decompose and treat organic substances contained therein.
本発明の吸着材を生物処理用担体として用い、この吸着材に生物膜を形成させれば、上水、中水、工場等の用水・排水などの廃液処理に利用することが可能である。例えば、上水処理では、アンモニアの硝化、農薬やトリハロメタン前駆物質等の有害物質の分解など、中水処理では、家庭用風呂水の浄化再生、大衆浴場やプール、観賞魚、活魚、養殖魚用の水槽等における水の循環再生など、工場排水処理では、各種洗浄水の再生、排水、下水の一次処理や高度処理等を行うのに好適である。 If the adsorbent of the present invention is used as a biological treatment carrier and a biofilm is formed on the adsorbent, it can be used for the treatment of waste liquids such as clean water, middle water, and industrial water / drainage. For example, in water treatment, nitrification of ammonia, decomposition of harmful substances such as agricultural chemicals and trihalomethane precursors, etc., in central water treatment, purification and regeneration of domestic bath water, public baths and pools, ornamental fish, live fish, and cultured fish In factory wastewater treatment such as water circulation and regeneration in water tanks, etc., it is suitable for regeneration of various washing water, primary treatment and advanced treatment of drainage and sewage.
また、本発明においては、本発明の吸着材を生物処理用担体として用い、この吸着材に生物膜を形成させれば、気体中の臭い成分を除去する脱臭材としても好適に使用することができる。本発明の吸着材は、例えば、下水処理施設から発生する悪臭の生物脱臭などに有用である。 Further, in the present invention, if the adsorbent of the present invention is used as a biological treatment carrier and a biofilm is formed on the adsorbent, it can be suitably used as a deodorizing material for removing odorous components in gas. it can. The adsorbent of the present invention is useful for, for example, biological deodorization of malodors generated from sewage treatment facilities.
以下に、実施例及び比較例を示して本発明を詳細に説明する。ただし、本発明は、実施例に限定されない。 Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples.
(実施例１〜３)
活性炭繊維と活性炭繊維に熱融着した熱可塑性樹脂繊維とを含む吸着材を以下のようにして作製した。活性炭繊維（アドール社製のＡ−７）１７質量部と、熱可塑性樹脂繊維（８３質量部）の第１の芯鞘型繊維として、鞘部がポリエチレン（融点１３０℃）、芯部がポリプロピレン（融点１６５℃）により形成された、芯部と鞘部との質量比率が１：１の芯鞘型複合繊維（ＮＢＦ(Ｈ)，２．２ｄｔｅｘ×５１ｍｍ、ダイワボウポリテック社製）と、熱可塑性樹脂繊維の第２の芯鞘型繊維として、鞘部がポリエチレン（融点１３０℃）、芯部がポリエチレンテレフタレート（融点２５５℃）により形成された、芯部と鞘部との質量比率が１：１の芯鞘型複合繊維（メルティー６０８０、２．２ｄｔｅｘ×５１ｍｍ、ユニチカ社製）とを、カーディングマシーンで開繊、混合し、１ｍ当たり６ｇのカードスライバー（６８５ゲレン）とした。なお、実施例１〜３における第１の芯鞘型繊維及び第２の芯鞘型繊維の割合は、それぞれ、表１に記載の組成の通りである。次に、このカードスライバーを１７０℃のエアジェットが吹き込まれた円筒状ヒータ内を通過させて加熱し、第１の芯鞘型繊維と第２の芯鞘型繊維とを活性炭繊維に部分的に熱融着させた後、常温の空気が吹き込まれた外径８ｍｍの六葉断面のノズルに７５ｃｍ／分で導入して圧縮成形しながら冷却し、外径８ｍｍの六葉断面の棒状の繊維集束体を得た。得られた繊維収束体を長さ１０ｍｍに切断し、吸着材を得た。
(Examples 1-3)
An adsorbent containing activated carbon fibers and thermoplastic resin fibers thermally fused to the activated carbon fibers was prepared as follows. As the first core-sheath fiber of 17 parts by mass of activated carbon fiber (A-7 manufactured by Ador) and thermoplastic resin fiber (83 parts by mass), the sheath part is polyethylene (melting point 130 ° C.), and the core part is polypropylene ( A core-sheath type composite fiber (NBF (H), 2.2 dtex × 51 mm, manufactured by Daiwabo Polytech Co., Ltd.) having a mass ratio of the core part to the sheath part of 1: 1, formed by a melting point of 165 ° C.) and a thermoplastic resin As the second core-sheath fiber of the fiber, the sheath part is made of polyethylene (melting point 130 ° C.), the core part is made of polyethylene terephthalate (melting point 255 ° C.), and the mass ratio of the core part to the sheath part is 1: 1. A core-sheath type composite fiber (Melty 6080, 2.2 dtex × 51 mm, manufactured by Unitika Co., Ltd.) was opened and mixed with a carding machine to obtain a card sliver (685 gelen) of 6 g per 1 m. In addition, the ratio of the 1st core sheath type | mold fiber and the 2nd core sheath type | mold fiber in Examples 1-3 is as the composition of Table 1, respectively. Next, the card sliver is heated by passing through a cylindrical heater into which an air jet of 170 ° C. is blown, and the first core-sheath fiber and the second core-sheath fiber are partially formed on the activated carbon fiber. After heat-sealing, it is introduced into a 6-leaf cross-section nozzle with an outer diameter of 8 mm blown at room temperature and cooled at 75 cm / min. Got the body. The obtained fiber converging body was cut into a length of 10 mm to obtain an adsorbent.
なお、実施例１〜３で用いた活性炭繊維の比表面積は８５０ｍ2／ｇであった。当該比表面積は、窒素を被吸着物質として用いたＢＥＴ法で測定した。活性炭繊維の窒素ガス吸着量は、商品名「ＡＵＴＯＳＯＲＢ−６」（ＱＵＡＮＴＣＨＲＯＭＥ製）を用いて測定した。細孔分布の解析は、付属の解析プログラムで実施した。また、活性炭繊維の全細孔容積は０．３５ｍｌ／ｇであった。当該全細孔容積は、窒素の最大吸着量から計算した。 In addition, the specific surface area of the activated carbon fiber used in Examples 1-3 was 850 m < 2 > / g. The specific surface area was measured by the BET method using nitrogen as an adsorbed substance. The nitrogen gas adsorption amount of the activated carbon fiber was measured using a trade name “AUTOSORB-6” (manufactured by QUANTCHROME). The analysis of the pore distribution was carried out with the attached analysis program. The total pore volume of the activated carbon fiber was 0.35 ml / g. The total pore volume was calculated from the maximum adsorption amount of nitrogen.
実施例１〜３で得られた吸着剤の見掛密度は、８５ｇ／Ｌであった。 The apparent density of the adsorbents obtained in Examples 1 to 3 was 85 g / L.
（比較例１）
熱可塑性樹脂繊維として、鞘部がポリエチレン（融点１３０℃）、芯部がポリプロピレン（融点１６５℃）により形成された、芯部と鞘部との質量比率が１：１の芯鞘型複合繊維（ＮＢＦ(Ｈ)，２．２ｄｔｅｘ×５１ｍｍ、ダイワボウポリテック社製）８３質量部のみを使用したこと以外は、実施例１と同様にして、吸着材を得た。
(Comparative Example 1)
As a thermoplastic resin fiber, a sheath-core composite fiber having a sheath portion made of polyethylene (melting point 130 ° C.) and a core portion made of polypropylene (melting point 165 ° C.) and having a mass ratio of the core portion to the sheath portion of 1: 1 ( An adsorbent was obtained in the same manner as in Example 1 except that only 83 parts by mass of NBF (H), 2.2 dtex × 51 mm, manufactured by Daiwabo Polytech Co., Ltd. was used.
（比較例２）
熱可塑性樹脂繊維として鞘部がポリエチレン（融点１３０℃）、芯部がポリエチレンテレフタレート（融点２５５℃）により形成された、芯部と鞘部との質量比率が１：１の芯鞘型複合繊維（メルティー６０８０、２．２ｄｔｅｘ×５１ｍｍ、ユニチカ社製）８３質量部のみを使用したこと以外は、実施例１と同様にして、吸着材を得た。
(Comparative Example 2)
A core-sheath type composite fiber having a mass ratio of 1: 1 between the core part and the sheath part formed of polyethylene (melting point: 130 ° C.) as the thermoplastic resin fiber and polyethylene terephthalate (melting point: 255 ° C.) as the core part. An adsorbent was obtained in the same manner as in Example 1 except that only 83 parts by mass (Melty 6080, 2.2 dtex × 51 mm, manufactured by Unitika) was used.
＜吸着材の弾力評価＞
実施例１〜３及び比較例１，２で得られた吸着材の触感を手で確認し、以下の基準により、弾力評価を行った。結果を表１に示す。
５点：適度な硬さと十分な弾力を有し、実用上好ましいレベルであった。
４点：やや柔らかいが弾力を有するか、または、やや硬いが弾力性を有し、実用上全く問題ないレベルであった。
３点：柔らかいが弾力を有するか、または、硬いが弾力性を有し、実用上問題ないレベルであった。
２点：柔らかく弾力にやや劣るか、または、硬く弾力性にやや劣り、実用上やや問題あるレベルであった。
１点：柔らかすぎて弾力に劣るか、または、硬すぎて弾力性に劣り、実用上問題あるレベルであった。
<Evaluation of elasticity of adsorbent>
The tactile sensations of the adsorbents obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were confirmed by hand, and the elasticity was evaluated according to the following criteria. The results are shown in Table 1.
5 points: moderate hardness and sufficient elasticity, practically preferred level.
4 points: Slightly soft but elastic, or slightly hard but elastic, practically no problem.
3 points: soft but elastic, or hard but elastic, practically no problem.
Two points: Soft and slightly inferior in elasticity, or hard and slightly inferior in elasticity, and a practically problematic level.
1 point: It was too soft and inferior in elasticity, or too hard and inferior in elasticity, so that it was a practically problematic level.
＜成形性評価＞
実施例１〜３及び比較例１，２における吸着材を成形する際の成形性を、以下の基準により、成形性評価を行った。結果を表１に示す。
５点：吸着材中央部分の繊維同士の接点に熱融着部分が非常に多く、かつ、円筒状ヒータ内を通過させた際の繊維集束体の切断が少ないため、非常に成形性に優れていた。
４点：吸着材中央部分の繊維同士の接点に熱融着部分が多く、かつ、円筒状ヒータ内を通過させた際の繊維集束体の切断が少ないため、成形性に優れていた。
３点：吸着材中央部分の繊維同士の接点に熱融着部分がやや多く、かつ、円筒状ヒータ内を通過させた際の繊維集束体の切断が少ないため、成形性は実用上問題ないレベルであった。
２点：吸着材中央部分の繊維同士の接点に熱融着部分がやや少ない、または、円筒状ヒータ内を通過させた際の繊維集束体の切断がやや多いため、成形性は実用上やや問題のあるレベルであった。
１点：吸着材中央部分の繊維同士の接点に熱融着部分が少ない、または、円筒状ヒータ内を通過させた際の繊維集束体の切断が多いため、成形性は実用上問題のあるレベルであった。
<Formability evaluation>
The moldability when molding the adsorbents in Examples 1 to 3 and Comparative Examples 1 and 2 was evaluated based on the following criteria. The results are shown in Table 1.
5 points: The heat-bonding part is very large at the contact point between the fibers in the central part of the adsorbent, and the fiber bundling body is hardly cut when it passes through the cylindrical heater. It was.
Four points: The contact point between the fibers in the central portion of the adsorbent material had many heat-sealed portions, and the fiber bundles were hardly cut when passed through the cylindrical heater, so that the moldability was excellent.
3 points: There is a little heat fusion at the contact point between the fibers in the center of the adsorbent, and there is little cutting of the fiber bundling body when passing through the cylindrical heater, so the level of formability is practically acceptable. Met.
2 points: Formability is a little problematic for practical use because the heat fusion part is slightly less at the contact point between the fibers in the central part of the adsorbent, or the fiber bundling body is slightly cut when passing through the cylindrical heater. There was a certain level.
1 point: Formability is a practically problematic level because there are few heat fusion parts at the contact points between the fibers in the central part of the adsorbent, or there are many cuts of the fiber bundle when passing through a cylindrical heater. Met.
表１に示されるように、実施例１〜３では、吸着材の弾力に優れており、成形性も優れていることが分かる。実施例１〜３の吸着材においては、第１の芯鞘型繊維の鞘部が融点の低いポリエチレン、芯部が当該鞘部よりも融点の高いポリプロピレンにより形成されていることに加えて、第２の芯鞘型繊維の鞘部が融点の低いポリエチレンにより形成され、芯部が融点が高いポリエチレンテレフタレートにより形成されているため、第１及び第２の芯鞘型繊維の表面部分（鞘部分）が、共に、加熱により素早く溶融すると考えられる。これにより、吸着材の中央部分にまで溶融が進行しやすく、吸着材全体において均一性高く部分的な熱融着が生じるものと考えられる。さらに、第１及び第２の芯鞘型繊維の表面部分の溶融にやや遅れて、第１の芯鞘型繊維の芯部のポリプロピレンが軟化することにより、第２の芯鞘型繊維の形状が加熱時の成形に追従して変化しやすくなり、吸着材の冷却後の形状において応力の低減された形状になっていると考えられる。さらに、第２の芯鞘型繊維の芯部を形成するポリエチレンテレフタレートは融点が高いため、成形後の吸着材の形状は維持されやすいと考えられる。以上の相乗効果により、本発明の吸着材においては、加熱による優れた成形性と、冷却後に適度な弾力が発現しているものと考えられる。 As Table 1 shows, in Examples 1-3, it turns out that the elasticity of an adsorbent is excellent and the moldability is also excellent. In the adsorbents of Examples 1 to 3, the sheath of the first core-sheath fiber is formed of polyethylene having a low melting point, and the core is formed of polypropylene having a melting point higher than that of the sheath. Since the core portion of the core-sheath type fiber 2 is formed of polyethylene having a low melting point and the core portion is formed of polyethylene terephthalate having a high melting point, the surface portions (sheath portions) of the first and second core-sheath fibers However, both are believed to melt quickly upon heating. Thereby, melting is likely to proceed to the central portion of the adsorbent, and it is considered that partial heat fusion occurs with high uniformity throughout the adsorbent. Furthermore, the shape of the second core-sheath fiber is softened by the softening of the polypropylene in the core of the first core-sheath fiber slightly after the melting of the surface portions of the first and second core-sheath fibers. It tends to change following the molding at the time of heating, and it is considered that the shape after the cooling of the adsorbent has a reduced stress. Furthermore, since the polyethylene terephthalate forming the core portion of the second core-sheath fiber has a high melting point, it is considered that the shape of the adsorbent after molding is easily maintained. Due to the above synergistic effect, it is considered that the adsorbent of the present invention exhibits excellent moldability by heating and appropriate elasticity after cooling.
また、第１の芯鞘型繊維と第２の芯鞘型繊維の配合比を１：２〜１：５の範囲設定した実施例１，２では、弾力に非常に優れていた。また、第１の芯鞘型繊維と第２の芯鞘型繊維の配合比を１：３．５〜１：４．５の範囲設定した実施例１の吸着材は、弾力に非常に優れていた。 In Examples 1 and 2 in which the blending ratio of the first core-sheath fiber and the second core-sheath fiber was set in the range of 1: 2 to 1: 5, the elasticity was very excellent. In addition, the adsorbent of Example 1 in which the blending ratio of the first core-sheath fiber and the second core-sheath fiber is set in the range of 1: 3.5 to 1: 4.5 is very excellent in elasticity. It was.
一方、実施例１〜３で使用した第１の芯鞘型繊維と第２の芯鞘型繊維のいずれか一方のみを熱可塑性樹脂繊維として用いた比較例１及び比較例２では、弾力及び成形性の点で実施例１〜３に比して著しく劣っていた。これは、比較例１においては、熱可塑性樹脂繊維として芯部がポリプロピレン、鞘部がポリエチレンにより形成された繊維のみを用いているため、成形時の加熱によって、融点の低いポリエチレンが吸着材の表面部分において素早く溶融するが、該表面部分において芯部のポリプロピレンも溶融してしまい、冷却後には表面部分でポリエチレンとポリプロピレンの溶融物が固化した硬い吸着材になり、弾力及び成形性の点で実施例１〜３に比して著しく劣っていたと考えられる。一方、比較例２においては、芯部がポリエチレンテレフタレート、鞘部がポリエチレンにより形成された繊維のみを用いているため、結果として、柔らかく、弾力のない吸着材になり、弾力及び成形性の点で実施例１〜３に比して著しく劣っていた。 On the other hand, in Comparative Example 1 and Comparative Example 2 in which only one of the first core-sheath fiber and the second core-sheath fiber used in Examples 1 to 3 was used as the thermoplastic resin fiber, elasticity and molding It was remarkably inferior to Examples 1-3 in the point of property. This is because, in Comparative Example 1, only the fiber having the core part made of polypropylene and the sheath part made of polyethylene is used as the thermoplastic resin fiber. It melts quickly in the part, but the core polypropylene also melts in the surface part, and after cooling it becomes a hard adsorbent with a solidified polyethylene and polypropylene melt in the surface part, which is carried out in terms of elasticity and moldability It is thought that it was remarkably inferior compared with Examples 1-3. On the other hand, in Comparative Example 2, since only the fiber in which the core part is made of polyethylene terephthalate and the sheath part is made of polyethylene is used, the result is a soft, non-elastic adsorbent, and in terms of elasticity and moldability. It was remarkably inferior compared with Examples 1-3.
Claims (12)
前記熱可塑性樹脂繊維は、芯鞘構造を有する第１の芯鞘型繊維と、芯鞘構造を有する第２の芯鞘型繊維とを有し、
前記第１の芯鞘型繊維は、鞘部がポリオレフィン樹脂Ａにより形成され、芯部が前記ポリオレフィン樹脂Ａよりも融点が高いポリオレフィン樹脂Ｂにより形成されており、
前記第２の芯鞘型繊維は、鞘部が前記ポリオレフィン樹脂Ｂよりも融点の低いポリオレフィン樹脂Ｃにより形成され、芯部が前記ポリオレフィン樹脂Ｂよりも融点が高い熱可塑性樹脂Ｄにより形成されており、
前記第１の芯鞘型繊維及び第２の芯鞘型繊維が、それぞれ、部分的に前記活性炭繊維に熱融着しており、かつ、前記第１の芯鞘型繊維及び第２の芯鞘型繊維が、互いに部分的に熱融着しており、
前記第１の芯鞘型繊維と、前記第２の芯鞘型繊維との質量比が、１：１．５〜１：５の範囲にあり、
前記活性炭繊維の割合が１０〜２０質量％であり、前記熱可塑性樹脂繊維の割合が９０〜８０質量％であり、
最大直径が３〜１５ｍｍであり、長さが２〜５０ｍｍの繊維集束体の形状である、吸着材。 An adsorbent comprising activated carbon fibers and thermoplastic resin fibers thermally fused to the activated carbon fibers,
The thermoplastic resin fiber has a first core-sheath fiber having a core-sheath structure, and a second core-sheath fiber having a core-sheath structure,
The first core-sheath fiber has a sheath part formed of a polyolefin resin A, and a core part formed of a polyolefin resin B having a melting point higher than that of the polyolefin resin A.
The second core-sheath fiber has a sheath part formed of a polyolefin resin C having a melting point lower than that of the polyolefin resin B, and a core part formed of a thermoplastic resin D having a melting point higher than that of the polyolefin resin B. ,
The first core-sheath fiber and the second core-sheath fiber are partially heat-sealed to the activated carbon fiber, respectively, and the first core-sheath fiber and the second core-sheath Mold fibers are partially heat-sealed with each other,
The mass ratio of the first core-sheath fiber and the second core-sheath fiber is in the range of 1: 1.5 to 1: 5,
The ratio of the activated carbon fiber is 10 to 20% by mass, the ratio of the thermoplastic resin fiber is 90 to 80% by mass,
An adsorbent in the form of a fiber bundle having a maximum diameter of 3 to 15 mm and a length of 2 to 50 mm .
前記活性炭繊維、前記第１の芯鞘型繊維及び前記第２の芯鞘型繊維を含む繊維束を熱処理する工程を含む、吸着材の製造方法。 A manufacturing method of the adsorbent according to any one of claims 1 to 9
The manufacturing method of an adsorbent including the process of heat-processing the fiber bundle containing the said activated carbon fiber, the said 1st core-sheath-type fiber, and the said 2nd core-sheath-type fiber.
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