JP3085486B2 - Porous acrylonitrile fiber - Google Patents
Porous acrylonitrile fiberInfo
- Publication number
- JP3085486B2 JP3085486B2 JP04142117A JP14211792A JP3085486B2 JP 3085486 B2 JP3085486 B2 JP 3085486B2 JP 04142117 A JP04142117 A JP 04142117A JP 14211792 A JP14211792 A JP 14211792A JP 3085486 B2 JP3085486 B2 JP 3085486B2
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- fiber
- water
- porous
- pores
- polymer
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Description
【0001】[0001]
【産業上の利用分野】本発明は、多孔質アクリロニトリ
ル(以下ANという)系繊維に関するものであり、さら
に詳しくは多孔質構造を有する繊維の細孔が繊維表面と
連通することにより吸着、吸蔵等のデバイスとしても用
いることのできる耐熱性に優れ、形態保持性のあるAN
系繊維に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to porous acrylonitrile (hereinafter referred to as "AN") fibers, and more particularly, to adsorption, occlusion, etc., when the pores of fibers having a porous structure communicate with the fiber surface. AN with excellent heat resistance and shape retention that can be used as a device
It relates to a system fiber.
【0002】[0002]
【従来の技術】従来から多孔質AN系繊維を得るために
種々の方法が試みられている。例えば特公昭60ー11
124号公報には、酢酸セルロースをAN紡糸原液に添
加することにより吸水性の多孔質AN系繊維を形成する
ことを提案しているが、酢酸セルロースを添加した紡糸
原液はAN系重合体単独の紡糸原液に較べて原液の安定
性および可紡性に劣るものであり、工業的に十分満足さ
れるものではなく、また酢酸セルロースの変性のために
紡出糸条の耐熱性が低下し繊維製造工程中のトラブルの
原因になり、その上製品の品質も十分なものが得られな
い。2. Description of the Related Art Conventionally, various methods have been tried to obtain porous AN fibers. For example, Japanese Patent Publication No. 60-11
No. 124 proposes to form a water-absorbing porous AN fiber by adding cellulose acetate to the AN spinning stock solution. However, the spinning stock solution to which cellulose acetate is added is composed of the AN polymer alone. The stability and spinnability of the stock solution are inferior to those of the stock solution for spinning, and are not satisfactory industrially enough. It causes trouble during the process, and the quality of the product is not sufficient.
【0003】また特公昭61ー42005号公報では非
揮発性溶媒を添加し、乾式紡糸した後に該溶媒を抽出す
ることにより吸水性の多孔質のAN系繊維を形成してい
る。ところが、一般にAN系繊維の製造工程では紡糸溶
剤を回収することで製造コスト低減を図っているが、こ
のような手法は溶剤の回収工程に多大な負荷をかけるも
のであり、工業的に十分満足されるものではない。[0003] In Japanese Patent Publication No. Sho 61-42005, a non-volatile solvent is added, the solvent is extracted after dry spinning, and a water-absorbing porous AN fiber is formed. However, in general, in the production process of AN-based fibers, the production cost is reduced by recovering the spinning solvent. However, such a method imposes a great load on the recovery process of the solvent, and is industrially satisfactory. It is not something to be done.
【0004】さらにまた、特開昭47ー25416号公
報、特公昭48ー8285号公報には製造工程中の膨潤
ゲルトウに水溶性化合物を充填し、乾燥、後処理の後
で、充填物を溶出させ、ボイドを再生する方法が記載さ
れており、また、特開昭47ー25418号公報には膨
潤ゲルトウを湿熱処理して微小なボイドを残存させて、
いずれもAN系繊維に吸湿性を付与する方法が記載され
ているが、従来のこの手段は繊維物性および繊維の染色
性を満足させるためにボイドの存在を極力抑えるため
に、熱的に極めて不安定なものであり、沸水中処理、ス
チーミング処理、アイロン処理等においてボイドが消滅
する或いは繊維製品の形態保持性が低下するなどの重大
な品質低下がみられる。さらにこうした微小なボイド
は、ボイド同士がお互いに独立して存在しやすく、各々
のボイド間で通路となり得る構造が出来にくい点で効果
的ではない。Further, Japanese Patent Application Laid-Open No. 47-25416 and Japanese Patent Publication No. 48-8285 disclose a method in which a swollen gel tow in the production process is filled with a water-soluble compound, and after drying and post-treatment, the filler is eluted. A method for regenerating voids is described, and JP-A-47-25418 discloses a method in which swelled gel tow is subjected to a wet heat treatment to leave fine voids.
In both cases, a method for imparting hygroscopicity to AN-based fibers is described. However, this conventional method is extremely thermally impaired in order to minimize the presence of voids in order to satisfy fiber physical properties and fiber dyeability. It is stable, and significant quality deterioration such as disappearance of voids or deterioration of form retention of textiles in boiling water treatment, steaming treatment, ironing treatment and the like is observed. Furthermore, such minute voids are not effective in that voids are likely to exist independently of each other, and it is difficult to form a structure that can serve as a passage between each void.
【0005】またさらに、特開昭63ー309613号
公報には未乾燥の標準湿式紡糸AN系繊維のTg以下の
沸点を有する有機液体と未乾燥中繊維内に含まれている
全ての水を実質的に置換し、繊維Tg以下の温度で乾燥
し、多孔質のAN系繊維を得る方法が記載されている
が、上述したように溶剤の回収に多大な負荷をかけるう
えに、沸点の低い有機液体の回収であるだけに工業的に
有利ではない。Further, Japanese Unexamined Patent Publication (Kokai) No. 63-309613 discloses an organic liquid having a boiling point of Tg or less of undried standard wet-spun AN-based fiber and all water contained in the undried fiber. The method described above obtains a porous AN-based fiber by substituting and drying at a temperature equal to or lower than the fiber Tg. However, as described above, a large load is applied to the recovery of the solvent, and an organic solvent having a low boiling point is used. It is not industrially advantageous simply because it is liquid recovery.
【0006】以上のごとく、多孔質のAN系繊維は主に
吸水性、吸湿性の機能を有する衣料、寝装、インテリア
用途向けに改良されて来てはいるものの、熱的に安定で
且つ繊維製品の形態保持性に優れさらに新しい機能を付
与され、製造方法の経済性も満足する多孔質AN系繊維
は得られていないのが現状である。As described above, porous AN-based fibers have been improved for use in clothing, bedding, and interiors having a water-absorbing and moisture-absorbing function, but are thermally stable and have high fiber-absorbing properties. At present, a porous AN-based fiber which is excellent in shape retention of a product and further provided with a new function and satisfies the economic efficiency of the production method has not been obtained.
【0007】[0007]
【発明が解決しようとする課題】本発明の目的は、熱的
に安定で且つ繊維製品の形態保持性を有し、多孔質構造
を有する繊維の細孔が繊維表面と連通することにより従
来の吸水性の機能はもとより吸着、吸蔵等のデバイスと
しても用いることができ、且つ工業的に有利な多孔質A
N系繊維を提供することにある。SUMMARY OF THE INVENTION It is an object of the present invention to provide a conventional fiber having pores of a fiber which is thermally stable, retains the shape of a fiber product, and has a porous structure, and communicates with the fiber surface. It can be used not only as a water-absorbing function but also as a device for adsorption and occlusion.
An object of the present invention is to provide N-based fibers.
【0008】[0008]
【課題を解決するための手段】このような本発明の上記
目的は、95重量%以上のアクリロニトリルを結合含有
するアクリロニトリル系重合体の無機系溶剤原液を湿式
紡糸して得られる延伸後未乾燥繊維を120〜150℃
の温度で湿熱処理を行うことにより得られるスキン層を
有しない多孔質構造でなる繊維であって、該多孔質構造
を形成する細孔は平均細孔径が100〜6000Åで、
該細孔は連結し且つ繊維表面に連通していることを特徴
とする多孔質アクリロニトリル系繊維により達成するこ
とができる。SUMMARY OF THE INVENTION The object of the present invention is to provide an acrylonitrile polymer containing 95% by weight or more of an acrylonitrile-based polymer in an inorganic solvent stock solution after wet-spinning. 120-150 ° C
Is a fiber having a porous structure without a skin layer obtained by performing a wet heat treatment at a temperature of, the pores forming the porous structure have an average pore diameter of 100 to 6000 °,
The pores can be achieved by a porous acrylonitrile-based fiber, which is connected and communicates with the fiber surface.
【0009】このような本発明の多孔質AN系繊維は、
繊維内に適切な細孔径を有する細孔が存在し、各々の細
孔が繊維内部で連結しており、且つスキン層を有しない
が故に繊維表面と連通し、熱的に安定で且つ繊維製品の
形態保持性を有することから吸着、吸蔵等のデバイスと
して用いることができるものである。[0009] Such a porous AN-based fiber of the present invention comprises:
There are pores having an appropriate pore diameter in the fiber, each pore is connected inside the fiber, and because it does not have a skin layer, it communicates with the fiber surface, and is thermally stable and a fiber product It can be used as a device for adsorption, occlusion, etc., because it has the shape retention property.
【0010】以下、本発明を詳述する。上述の如き特異
構造を有する多孔質AN系繊維において、ANを95重
量%以上結合含有するAN系重合体を繊維構造に形成せ
しめることが重要である。AN系重合体のAN含有量が
95重量%に満たない場合は、各々の細孔が繊維内部で
連結せず、さらに繊維にスキン層を形成してしまい繊維
表面と連通しないことになる。また、熱的に安定で、且
つ繊維製品の形態保持性を得るという初期の目的を達成
する多孔質AN系繊維が得られなくなる。Hereinafter, the present invention will be described in detail. In the porous AN-based fiber having a specific structure as described above, it is important to form an AN-based polymer containing 95% by weight or more of AN into a fiber structure. When the AN content of the AN-based polymer is less than 95% by weight, the pores are not connected inside the fiber, and further, a skin layer is formed on the fiber and the fiber does not communicate with the fiber surface. Further, it is impossible to obtain a porous AN-based fiber which is thermally stable and achieves the initial purpose of obtaining the form retention of the fiber product.
【0011】また上記AN系重合体は、周知の重合手段
である懸濁重合法、乳化重合法、溶液重合法等によって
製造することができる。また該重合体は、所定量のAN
と他にANと共重合可能な不飽和ビニル化合物とを共重
合することによって作成される。かかる不飽和ビニル化
合物としては、アクリル酸、メタクリル酸又はこれらの
メチルエステル、エチルエステル等のエステル類;アク
リルアミド、メタクリルアミド又はこれらのNーアルキ
ル置換体;酢酸ビニル、プロピオン酸ビニル等のビニル
エステル類;塩化ビニル、臭化ビニル、塩化ビニリデン
等のハロゲン化ビニル又はビニリデン類;ビニルスルホ
ン酸、pースチレンスルホン酸等の不飽和スルホン酸又
はこれらの塩類;アクリル酸、メタクリル酸のジメチル
アミノエチルエステル;スチレン等を単独又は併用して
用いることができる。The AN polymer can be produced by well-known polymerization means such as suspension polymerization, emulsion polymerization, and solution polymerization. Further, the polymer has a predetermined amount of AN.
And other unsaturated vinyl compounds copolymerizable with AN. Examples of such unsaturated vinyl compounds include acrylic acid, methacrylic acid or esters thereof such as methyl ester and ethyl ester; acrylamide, methacrylamide or N-alkyl-substituted products thereof; vinyl esters such as vinyl acetate and vinyl propionate; Vinyl halides or vinylidenes such as vinyl chloride, vinyl bromide, and vinylidene chloride; unsaturated sulfonic acids such as vinyl sulfonic acid and p-styrene sulfonic acid and salts thereof; dimethylaminoethyl ester of acrylic acid and methacrylic acid; styrene Etc. can be used alone or in combination.
【0012】このようにして作製された重合体は、無機
系の繊維溶剤に溶解して紡糸原液となし、公知のノズル
で湿式紡糸される。かかる紡糸において、各々の細孔が
繊維内部で連結し、且つ繊維表面に連通するためには通
常の紡糸条件では困難であり、下記の手段を選択するこ
とによりなされ得る。The polymer thus produced is dissolved in an inorganic fiber solvent to form a spinning dope, and is wet-spun with a known nozzle. In such spinning, it is difficult under ordinary spinning conditions to connect each pore inside the fiber and communicate with the fiber surface, and it can be achieved by selecting the following means.
【0013】即ち、ロダン酸ソーダ等の無機塩を溶剤に
用いた場合の例で説明すれば、上述の如くノズルから紡
糸された繊維を5℃〜15℃、好ましくは5℃〜10℃
の凝固浴条件下で凝固させ、水洗、7〜15倍の延伸、
さらに120℃〜150℃、好ましくは130℃〜15
0℃で湿熱処理を行い、その後80℃以上で乾燥するこ
とにより作製される。凝固浴温度が5℃に満たない場合
は各々の細孔が繊維内部で連結し、且つ繊維表面に連通
してなる多孔質AN系繊維を得るという初期の目的を達
成することができない。またかかる上限を越えると可紡
性が低下し好ましくない。延伸倍率がかかる範囲を満た
さない場合は、繊維に適度な強度が付与し得ない、単糸
切れ等の問題が惹起し好ましくない。That is, in the case where an inorganic salt such as sodium rhodanate is used as a solvent, the fiber spun from the nozzle as described above is used at 5 ° C. to 15 ° C., preferably 5 ° C. to 10 ° C.
Coagulation under coagulation bath conditions, washing with water, stretching 7 to 15 times,
120 ° C to 150 ° C, preferably 130 ° C to 15 ° C
It is produced by performing a wet heat treatment at 0 ° C. and then drying at 80 ° C. or higher. If the coagulation bath temperature is lower than 5 ° C., the initial purpose of obtaining a porous AN-based fiber in which the pores are connected inside the fiber and communicate with the fiber surface cannot be achieved. If the upper limit is exceeded, the spinnability is undesirably reduced. If the draw ratio does not satisfy the above range, it is not preferable because suitable strength cannot be imparted to the fibers and problems such as breakage of single yarns occur.
【0014】一方湿熱処理がかかる温度下限に満たない
場合は熱的に安定な繊維を得ることができず、150℃
以上では繊維形態を保つことができず発明が達成されな
い。また乾燥条件において、かかる温度以下の場合は繊
維の乾燥に時間がかかり工業的に有利ではない。On the other hand, if the temperature of the wet heat treatment is less than the lower limit, a thermally stable fiber cannot be obtained,
Above, the fiber form cannot be maintained and the invention cannot be achieved. On the other hand, if the drying temperature is lower than such a temperature, it takes a long time to dry the fiber, which is not industrially advantageous.
【0015】また、本願に係る細孔の平均細孔径は10
0Å〜6000Åで有ることが必要であり、かかる下限
範囲を満たさない場合は吸着、吸蔵等のデバイスとして
用いることのできる耐熱性に優れ、且つ形態保持性のあ
るAN系繊維を得ることができない。また、かかる上限
範囲を満たさない場合は、紡糸時の糸切れ、AN系繊維
の強度等の繊維物性を得ることができない。The average pore diameter of the pores according to the present invention is 10
It is necessary to be 0 ° to 6000 °, and if the lower limit is not satisfied, it is not possible to obtain an AN fiber having excellent heat resistance and shape retention that can be used as a device for adsorption, occlusion and the like. If the upper limit is not satisfied, fiber properties such as yarn breakage during spinning and the strength of AN-based fiber cannot be obtained.
【0016】上述した平均細孔径を有する多孔質繊維の
細孔は独立したものでなく、各々の細孔が連結し且つ繊
維表面に連通していることが必要である。かかる条件を
満たさない場合は、繊維の細孔を吸着、吸蔵等のデバイ
スとして活用することができないので、繊維表面のみ若
しくは繊維表面近傍しか活用されない。The pores of the porous fiber having the above average pore diameter are not independent, and it is necessary that each pore is connected and communicates with the fiber surface. If these conditions are not satisfied, the pores of the fiber cannot be used as a device for adsorbing or occluding the fiber, so that only the fiber surface or only the vicinity of the fiber surface is used.
【0017】特に、95重量%以上のANを結合含有す
るAN系重合体の無機系溶剤原液を湿式紡糸し、延伸後
未乾燥繊維を120〜150℃、好ましくは130〜1
50℃の温度で湿熱処理を行う条件を結合採択すること
が重要であり、これにより得られる多孔質AN系繊維
は、熱的に安定であり且つ繊維製品の形態保持性を有す
るのみならず、また相互に連結した細孔でなる微多孔質
構造を有する繊維の細孔径が100〜6000Åで繊維
表面と連通していることにより、優れた吸着・吸蔵機能
を有し且つ適度な繊維物性を有するが故に良好な商品価
値に富むものとなる。In particular, an inorganic solvent stock solution of an AN polymer containing 95% by weight or more of AN is wet-spun, and after stretching, the undried fibers are heated to 120 to 150 ° C., preferably 130 to 150 ° C.
It is important to adopt a combination of conditions for performing the wet heat treatment at a temperature of 50 ° C., and the resulting porous AN-based fiber is not only thermally stable and has a shape retention property of the fiber product, but also In addition, the fibers having a microporous structure consisting of interconnected pores have a pore diameter of 100 to 6000 ° and communicate with the fiber surface, so that they have an excellent adsorption / occlusion function and have moderate fiber properties. Therefore, it has good commercial value.
【0018】また本発明の異なる実施態様として次の態
様を挙げることができる。即ち、前記多孔質AN系繊維
の作製に際し、重合体成分中に下記吸水性樹脂を導入す
るという手段である。かかる吸水性樹脂とは、重合体反
復単位400個あたり1〜15個、好ましくは2〜10
個の架橋結合を有し、絶乾状態で0.5μ以下、好まし
くは0.2μ以下の粒子径及び20〜300cc/g、好
ましくは30〜150cc/gの水膨潤度を有し、水及び
AN系重合体の溶剤に不溶性の樹脂である。The following embodiments can be cited as different embodiments of the present invention. That is, a method of introducing the following water-absorbing resin into the polymer component when producing the porous AN-based fiber. Such a water-absorbing resin is 1 to 15, preferably 2 to 10 per 400 polymer repeating units.
Having a particle size of 0.5 μm or less, preferably 0.2 μm or less, and a water swelling degree of 20 to 300 cc / g, preferably 30 to 150 cc / g in an absolutely dry state. It is a resin that is insoluble in the solvent of the AN polymer.
【0019】かかる吸水性樹脂の配合割合は、AN系重
合体重量に対して1〜6重量%未満、好ましくは1〜5
重量%の範囲から選択できる。かかる吸水性樹脂の導入
は、重合体紡糸原液に上記割合を満足するように添加混
合すればよい。紡糸以降は前記した手段を採用して多孔
質AN系繊維が製造される。なお、かかる吸水性樹脂の
作製方法については、前記特性を満足するものが得られ
るならば何ら限定されないが、かかる特性を有する樹脂
を工業的有利に作製し得る点で例えば次のような方法を
挙げることができる。The mixing ratio of the water-absorbing resin is 1 to less than 6% by weight, preferably 1 to 5% by weight, based on the weight of the AN-based polymer.
It can be selected from the range of weight%. The water-absorbing resin may be introduced and mixed with the polymer spinning solution so as to satisfy the above ratio. After spinning, the porous AN-based fiber is manufactured by using the above-described means. The method for producing such a water-absorbent resin is not particularly limited as long as a resin that satisfies the above properties is obtained.However, for example, the following method can be used to industrially produce a resin having such properties. Can be mentioned.
【0020】即ち、粒子径0.5μ以下、好ましくは
0.2μ以下であり、重合体を構成する単量体全量に対
して好ましくは50重量%以上、更に好ましくは70重
量%以上のAN、所定量の架橋性モノマーおよびANと
共重合し得る他のビニルモノマーとの架橋AN系共重合
体の水分散体に、常法に従ってアルカリ物質を作用させ
てカルボキシル基を導入することにより20〜300cc
/g、好ましくは30〜150cc/gの水膨潤度を有す
る吸水性樹脂または該樹脂の水分散体を工業的有利に作
製することができる。That is, AN having a particle size of 0.5 μm or less, preferably 0.2 μm or less, and preferably 50% by weight or more, more preferably 70% by weight or more, based on the total amount of monomers constituting the polymer. An aqueous substance of a crosslinked AN copolymer with a predetermined amount of a crosslinkable monomer and another vinyl monomer copolymerizable with AN is treated with an alkali substance according to a conventional method to introduce a carboxyl group, thereby obtaining 20 to 300 cc.
/ G, preferably 30 to 150 cc / g, of a water-absorbent resin or an aqueous dispersion of the resin can be produced industrially advantageously.
【0021】なお、かかる吸水性樹脂を水分散体の形態
で作製、使用する場合には、該水分散体が下記関係数式
1を満たす状態の、全体がゼリー状に固化するため、予
めアルカリ処理する媒体中に水混和性有機溶媒或いは電
解質塩類を共存させるなどの手段により、吸水性樹脂を
収縮させて固化するのを回避して水分散体の形態を維持
させることが好ましい。When such a water-absorbent resin is prepared and used in the form of an aqueous dispersion, the aqueous dispersion satisfies the following relational expression 1 and the whole solidifies in a jelly form. It is preferable to maintain the form of the aqueous dispersion by avoiding shrinkage and solidification of the water-absorbent resin by means such as coexistence of a water-miscible organic solvent or an electrolyte salt in the medium.
【0022】[0022]
【数1】 (Equation 1)
【0023】 但し、C;水分散体中の吸水性樹脂濃度(重量%) S;吸水性樹脂の水膨潤度(cc/g) W;水分散体中の水の割合(重量%)Where, C: concentration of water-absorbent resin in water dispersion (% by weight) S: degree of water swelling of water-absorbent resin (cc / g) W: ratio of water in water dispersion (% by weight)
【0024】なお、上記架橋性モノマーとしては、例え
ばアクリル酸もしくはメタクリル酸のジエステル類、ト
リエステル類もしくはテトラエステル類や、不飽和カル
ボン酸のアリルエステル類、多価カルボン酸のジアリル
エステル類、ジビニル系酸無水物類、ジビニルスルホ
ン、メチレンビスアクリルアミド、或いはジビニルベン
ゼン及びそのアルキル又はハロゲン置換体の如き分子内
に共重合可能な二重結合を2個以上有する架橋性単量体
及び/又は上記不飽和カルボン酸もしくは不飽和スルホ
ン酸のグリシジルエステルや、不飽和グリシジルエーテ
ルの如き分子内に少なくとも1個のエポキシ基を有する
架橋性単量体を例示することが出来る。Examples of the crosslinkable monomer include diesters, triesters or tetraesters of acrylic acid or methacrylic acid, allyl esters of unsaturated carboxylic acids, diallyl esters of polycarboxylic acids, and divinyl esters. A crosslinkable monomer having two or more copolymerizable double bonds in a molecule such as acid anhydrides, divinyl sulfone, methylenebisacrylamide, or divinylbenzene and its alkyl- or halogen-substituted product; Examples thereof include glycidyl esters of saturated carboxylic acids or unsaturated sulfonic acids, and crosslinkable monomers having at least one epoxy group in the molecule, such as unsaturated glycidyl ether.
【0025】かかる例示の架橋性単量体は前記共重合成
分として使用して重合時もしくは重合終了後に架橋せし
めることにより容易に架橋AN系共重合体を作製すると
いう目的を達成することができ、なかでも、分子内に共
重合可能な二重結合を2個以上有し、アルカリ耐性の大
きいジビニルスルホン、メチレンビスアクリルアミド、
ジビニルベンゼンなどの架橋性単量体を共重合成分とし
て使用することが望ましい。なお、上記微細粒子径の架
橋AN系共重合体の作製方法については例えば本出願人
に係る特許第1009923号発明を採用して有利に実
施することができる。The cross-linkable monomer of this example can be used as the above-mentioned copolymerization component and cross-linked at the time of polymerization or after the polymerization is completed, thereby easily achieving the object of preparing a cross-linked AN copolymer. Among them, divinyl sulfone, methylene bisacrylamide, which has two or more copolymerizable double bonds in the molecule and has high alkali resistance,
It is desirable to use a crosslinkable monomer such as divinylbenzene as a copolymer component. The method for producing the crosslinked AN-based copolymer having the fine particle diameter can be advantageously implemented, for example, by employing the invention of Japanese Patent No. 1009923 of the present applicant.
【0026】また、かかる吸水性樹脂として架橋AN系
共重合体が成分として共存する樹脂を使用することによ
り、繊維形成マトリックスポリマー(AN系重合体)と
の混和性或いは曳糸性等が一段と改善されるので望まし
い。Further, by using a resin in which a crosslinked AN copolymer is present as a component as such a water absorbing resin, the miscibility with the fiber-forming matrix polymer (AN polymer) or the spinnability is further improved. Is desirable.
【0027】このように吸水性樹脂を導入してなる多孔
質AN系繊維は、前記した吸水性樹脂を含有しない多孔
質AN系繊維と同様熱的に安定で且つ繊維製品の形態保
持性を有し、また微多孔質構造を有する繊維の細孔がミ
クロとマクロの細孔を有し、各々の細孔が繊維内部で連
結し、且つ繊維表面と連通して、吸水性はもとより優れ
た吸着、吸蔵機能を有し、適度な繊維物性を有するが故
に良好な商品価値に富むものとなる。The porous AN fiber into which the water-absorbing resin is introduced as described above is thermally stable and retains the form retention of the fiber product similarly to the porous AN fiber containing no water-absorbing resin. In addition, the pores of the fiber having a microporous structure have micro and macro pores, and each pore is connected inside the fiber and communicates with the fiber surface, so that not only water absorption but also excellent adsorption It has an occlusion function and moderate fiber properties, so that it has good commercial value.
【0028】[0028]
【作用】本願にかかる多孔質AN系繊維は、無機系溶剤
原液からの湿式紡糸で繊維形成される凝固過程で、より
積極的に微多孔質構造が繊維内部に形成される一方、繊
維表面はAN系重合体の高AN含有率に由来して、後続
する湿熱処理での内部水分の絞り出しによる細孔の表面
連通(開孔)を促すことになる粗構造となる。その構造
の基をなす細孔は、AN系重合体のAN含有率や紡糸後
未乾燥繊維の湿熱処理条件の効果でミクロとマクロなも
のとなり、且つそれぞれが連結して繊維表面にまで連通
している。かかる基材及び構造の特殊性が、本発明繊維
の諸特性や機能を発現するのであろう。In the coagulation process in which the porous AN fiber according to the present invention is formed by wet spinning from an inorganic solvent stock solution, a microporous structure is more actively formed inside the fiber, while the fiber surface is Due to the high AN content of the AN-based polymer, a coarse structure that promotes surface communication (opening) of pores by squeezing out internal moisture in the subsequent wet heat treatment is obtained. The pores that form the basis of the structure become micro and macro due to the effect of the AN content of the AN polymer and the wet heat treatment conditions of the undried fibers after spinning, and they are connected to communicate with the fiber surface. ing. Such special properties of the base material and the structure may express various properties and functions of the fiber of the present invention.
【0029】[0029]
【実施例】以下に本発明の理解を容易にするため実施例
を示すが、これらはあくまで例示的なものであり、本発
明の要旨はこれらにより限定されるものではない。な
お、実施例中、部及び百分率は特に断りのない限り重量
基準で示す。なお、実施例において記述する細孔径は下
記の方法で測定したものである。 (1)細孔径 島津ーマイクロメリティックス ポアサイザー 931
0形 を使用して、繊維内の細孔径を測定した。The following examples are provided to facilitate understanding of the present invention, but are merely illustrative, and the gist of the present invention is not limited thereto. In the examples, parts and percentages are shown on a weight basis unless otherwise specified. The pore diameter described in the examples is measured by the following method. (1) Pore size Shimadzu-Micromeritics Pore Sizer 931
The pore size in the fiber was measured using Form 0.
【0030】[0030]
【1】表1に示すようにAN、アクリル酸メチル(M
A)及びメタアリルスルホン酸ソーダ(MAS)を用
い、重合体組成を種々変化させて作製したAN系重合体
を用い、それぞれロダン酸ソーダ水溶液に溶解して紡糸
原液を作製した。これらの紡糸原液を用いて、湿式紡糸
を行い6種類のAN系繊維を作製した。すなわち、凝固
は5℃の12%ロダン酸ソーダ水溶液中で行い、次いで
水洗、10倍延伸を施し、得られた未乾燥繊維を130
℃×10分間の条件でスチームを用いて湿熱処理を行
い、さらに100℃で20分間乾燥して試料繊維を得
た。各々のAN系繊維の性能を表1に示す。As shown in Table 1, AN, methyl acrylate (M
A) and an AN-based polymer prepared by changing the polymer composition in various ways using sodium methallyl sulfonate (MAS) were respectively dissolved in an aqueous sodium rhodanate solution to prepare a spinning stock solution. Using these spinning solutions, wet spinning was performed to produce six types of AN fibers. That is, coagulation is performed in a 12% aqueous solution of sodium rhodanate at 5 ° C., followed by washing with water and 10-fold stretching.
The sample was subjected to wet heat treatment using steam at a temperature of 10 ° C. × 10 minutes, and further dried at 100 ° C. for 20 minutes to obtain a sample fiber. Table 1 shows the performance of each AN-based fiber.
【0031】なお、表中透明性はジメチルフタレートに
エチルアルコールを添加して、屈折率を1.506(ア
クリル繊維と同じ屈折率)に調整した液に繊維を浸漬さ
せて透明状態の肉眼観察を実施した結果である(繊維内
部が緻密化している或いは繊維内細孔が表面に連通して
いる場合は透明にみえ、繊維内の細孔が表面に連通して
いない場合は溶液が白濁してみえる。表中透明性の欄の
〇印は透明、×印は白濁していることを示す。)。The transparency in the table was determined by adding ethyl alcohol to dimethyl phthalate and immersing the fiber in a liquid whose refractive index was adjusted to 1.506 (the same refractive index as that of acrylic fiber). The results are as follows (If the inside of the fiber is dense or pores in the fiber are connected to the surface, it looks transparent. If the pores in the fiber are not connected to the surface, the solution becomes cloudy. In the table, the symbol “〇” in the column of transparency indicates that it is transparent, and the symbol “X” indicates that it is cloudy.)
【0032】また、染料吸着状態はマエダ化成(株)製
クリスタルバイオレットブルーを用いて濃度1000pp
m 溶液に調整し、繊維を室温(20℃)で該溶液に30
分間浸漬して染料の吸着状態を顕微鏡で観察した結果で
ある(繊維内の細孔が表面に連通していない場合は染料
が繊維内に浸透しない。表中染料吸着状態の欄の〇印は
染料が繊維内に浸透していることを、×印は浸透してい
ないことを示す。なお後述の不織布についての染料吸着
状態も同じ意味である。)。The dye adsorption state was measured using Crystal Violet Blue manufactured by Maeda Kasei Co., Ltd. at a density of 1000 pp.
m, adjust the fibers to room temperature (20 ° C.)
This is the result of observing the adsorption state of the dye with a microscope after immersion for a minute. (If the pores in the fiber do not communicate with the surface, the dye does not penetrate into the fiber. The mark “x” indicates that the dye has penetrated into the fiber, and the mark “x” indicates that the dye has not penetrated into the fiber.
【0033】[0033]
【表1】 [Table 1]
【0034】本願発明をみたす試料No.4〜6は適当
な平均細孔径を有し、かつ該細孔が連結して繊維表面に
連通していることが理解される。The sample No. which satisfies the present invention. Nos. 4 to 6 have an appropriate average pore diameter, and it is understood that the pores are connected to communicate with the fiber surface.
【0035】次いで、上記6種の繊維と熱融着繊維メル
ティTypeー110(ユニチカ(株)製)を用いて、
多孔質AN系繊維/熱融着繊維=40/60の配合比で
150℃×5分間で熱融着不織布6種類を作製した。作
製後の不織布を上述と同様にクリスタルバイオレットブ
ルー染液に浸漬して染料吸着状態を観察した。その結果
を下記表2に示す。Next, using the above-mentioned six kinds of fibers and the heat-fused fiber Melty Type-110 (manufactured by Unitika Ltd.),
Six kinds of heat-fused nonwoven fabric were produced at a mixing ratio of porous AN-based fiber / heat-fused fiber = 40/60 at 150 ° C. for 5 minutes. The nonwoven fabric after the preparation was immersed in a crystal violet blue dyeing solution in the same manner as described above, and the dye adsorption state was observed. The results are shown in Table 2 below.
【0036】[0036]
【表2】 [Table 2]
【0037】表2のように、本願発明の95重量%以上
のANを結合含有し、且つ湿熱処理条件も推奨条件を満
たさなければ、特定の細孔の形成や熱負荷によっても細
孔形態がつぶれることのない熱安定性の付与された細孔
とはならず、目的の多孔質AN系繊維が得られないこと
が判る。As shown in Table 2, when 95% by weight or more of AN of the present invention is bonded and contained, and the wet heat treatment conditions do not satisfy the recommended conditions, the pore morphology can be changed by the formation of specific pores or heat load. It does not become a pore having thermal stability imparted without being crushed, and it is understood that a target porous AN-based fiber cannot be obtained.
【0038】[0038]
【2】実施例1で作製したNo.5の重合体を用いて湿
熱処理条件を下記表3の如く行う以外は実施例1と同様
にして下記5種類の繊維を得た後、実施例1と同様にし
て5種類の熱融着不織布を作製した。その評価結果を下
記表3に併せて示す。[2] No. 2 produced in Example 1 After obtaining the following five types of fibers in the same manner as in Example 1 except that the wet heat treatment conditions are performed as shown in Table 3 below using the polymer of No. 5, five types of heat-fused nonwoven fabrics are obtained in the same manner as in Example 1. Was prepared. The evaluation results are shown in Table 3 below.
【0039】[0039]
【表3】 [Table 3]
【0040】表3に示すように、実施例1と同様に本願
発明の95重量%以上のANを結合含有し、且つ湿熱処
理条件も推奨条件を満たさなければ、繊維細孔形成及び
熱安定性の付与された多孔質AN系繊維が得られないこ
とが明瞭に判る。As shown in Table 3, as in Example 1, when 95% by weight or more of the AN of the present invention was bound and contained, and the conditions of the wet heat treatment did not satisfy the recommended conditions, fiber pore formation and thermal stability It can be clearly seen that a porous AN-based fiber to which no.
【0041】[0041]
【1】通常のAN系繊維(エクスラン(株)製 K8
3d ×51mm)を用いて実施例1と同様の実験を行って
比較した。その結果を下記表4に示す。[1] Ordinary AN fiber (K8 manufactured by Exlan Corporation)
(3d × 51 mm) and the same experiment as in Example 1 was performed and compared. The results are shown in Table 4 below.
【0042】[0042]
【表4】 [Table 4]
【0043】表4に示すように、通常のAN系繊維の透
明性の結果は、繊維が緻密化しているために(繊維内に
細孔がない)上記の結果になるが、染料吸着は全くなさ
れず、細孔の繊維表面への連通も無論存在せず当然本願
発明を満たすものではない。As shown in Table 4, the results of the transparency of ordinary AN fibers are the same as those described above because the fibers are dense (no pores in the fibers), but the dye adsorption is not at all. Of course, communication of the pores with the fiber surface does not exist, of course, and does not satisfy the present invention.
【0044】[0044]
【3】本実施例の紡糸を行うに際し、紡糸原液としては
実施例1の試料No.5の重合体紡糸原液に下記の方法
で作製した吸水性樹脂水分散体(粘度が100センチポ
イズになるようにロダン酸ソーダを添加)を、該重合体
重量に対し吸水性樹脂が3%となるように添加したもの
を用いた。吸水性樹脂微粒子は紡糸原液中において凝集
することはなく、また紡糸時ノズル詰まり、糸切れ等の
問題は何等惹起しなかった。紡糸以降は実施例1と同様
な方法を採用して多孔質AN系繊維を作製した。[3] In spinning of this example, the sample solution of Example 1 was used as a spinning solution. The water-absorbent resin aqueous dispersion (added with sodium rhodanate so that the viscosity becomes 100 centipoise) prepared by the following method was added to the polymer spinning stock solution of No. 5, and the water-absorbent resin was 3% based on the weight of the polymer. Used as described above. The water-absorbent resin fine particles did not agglomerate in the spinning dope, and did not cause any problems such as nozzle clogging and yarn breakage during spinning. After spinning, a porous AN-based fiber was produced using the same method as in Example 1.
【0045】このようにして得られた該繊維は、平均細
孔径5300Åの細孔を有し、繊維強度2.55(g/d)
で、さらに透明性に問題なく且つ不織布作製前後の染料
吸着も十分であり、熱的にも安定な多孔質AN系繊維で
あることが示された。The fiber thus obtained has pores having an average pore diameter of 5300 ° and a fiber strength of 2.55 (g / d).
Thus, it was shown that there was no problem in the transparency and the dye adsorption before and after the preparation of the nonwoven fabric was sufficient, and that the porous AN fiber was thermally stable.
【0046】なお、上記において用いた吸水性樹脂は次
のようにして作製した。即ち、AN76部、MA20
部、メチレンビスアクリルアミド(MBA)2部および
pースチレンスルホン酸ソーダ(SpSS)2部ならび
に水233部を2リットルのオートクレイブ中に仕込
み、さらに重合開始剤としてtertーブチルパーオキ
シドを単量体総量に対して0.5%添加した後密閉し、
次いで攪拌下に150℃×20分重合した。反応終了
後、攪拌を継続しながら約90℃まで冷却した後生成物
をオートクレイブから取り出した。この架橋AN系共重
合体エマルジョン中に分散する重合体の粒子径は0.1
μであった。The water-absorbing resin used in the above was prepared as follows. That is, AN76 part, MA20
Parts, 2 parts of methylenebisacrylamide (MBA), 2 parts of sodium p-styrenesulfonate (SpSS) and 233 parts of water were charged into a 2 liter autoclave, and tert-butyl peroxide was used as a polymerization initiator with a monomer. After adding 0.5% to the total amount, it is sealed,
Then, polymerization was carried out at 150 ° C. for 20 minutes with stirring. After the completion of the reaction, the mixture was cooled to about 90 ° C. while continuing stirring, and then the product was taken out of the autoclave. The particle size of the polymer dispersed in the crosslinked AN copolymer emulsion is 0.1
μ.
【0047】次に、重合体濃度を25%に調整した上記
エマルジョン20部を、3%の苛性ソーダ水溶液80部
に添加し、攪拌下に95℃×30分アルカリ処理を施し
た。得られた吸水性樹脂は架橋AN系共重合体芯部を有
しており、0.1μの粒子径および70cc/gの水膨潤度
を有していた。Next, 20 parts of the above emulsion whose polymer concentration was adjusted to 25% was added to 80 parts of a 3% aqueous solution of caustic soda, and subjected to alkali treatment at 95 ° C. for 30 minutes with stirring. The obtained water-absorbent resin had a core of a crosslinked AN copolymer, and had a particle diameter of 0.1 μm and a water swelling degree of 70 cc / g.
【0048】なお、上記水膨潤度は次の方法で測定、算
出したものである。吸水性樹脂約0.5gを純水中に浸
漬し、25℃で24時間経過後、水膨潤状態の吸水性樹
脂を濾紙の間にはさみ樹脂粒子間の水を除去する。この
ようにして調整した試料の重量(W1)を測定する。次
に該試料を80℃の真空乾燥機中で恒量になるまで乾燥
して重量(W2)を測定する。以上の測定結果より、次
の数式2に従って算出する。The degree of water swelling was measured and calculated by the following method. About 0.5 g of water-absorbent resin is immersed in pure water, and after 24 hours at 25 ° C., the water-absorbent resin in a water-swelled state is sandwiched between filter papers to remove water between resin particles. The weight (W1) of the sample thus adjusted is measured. Next, the sample is dried in a vacuum dryer at 80 ° C. until a constant weight is obtained, and the weight (W2) is measured. Based on the above measurement results, it is calculated according to the following mathematical formula 2.
【0049】[0049]
【数2】 (Equation 2)
【0050】[0050]
【発明の効果】本発明によって得られる多孔質AN系繊
維は、熱的に安定であり且つ繊維製品の形態保持性に優
れ、また多孔質構造を有する繊維の細孔が100〜60
00Åで繊維表面と連通し、吸水性はもとより優れた吸
着・吸蔵機能を有し、以て殺虫剤、抗菌剤、土壌改良剤
等種々の薬剤を含浸・担持させることも可能であり、ま
た吸着剤、触媒担体等のデバイスとしても適用すること
ができる。Industrial Applicability The porous AN fiber obtained by the present invention is thermally stable, has excellent shape retention of a fiber product, and has a porous structure having pores of 100 to 60.
It has excellent adsorption and storage functions as well as water absorption, and can impregnate and carry various agents such as insecticides, antibacterial agents, and soil conditioners. It can also be applied as a device such as an agent or a catalyst carrier.
Claims (1)
合含有するアクリロニトリル系重合体の無機系溶剤原液
を湿式紡糸して得られる延伸後未乾燥繊維を120〜1
50℃の温度で湿熱処理を行うことにより得られるスキ
ン層を有しない多孔質構造でなる繊維であって、該多孔
質構造を形成する細孔は平均細孔径が100〜6000
Åで、該細孔は連結し且つ繊維表面に連通していること
を特徴とする多孔質アクリロニトリル系繊維。An acrylonitrile-based polymer solution containing 95% by weight or more of acrylonitrile bonded to an inorganic solvent stock solution is subjected to wet spinning to obtain a stretched undried fiber of from 120 to 1%.
A fiber having a porous structure without a skin layer obtained by performing a wet heat treatment at a temperature of 50 ° C., wherein the pores forming the porous structure have an average pore diameter of 100 to 6000.
The porous acrylonitrile-based fiber, wherein the pores are connected and communicate with the fiber surface.
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JP04142117A JP3085486B2 (en) | 1992-05-06 | 1992-05-06 | Porous acrylonitrile fiber |
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Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP04142117A JP3085486B2 (en) | 1992-05-06 | 1992-05-06 | Porous acrylonitrile fiber |
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JPH05311508A JPH05311508A (en) | 1993-11-22 |
JP3085486B2 true JP3085486B2 (en) | 2000-09-11 |
Family
ID=15307804
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WO2010038486A1 (en) | 2008-10-02 | 2010-04-08 | 名古屋油化株式会社 | Sound absorbing material, multilayer sound absorbing material, molded multilayer sound absorbing material, sound absorbing interior material, and sound absorbing floor covering material |
JP6510561B2 (en) * | 2015-01-14 | 2019-05-08 | Sdpグローバル株式会社 | Absorbent articles |
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1992
- 1992-05-06 JP JP04142117A patent/JP3085486B2/en not_active Expired - Fee Related
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JPH05311508A (en) | 1993-11-22 |
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