JP6315302B2 - Cross-linked acrylate-based ultrafine fiber structure - Google Patents
Cross-linked acrylate-based ultrafine fiber structure Download PDFInfo
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- JP6315302B2 JP6315302B2 JP2013110823A JP2013110823A JP6315302B2 JP 6315302 B2 JP6315302 B2 JP 6315302B2 JP 2013110823 A JP2013110823 A JP 2013110823A JP 2013110823 A JP2013110823 A JP 2013110823A JP 6315302 B2 JP6315302 B2 JP 6315302B2
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- carboxyl group
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- crosslinked acrylate
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims description 83
- 229920001410 Microfiber Polymers 0.000 title claims description 63
- 239000000835 fiber Substances 0.000 claims description 110
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 63
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 31
- 239000013566 allergen Substances 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 23
- 238000004132 cross linking Methods 0.000 claims description 22
- -1 polyethylene Polymers 0.000 claims description 20
- 239000002657 fibrous material Substances 0.000 claims description 17
- 230000007062 hydrolysis Effects 0.000 claims description 12
- 238000006460 hydrolysis reaction Methods 0.000 claims description 12
- 239000002781 deodorant agent Substances 0.000 claims description 9
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 239000004745 nonwoven fabric Substances 0.000 description 50
- 238000010521 absorption reaction Methods 0.000 description 34
- 239000002121 nanofiber Substances 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 16
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 10
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- 238000005259 measurement Methods 0.000 description 10
- 229910017604 nitric acid Inorganic materials 0.000 description 10
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 8
- 230000001877 deodorizing effect Effects 0.000 description 8
- 238000001523 electrospinning Methods 0.000 description 8
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- 239000002253 acid Substances 0.000 description 7
- 238000010306 acid treatment Methods 0.000 description 7
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 238000004332 deodorization Methods 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000002779 inactivation Effects 0.000 description 5
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 229920001213 Polysorbate 20 Polymers 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
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- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 150000002429 hydrazines Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- 125000002560 nitrile group Chemical group 0.000 description 2
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- FBOUIAKEJMZPQG-AWNIVKPZSA-N (1E)-1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)pent-1-en-3-ol Chemical compound C1=NC=NN1/C(C(O)C(C)(C)C)=C/C1=CC=C(Cl)C=C1Cl FBOUIAKEJMZPQG-AWNIVKPZSA-N 0.000 description 1
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical group NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 description 1
- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 description 1
- 241000238876 Acari Species 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 238000002965 ELISA Methods 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
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- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920002873 Polyethylenimine Chemical group 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
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- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- KQWLJXPRTSCUOO-UHFFFAOYSA-N aminoazanium;bromate Chemical compound [NH3+]N.[O-]Br(=O)=O KQWLJXPRTSCUOO-UHFFFAOYSA-N 0.000 description 1
- BIVUUOPIAYRCAP-UHFFFAOYSA-N aminoazanium;chloride Chemical compound Cl.NN BIVUUOPIAYRCAP-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 229940098773 bovine serum albumin Drugs 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
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- 125000002843 carboxylic acid group Chemical group 0.000 description 1
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- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
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- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
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- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
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- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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- 229910052700 potassium Inorganic materials 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、消臭性能、吸放湿性、抗アレルゲン性能等を有する架橋アクリレート系超極細繊維構造体に関する。 The present invention relates to a crosslinked acrylate-based ultrafine fiber structure having deodorant performance, moisture absorption / release properties, antiallergen performance, and the like.
近年の健康、快適性に対する意識の高まりから、消臭性能、抗アレルゲン性能、吸放湿性等の機能を有する素材の開発が求められており、繊維分野においてもこれら性能を付与した素材の開発が盛んに行なわれている。中でも、架橋アクリレート系繊維は様々な機能を発現しうる素材として開発が進められており、たとえば、消臭性能を有するアクリレート系繊維（特許文献１）、吸放湿性能を有するアクリレート系繊維（特許文献２）および、抗アレルゲン性能を有するアクリレート系繊維（特許文献３）が知られている。 With the recent increase in awareness of health and comfort, the development of materials with functions such as deodorant performance, anti-allergen performance, and moisture absorption / release properties is required. It is actively performed. Among these, cross-linked acrylate fibers are being developed as materials capable of expressing various functions. For example, acrylate fibers having deodorizing performance (Patent Document 1), acrylate fibers having moisture absorption / release performance (patents) Document 2) and acrylate fibers having antiallergen performance (Patent Document 3) are known.
しかし、これらの従来のアクリレート系繊維に関する技術では、消臭や吸湿の速度、容量等の性能面の向上に限界があり、更なる高性能化のニーズに対して必ずしも満足できる性能を提供するものではなかった。 However, these conventional acrylate fiber technologies have limitations in improving performance such as deodorization and moisture absorption speed, capacity, etc., and provide performance that is always satisfactory for the need for higher performance. It wasn't.
本発明は、かかる従来技術の現状に鑑みて創案されたものであり、その目的は、消臭性能、抗アレルゲン性能、吸放湿性等において、これまで知られていた架橋アクリレート系繊維材料と比較し、速度、容量等の面で卓越した性能を有する機能性架橋アクリレート系超極細繊維構造体を提供することにある。 The present invention was devised in view of the current state of the prior art, and its purpose is to compare with cross-linked acrylate fiber materials known so far in terms of deodorizing performance, anti-allergen performance, moisture absorption / release properties, etc. Another object of the present invention is to provide a functional cross-linked acrylate-based ultrafine fiber structure having excellent performance in terms of speed and capacity.
本発明者は、上述の目的を達成するために鋭意検討を進めた結果、従来にない１３〜１３００ｎｍという極めて小さい繊維径を有する架橋アクリレート系繊維を得ることに成功し、かかる超極細の架橋アクリレート系繊維を含む繊維構造体が、消臭性能、抗アレルゲン性能、吸放湿性等において、これまで知られていた材料と比較し、速度、容量等の面で卓越した性能を有することを見出し、本発明に到達した。 As a result of diligent investigations to achieve the above-mentioned object, the present inventor succeeded in obtaining a crosslinked acrylate fiber having an extremely small fiber diameter of 13 to 1300 nm, which has not been conventionally obtained, and such an ultrafine crosslinked acrylate. It has been found that a fiber structure containing a fiber has superior performance in terms of speed, capacity, etc. in terms of deodorant performance, anti-allergen performance, moisture absorption / release properties, etc. The present invention has been reached.
即ち、本発明は以下の手段により達成される。
（１） １〜１０ｍｍｏｌ／ｇのカルボキシル基および架橋構造を含有し、かつ、平均繊維径が１３〜１３００ｎｍである架橋アクリレート系超極細繊維が、該繊維以外の繊維からなり、かつ、鞘部がポリエチレンである芯鞘構造の熱融着性繊維を７ｇ／ｍ２以上含む繊維素材上に積層され、該繊維素材に接着されている架橋アクリレート系超極細繊維構造体であって、前記繊維素材上に一体化された平均繊維径が１０〜１０００ｎｍのポリアクリロニトリル系超極細繊維を含む繊維構造体に１分子中の窒素数が２以上である窒素含有化合物による架橋処理および加水分解処理を施して得られることを特徴とする架橋アクリレート系超極細繊維構造体。
（２） （１）に記載の架橋アクリレート系超極細繊維構造体であって、かつ、該構造体を構成する架橋アクリレート系超極細繊維が、カルボキシル基として１〜１０ｍｍｏｌ／ｇのＨ型カルボキシル基を含むものである架橋アクリレート系超極細繊維構造体を含有するアレルゲン除去材。
（３） （１）に記載の架橋アクリレート系超極細繊維構造体であって、かつ、該構造体を構成する架橋アクリレート系超極細繊維が、カルボキシル基として１〜１０ｍｍｏｌ／ｇのＨ型カルボキシル基を含むものである架橋アクリレート系超極細繊維構造体を含有する消臭材。
（４） （１）に記載の架橋アクリレート系超極細繊維構造体であって、かつ、該構造体を構成する架橋アクリレート系超極細繊維が、カルボキシル基として１〜１０ｍｍｏｌ／ｇの塩型カルボキシル基を含むものである架橋アクリレート系超極細繊維構造体を含有する吸湿材。
（５） （１）に記載の架橋アクリレート系超極細繊維構造体を有するフィルター。
That is, the present invention is achieved by the following means.
(1) A crosslinked acrylate-based ultrafine fiber having a carboxyl group of 1 to 10 mmol / g and a crosslinked structure and having an average fiber diameter of 13 to 1300 nm is composed of fibers other than the fibers, and the sheath part A cross-linked acrylate-based ultrafine fiber structure that is laminated on a fiber material containing 7 g / m 2 or more of a heat-sealable fiber having a core-sheath structure that is polyethylene and is bonded to the fiber material, Obtained by subjecting a fiber structure containing polyacrylonitrile-based ultrafine fibers having an average fiber diameter of 10 to 1000 nm integrated to a cross-linking treatment and hydrolysis treatment with a nitrogen-containing compound having 2 or more nitrogen atoms in one molecule. A cross-linked acrylate-based ultrafine fiber structure characterized in that
( 2 ) The crosslinked acrylate-based ultrafine fiber structure according to (1), wherein the crosslinked acrylate-based ultrafine fiber constituting the structure has 1 to 10 mmol / g of an H-type carboxyl group as a carboxyl group An allergen-removing material comprising a crosslinked acrylate-based ultrafine fiber structure that contains
( 3 ) The crosslinked acrylate-based ultrafine fiber structure according to (1), wherein the crosslinked acrylate-based ultrafine fiber constituting the structure is an H-type carboxyl group having 1 to 10 mmol / g as a carboxyl group. A deodorant containing a crosslinked acrylate-based ultrafine fiber structure that contains
( 4 ) The crosslinked acrylate-based ultrafine fiber structure according to (1), wherein the crosslinked acrylate-based ultrafine fiber constituting the structure has a carboxyl group of 1 to 10 mmol / g as a carboxyl group Hygroscopic material containing a crosslinked acrylate-based ultrafine fiber structure that contains
( 5 ) A filter having the crosslinked acrylate-based ultrafine fiber structure according to (1).
本発明の特筆すべき効果は、これまで知られていた材料では到底達成できなかった消臭、吸湿、抗アレルゲン性能等の速度性能、容量性能等に優れた繊維構造体を提供し得た点である。また、本発明の架橋アクリレート系超極細繊維構造体からなる不織布は、従来知られている架橋アクリレート系繊維からなる通常繊維径で得られる不織布では到底得られない強度を持つため、フィルターをはじめ、さまざまな用途、分野の製品に容易に適用できる。 The remarkable effect of the present invention is that it was possible to provide a fiber structure excellent in speed performance, capacity performance, etc., such as deodorization, moisture absorption, antiallergen performance, which could not be achieved with materials known so far. It is. In addition, the nonwoven fabric composed of the crosslinked acrylate-based ultrafine fiber structure of the present invention has a strength that cannot be obtained with a conventional fiber diameter of a conventional crosslinked acrylate-based fiber. It can be easily applied to products in various applications and fields.
本発明の繊維構造体は１〜１０ｍｍｏｌ／ｇのカルボキシル基および架橋構造を含有し、かつ、平均繊維径が１３〜１３００ｎｍである架橋アクリレート系超極細繊維を含む架橋アクリレート系超極細繊維構造体である。 The fiber structure of the present invention is a crosslinked acrylate-based ultrafine fiber structure containing a crosslinked acrylate-based ultrafine fiber having a carboxyl group of 1 to 10 mmol / g and a crosslinked structure, and having an average fiber diameter of 13 to 1300 nm. is there.
本発明の繊維構造体が、優れた消臭性能、抗アレルゲン性能、吸放湿性能を発現する理由としては該繊維構造体に含まれる架橋アクリレート系繊維が超極細繊維であり、従来知られている架橋アクリレート系繊維と比較して比表面積が圧倒的に大きいことが挙げられる。すなわち、繊維単位重量あたりの表層部に存在するカルボキシル基量に秀でているため、アレルゲン物質、悪臭物質あるいは水蒸気などの除去対象物質をすばやく、多量に吸着することができるのである。 The reason why the fiber structure of the present invention exhibits excellent deodorizing performance, anti-allergen performance, and moisture absorption / release performance is that the crosslinked acrylate fiber contained in the fiber structure is an ultrafine fiber, and has been conventionally known. It is mentioned that the specific surface area is overwhelmingly large compared to the crosslinked acrylate fiber. That is, since it is excellent in the amount of carboxyl groups present in the surface layer part per unit weight of the fiber, it is possible to adsorb quickly and a large amount of a substance to be removed such as an allergen substance, malodorous substance or water vapor.
本発明に採用する架橋アクリレート系超極細繊維のカルボキシル基の量としては、１〜１０ｍｍｏｌ／ｇであり、好ましくは２〜１０ｍｍｏｌ／ｇ、より好ましくは５〜１０ｍｍｏｌ／ｇである。カルボキシル基の量が下限に満たない場合には、十分な消臭性能、抗アレルゲン性能、吸放湿性能が得られないことがあり、上限を超える場合には、繊維の水膨潤性が高くなりすぎ実用上満足し得る繊維物性が得られないことがある。 The amount of the carboxyl group of the crosslinked acrylate-based ultrafine fiber employed in the present invention is 1 to 10 mmol / g, preferably 2 to 10 mmol / g, more preferably 5 to 10 mmol / g. If the amount of the carboxyl group is less than the lower limit, sufficient deodorant performance, antiallergen performance, moisture absorption / release performance may not be obtained, and if the amount exceeds the upper limit, the water swellability of the fiber increases. In some cases, fiber properties that are practically satisfactory cannot be obtained.
カルボキシル基の状態としては、対イオンがＨ、すなわちＣＯＯＨの形（以下、Ｈ型カルボキシル基とも言う）であれば、アンモニア、トリエチルアミン、ピリジン等のアミン系ガス等の消臭性能や抗アレルゲン性能に関して優れた性能が発現する。抗アレルゲン性能については、除去対象となるアレルゲンは特に限定されないが、花粉やダニなどから発生するアレルゲンを効率よく除去することができる。なお、抗アレルゲン性能を発現する理由は定かではないが、Ｈ型カルボキシル基とアレルゲン物質が相互作用することにより、繊維にアレルゲンが吸着するのではないかと考えられる。 As for the state of the carboxyl group, if the counter ion is H, that is, in the form of COOH (hereinafter also referred to as H-type carboxyl group), the deodorization performance and antiallergen performance of amine gases such as ammonia, triethylamine, pyridine, etc. Excellent performance appears. Regarding the anti-allergen performance, the allergen to be removed is not particularly limited, but allergens generated from pollen, mites and the like can be efficiently removed. In addition, although the reason for developing anti-allergen performance is not clear, it is thought that the allergen is adsorbed to the fiber by the interaction between the H-type carboxyl group and the allergen substance.
また、カルボキシル基の状態として、対イオンがＨ以外のカチオン（以下、塩型カルボキシル基とも言う）であれば、酢酸、イソ吉草酸等の酸性ガス、ホルムアルデヒド等のアルデヒドに対する優れた消臭性能、及び吸放湿性能が発現する。 In addition, if the counter ion is a cation other than H (hereinafter also referred to as a salt-type carboxyl group) as the carboxyl group state, it has excellent deodorizing performance against acid gases such as acetic acid and isovaleric acid, and aldehydes such as formaldehyde, And moisture absorption / release performance is exhibited.
また、本発明に採用する架橋アクリレート系超極細繊維においては、架橋構造を有することで、水との親和性の高いカルボキシル基を多量に有するにもかかわらず、水に溶解せず、水膨潤も抑制され、実用上満足し得る物性を保持することができる。 In addition, the crosslinked acrylate-based ultrafine fiber employed in the present invention has a crosslinked structure, so that it does not dissolve in water and has water swelling despite having a large amount of carboxyl groups with high affinity for water. It is suppressed, and the physical properties that can be satisfied in practice can be maintained.
本発明に採用する架橋アクリレート系超極細繊維の平均繊維径としては、１３〜１３００ｎｍであり、下限については好ましくは５０ｎｍ、より好ましくは１００ｎｍ、上限については好ましくは９００ｎｍ、より好ましくは７００ｎｍである。平均繊維径が上限を超える場合には、従来の架橋アクリレート系繊維に対して、消臭性能、抗アレルゲン性能、吸放湿性能などにおける優位性が十分に得られないことがある。一方、平均繊維径が下限に満たない繊維は現在の技術においては製造が難しく、実用的ではない。 The average fiber diameter of the crosslinked acrylate-based ultrafine fibers employed in the present invention is from 13 to 1300 nm, preferably about 50 nm, more preferably about 100 nm, and preferably about 900 nm, more preferably about 700 nm. When the average fiber diameter exceeds the upper limit, the superiority in deodorant performance, antiallergen performance, moisture absorption / release performance, etc. may not be sufficiently obtained over conventional crosslinked acrylate fibers. On the other hand, fibers having an average fiber diameter less than the lower limit are difficult to manufacture with the current technology and are not practical.
上述した本発明に採用する架橋アクリレート系超極細繊維は、平均繊維径が１０〜１０００ｎｍのポリアクリロニトリル系超極細繊維（以下、ＰＡＮ系ナノファイバーともいう）に１分子中の窒素数が２以上である窒素含有化合物による架橋処理および加水分解処理を施して得ることができる。 The above-mentioned crosslinked acrylate-based ultrafine fiber employed in the present invention has a polyacrylonitrile-based ultrafine fiber (hereinafter also referred to as a PAN-based nanofiber) having an average fiber diameter of 10 to 1000 nm and has 2 or more nitrogen atoms in one molecule. It can be obtained by performing a crosslinking treatment and a hydrolysis treatment with a certain nitrogen-containing compound.
上記ＰＡＮ系ナノファイバーはアクリロニトリルを４０重量％以上、好ましくは５０重量％以上含有するアクリロニトリル系重合体により形成された繊維である。従って、該アクリロニトリル系重合体としては、アクリロニトリル単独重合体のほかに、アクリロニトリルと他のモノマーとの共重合体も採用できる。共重合体における他のモノマーとしては、特に限定はないが、ハロゲン化ビニル及びハロゲン化ビニリデン；（メタ）アクリル酸エステル（なお（メタ）の表記は、該メタの語の付いたもの及び付かないものの両方を表す）；メタリルスルホン酸、ｐ−スチレンスルホン酸等のスルホン酸基含有モノマー及びその塩；（メタ）アクリル酸、イタコン酸等のカルボン酸基含有モノマー及びその塩；アクリルアミド、スチレン、酢酸ビニル等が挙げられる。 The PAN-based nanofiber is a fiber formed of an acrylonitrile-based polymer containing acrylonitrile in an amount of 40% by weight or more, preferably 50% by weight or more. Therefore, as the acrylonitrile-based polymer, a copolymer of acrylonitrile and another monomer can be employed in addition to the acrylonitrile homopolymer. Other monomers in the copolymer are not particularly limited, but vinyl halides and vinylidene halides; (meth) acrylic acid esters (note that (meth) is indicated with or without the word “meta”. Sulfonic acid group-containing monomers such as methallyl sulfonic acid and p-styrene sulfonic acid and salts thereof; carboxylic acid group-containing monomers such as (meth) acrylic acid and itaconic acid and salts thereof; acrylamide, styrene, Examples include vinyl acetate.
かかるＰＡＮ系ナノファイバーの製造手段に限定はなく、適宜公知の手段が用いられるが、エレクトロスピニング法は印加電圧、溶液濃度、スプレーの距離、エレクトロスピニング環境の温湿度を調節することにより繊維径をコントロールすることが可能であり有利な方法といえる。 There are no limitations on the means for producing such PAN-based nanofibers, and known means are used as appropriate. In the electrospinning method, the fiber diameter is adjusted by adjusting the applied voltage, the solution concentration, the spray distance, and the temperature and humidity of the electrospinning environment. It can be controlled and is an advantageous method.
また、ＰＡＮ系ナノファイバーの形態については限定するものでないが、後述の化学処理時の取り扱い性を考えると不織布の形態が好ましい。また、エレクトロスピニング法で得られた不織布の場合、フィラメントがナノレベルで交絡している状態となっているため、通常の不織布に比べて強度に優れている。一般に架橋アクリレート系繊維は引張強度などの繊維物性があまり高くないが、かかるエレクトロスピニング法で得られたＰＡＮ系ナノファイバーの不織布を原料として用いることで、従来の架橋アクリレート系繊維の不織布に比べて飛躍的に高い強度を有する架橋アクリレート系繊維の不織布を得ることができる。また、かかる不織布をフィルターに用いた場合、捕集効率が高く、圧力損失も小さいフィルターとすることが期待できる。 Moreover, although it does not limit about the form of a PAN-type nanofiber, the form of a nonwoven fabric is preferable when the handleability at the time of the chemical treatment mentioned later is considered. Moreover, in the case of the nonwoven fabric obtained by the electrospinning method, since the filament is in a state of being entangled at the nano level, it is superior in strength compared to a normal nonwoven fabric. In general, cross-linked acrylate fibers are not very high in fiber properties such as tensile strength, but using non-woven fabrics of PAN-based nanofibers obtained by this electrospinning method as a raw material, compared with conventional non-woven fabrics of cross-linked acrylate fibers A non-woven fabric of cross-linked acrylate fibers having dramatically high strength can be obtained. Moreover, when such a nonwoven fabric is used for a filter, it can be expected that the filter has high collection efficiency and low pressure loss.
本発明においては上述したＰＡＮ系ナノファイバーに１分子中の窒素数が２以上である窒素含有化合物による架橋処理を施す。この架橋処理により、ＰＡＮ系ナノファイバー中のニトリル基と１分子中の窒素数が２以上である窒素含有化合物が反応して、架橋構造が形成され、これに伴い繊維中の窒素含有量が増加する。該架橋処理に採用しうる１分子中の窒素数が２以上である窒素含有化合物としては、水加ヒドラジン、硫酸ヒドラジン、塩酸ヒドラジン、臭素酸ヒドラジン等のヒドラジン系化合物やエチレンジアミン、ヘキサメチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、ポリエチレンイミン等のアミノ基を複数有する化合物等が例示される。中でもヒドラジン系化合物は、反応しやすく、コスト的にも有利であり、好ましい。 In the present invention, the above-described PAN-based nanofiber is subjected to a crosslinking treatment with a nitrogen-containing compound having 2 or more nitrogen atoms in one molecule. By this crosslinking treatment, the nitrile group in the PAN-based nanofiber reacts with the nitrogen-containing compound having 2 or more nitrogen atoms in one molecule to form a crosslinked structure, which increases the nitrogen content in the fiber. To do. Nitrogen-containing compounds having 2 or more nitrogen atoms in one molecule that can be used for the crosslinking treatment include hydrazine compounds such as hydrazine hydrate, hydrazine sulfate, hydrazine hydrochloride, hydrazine bromate, ethylenediamine, hexamethylenediamine, and diethylenetriamine. And compounds having a plurality of amino groups such as triethylenetetramine and polyethyleneimine. Of these, hydrazine compounds are preferable because they are easy to react and advantageous in terms of cost.
１分子中の窒素数が２以上である窒素含有化合物による架橋処理は、架橋構造が形成される限りにおいて制限はなく、該化合物の溶液中にＰＡＮ系ナノファイバーを浸漬し、５０〜１５０℃で反応させた場合に好ましい結果を得られる場合が多いが、ヒドラジン系化合物を用いる場合には、以下のような条件を採用することができる。 The crosslinking treatment with a nitrogen-containing compound having 2 or more nitrogen atoms in one molecule is not limited as long as a crosslinked structure is formed, and PAN-based nanofibers are immersed in a solution of the compound at 50 to 150 ° C. In many cases, preferable results are obtained when the reaction is carried out, but the following conditions can be employed when a hydrazine compound is used.
すなわち、ヒドラジン系化合物による架橋処理の具体的な処理条件としては、窒素含有量の増加を０．１〜１０重量％に調整しうる条件である限り採用できるが、ヒドラジン系化合物濃度５〜８０重量％の水溶液中、温度５０〜１２０℃で１〜５時間処理する手段が工業的に好ましい。ここで、窒素含有量の増加とはヒドラジン系化合物による架橋処理前のＰＡＮ系ナノファイバーの窒素含有量と該処理後のＰＡＮ系ナノファイバーの窒素含有量との差をいう。なお、窒素含有量の増加が下限に満たない場合には、最終的に実用上満足し得る物性の繊維が得られないことがあり、上限を超える場合には、十分な消臭性能、抗アレルゲン性能が得られないことがある。 That is, as specific treatment conditions for the crosslinking treatment with the hydrazine compound, it can be adopted as long as the increase in the nitrogen content can be adjusted to 0.1 to 10% by weight, but the hydrazine compound concentration is 5 to 80% by weight. A means for treating in a 50% aqueous solution at a temperature of 50 to 120 ° C. for 1 to 5 hours is industrially preferable. Here, the increase in the nitrogen content refers to the difference between the nitrogen content of the PAN-based nanofiber before the crosslinking treatment with the hydrazine-based compound and the nitrogen content of the PAN-based nanofiber after the treatment. If the increase in nitrogen content is less than the lower limit, fibers having physical properties that can be finally satisfied in practice may not be obtained. If the upper limit is exceeded, sufficient deodorant performance, antiallergen Performance may not be obtained.
かかる架橋処理を施された繊維は、該処理で残留した薬剤を十分に除去した後、酸処理を施しても良い。ここに使用する酸としては、硝酸、硫酸、塩酸等の鉱酸や、有機酸等が挙げられるが特に限定されない。該酸処理の条件としては、特に限定されないが、大概酸濃度３〜２０重量％、好ましくは７〜１５重量％の水溶液に、温度５０〜１２０℃で０．５〜１０時間繊維を浸漬するといった例が挙げられる。 The fiber subjected to the crosslinking treatment may be subjected to an acid treatment after sufficiently removing the drug remaining by the treatment. Examples of the acid used here include mineral acids such as nitric acid, sulfuric acid, and hydrochloric acid, and organic acids, but are not particularly limited. The conditions for the acid treatment are not particularly limited, but the fibers are usually immersed in an aqueous solution having an acid concentration of 3 to 20% by weight, preferably 7 to 15% by weight, at a temperature of 50 to 120 ° C. for 0.5 to 10 hours. An example is given.
上述のようにして架橋処理を施された繊維、あるいは、さらに酸処理を施された繊維は、次に加水分解処理を施される。該処理により、架橋処理時に未反応のまま残存しているニトリル基などが加水分解され、カルボキシル基が生成される。 The fiber subjected to the crosslinking treatment as described above or the fiber further subjected to the acid treatment is then subjected to a hydrolysis treatment. By this treatment, nitrile groups remaining unreacted during the crosslinking treatment are hydrolyzed to generate carboxyl groups.
かかる加水分解処理の手段としては、アルカリ金属水酸化物、アルカリ金属炭酸塩、アンモニア等の塩基性水溶液、あるいは、硝酸、硫酸、塩酸等の水溶液中に架橋処理を施された繊維を浸漬した状態で加熱処理する手段が挙げられる。具体的な処理条件としては、上述したカルボキシル基の量の範囲などを勘案し、処理薬剤の濃度、反応温度、反応時間等の諸条件を適宜設定すればよいが、一般的には、０．５〜１０重量％、好ましくは１〜５重量％の処理薬剤水溶液中、温度５０〜１２０℃で１〜１０時間処理する条件の範囲内で設定することが工業的、繊維物性的にも好ましい。なお、上述した架橋処理と同時に加水分解処理を行うことも出来る。 As a means for such hydrolysis treatment, a basic aqueous solution such as alkali metal hydroxide, alkali metal carbonate, ammonia, or a state in which a fiber subjected to crosslinking treatment is immersed in an aqueous solution such as nitric acid, sulfuric acid, hydrochloric acid, etc. And a means for heat treatment. As specific treatment conditions, various conditions such as the concentration of the treatment agent, reaction temperature, reaction time and the like may be appropriately set in consideration of the above-described range of the amount of carboxyl groups. It is preferable in terms of industrial and fiber properties to set within 5 to 10% by weight, preferably 1 to 5% by weight, of a treatment chemical aqueous solution at a temperature of 50 to 120 ° C. for 1 to 10 hours. In addition, a hydrolysis process can also be performed simultaneously with the crosslinking process mentioned above.
上述のようにして加水分解処理を施された繊維中には、加水分解処理に用いられたアルカリ金属水酸化物、アルカリ金属炭酸塩、アンモニア等の種類に応じたアルカリ金属やアンモニウムなどのカチオンを対イオンとする塩型カルボキシル基が生成しているが、引き続き、必要に応じてカルボキシル基の対イオンを変換する処理を行ってもよい。例えば、塩酸、酢酸、硝酸、硫酸等の酸性水溶液に浸漬処理すれば、対イオンが水素イオンに置換され、Ｈ型カルボキシル基とすることができる。また、硝酸塩、硫酸塩、塩酸塩などの金属塩水溶液によるイオン交換処理を行えば、所望の金属イオンを対イオンとする塩型カルボキシル基とすることができる。さらに、水溶液のｐＨや金属塩濃度・種類を調整することで、異種の対イオンを混在させたり、その割合を調整したりすることも可能である。 In the fiber subjected to the hydrolysis treatment as described above, a cation such as alkali metal or ammonium corresponding to the type of alkali metal hydroxide, alkali metal carbonate, ammonia or the like used in the hydrolysis treatment is contained. Although the salt-type carboxyl group used as a counter ion has been generated, a treatment for converting the counter ion of the carboxyl group may be performed as necessary. For example, when the immersion treatment is performed in an acidic aqueous solution such as hydrochloric acid, acetic acid, nitric acid, sulfuric acid, etc., the counter ion is replaced with a hydrogen ion, and an H-type carboxyl group can be obtained. Further, when an ion exchange treatment is performed with an aqueous metal salt solution such as nitrate, sulfate, or hydrochloride, a salt-type carboxyl group having a desired metal ion as a counter ion can be obtained. Furthermore, by adjusting the pH of the aqueous solution and the concentration and type of the metal salt, it is possible to mix different types of counter ions and to adjust the ratio thereof.
上述してきた本発明の架橋アクリレート系超極細繊維構造体は、架橋アクリレート系超極細繊維単独で構成されたものであってもよいし、他の素材と組み合わせて構成されたものであってよい。他の素材と組み合わせることで、より多くの用途で有用なものとできる。他の素材と組み合わせる場合、架橋アクリレート系超極細繊維の含有量を好ましくは１０重量％以上、より好ましくは３０重量％以上とすることで、架橋アクリレート系超極細繊維の消臭性能、吸湿性能、抗アレルゲン性能などの性能を有効に発現させることができる。 The above-described crosslinked acrylate-based ultrafine fiber structure of the present invention may be composed of a crosslinked acrylate-based ultrafine fiber alone or in combination with other materials. By combining with other materials, it can be useful for more applications. When combined with other materials, the content of the crosslinked acrylate-based ultrafine fiber is preferably 10% by weight or more, more preferably 30% by weight or more, so that the deodorization performance, moisture absorption performance of the crosslinked acrylate-based ultrafine fiber, Performance such as antiallergen performance can be effectively expressed.
ここで、他の素材と組み合わせる方法としては、例えば、上述したエレクトロスピニング法によるＰＡＮ系ナノファイバーの製造方法において、エレクトロスピニング可能な他の繊維素材を同時にエレクトロスピニングして、得られた繊維構造体に対して上述の架橋処理や加水分解処理を施す方法や、組み合わせたい他の繊維素材からなる支持体上にエレクトロスピニング法によりＰＡＮ系ナノファイバーを集積させ、得られた繊維構造体に対して上述の架橋処理や加水分解処理を施す方法などを挙げることができる。 Here, as a method of combining with other materials, for example, in the manufacturing method of the PAN-based nanofiber by the electrospinning method described above, the fiber structure obtained by simultaneously electrospinning other fiber materials that can be electrospun PAN-based nanofibers are accumulated by electrospinning on a support made of the above-mentioned crosslinking treatment or hydrolysis treatment or another fiber material to be combined, and the resulting fiber structure is described above. And a method of performing a crosslinking treatment and a hydrolysis treatment.
ナノファイバーのみで構成された繊維構造体は大変薄いため、一般に取り扱いが難しいが、上述した後者の方法で得られた繊維構造体であれば、他の繊維素材が支持体として働くので、取り扱い性の面で有利である。また、後者の方法においては、ＰＡＮ系ナノファイバーを他の繊維素材と一体化させておくことにより、得られる本発明の繊維構造体においても、架橋アクリレート系超極細繊維が他の繊維素材が一体化された状態となり、取り扱い性がさらに向上する。また機械的強度および耐摩擦性も向上し、具体的には、架橋アクリレート系超極細繊維の毛羽立ちや切断、架橋アクリレート系超極細繊維層の他の繊維素材からの剥離等が大幅に抑制される。 A fiber structure composed only of nanofibers is very thin and generally difficult to handle. However, if the fiber structure is obtained by the latter method described above, other fiber materials will serve as a support, and therefore handleability This is advantageous. In the latter method, the PAN-based nanofiber is integrated with another fiber material, so that in the obtained fiber structure of the present invention, the crosslinked acrylate-based ultrafine fiber is integrated with the other fiber material. The handling state is further improved. In addition, mechanical strength and friction resistance are also improved. Specifically, fluffing and cutting of crosslinked acrylate-based ultrafine fibers, peeling of crosslinked acrylate-based ultrafine fiber layers from other fiber materials, etc. are greatly suppressed. .
このときに、ＰＡＮ系ナノファイバーを他の繊維素材と一体化させる方法としては、たとえば、他の繊維素材からなる支持体中に熱融着性繊維を含有させておき、ＰＡＮ系ナノファイバーを集積させた後に、熱プレス等により熱融着させて接着する方法や、他の繊維素材からなる支持体上にＰＡＮ系ナノファイバーを集積させた後にケミカルボンドをスプレー加工し、乾燥させて接着させる方法などが挙げられる。ここで、熱融着性繊維としては、ポリプロピレン／ポリエチレン芯鞘繊維、熱融着性ポリエステル繊維などが、ケミカルボンドとしては、アクリル樹脂系接着剤、ウレタン樹脂系接着剤、エチレン−酢酸ビニル樹脂エマルジョン接着剤等が例示される。また、他の繊維素材からなる支持体の形態としては、不織布、織布、編地、紙状物などが挙げられる。 At this time, as a method of integrating the PAN-based nanofibers with other fiber materials, for example, heat-fusible fibers are contained in a support made of other fiber materials, and the PAN-based nanofibers are integrated. After heat treatment by heat press or the like, or by attaching PAN-based nanofibers on a support made of another fiber material and then spraying and bonding the chemical bonds Etc. Here, polypropylene / polyethylene core-sheath fiber, heat-fusible polyester fiber, etc. are used as the heat-fusible fiber, and acrylic resin adhesive, urethane resin-based adhesive, ethylene-vinyl acetate resin emulsion are used as chemical bonds. An adhesive etc. are illustrated. Examples of the form of the support made of other fiber materials include non-woven fabrics, woven fabrics, knitted fabrics, and paper-like materials.
また、他の繊維素材からなる支持体中に熱融着性繊維を含有させる場合においては、熱融着性繊維の目付として好ましくは７ｇ／ｍ２以上、より好ましくは１０ｇ／ｍ２、さらに好ましくは１５ｇ／ｍ２とすることが望ましい。熱融着性繊維の目付が７ｇ／ｍ２に満たない場合には、架橋処理や加水分解処理の際や、摩擦などにより架橋アクリレート系超極細繊維層が支持体から剥離する場合がある。 In addition, when heat-fusible fibers are contained in a support made of another fiber material, the basis weight of the heat-fusible fibers is preferably 7 g / m 2 or more, more preferably 10 g / m 2 , and still more preferably. Is preferably 15 g / m 2 . When the basis weight of the heat-fusible fiber is less than 7 g / m 2 , the cross-linked acrylate-based ultrafine fiber layer may be peeled off from the support during the cross-linking treatment or hydrolysis treatment or due to friction.
また、他の繊維素材としては特に制限はなく、公用されている天然繊維、有機繊維、半合成繊維、合成繊維が用いられ、さらには無機繊維、ガラス繊維等も用途によっては採用し得る。具体的な例としては、綿、麻、絹、羊毛、ナイロン、レーヨン、ポリエステル、アクリル繊維などを挙げることができる。 Moreover, there is no restriction | limiting in particular as another fiber raw material, The natural fiber, organic fiber, semi-synthetic fiber, and synthetic fiber currently used are used, Furthermore, inorganic fiber, glass fiber, etc. can be employ | adopted depending on a use. Specific examples include cotton, hemp, silk, wool, nylon, rayon, polyester, acrylic fiber, and the like.
本発明の架橋アクリレート系超極細繊維構造体の外観形態としては、糸、不織布、紙状物、シート状物、積層体、綿状体（球状や塊状のものを含む）等がある。該構造物内における架橋アクリレート系超極細繊維の含有形態としては、他素材との混合により、実質的に均一に分布させたもの、複数の層を有する構造の場合には、いずれかの層（単数でも複数でも良い）に集中して存在せしめたものや、夫々の層に特定比率で分布せしめたもの等がある。 Appearance forms of the crosslinked acrylate-based ultrafine fiber structure of the present invention include yarns, non-woven fabrics, paper-like materials, sheet-like materials, laminates, cotton-like materials (including spherical and massive materials), and the like. The inclusion form of the crosslinked acrylate-based ultrafine fiber in the structure is substantially uniformly distributed by mixing with other materials. In the case of a structure having a plurality of layers, any layer ( There are those that are concentrated in a single or plural number) and those that are distributed in a specific ratio in each layer.
本発明の架橋アクリレート系超極細繊維構造体は、単独あるいは他の部材と組み合わせて、アレルゲン除去材、消臭材あるいは吸湿材などとして利用することができる。他の部材としては、特に限定はなく、例えば、不織布、紙、金属板、フィルム、樹脂成形体などを挙げることができる。 The crosslinked acrylate-based ultrafine fiber structure of the present invention can be used as an allergen-removing material, a deodorizing material, a hygroscopic material or the like alone or in combination with other members. There is no limitation in particular as another member, For example, a nonwoven fabric, paper, a metal plate, a film, a resin molding etc. can be mentioned.
アレルゲン除去材あるいは消臭材として用いる場合には、架橋アクリレート系超極細繊維構造体を構成する架橋アクリレート系超極細繊維において、Ｈ型カルボキシル基を１〜１０ｍｍｏｌ／ｇ、好ましくは２〜１０ｍｍｏｌ／ｇ、さらにより好ましくは５〜１０ｍｍｏｌ／ｇ含有することが望ましい。また、吸湿材として用いる場合には、塩型カルボキシル基を１〜１０ｍｍｏｌ／ｇ、好ましくは２〜１０ｍｏｌ／ｇ、さらにより好ましくは５〜１０ｍｍｏｌ／ｇ含有することが望ましい。塩型カルボキシル基を構成するカウンターカチオンの種類としてはＬｉ、Ｎａ、Ｋなどのアルカリ金属、Ｍｇ、Ｃａなどのアルカリ土類金属、Ｃｕ、Ａｇ、Ｚｎなどの重金属、Ａｌ、４級アンモニウムなどを例示することができる。 When used as an allergen-removing material or deodorant, the crosslinked acrylate-based ultrafine fiber constituting the crosslinked acrylate-based ultrafine fiber structure has an H-type carboxyl group of 1 to 10 mmol / g, preferably 2 to 10 mmol / g. Even more preferably, it is desirable to contain 5-10 mmol / g. Moreover, when using as a hygroscopic material, it is desirable to contain 1-10 mmol / g of salt-type carboxyl groups, Preferably it is 2-10 mol / g, More preferably, it contains 5-10 mmol / g. Examples of the counter cation constituting the salt-type carboxyl group include alkali metals such as Li, Na and K, alkaline earth metals such as Mg and Ca, heavy metals such as Cu, Ag and Zn, Al and quaternary ammonium. can do.
上記に例示した本発明の架橋アクリレート系超極細繊維構造体の外観形態や含有形態、該繊維構造体を構成する他の素材、および該繊維構造体と組み合わせる他の部材をいかなるものとするかは、最終製品の種類（例えば、衣料品、フィルター、カーテンやカーペット、寝具やクッション、インソールなど）に応じて要求される機能、特性、形状や、かかる機能を発現することへの架橋アクリレート系超極細繊維の寄与の仕方等を勘案して適宜決定される。 What are the appearance forms and inclusion forms of the crosslinked acrylate-based ultrafine fiber structure of the present invention exemplified above, other materials constituting the fiber structure, and other members combined with the fiber structure? , Functions, properties, and shapes required for each type of final product (for example, clothing, filters, curtains and carpets, bedding, cushions, insoles, etc.), and cross-linked acrylate-based ultrafine to develop such functions It is determined as appropriate in consideration of how the fiber contributes.
以下に本発明の理解を容易にするために実施例を示すが、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。 Examples are shown below for facilitating the understanding of the present invention. However, these are merely examples, and the gist of the present invention is not limited thereto. In the examples, parts and percentages are based on weight unless otherwise specified.
＜抗アレルゲン性能の評価（１）：ダニアレルゲン不活化率＞
精製ダニ抗原Ｄｅｒ ｆＩＩ（生化学工業社製）２μｇを含むリン酸緩衝液２０ｍＬ中に試料１５ｍｇを加えたもの、および、コントロールとして繊維試料を加えないものを３０℃×１８時間処理し、これらの上澄み液について酵素免疫測定法（ＥＬＩＳＡ）でダニアレルゲン量を測定した。
<Evaluation of anti-allergen performance (1): mite allergen inactivation rate>
A sample obtained by adding 15 mg of a sample to 20 mL of a phosphate buffer containing 2 μg of purified mite antigen Der fII (manufactured by Seikagaku Corporation) and a sample without adding a fiber sample as a control were treated at 30 ° C. for 18 hours. The amount of mite allergen in the supernatant was measured by enzyme immunoassay (ELISA).
具体的には、まず、一次抗体のモノクローナル抗体１５Ｅ１１（生化学工業（株）製）をマイクロプレートの各ウェルに５０μＬずつ分注して室温で３時間静置させた後、プレートをＰＢＳ−Ｔ（ＰＢＳ（リン酸緩衝生理食塩水、０．０１ｍｏｌ／ｌ、ｐＨ７．２〜７．４）の０．０５％ポリオキシエチレン（２０）ソルビタンモノラウレート（和光純薬（株）製、Ｔｗｅｅｎ２０相当品）溶液）で３回洗浄した。続いて、１％ＢＳＡ（ナカライテスク（株）製、ウシ血清アルブミン（Ｆ−Ｖ）、ｐＨ５．２）を含むＰＢＳ−Ｔを各ウェルに３００μＬずつ分注し、４℃で１２時間静置させた後、ＰＢＳ−Ｔで３回洗浄した。次に、上述の上澄み液を各ウェルに５０μＬずつ分注し、室温で２時間静置させた後、ＰＢＳ−Ｔで３回洗浄した。続いて二次抗体のペルオキシターゼ標識したモノクローナル抗体１３Ａ４（生化学工業（株）製）を各ウェルに５０μＬずつ分注し、室温で２時間静置させた後、ＰＢＳ−Ｔで４回洗浄した。次にＴＭＢ試薬（フナコシ（株）製）を各ウェルに１００μＬずつ分注し、５分間反応させた。その後１Ｍの塩酸を各ウェルに１００μＬずつ分注し、反応を停止させてマイクロプレートリーダー（Ｂｉｏ−Ｒａｄ Ｌａｂｏｒａｔｏｒｉｅｓ Ｉｎｃ 製）で吸光度（測定波長４９０ｎｍ）を測定した。得られた測定値から検量線を用いて上澄み液中のダニアレルゲン濃度を求め、不活化率を次式により算出した。
不活化率（％）＝｛１−（Ａ／Ｂ）｝×１００
（Ａ＝試料を加えた場合のアレルゲン濃度、Ｂ＝コントロールのアレルゲン濃度）
Specifically, first, monoclonal antibody 15E11 (manufactured by Seikagaku Corporation) as a primary antibody was dispensed into each well of a microplate by 50 μL and allowed to stand at room temperature for 3 hours, and then the plate was washed with PBS-T. (PBS (phosphate buffered saline, 0.01 mol / l, pH 7.2 to 7.4) 0.05% polyoxyethylene (20) sorbitan monolaurate (Wako Pure Chemical Industries, Ltd., equivalent to Tween 20) Product) solution) three times. Subsequently, 300 μL of PBS-T containing 1% BSA (manufactured by Nacalai Tesque, Inc., bovine serum albumin (F-V), pH 5.2) was dispensed into each well and allowed to stand at 4 ° C. for 12 hours. And then washed 3 times with PBS-T. Next, 50 μL of the above supernatant was dispensed into each well, allowed to stand at room temperature for 2 hours, and then washed three times with PBS-T. Subsequently, a secondary antibody peroxidase-labeled monoclonal antibody 13A4 (manufactured by Seikagaku Corporation) was dispensed at 50 μL per well, allowed to stand at room temperature for 2 hours, and then washed 4 times with PBS-T. Next, 100 μL of TMB reagent (manufactured by Funakoshi Co., Ltd.) was dispensed into each well and allowed to react for 5 minutes. Then, 100 μL of 1 M hydrochloric acid was dispensed into each well, the reaction was stopped, and the absorbance (measurement wavelength: 490 nm) was measured with a microplate reader (Bio-Rad Laboratories Inc.). The mite allergen concentration in the supernatant was determined from the obtained measured value using a calibration curve, and the inactivation rate was calculated by the following formula.
Inactivation rate (%) = {1- (A / B)} × 100
(A = allergen concentration when sample is added, B = control allergen concentration)
＜抗アレルゲン性能の評価（２）：スギアレルゲン不活化率＞
上記のアレルゲン除去性能の評価（１）において、精製ダニ抗原Ｄｅｒ ｆＩＩ（生化学工業社製）２μｇに代えて、精製スギ花粉抗原Ｃｒｙ Ｊ１（生化学工業社製）１μｇを用いたこと、並びに、一次抗体としてモノクローナル抗体０１３（生化学工業社製）、二次抗体としてペルオキシターゼ標識したモノクローナル抗体０５３（生化学工業社製）を用いたこと以外は同様にして測定を行い、スギアレルゲン不活化率を求めた。
<Evaluation of anti-allergen performance (2): Sumi allergen inactivation rate>
In the evaluation of allergen removal performance (1), instead of 2 μg of purified mite antigen Der fII (Seikagaku Corporation), 1 μg of purified cedar pollen antigen Cry J1 (Seikagaku Corporation) was used, and Measurement was carried out in the same manner except that monoclonal antibody 013 (manufactured by Seikagaku Corporation) was used as the primary antibody and peroxidase-labeled monoclonal antibody 053 (manufactured by Seikagaku Corporation) was used as the secondary antibody. Asked.
＜消臭性能の測定＞
評価サンプル６０ｍｇを入れたテドラーバックに５０ｐｐｍのアンモニアガス１５Ｌを加え、各経過時間ごとのアンモニアガス濃度をガス検知管で測定した。
<Measurement of deodorization performance>
15 L of 50 ppm ammonia gas was added to the Tedlar bag containing 60 mg of the evaluation sample, and the ammonia gas concentration for each elapsed time was measured with a gas detector tube.
＜飽和吸湿率の測定＞
試料を熱風乾燥機で１０５℃、１６時間乾燥して重量を測定する（Ｃ［ｇ］）。次に該試料を２０℃、９０％ＲＨの条件に調節した恒温恒湿器に２４時間入れておく。このようにして吸湿させた試料の重量を測定する。（Ｄ［ｇ］）。以上の測定結果から、次式によって算出する。
飽和吸湿率［％］＝（Ｄ−Ｃ）／Ｃ×１００
<Measurement of saturated moisture absorption>
The sample is dried with a hot air dryer at 105 ° C. for 16 hours, and the weight is measured (C [g]). Next, the sample is placed in a thermo-hygrostat adjusted to 20 ° C. and 90% RH for 24 hours. The weight of the sample thus absorbed is measured. (D [g]). From the above measurement results, calculation is performed according to the following equation.
Saturated moisture absorption [%] = (D−C) / C × 100
＜吸放湿速度の測定＞
試料を熱風乾燥機で１０５℃、１６時間乾燥して重量を測定する（Ｅ［ｇ］）。該試料について、恒温恒湿器を用いて、２０℃、９０％ＲＨ下での吸湿と２０℃、４０％下での放湿を２４時間ずつ繰り返しながら、経時的に試料の重量を測定し（Ｆ［ｇ］）、次式によって算出した吸湿率をプロットすることで吸放湿速度を評価する。
吸湿率［％］＝（Ｆ−Ｅ）／Ｅ×１００
<Measurement of moisture absorption / release rate>
The sample is dried with a hot air dryer at 105 ° C. for 16 hours and the weight is measured (E [g]). Using a thermo-hygrostat, the weight of the sample was measured over time while repeating moisture absorption at 20 ° C. and 90% RH and moisture release at 20 ° C. and 40% each for 24 hours ( F [g]), the moisture absorption / release rate is evaluated by plotting the moisture absorption rate calculated by the following equation.
Moisture absorption [%] = (FE) / E × 100
＜Ｈ型カルボキシル基量の測定＞
十分乾燥した試料約１ｇを精秤し（Ｗ１［ｇ］）、これに２００ｍｌの水を加え、０．１ｍｏｌ／ｌ水酸化ナトリウム水溶液で常法に従って滴定曲線を求めた。該滴定曲線からＣＯＯＨに消費された水酸化ナトリウム水溶液消費量（Ｖ１［ｍｌ］）を求め、次式によってＨ型カルボキシル基量を算出した。
Ｈ型カルボキシル基量［ｍｍｏｌ／ｇ］＝０．１×Ｖ１／Ｗ１
<Measurement of H-type carboxyl group content>
About 1 g of a sufficiently dried sample was precisely weighed (W1 [g]), 200 ml of water was added thereto, and a titration curve was obtained according to a conventional method using a 0.1 mol / l sodium hydroxide aqueous solution. The consumption amount of the aqueous sodium hydroxide solution consumed by COOH (V1 [ml]) was determined from the titration curve, and the amount of H-type carboxyl group was calculated by the following formula.
H-type carboxyl group amount [mmol / g] = 0.1 × V1 / W1
＜塩型カルボキシル基量＞
塩型カルボキシル基量は、次式によって求める。
塩型カルボキシル基量［ｍｍｏｌ／ｇ］＝（全カルボキシル基量）−（Ｈ型カルボキシル基量）
ここで、全カルボキシル基量については、試料に１ｍｏｌ／ｌ塩酸水溶液を添加してｐＨ２とし、予め試料に含まれるカルボキシル基を全てＨ型カルボキシル基としたうえで、上記の＜Ｈ型カルボキシル基量の測定＞と同様にして求める。
<Amount of salt-type carboxyl group>
The amount of the salt-type carboxyl group is determined by the following formula.
Salt-type carboxyl group amount [mmol / g] = (total carboxyl group amount) − (H-type carboxyl group amount)
Here, the total amount of carboxyl groups was adjusted to pH 2 by adding a 1 mol / l hydrochloric acid aqueous solution to the sample, and all the carboxyl groups contained in the sample were converted to H-type carboxyl groups in advance. It is obtained in the same manner as the measurement of
＜不織布強度の測定＞
テンシロン（オリエンテック社製／ＲＴＡ−５００）を用いて、幅２．５ｃｍの不織布サンプルをチャックにセットし、引張速度５０ｍｍ／分で引張試験を行った時の、破断した荷重を測定した。
<Measurement of nonwoven fabric strength>
Using Tensilon (Orientec Co., Ltd./RTA-500), a non-woven fabric sample having a width of 2.5 cm was set on a chuck, and the fractured load when a tensile test was performed at a tensile speed of 50 mm / min was measured.
＜平均繊維径の測定＞
走査型電子顕微鏡観察で任意に５０本の繊維の繊維径を測定し、その平均値を平均繊維径とした。
<Measurement of average fiber diameter>
The fiber diameter of 50 fibers was arbitrarily measured by observation with a scanning electron microscope, and the average value was defined as the average fiber diameter.
＜実施例１＞
アクリロニトリル９０％及びアクリル酸メチル１０％からなるアクリロニトリル系重合体をＮ，Ｎ−ジメチルホルムアミドに溶解して、エレクトロスピニングを実施し、平均繊維径４０５ｎｍのＰＡＮ系ナノファイバー不織布を得た。得られたＰＡＮ系ナノファイバー不織布に、１５％ヒドラジン水溶液中で１１０℃×３時間架橋導入処理を行い水洗した。次に、８％硝酸水溶液中で１１０℃×１時間酸処理を行い水洗した。続いて５％水酸化ナトリウム水溶液中で、９０℃×２時間加水分解処理を行い水洗し、カルボキシル基が塩型の架橋アクリレート系超極細繊維からなる不織布を得た。得られた不織布の塩型カルボキシル基量、平均繊維径、飽和吸湿率を表１に示す。また吸放湿速度を評価した結果を図１、図２に、得られた不織布のＳＥＭ写真を図４に示す。
<Example 1>
An acrylonitrile polymer composed of 90% acrylonitrile and 10% methyl acrylate was dissolved in N, N-dimethylformamide and electrospun to obtain a PAN nanofiber nonwoven fabric having an average fiber diameter of 405 nm. The resulting PAN-based nanofiber nonwoven fabric was subjected to a crosslinking introduction treatment in a 15% hydrazine aqueous solution at 110 ° C. for 3 hours and washed with water. Next, it was acid-treated in an 8% aqueous nitric acid solution at 110 ° C. for 1 hour and washed with water. Subsequently, it was hydrolyzed in a 5% aqueous sodium hydroxide solution at 90 ° C. for 2 hours and washed with water to obtain a non-woven fabric made of a crosslinked acrylate-based ultrafine fiber having a carboxyl group as a salt group. Table 1 shows the amount of salt-type carboxyl group, average fiber diameter, and saturated moisture absorption of the obtained nonwoven fabric. Moreover, the result of having evaluated the moisture absorption / release rate is shown in FIG. 1 and FIG. 2, and the SEM photograph of the obtained nonwoven fabric is shown in FIG.
＜比較例１＞
アクリロニトリル９０％及びアクリル酸メチル１０％からなるアクリロニトリル系重合体１０部を４８％のロダンソ−ダ水溶液９０部に溶解した紡糸原液を、常法に従って紡糸、延伸した後、乾燥して単繊維径が８μｍのＰＡＮ系繊維を得た。得られた繊維に、１５％ヒドラジン水溶液中で１１０℃×３時間架橋導入処理を行い水洗した。次に、８％硝酸水溶液中で１１０℃×１時間酸処理を行い水洗した後、５％水酸化ナトリウム水溶液中で、９０℃×２時間加水分解処理を行い水洗し、カルボキシル基が塩型の架橋アクリレート繊維を得た。得られた繊維の塩型カルボキシル基量、平均繊維径、飽和吸湿率を表１に示す。また吸放湿速度を評価した結果を図１、図２に示す。
<Comparative Example 1>
A spinning stock solution prepared by dissolving 90 parts of acrylonitrile-based polymer consisting of 90% acrylonitrile and 10% methyl acrylate in 90 parts of a 48% rhodasoda aqueous solution was spun and stretched according to a conventional method, and then dried to obtain a single fiber diameter. An 8 μm PAN-based fiber was obtained. The obtained fiber was subjected to a crosslinking introduction treatment in a 15% hydrazine aqueous solution at 110 ° C. for 3 hours and washed with water. Next, it was subjected to an acid treatment in an 8% aqueous nitric acid solution at 110 ° C. for 1 hour and washed with water, followed by a hydrolytic treatment in an aqueous 5% sodium hydroxide solution at 90 ° C. for 2 hours, and washed with water. Cross-linked acrylate fibers were obtained. Table 1 shows the amount of salt-type carboxyl group, average fiber diameter, and saturated moisture absorption of the obtained fiber. The results of evaluating the moisture absorption / release rate are shown in FIGS.
＜実施例２〜４、比較例２＞
アクリロニトリル９０％及びアクリル酸メチル１０％からなるアクリロニトリル系重合体をＮ，Ｎ−ジメチルホルムアミドに溶解して、エレクトロスピニングを実施し、走査型電子顕微鏡測定で平均繊維径は９８０ｎｍのＰＡＮ系ナノファイバー不織布を得た。得られたＰＡＮ系ナノファイバー不織布に、１５％ヒドラジン水溶液中で１１０℃×３時間架橋導入処理を行い水洗した。次に、８％硝酸水溶液中で１１０℃×１時間酸処理を行い水洗した。続いて５％水酸化ナトリウム水溶液中で、９０℃で加水分解処理を行い水洗し、カルボキシル基が塩型の架橋アクリレート系超極細繊維からなる不織布を得た。なお、３０分〜２時間の範囲で加水分解時間を変えることにより、カルボキシル基量を調整した。得られた不織布の塩型カルボキシル基量、平均繊維径、飽和吸湿率を表１に、実施例２の吸放湿速度を評価した結果を図２に示す。
<Examples 2 to 4, Comparative Example 2>
An acrylonitrile polymer composed of 90% acrylonitrile and 10% methyl acrylate is dissolved in N, N-dimethylformamide, electrospun, and a PAN nanofiber nonwoven fabric having an average fiber diameter of 980 nm as measured by a scanning electron microscope Got. The resulting PAN-based nanofiber nonwoven fabric was subjected to a crosslinking introduction treatment in a 15% hydrazine aqueous solution at 110 ° C. for 3 hours and washed with water. Next, it was acid-treated in an 8% aqueous nitric acid solution at 110 ° C. for 1 hour and washed with water. Then, it hydrolyzed at 90 degreeC in 5% sodium hydroxide aqueous solution, and it washed with water, and obtained the nonwoven fabric which consists of bridge | crosslinking acrylate type | system | group super extra fine fiber in which a carboxyl group is a salt type. In addition, the amount of carboxyl groups was adjusted by changing the hydrolysis time in the range of 30 minutes to 2 hours. Table 1 shows the salt-type carboxyl group amount, average fiber diameter, and saturated moisture absorption rate of the obtained nonwoven fabric, and FIG. 2 shows the results of evaluating the moisture absorption / release rate of Example 2.
＜実施例５＞
実施例１で得られた不織布を、１０％硝酸水溶液中で常温×２４時間酸処理を行い水洗し、カルボキシル基がＨ型の架橋アクリレート系超極細繊維からなる不織布を得た。得られた繊維は９９％を超えるダニアレルゲン不活化率を有するものであった。また、得られた繊維のＨ型カルボキシル基量、平均繊維径、スギ花粉に対する抗アレルゲン性能を表２に、アンモニア消臭性能を評価した結果を図３に示す。
<Example 5>
The nonwoven fabric obtained in Example 1 was subjected to an acid treatment in a 10% nitric acid aqueous solution at room temperature for 24 hours and washed with water to obtain a nonwoven fabric composed of crosslinked acrylate-based ultrafine fibers having an H-type carboxyl group. The obtained fiber had a mite allergen inactivation rate exceeding 99%. Moreover, the H-type carboxyl group amount of the obtained fiber, the average fiber diameter, the antiallergen performance with respect to a cedar pollen are shown in Table 2, and the result of having evaluated ammonia deodorizing performance is shown in FIG.
＜比較例３＞
比較例１で得られた繊維を、１０％硝酸水溶液中で常温×２４時間酸処理を行い水洗し、カルボキシル基がＨ型の架橋アクリレート繊維を得た。得られた繊維のＨ型カルボキシル基量、平均繊維径、スギ花粉に対する抗アレルゲン性能を表２に、アンモニア消臭性能を評価した結果を図３に示す。
<Comparative Example 3>
The fiber obtained in Comparative Example 1 was subjected to an acid treatment in a 10% nitric acid aqueous solution at room temperature for 24 hours and washed with water to obtain a crosslinked acrylate fiber having an H-type carboxyl group. The amount of H-type carboxyl groups, average fiber diameter, and antiallergen performance against cedar pollen of the obtained fiber are shown in Table 2, and the results of evaluating ammonia deodorizing performance are shown in FIG.
＜実施例６〜８、比較例４＞
実施例２〜４、比較例２で得られた不織布を、１０％硝酸水溶液中で、常温×２４時間酸処理を行い水洗し、カルボキシル基がＨ型の架橋アクリレート系超極細繊維からなる不織布を得た。得られた繊維のＨ型カルボキシル基量、平均繊維径、スギ花粉に対する抗アレルゲン性能を表２に示す。
<Examples 6 to 8, Comparative Example 4>
The nonwoven fabrics obtained in Examples 2 to 4 and Comparative Example 2 were subjected to acid treatment in a 10% nitric acid aqueous solution at room temperature for 24 hours and washed with water, and a nonwoven fabric composed of a crosslinked acrylate-based ultrafine fiber having an H-type carboxyl group. Obtained. Table 2 shows the H-type carboxyl group amount, average fiber diameter, and anti-allergen performance against cedar pollen of the obtained fiber.
＜実施例９＞
アクリロニトリル９０％及びアクリル酸メチル１０％からなるアクリロニトリル系重合体をＮ，Ｎ−ジメチルホルムアミドに溶解して、ポリプロピレン／ポリエチレンの芯／鞘構造の熱融着性繊維の不織布支持体（目付２９．３ｇ／ｍ２）上にエレクトロスピニングを実施し、支持体上に平均繊維径２００ｎｍのＰＡＮ系ナノファイバー不織布を集積させた。その後熱プレスを行い支持体とＰＡＮ系ナノファイバー不織布を一体化させた。得られた支持体を持つＰＡＮ系ナノファイバー不織布に、１５％ヒドラジン水溶液中で１１０℃×３時間架橋導入処理を行い水洗した。次に、８％硝酸水溶液中で１１０℃×１時間酸処理を行い水洗した。続いて５％水酸化ナトリウム水溶液中で、９０℃×２時間加水分解処理を行い水洗し、支持体を持ったカルボキシル基が塩型の架橋アクリレート系超極細繊維からなる不織布を得た。得られた不織布の支持体層側からのＳＥＭ写真を図５に、ナノファイバー層側からのＳＥＭ写真を図６に示す。
<Example 9>
An acrylonitrile polymer consisting of 90% acrylonitrile and 10% methyl acrylate is dissolved in N, N-dimethylformamide, and a non-woven fabric support of a heat-fusible fiber having a core / sheath structure of polypropylene / polyethylene (weight: 29.3 g) Electrospinning was performed on / m 2 ), and a PAN-based nanofiber nonwoven fabric having an average fiber diameter of 200 nm was accumulated on the support. Thereafter, hot pressing was performed to integrate the support and the PAN-based nanofiber nonwoven fabric. The obtained PAN-based nanofiber nonwoven fabric having a support was subjected to a crosslinking introduction treatment at 110 ° C. for 3 hours in a 15% hydrazine aqueous solution and washed with water. Next, it was acid-treated in an 8% aqueous nitric acid solution at 110 ° C. for 1 hour and washed with water. Subsequently, it was hydrolyzed in a 5% aqueous sodium hydroxide solution at 90 ° C. for 2 hours and washed with water to obtain a nonwoven fabric having a support and a carboxyl group having a salt-type crosslinked acrylate-based ultrafine fiber. The SEM photograph from the support body layer side of the obtained nonwoven fabric is shown in FIG. 5, and the SEM photograph from the nanofiber layer side is shown in FIG.
＜比較例５＞
実施例９において、ポリプロピレン／ポリエチレンの芯／鞘構造の熱融着性繊維の不織布支持体として目付が６．１ｇ／ｍ２のものを使用すること以外は同様に処理を施したところ、実施例９と同様の塩型カルボキシル基量、平均繊維径を有する架橋アクリレート系超極細繊維からなる不織布が得られるものの、架橋アクリレート系超極細繊維からなる層が支持体からは剥離する結果となった。
< Comparative Example 5 >
In Example 9, when a non-woven fabric support of a heat-fusible fiber having a core / sheath structure of polypropylene / polyethylene was used except that a fabric having a basis weight of 6.1 g / m 2 was used, Although a non-woven fabric made of a crosslinked acrylate-based ultrafine fiber having the same salt-type carboxyl group amount and average fiber diameter as in No. 9 was obtained, the layer made of the crosslinked acrylate-based ultrafine fiber was peeled off from the support.
表１に示すように、実施例１と比較例１においては、塩型カルボキシル基量および飽和吸湿率が同程度であるにもかかわらず、図１及び図２のように、比較例１に対して実施例１の不織布は、初期の乾燥状態から極めて短時間で飽和吸湿状態に達し、低湿度条件下に移行後は速やかに放湿しており、卓越した吸放湿速度を有していることが分かる。また、実施例２の不織布は、比較例１の繊維よりも塩型カルボキシル基量が少ないにもかかわらず、吸湿速度ははるかに上回っている。これらより、架橋アクリレート系繊維を極細化することによって、吸放湿速度が飛躍的に向上することが理解される。 As shown in Table 1, in Example 1 and Comparative Example 1, although the amount of salt-type carboxyl groups and the saturated moisture absorption are similar, as shown in FIG. 1 and FIG. The nonwoven fabric of Example 1 reached a saturated moisture absorption state in an extremely short time from the initial dry state, and quickly dehumidified after shifting to a low humidity condition, and had an excellent moisture absorption and desorption rate. I understand that. Moreover, although the nonwoven fabric of Example 2 has a salt-type carboxyl group amount smaller than the fiber of Comparative Example 1, the moisture absorption rate is far higher. From these, it is understood that the moisture absorption / release rate is remarkably improved by making the crosslinked acrylate fiber extremely fine.
また、比較例２の不織布は、実施例１〜４の不織布と同様に超極細繊維からなっているが、カルボキシル基が１ｍｍｏｌ／ｇ未満であり、天然繊維であるセルロースに劣る飽和吸湿率しか有していないため、吸湿素材としての架橋アクリレート系繊維の主要な優位性を発揮できず、実用上の利用価値が半減している。 Further, the nonwoven fabric of Comparative Example 2 is composed of ultrafine fibers as in the nonwoven fabrics of Examples 1 to 4, but has a carboxyl group of less than 1 mmol / g and has only a saturated moisture absorption rate that is inferior to cellulose, which is a natural fiber. Therefore, the main advantage of the cross-linked acrylate fiber as a moisture-absorbing material cannot be exhibited, and the practical utility value is halved.
表２から、Ｈ型カルボキシル基量を１ｍｍｏｌ／ｇ以上有する実施例５〜８の不織布は、良好な抗アレルゲン性能を有しており、その中でもＨ型カルボキシル基を５ｍｍｏｌ／ｇ以上有する実施例５，６においてはアレルゲンをほぼ完全に不活化できることが分かる。一方、比較例３で得られた従来技術の架橋アクリレート繊維に関しては、アレルゲンの不活化がほとんどできていないことから、架橋アクリレート系繊維を極細化することによって、抗アレルゲン性能が飛躍的に向上することが理解される。 From Table 2, the nonwoven fabrics of Examples 5 to 8 having an H-type carboxyl group amount of 1 mmol / g or more have good antiallergen performance, and among them, Example 5 having an H-type carboxyl group of 5 mmol / g or more. 6 show that the allergen can be almost completely inactivated. On the other hand, regarding the crosslinked acrylate fiber of the prior art obtained in Comparative Example 3, the allergen is hardly inactivated, and thus the anti-allergen performance is dramatically improved by making the crosslinked acrylate fiber extremely fine. It is understood.
また、表２に示すように、実施例５と比較例３においては、Ｈ型カルボキシル基量が同程度であるにもかかわらず、図３のように、実施例５の不織布は、比較例３の繊維と比較し、短時間でアンモニアを検出限界以下まで除去しており、卓越した消臭速度を有することが分かる。これらより、架橋アクリレート系繊維を極細化することによって、消臭速度が飛躍的に向上することが理解される。 Moreover, as shown in Table 2, in Example 5 and Comparative Example 3, the nonwoven fabric of Example 5 was compared with Comparative Example 3 as shown in FIG. It can be seen that ammonia is removed to below the detection limit in a short time as compared with the fiber, and has an excellent deodorization rate. From these, it is understood that the deodorization rate is remarkably improved by making the crosslinked acrylate fiber extremely fine.
また、図４からわかるように、ＰＡＮ系ナノファイバーの不織布を原料として用いて得られた本発明の架橋アクリレート系超極細繊維構造体においては、フィラメントがナノレベルで交絡している状態となっている。かかる構造体は目付け３ｇ／ｍ２、不織布強度１５７Ｎ／２．５ｃｍであり、架橋アクリレート系繊維の不織布として従来にない高い強度を保持していた。 In addition, as can be seen from FIG. 4, in the crosslinked acrylate-based ultrafine fiber structure of the present invention obtained using a non-woven fabric of PAN-based nanofiber as a raw material, the filaments are entangled at the nano level. Yes. Such a structure has a weight per unit area of 3 g / m 2 and a nonwoven fabric strength of 157 N / 2.5 cm, and has maintained a high strength that has not been obtained conventionally as a nonwoven fabric of crosslinked acrylate fibers.
実施例９においては、図５及び図６に示すように、支持体と架橋アクリレート系超極細繊維が一体となった不織布が得られており、取り扱い性は向上し、また機械的強度および耐摩擦性も良好であった。 In Example 9, as shown in FIGS. 5 and 6, a nonwoven fabric in which the support and the crosslinked acrylate-based ultrafine fiber are integrated is obtained, the handleability is improved, and the mechanical strength and friction resistance are improved. The property was also good.
Claims (5)
A filter having the crosslinked acrylate-based ultrafine fiber structure according to claim 1.
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| JP2015013246A (en) * | 2013-07-04 | 2015-01-22 | Jsr株式会社 | Absorbing and desorbing agent, composition containing absorbing and desorbing agent, molding and air-conditioning system |
| JP2017074575A (en) * | 2015-10-14 | 2017-04-20 | 近藤工業株式会社 | Low-density air filter medium manufacturing method and low-density air filter medium |
| JP6877700B2 (en) * | 2016-04-14 | 2021-05-26 | 日本エクスラン工業株式会社 | High-bulk, high-heat-sustaining fibers, and fiber structures, deodorant materials, and batting containing the fibers. |
| KR101831699B1 (en) | 2016-08-09 | 2018-02-23 | 충남대학교 산학협력단 | Oxy-PAN nanofibrous web as adsorbent for heavy metal ions and manufacturing method thereof |
| TWI793244B (en) * | 2018-01-24 | 2023-02-21 | 日商日本Ｅｘｌａｎ工業股份有限公司 | Water-absorbing fiber precursor, water-absorbing nonwoven fabric precursor and water-absorbing nonwoven fabric; as well as facial mask containing the same and face mask having lotion already filled with, and their manufacturing method |
| CN113797649B (en) * | 2021-08-12 | 2022-03-25 | 浙江大学 | Antibacterial and antivirus air filtering material and preparation method thereof |
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| JP4880929B2 (en) * | 2005-07-07 | 2012-02-22 | 帝人テクノプロダクツ株式会社 | Composite structure and filter using the same |
| JP5327418B2 (en) * | 2007-02-09 | 2013-10-30 | 日本エクスラン工業株式会社 | Cross-linked acrylate fiber for allergen removal and fiber structure for allergen removal containing the fiber |
| JP2009293153A (en) * | 2008-06-05 | 2009-12-17 | Toyobo Co Ltd | Fiber assembly and aeration part of light source casing produced by using the same |
| US8939295B2 (en) * | 2009-02-17 | 2015-01-27 | Essentra Porous Technologies Corp. | Multi-layer, fluid transmissive fiber structures containing nanofibers and a method of manufacturing such structures |
| JP5600397B2 (en) * | 2009-04-28 | 2014-10-01 | 北越紀州製紙株式会社 | Filter medium for air filter having electrospun nanofiber layer |
| JP2010274144A (en) * | 2009-05-26 | 2010-12-09 | Toyobo Co Ltd | Filter medium |
| JP5846621B2 (en) * | 2010-03-04 | 2016-01-20 | ダイワボウホールディングス株式会社 | Filter material and method for producing the same |
| JP2012012710A (en) * | 2010-06-29 | 2012-01-19 | Kao Corp | Nanofiber sheet |
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