JPH11279943A - Moisture absorptive and heat build-up cellulosic fiber and its production - Google Patents
Moisture absorptive and heat build-up cellulosic fiber and its productionInfo
- Publication number
- JPH11279943A JPH11279943A JP10085860A JP8586098A JPH11279943A JP H11279943 A JPH11279943 A JP H11279943A JP 10085860 A JP10085860 A JP 10085860A JP 8586098 A JP8586098 A JP 8586098A JP H11279943 A JPH11279943 A JP H11279943A
- Authority
- JP
- Japan
- Prior art keywords
- cellulose
- water
- moisture
- absorbing
- heat
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 38
- 229920002678 cellulose Polymers 0.000 claims abstract description 34
- 239000001913 cellulose Substances 0.000 claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 27
- 238000005406 washing Methods 0.000 claims abstract description 18
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 13
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000003277 amino group Chemical group 0.000 claims abstract description 12
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 7
- 229920003043 Cellulose fiber Polymers 0.000 claims description 61
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- -1 alkali metal salt Chemical class 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 239000003505 polymerization initiator Substances 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims 2
- 238000006297 dehydration reaction Methods 0.000 claims 2
- 238000004581 coalescence Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 5
- 238000012644 addition polymerization Methods 0.000 abstract description 2
- 230000000977 initiatory effect Effects 0.000 abstract 1
- 125000002348 vinylic group Chemical group 0.000 abstract 1
- 235000010980 cellulose Nutrition 0.000 description 22
- 239000011347 resin Substances 0.000 description 18
- 229920005989 resin Polymers 0.000 description 18
- 238000010521 absorption reaction Methods 0.000 description 17
- 229920000742 Cotton Polymers 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 230000008859 change Effects 0.000 description 8
- 239000004744 fabric Substances 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- 230000020169 heat generation Effects 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000010025 steaming Methods 0.000 description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 229920000297 Rayon Polymers 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 3
- 239000003518 caustics Substances 0.000 description 3
- 238000012937 correction Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000002964 rayon Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000035900 sweating Effects 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 240000008574 Capsicum frutescens Species 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000001153 anti-wrinkle effect Effects 0.000 description 1
- 230000000386 athletic effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005517 mercerization Methods 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は吸湿発熱性セルロー
ス繊維およびその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hygroscopic and exothermic cellulose fiber and a method for producing the same.
【０００２】[0002]
【従来の技術】冬季の運動着や外衣用の素材として、吸
湿発熱性の繊維が開発され、市販されている。汗をかい
て屋外へ出たり、屋外で汗をかいた場合などにその湿気
が冷されて肌寒さを感じる状況であっても、これらの繊
維素材を用いた衣料を着用することにより、汗を吸収し
た衣料は発熱するため、体を保温し、快適な状態を保持
することができる。2. Description of the Related Art Moisture-absorbing and heat-generating fibers have been developed and commercially available as materials for winter athletic clothing and outer garments. Even if you are sweating outdoors or sweating outdoors, even in situations where the moisture cools down and you feel chilly, wearing clothing made of these fiber materials will reduce sweat. Since the absorbed clothing generates heat, it can keep the body warm and maintain a comfortable state.
【０００３】特公平７−５９７６２号公報には吸放湿吸
水発熱性繊維として、親水基を高密度で強架橋してなる
化学変成体を有するアクリル系繊維、具体例として親水
基がカルボン酸ソーダであるアクリル酸系吸放湿吸水発
熱性繊維の存在、および各種繊維材料にシリカゲルやモ
レキュラーシーブのような吸湿時や吸水時に吸湿熱を発
生する乾燥剤の粉末を混合した吸放湿吸水発熱性繊維の
存在について言及している。しかし吸湿発熱性セルロー
ス繊維については記載がない。[0003] Japanese Patent Publication No. 7-59762 discloses an acrylic fiber having a chemically denatured product obtained by strongly cross-linking a hydrophilic group at a high density as a moisture absorbing / releasing water-absorbing heat-generating fiber. The presence of acrylic acid-based moisture-absorbing and heat-generating fibers, and moisture-absorbing and moisture-absorbing heat-generating properties by mixing various fiber materials with a desiccant powder that generates moisture-absorbing heat when absorbing moisture or absorbing water, such as silica gel or molecular sieve It mentions the presence of fibers. However, there is no description about the moisture-absorbing and exothermic cellulose fibers.
【０００４】また特開平８−３１１７６７号公報は、合
成繊維やセルロース繊維にアミノ基、カルボキシル基ま
たはヒドロキシル基を導入した湿潤発熱性繊維について
記載しており、セルロースにアンモニアおよびその誘導
体と反応する化合物を付加し、これにアンモニアおよび
その誘導体を付加することによりアミノ基を導入した湿
潤発熱性のセルロース繊維を開示している。しかしこの
発明にはセルロースにＮ-メチロール（メタ）アクリル
アミド（以下、Ｎ-ＭＡＭとも略称する）を付加するこ
とについても、そのビニル基を開始点として重合性ビニ
ル化合物を重合することについても記載されていない。Japanese Unexamined Patent Publication (Kokai) No. 8-31167 describes a wet heat-generating fiber in which an amino group, a carboxyl group or a hydroxyl group is introduced into a synthetic fiber or a cellulose fiber. And wet-heat-producing cellulose fibers having amino groups introduced therein by adding ammonia and derivatives thereof. However, this invention also describes addition of N-methylol (meth) acrylamide (hereinafter, also referred to as N-MAM) to cellulose and polymerization of a polymerizable vinyl compound starting from the vinyl group. Not.
【０００５】セルロース繊維の防しわ性、防縮性、強伸
度、染色性、風合等の性質を改良する技術として、セル
ロースにＮ-ＭＡＭを反応させることが知られている。
そのひとつは木綿繊維内でＮ-ＭＡＭの重合と縮合を起
こさせて防しわ性を改良するというものである。またセ
ルロース繊維の６位ＯＨ基にＮ-ＭＡＭを付加してエー
テル化セルロースを形成し、これに第２段としてこのエ
ーテル化セルロースをＫＯＨ水溶液の存在で処理するこ
とにより２位のＯＨと反応させてセルロースを架橋する
か、アルカリと反応させる代わりに過硫酸アンモニウム
（以下、ＡＰＳと略称する）水溶液に浸漬してからキュ
アリングしてフリーラジカル重合により架橋することに
より、セルロース繊維のしわ回復性を改良するものであ
る。また第２段の改良法としてメタクリルアミド、エチ
ルアクリレート、２-ヒドロキシエチルメタクリレート
等を共重合することも知られている。しかし、吸湿発熱
性の付与については知られていない。[0005] As a technique for improving properties such as wrinkle resistance, shrink resistance, high elongation, dyeability and hand of cellulose fibers, it is known to react cellulose with N-MAM.
One of them is to improve the anti-wrinkle property by causing polymerization and condensation of N-MAM in cotton fiber. Also, N-MAM is added to the 6-OH group of the cellulose fiber to form etherified cellulose, and as a second step, the etherified cellulose is treated with an aqueous KOH solution to react with the 2-position OH. Improve the wrinkle recovery of cellulose fibers by crosslinking the cellulose fibers by immersion in an aqueous solution of ammonium persulfate (hereinafter abbreviated as APS) instead of reacting with alkali or curing and then free-radical polymerization. Is what you do. It is also known that methacrylamide, ethyl acrylate, 2-hydroxyethyl methacrylate and the like are copolymerized as a second-stage improvement method. However, there is no known method of imparting heat of moisture absorption.
【０００６】[0006]
【発明が解決しようとする課題】本発明の目的は、優れ
た吸湿発熱性を有し、その洗濯耐久性も高く、しかも未
加工と同等のセルロース繊維の風合を有しているセルロ
ース繊維およびこのセルロース繊維を少なくとも１成分
とするセルロース繊維製品、ならびにその製造方法を提
供することである。SUMMARY OF THE INVENTION It is an object of the present invention to provide a cellulose fiber which has excellent heat-absorbing and heat-generating properties, has high washing durability, and has the same feeling as unprocessed cellulose fiber. An object of the present invention is to provide a cellulose fiber product containing the cellulose fiber as at least one component, and a method for producing the same.
【０００７】[0007]
【課題を解決するための手段】本発明は、セルロース１
００重量部に対してＮ-メチロール（メタ）アクリルア
ミド（Ｎ-ＭＡＭ）が０.３〜２.５重量部、−ＣＯＯＸ
（Ｘ：Ｈ，ＮＨ4またはアルカリ金属）で示されるカル
ボキシル基またはアミノ基を有する少なくとも１種の水
溶性ビニル重合性化合物が５〜４５重量部化学結合した
吸湿発熱性セルロース繊維に関する。詳しくは、本発明
は、セルロースに結合したＮ-ＭＡＭに上記ビニル重合
性化合物が付加重合した上記の吸湿発熱性セルロース繊
維に関する。また、本発明は、上記の吸湿発熱性セルロ
ース繊維を少なくとも１成分として含む吸湿発熱性セル
ロース繊維製品に関する。The present invention relates to a cellulose 1
0.3 to 2.5 parts by weight of N-methylol (meth) acrylamide (N-MAM) based on 00 parts by weight, -COOX
The present invention relates to a moisture-absorbing and heat-generating cellulose fiber obtained by chemically bonding 5 to 45 parts by weight of at least one water-soluble vinyl polymerizable compound having a carboxyl group or an amino group represented by (X: H, NH 4 or an alkali metal). More specifically, the present invention relates to the above-mentioned moisture-absorbing and heat-generating cellulose fiber obtained by addition-polymerizing the above-mentioned vinyl polymerizable compound to N-MAM bonded to cellulose. The present invention also relates to a moisture-absorbing and heat-generating cellulose fiber product containing the above-mentioned moisture-absorbing and heat-producing cellulose fiber as at least one component.
【０００８】更にまた、本発明は、Ｎ-メチロール（メ
タ）アクリルアミドを含む水溶液を含浸したセルロース
繊維またはセルロース繊維を少なくとも１成分とするセ
ルロース繊維製品中にてＮ-メチロール（メタ）アクリ
ルアミドをセルロースの水酸基に結合させてセルロース
中にビニル基を導入する第１工程、水溶性重合開始剤お
よび−ＣＯＯＸ（Ｘ：Ｈ，ＮＨ4またはアルカリ金属）
で示されるカルボキシル基またはアミノ基を有する少な
くとも１種の水溶性ビニル重合性化合物を含む水溶液中
に第１工程で得られた繊維または繊維製品を浸漬し、次
いで脱水、加熱することによりセルロース中に導入され
た上記ビニル基を開始点として上記水溶性ビニル重合性
化合物を重合する第２工程、および上記水溶性ビニル重
合性化合物重合体を付加したセルロース繊維またはセル
ロース繊維を少なくとも１成分とするセルロース繊維製
品を高湿度条件下または湿潤状態下に保持したのち水洗
および乾燥を行う第３工程からなる上記の吸湿発熱性セ
ルロース繊維またはセルロース繊維製品の製造方法に関
する。Further, the present invention relates to a method for converting N-methylol (meth) acrylamide into cellulose fibers in a cellulose fiber impregnated with an aqueous solution containing N-methylol (meth) acrylamide or a cellulose fiber product containing at least one cellulose fiber. First step of introducing vinyl group into cellulose by bonding to hydroxyl group, water-soluble polymerization initiator and -COOX (X: H, NH 4 or alkali metal)
The fiber or fiber product obtained in the first step is immersed in an aqueous solution containing at least one water-soluble vinyl polymerizable compound having a carboxyl group or an amino group represented by A second step of polymerizing the water-soluble vinyl polymerizable compound with the introduced vinyl group as a starting point, and a cellulose fiber to which the water-soluble vinyl polymerizable compound polymer is added or a cellulose fiber containing at least one cellulose fiber The present invention relates to a method for producing the above-mentioned moisture-absorbing and heat-generating cellulose fiber or cellulose fiber product, comprising a third step of washing and drying after keeping the product under a high humidity condition or a wet condition.
【０００９】本発明の吸湿発熱性セルロース繊維は、製
造の第３工程で高湿度条件下に保たれ、特にスチーミン
グ処理が行われているため、水溶性ビニル重合性化合物
がＮ-ＭＡＭのビニル基開始点として付加重合して強固
にセルロースに結合している。このため、これまで得ら
れた吸湿発熱性セルロース繊維に比べてより優れた吸湿
性とより優れた発熱性を有しており、加えて洗濯等によ
り容易にその性能が低下しない耐久性を有している。ま
た一般に従来の樹脂加工によればセルロース繊維の風合
の低下が不可避であったが、本発明の吸湿発熱性セルロ
ース繊維は未加工のセルロース繊維の風合を保持してい
るという特徴がある。[0009] The moisture-absorbing and heat-generating cellulose fiber of the present invention is kept under high humidity conditions in the third step of production, and particularly subjected to a steaming treatment, so that the water-soluble vinyl polymerizable compound is N-MAM vinyl. It is addition-polymerized as a group starting point and is firmly bound to cellulose. For this reason, it has better hygroscopicity and better heat generation than the hygroscopic heat-generating cellulosic fibers obtained so far, and also has a durability such that its performance is not easily deteriorated by washing or the like. ing. In general, the conventional resin processing inevitably lowers the feel of the cellulose fiber, but the moisture-absorbing and heat-generating cellulose fiber of the present invention is characterized by retaining the feel of the unprocessed cellulose fiber.
【００１０】[0010]
【発明の実施の形態】本発明の吸湿発熱性セルロース繊
維は、セルロース繊維にＮ-ＭＡＭおよび−ＣＯＯＸ
（Ｘ：Ｈ，ＮＨ4またはアルカリ金属）で示されるカル
ボキシル基またはアミノ基を有する少なくとも１種の水
溶性ビニル重合性化合物が化学結合したものである。本
発明においては、まずセルロースの水酸基にＮ-ＭＡＭ
がエーテル結合で導入される。これによりセルロースに
ビニル基が導入され、このビニル基を開始点として、次
に−ＣＯＯＸ（Ｘ：Ｈ，ＮＨ4またはアルカリ金属）で
示されるカルボキシル基またはアミノ基を有する少なく
とも１種の水溶性ビニル重合性化合物が５〜４５重量部
が付加重合される。こうして導入された−ＣＯＯＸ
（Ｘ：Ｈ，ＮＨ4またはアルカリ金属）で示されるカル
ボキシル基および／またはアミノ基によってセルロース
に優れた吸湿発熱性が付与されたものである。BEST MODE FOR CARRYING OUT THE INVENTION The moisture-absorbing and heat-generating cellulose fiber of the present invention comprises N-MAM and -COOX
At least one water-soluble vinyl polymerizable compound having a carboxyl group or an amino group represented by (X: H, NH 4 or an alkali metal) is chemically bonded. In the present invention, first, N-MAM is added to the hydroxyl group of cellulose.
Is introduced by an ether bond. As a result, a vinyl group is introduced into cellulose, and starting from this vinyl group, at least one water-soluble vinyl having a carboxyl group or an amino group represented by -COOX (X: H, NH 4 or an alkali metal). 5-45 parts by weight of the polymerizable compound is subjected to addition polymerization. -COOX thus introduced
(X: H, NH 4 or alkali metal) Carboxyl group and / or amino group represented by cellulose give excellent heat absorption and heat generation to cellulose.
【００１１】Ｎ-ＭＡＭはセルロース繊維１００重量部
に対して０.３〜２.５重量部、好ましくは０.５〜２.０
重量部、より好ましくは０.５〜１.５重量部の割合で導
入される。N-MAM is used in an amount of 0.3 to 2.5 parts by weight, preferably 0.5 to 2.0 parts by weight, based on 100 parts by weight of the cellulose fiber.
It is introduced in a proportion of 0.5 parts by weight, more preferably 0.5 to 1.5 parts by weight.
【００１２】Ｎ-ＭＡＭをセルロース繊維の水酸基にエ
ーテル結合（縮合反応）により導入する反応（第１工
程）は１〜５重量％濃度のＮ-ＭＡＭと０.３〜２重量％
のエーテル化触媒類、例えばＮＨ4Ｃｌを含む室温（冬
季には１０℃程度、夏季には３０℃程度）の水溶液中に
セルロース繊維を１〜６０秒間浸漬（Ｐａｄ）し、つぎ
にセルロース繊維を水相から取り出し、含水率５０〜１
１０重量％まで絞った後、１１０〜１３０℃で５０〜１
２０秒間乾燥する（Ｄｒｙ）。次いでこれを１４０〜１
６０℃で６０〜１８０秒間熱処理する（Ｃｕｒｅ）。こ
のような処理は、以降本明細書中ではＰａｄ（室温、１
〜６０秒）−Ｄｒｙ（１１０〜１３０℃、５０〜１２０
秒）−Ｃｕｒｅ（１４０〜１６０℃、６０〜１８０秒）
のように表すこともある。セルロース繊維はシルケット
処理（苛性ソーダまたは液体アンモニア）をしたものを
使用するのが好ましい。The reaction (first step) of introducing N-MAM to the hydroxyl group of the cellulose fiber by an ether bond (condensation reaction) is carried out at a concentration of 1 to 5% by weight of N-MAM and 0.3 to 2% by weight.
The cellulose fibers are immersed (Pad) in an aqueous solution containing etherification catalysts such as NH 4 Cl at room temperature (about 10 ° C. in winter and about 30 ° C. in summer) for 1 to 60 seconds. Remove from water phase, water content 50-1
After squeezing to 10% by weight, 50 to 1 at 110 to 130 ° C
Dry for 20 seconds (Dry). Then this is 140-1
Heat treatment at 60 ° C. for 60 to 180 seconds (Cure). Such processing is hereinafter referred to as Pad (room temperature, 1
６０60 seconds) -Dry (110 to 130 ° C., 50 to 120
Sec) -Cure (140-160 ° C, 60-180 sec)
It may be expressed as follows. It is preferable to use a cellulose fiber which has been subjected to mercerization treatment (caustic soda or liquid ammonia).
【００１３】次に、Ｎ-ＭＡＭを付加したＮ-ＭＡＭセル
ロースには、第２工程として水溶性ビニル重合性化合物
がＮ-ＭＡＭのビニル基を開始点としてグラフト重合さ
れる。水溶性ビニル重合性化合物は−ＣＯＯＸ（Ｘ：
Ｈ，ＮＨ4またはアルカリ金属）で示されるカルボキシ
ル基またはアミノ基を有するものであり、これらの水溶
性ビニル重合性化合物は１種類であってもよいし、２種
以上が混合されていてもよい。好ましい水溶性ビニル重
合性化合物は（メタ）アクリル酸ナトリウム、（メタ）
アクリル酸、（メタ）アクリルアミドである。特に好ま
しいものは（メタ）アクリル酸ナトリウムである。水溶
性ビニル重合性化合物はセルロース繊維１００重量部に
対して５〜４５重量部、好ましくは７〜４５重量部、よ
り好ましくは１０〜４５重量部である。Next, a water-soluble vinyl polymerizable compound is graft-polymerized to N-MAM cellulose to which N-MAM has been added, starting from the vinyl group of N-MAM as a second step. The water-soluble vinyl polymerizable compound is -COOX (X:
H, NH 4 or an alkali metal), and these water-soluble vinyl polymerizable compounds may be of one type or a mixture of two or more types. . Preferred water-soluble vinyl polymerizable compounds are sodium (meth) acrylate and (meth)
Acrylic acid and (meth) acrylamide. Particularly preferred is sodium (meth) acrylate. The water-soluble vinyl polymerizable compound is used in an amount of 5 to 45 parts by weight, preferably 7 to 45 parts by weight, more preferably 10 to 45 parts by weight, based on 100 parts by weight of the cellulose fiber.
【００１４】水溶性ビニル重合性化合物をＮ-ＭＡＭセ
ルロースにグラフトする第２工程の反応は、次の条件で
行われる。水溶性ビニル重合化合物を５〜３０重量％、
苛性アルカリを０〜１４重量％および水溶性ラジカル重
合開始剤を０.１〜１重量％の濃度で溶解した水溶液中
に、第１工程で得られたＮ-ＭＡＭセルロースを浴比
１：１０〜１：５０で上記水溶液に浸漬し、Ｐａｄ（室
温、１〜６０秒）−Ｄｒｙ（１１０〜１３０℃、５０〜
１２０秒）の条件で処理を行う。Ｐａｄした後の絞り率
は５０〜１１０％が好ましい。加熱によりＮ-ＭＡＭセ
ルロース中のＮ-ＭＡＭのビニル基から重合性化合物の
重合が開始され、セルロースに−ＣＯＯＸ（Ｘ：Ｈ，Ｎ
Ｈ4またはアルカリ金属）で示されるカルボキシル基ま
たはアミノ基をもった重合体がグラフトされる。セルロ
ース間に部分的に架橋が形成されても問題ではない。第
２工程の反応に於ける、苛性アルカリとしては、水酸化
ナトリウム、水酸化カリウム等を利用できる。また水溶
液ラジカル重合開始剤としては、過硫酸カリウム、過硫
酸アンモニウム、過硫酸ナトリウム、過酸化水素等を利
用できる。The reaction in the second step of grafting the water-soluble vinyl polymerizable compound to N-MAM cellulose is performed under the following conditions. 5 to 30% by weight of a water-soluble vinyl polymer compound,
The N-MAM cellulose obtained in the first step is dissolved in an aqueous solution in which caustic alkali is dissolved at a concentration of 0 to 14% by weight and a water-soluble radical polymerization initiator at a concentration of 0.1 to 1% by weight, and a bath ratio of 1:10 to 10: Immerse in the aqueous solution at a ratio of 1:50, Pad (room temperature, 1 to 60 seconds) -Dry (110 to 130 ° C., 50 to
(120 seconds). The reduction ratio after padding is preferably 50 to 110%. Upon heating, polymerization of the polymerizable compound is started from the vinyl group of N-MAM in N-MAM cellulose, and -COOX (X: H, N
A polymer having a carboxyl group or an amino group represented by H 4 or an alkali metal) is grafted. It does not matter if crosslinks are partially formed between the celluloses. As the caustic alkali in the reaction of the second step, sodium hydroxide, potassium hydroxide and the like can be used. As the aqueous solution radical polymerization initiator, potassium persulfate, ammonium persulfate, sodium persulfate, hydrogen peroxide and the like can be used.
【００１５】第２工程の加熱反応で得られたグラフト化
セルロースは、第３工程として高湿度条件下に保持する
ことにより、セルロースへのグラフトがセットされる。
高湿度条件下とは、６０〜１００％ＲＨの範囲の湿度条
件を意味し、必ずしも高温であることを意味しない。こ
れは更にキスロール方式により湿った状態におくことを
含む。しかし湿度７０〜１００％ＲＨで室温（冬季には
１０℃程度、夏季には３０℃程度）〜１１０℃の温度に
保持するのがより好ましく、特に湿度９０〜１００％Ｒ
Ｈで１００〜１１０℃の過熱スチーマー中に保持するこ
とが好ましい。保持時間は、湿度および温度条件により
異なるが、１分〜１２時間で十分である。高湿度条件下
に保持するこのような処理により、得られたセルロース
繊維は、洗濯を含む長期の使用にわたって高い樹脂付加
率を、したがって高い湿潤発熱性を保持することができ
る。これが本発明の大きな特徴となっている。高湿度条
件下に保持する工程が終わった後、グラフト化セルロー
スは水洗して乾燥される。[0015] The grafted cellulose obtained by the heating reaction in the second step is set in a third step by keeping it under high humidity conditions to set the grafting on the cellulose.
The high humidity condition means a humidity condition in a range of 60 to 100% RH, and does not necessarily mean that the temperature is high. This further includes keeping the kiss roll system wet. However, it is more preferable to maintain the temperature at room temperature (about 10 ° C. in winter and about 30 ° C. in summer) to 110 ° C. at a humidity of 70 to 100% RH, particularly 90 to 100% RH.
It is preferred to keep the H in a superheated steamer at 100-110 ° C. The holding time varies depending on the humidity and temperature conditions, but 1 minute to 12 hours is sufficient. Such treatment, which is maintained under high humidity conditions, allows the resulting cellulose fibers to retain high resin loading over extended use, including washing, and thus high wet heat buildup. This is a major feature of the present invention. After the step of maintaining the high humidity condition, the grafted cellulose is washed with water and dried.
【００１６】[0016]
【実施例】以下、実施例により本発明をより具体的に説
明する。実施例 １ 苛性シルケット上がりの木綿セルロース繊維１００％の
ブロードを、Ｎ-メチロールアクリルアミドを３重量％
と塩化アンモニウムを１重量％溶解した室温（１０℃）
の水溶液（加工液）に、浴比１：５０で１０秒間浸漬し
た。セルロースを加工液から取り出し、絞り率６０％で
加工液を絞りとった後、１３０℃で１分間乾燥し、次い
で１５０℃で２分間熱処理した。〔以上第１工程〕 次に、メタクリル酸を１５重量％、水酸化ナトリウムを
７重量％および過硫酸アンモニウムを０.５重量％溶解
した室温の水溶液（加工液）に、第１工程で得られたブ
ロードを浴比１：５０で浸漬した。１０秒後ブロードを
加工液から取り出し、絞り率６０％で加工液を絞り取っ
た後、１３０℃の乾燥機中で２分間加熱した。〔以上第
２工程〕 加熱処理したブロードは、１００℃の過熱スチーマーで
３分間スチーミングを行った。次いで水洗、乾燥を行っ
て吸湿発熱性セルロース繊維製品を得た。〔以上第３工
程〕 得られた吸湿発熱性セルロース繊維製品の樹脂付加率は
１０.１％であった。ここで、樹脂付加率は次式によっ
て与えられる数値である：The present invention will be described more specifically with reference to the following examples. Example 1 100% cotton cellulosic fiber broadened from caustic mercerized, 3% by weight N-methylolacrylamide
And 1% by weight of ammonium chloride dissolved at room temperature (10 ° C)
Was immersed for 10 seconds in an aqueous solution (working liquid) at a bath ratio of 1:50. The cellulose was taken out of the working fluid, the working fluid was squeezed at a squeezing rate of 60%, dried at 130 ° C. for 1 minute, and then heat-treated at 150 ° C. for 2 minutes. [First Step] Next, the solution was obtained in the first step in an aqueous solution (working liquid) at room temperature in which 15% by weight of methacrylic acid, 7% by weight of sodium hydroxide, and 0.5% by weight of ammonium persulfate were dissolved. Broad was soaked at a bath ratio of 1:50. After 10 seconds, the broad was taken out of the working fluid, the working fluid was squeezed out at a squeezing rate of 60%, and then heated in a dryer at 130 ° C. for 2 minutes. [The above-mentioned second step] The heat-treated broad was steamed with an overheated steamer at 100 ° C for 3 minutes. Next, washing and drying were performed to obtain a moisture-absorbing and heat-generating cellulose fiber product. [The Third Step] The resin addition rate of the obtained moisture-absorbing and heat-generating cellulose fiber product was 10.1%. Here, the resin addition rate is a numerical value given by the following equation:
【数１】 (Equation 1)
【００１７】実施例 ２ 綿１００％のブロードの代わりに、Ｔ（ポリエステル）
／Ｃ（綿）（４５／５５）のブロードを用いた以外は実
施例１と同様にして吸湿発熱性セルロース繊維製品を得
た。 樹脂付加率：９.７％。 Example 2 Instead of 100% cotton broad, T (polyester)
A moisture-absorbing and heat-generating cellulose fiber product was obtained in the same manner as in Example 1 except that a broad band of / C (cotton) (45/55) was used. Resin addition rate: 9.7%.
【００１８】実施例 ３ 綿１００％のブロードの代わりに、綿１００％ニットを
用い絞り率を８０％にした以外は実施例１と同様にして
吸湿発熱性セルロース繊維製品を得た。樹脂付加率：１
７.８％。 Example 3 A moisture-absorbing and heat-generating cellulose fiber product was obtained in the same manner as in Example 1 except that a 100% cotton knit was used instead of the 100% cotton broadband and the drawing ratio was 80%. Resin addition rate: 1
7.8%.
【００１９】実施例 ４ 綿１００％のブロードの代わりに、レーヨン主体スパン
レース（レーヨン／ポリエステル＝７０／３０）を用い
絞り率を１１０％にした以外は実施例１と同様にして吸
湿発熱性セルロース繊維製品を得た。樹脂付加率：１
９.３％。 Example 4 Moisture-absorbing and heat-generating cellulose was prepared in the same manner as in Example 1, except that a rayon-based spunlace (rayon / polyester = 70/30) was used instead of the 100% cotton broad and the drawing ratio was 110%. A textile product was obtained. Resin addition rate: 1
9.3%.
【００２０】比較例 １ 実施例１において、第３工程のスチーミングを行わず、
第２工程終了後、水洗、乾燥しセルロース繊維製品を得
た。 樹脂付加率：３.７％。 Comparative Example 1 In Example 1, steaming in the third step was not performed.
After the completion of the second step, the product was washed with water and dried to obtain a cellulose fiber product. Resin addition rate: 3.7%.
【００２１】比較例 ２ 実施例２において、第３工程のスチーミングを行わず、
第２工程終了後、水洗、乾燥し、セルロース繊維製品を
得た。 樹脂付加率：３.５％。 Comparative Example 2 In Example 2, steaming in the third step was not performed.
After the completion of the second step, the product was washed with water and dried to obtain a cellulose fiber product. Resin addition rate: 3.5%.
【００２２】比較例 ３ 実施例３において、第３工程のスチーミングを行わず、
第２工程終了後、水洗、乾燥しセルロース繊維製品を得
た。 樹脂付加率：４.２％。 Comparative Example 3 In Example 3, steaming in the third step was not performed.
After the completion of the second step, the product was washed with water and dried to obtain a cellulose fiber product. Resin addition rate: 4.2%.
【００２３】比較例 ４ 実施例４において、第３工程のスチーミングを行わず、
第２工程終了後、水洗、乾燥しセルロース繊維製品を得
た。 樹脂付加率：４.９％。 Comparative Example 4 In Example 4, steaming in the third step was not performed.
After the completion of the second step, the product was washed with water and dried to obtain a cellulose fiber product. Resin addition rate: 4.9%.
【００２４】吸湿発熱性およびその洗濯耐久性の評価 実施例１〜実施例４で得られた加工生地およびこれを下
記の条件で洗濯１０回行ったものについて、下記のよう
にして吸湿発熱性およびその洗濯耐久性を評価した。ま
た比較として、未処理のセルロース繊維製品および第３
工程を行わなかったもの（比較例１〜比較例４）を同時
に評価した。結果を図１〜図４および表１〜表４に示し
た。 Evaluation of Heat Absorption and Moisture Absorption and Washing Durability The processed fabrics obtained in Examples 1 to 4 and those subjected to washing 10 times under the following conditions were subjected to the following processes. The washing durability was evaluated. For comparison, untreated cellulose fiber products and
Those in which the process was not performed (Comparative Examples 1 to 4) were simultaneously evaluated. The results are shown in FIGS. 1 to 4 and Tables 1 to 4.
【００２５】〔吸湿発熱性試験法〕絶乾処理し３０℃に
保持した試料生地を３０℃×９０％ＲＨの環境下に移
し、直後から１０分間にわたって試料表面温度の変化を
「サーモビュア」（ＮＥＣ三栄（株）製）を用いて経時
的に測定した。測定は試料を木枠に固定して通気性を確
保した状態で行い、更に試料表面温度は、中心部分の平
均値をとった。 サーモビュアの使用条件： 検出波長 ８〜１３μｍ、放射率 １で測定。 〔洗濯方法〕下記の条件で一定回数（１０回）洗濯を行
い、吸湿発熱性、吸湿性、樹脂付着量の洗濯耐久性試験
に供した。 洗濯条件：家庭洗濯に準じたＪＩＳ Ｌ０２１７ １０３
法によった。[Test Method for Moisture Absorption and Heat Generation] A sample cloth kept at 30 ° C., which had been completely dried, was transferred to an environment of 30 ° C. × 90% RH, and the change of the sample surface temperature was measured for 10 minutes immediately afterward by “Thermoviewer” (NEC). It was measured over time using Sanei Co., Ltd.). The measurement was carried out in a state where the sample was fixed to a wooden frame to ensure air permeability, and the sample surface temperature was an average value at the center. Thermoviewer usage conditions: Measured at a detection wavelength of 8 to 13 μm and an emissivity of 1. [Washing Method] Washing was carried out a fixed number of times (10 times) under the following conditions, and subjected to a washing durability test for moisture absorption heat generation, moisture absorption, and resin adhesion amount. Laundry conditions: JIS L0217 103 according to home laundry
According to the law.
【００２６】[0026]
【表１】 [Table 1]
【００２７】[0027]
【表２】 [Table 2]
【００２８】[0028]
【表３】 [Table 3]
【００２９】[0029]
【表４】 [Table 4]
【００３０】樹脂付加率と吸湿率、最大温度差およびそ
れらの洗濯耐久性との関係 実施例１〜実施例４において、第２工程のメタクリル酸
および水酸化ナトリウムの濃度を変化させることにより
セルロース繊維への樹脂付加率の種々異なるものを作製
した。樹脂付加率の異なるそれぞれの試料について、下
記のようにして吸湿率および最大温度差を測定した。ま
た洗濯を１０回行ったものについても同様の測定を行
い、これら特性の洗濯耐久性を評価した。得られた結果
を表５〜表８に示した。The resin addition rate and the moisture absorption rate, the maximum temperature difference and the
Relationship with Washing Durability In Examples 1 to 4, various kinds of resins having different resin addition rates to cellulose fibers were produced by changing the concentrations of methacrylic acid and sodium hydroxide in the second step. For each sample having a different resin addition rate, the moisture absorption rate and the maximum temperature difference were measured as described below. In addition, the same measurement was carried out for those which were washed 10 times, and the washing durability of these characteristics was evaluated. Tables 5 to 8 show the obtained results.
【００３１】〔吸湿率測定〕絶乾処理した試料生地を２
０℃×６５％ＲＨまたは３０℃×９０％ＲＨの環境下に
移し、その重量変化から次式により求めた。[Measurement of moisture absorption rate]
The sample was transferred to an environment of 0 ° C. × 65% RH or 30 ° C. × 90% RH, and the weight change was determined by the following equation.
【数２】 Ｗ1：２０℃、６５％ＲＨまたは３０℃、９０％ＲＨの環
境下２４時間後の生地重量、 Ｗ0：絶乾重量。 〔最大温度差〕最大温度差とは未加工生地と加工生地と
の吸湿発熱の生地表面温度の経時変化において、ある時
間における温度差が最大となる温度差をいう。(Equation 2) W 1 : dough weight after 24 hours in an environment of 20 ° C., 65% RH or 30 ° C., 90% RH, W 0 : absolute dry weight. [Maximum temperature difference] The maximum temperature difference refers to a temperature difference at which a temperature difference at a certain time becomes maximum in a time-dependent change in the surface temperature of the fabric due to moisture absorption and heat generation between the unprocessed fabric and the processed fabric.
【００３２】[0032]
【表５】 [Table 5]
【００３３】[0033]
【表６】 [Table 6]
【００３４】[0034]
【表７】 [Table 7]
【００３５】[0035]
【表８】 [Table 8]
【００３６】[0036]
【発明の効果】羊毛並の吸湿発熱性を有する綿等のセル
ロース繊維およびセルロース繊維製品であり、しかも従
来のセルロース繊維と同等の風合を備えている。また本
発明の吸湿発熱性繊維は、通常の繊維メーカーであれば
通常どこでも所有している加工設備である樹脂加工設備
（Pad-Dry-Cure）およびスチーマーを用いて製造できる
という利点がある。Industrial Applicability Cellulose fibers and cellulosic fiber products, such as cotton, having the same moisture-absorbing and heat-generating properties as wool, and have the same feeling as conventional cellulose fibers. Further, the moisture-absorbing heat-generating fiber of the present invention has an advantage that it can be produced using a resin processing facility (Pad-Dry-Cure) and a steamer, which are processing facilities normally owned by ordinary fiber manufacturers everywhere.
【図１】は実施例１で吸湿発熱性処理した綿ブロード、
および相当する未加工ブロード、比較例１のブロードの
吸湿による生地表面温度変化を示すグラフ。 ａ）加工上がり、ｂ）洗濯１０回後。FIG. 1 is a cotton broad treated in Example 1 with moisture absorption and heat generation.
7 is a graph showing a change in the dough surface temperature due to moisture absorption of the corresponding untreated broad and the broad of Comparative Example 1. a) After processing, b) After 10 washes.
【図２】は実施例２の吸湿発熱性処理したＴ／Ｃブロー
ド、および相当する未加工Ｔ／Ｃ、比較例１のＴ／Ｃの
吸湿による生地表面温度変化を示すグラフ。 ａ）加工上がり、ｂ）洗濯１０回後。FIG. 2 is a graph showing the change in fabric surface temperature due to moisture absorption of the T / C broad and the corresponding unprocessed T / C of Example 2 and the corresponding T / C of Comparative Example 1. a) After processing, b) After 10 washes.
【図３】は実施例３の吸湿発熱性処理した綿１００％ニ
ット、および相当する未加工綿ニット、比較例１の綿ニ
ットの吸湿による生地表面温度変化を示すグラフ。ａ）
加工上がり、ｂ）洗濯１０回後。FIG. 3 is a graph showing the change in the fabric surface temperature due to moisture absorption of the cotton knit of Comparative Example 1 and the corresponding 100% cotton knit treated with moisture absorption and heat generation of Example 3, and the corresponding raw cotton knit. a)
After processing, b) after 10 washings.
【図４】は実施例４の吸湿発熱性処理したレーヨン／ポ
リエステルスパンレース、および相当する未加工スパン
レース、比較例１のスパンレースの吸湿による生地表面
温度変化を示すグラフ。ａ）加工上がり、ｂ）洗濯１０
回後。FIG. 4 is a graph showing the change in fabric surface temperature due to moisture absorption of the rayon / polyester spunlace treated in Example 4 and the corresponding raw spunlace, and the spunlace of Comparative Example 1. a) finished processing, b) washing 10
After times.
１：本発明の吸湿発熱性処理した試料、 ２：第３工程を実施していない樹脂加工試料、 ３：未処理試料。 1: a sample subjected to the heat-absorbing and exothermic treatment of the present invention, 2: a resin processed sample not subjected to the third step, 3: an untreated sample.
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成１０年１１月２５日[Submission date] November 25, 1998
【手続補正１】[Procedure amendment 1]
【補正対象書類名】図面[Document name to be amended] Drawing
【補正対象項目名】全図[Correction target item name] All figures
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【図１】 FIG.
【図２】 FIG. 2
【図３】 FIG. 3
【図４】 FIG. 4
───────────────────────────────────────────────────── フロントページの続き (72)発明者 金谷 薫 大阪府大阪市中央区久太郎町２丁目４番31 号 倉敷紡績株式会社大阪本社内 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Kaoru Kanaya 2-4-131 Kutaro-cho, Chuo-ku, Osaka-shi, Osaka Kurashiki Spinning Co., Ltd. Osaka head office
Claims (7)
チロール（メタ）アクリルアミドが０.３〜２.５重量
部、−ＣＯＯＸ（Ｘ：Ｈ，ＮＨ4またはアルカリ金属）
で示されるカルボキシル基またはアミノ基を有する少な
くとも１種の水溶性ビニル重合性化合物が５〜４５重量
部化学結合した吸湿発熱性セルロース繊維。1. N-methylol (meth) acrylamide is 0.3 to 2.5 parts by weight based on 100 parts by weight of cellulose, -COOX (X: H, NH 4 or alkali metal)
5. A moisture-absorbing and heat-generating cellulose fiber in which 5 to 45 parts by weight of at least one water-soluble vinyl polymerizable compound having a carboxyl group or an amino group is chemically bonded.
（メタ）アクリルアミドに上記ビニル重合性化合物が付
加重合した請求項１記載の吸湿発熱性セルロース繊維。2. The moisture-absorbing and heat-generating cellulose fiber according to claim 1, wherein said vinyl polymerizable compound is addition-polymerized to N-methylol (meth) acrylamide bonded to cellulose.
カリ金属塩またはメタクリル酸のアルカリ金属塩である
請求項１または２に記載の吸湿発熱性セルロース繊維。3. The moisture-absorbing and heat-generating cellulose fiber according to claim 1, wherein the vinyl polymerizable compound is an alkali metal salt of acrylic acid or an alkali metal salt of methacrylic acid.
の吸湿発熱性セルロース繊維を少なくとも１成分として
含む吸湿発熱性セルロース繊維製品。4. A moisture-absorbing and heat-generating cellulose fiber product comprising the moisture-absorbing and heat-generating cellulose fiber according to claim 1, as at least one component.
を含む水溶液を含浸したセルロース繊維中にてＮ-メチ
ロール（メタ）アクリルアミドをセルロースの水酸基に
結合させてセルロース中にビニル基を導入する第１工
程、水溶性重合開始剤および−ＣＯＯＸ（Ｘ：Ｈ，ＮＨ
4またはアルカリ金属）で示されるカルボキシル基また
はアミノ基を有する少なくとも１種の水溶性ビニル重合
性化合物を含む水溶液中に第１工程で得られた繊維を浸
漬し、次いで脱水、加熱することによりセルロース中に
導入された上記ビニル基を開始点として上記水溶性ビニ
ル重合性化合物を重合する第２工程、および上記水溶性
ビニル重合性化合物重合体を付加したセルロース繊維を
高湿度条件下または湿潤状態下に保持したのち水洗およ
び乾燥を行う第３工程からなる請求項１、２または３の
いずれかに記載の吸湿発熱性セルロース繊維の製造方
法。5. A first step in which N-methylol (meth) acrylamide is bonded to hydroxyl groups of cellulose in cellulose fibers impregnated with an aqueous solution containing N-methylol (meth) acrylamide to introduce a vinyl group into cellulose. Water-soluble polymerization initiator and -COOX (X: H, NH
4 or alkali metal), the fiber obtained in the first step is immersed in an aqueous solution containing at least one water-soluble vinyl polymerizable compound having a carboxyl group or an amino group, followed by dehydration and heating to obtain cellulose. A second step of polymerizing the water-soluble vinyl polymerizable compound with the vinyl group introduced therein as a starting point, and subjecting the cellulose fiber added with the water-soluble vinyl polymerizable compound polymer to a high humidity condition or a wet state. 4. The method for producing a moisture-absorbing and heat-generating cellulose fiber according to claim 1, comprising a third step of washing with water and drying after holding.
を含む水溶液を含浸した、セルロース繊維を少なくとも
１成分として含むセルロース繊維製品中にてＮ-メチロ
ール（メタ）アクリルアミドをセルロースの水酸基に結
合させてセルロース中にビニル基を導入する第１工程、
水溶性重合開始剤および−ＣＯＯＸ（Ｘ：Ｈ，ＮＨ4ま
たはアルカリ金属）で示されるカルボキシル基またはア
ミノ基を有する少なくとも１種の水溶性ビニル重合性化
合物を含む水溶液中に第１工程で得られた繊維製品を浸
漬し、次いで脱水、加熱することによりセルロース中に
導入された上記ビニル基を開始点として上記水溶性ビニ
ル重合性化合物を重合する第２工程、および上記水溶性
ビニル重合性化合物重合体を付加した繊維製品を高湿度
条件下または湿潤状態下に保持したのち水洗および乾燥
を行う第３工程からなる請求項４に記載の吸湿発熱性セ
ルロース繊維製品の製造方法。6. In a cellulose fiber product impregnated with an aqueous solution containing N-methylol (meth) acrylamide and containing cellulose fibers as at least one component, N-methylol (meth) acrylamide is bonded to the hydroxyl groups of cellulose to form cellulose. A first step of introducing a vinyl group into
It is obtained in the first step in an aqueous solution containing a water-soluble polymerization initiator and at least one water-soluble vinyl polymerizable compound having a carboxyl group or an amino group represented by -COOX (X: H, NH 4 or an alkali metal). A second step of immersing the fibrous product thus obtained, followed by dehydration and heating to polymerize the water-soluble vinyl polymerizable compound starting from the vinyl group introduced into the cellulose, and the polymerization of the water-soluble vinyl polymerizable compound. 5. The method for producing a moisture-absorbing and heat-generating cellulose fiber product according to claim 4, comprising a third step of washing and drying after maintaining the fiber product to which the coalescence has been added under a high humidity condition or a wet condition.
燥とそれに続く１４０〜１６０℃での熱処理、第２工程
の反応を１１０〜１３０℃での加熱により行い、第３工
程の高湿度条件または湿潤状態が１００〜１１０℃の高
温水蒸気中での蒸気処理である請求項５または６記載の
吸湿発熱性セルロース繊維または吸湿発熱性セルロース
繊維製品の製造方法。7. The reaction of the first step is carried out by drying at 110 to 130 ° C. followed by heat treatment at 140 to 160 ° C., and the reaction of the second step is carried out by heating at 110 to 130 ° C. The method for producing a moisture-absorbing and exothermic cellulose fiber or a moisture-absorbing and exothermic cellulose fiber product according to claim 5 or 6, wherein the condition or wet state is steam treatment in high-temperature steam at 100 to 110 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10085860A JP2898623B1 (en) | 1998-03-31 | 1998-03-31 | Hygroscopic heat-generating cellulose fiber and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10085860A JP2898623B1 (en) | 1998-03-31 | 1998-03-31 | Hygroscopic heat-generating cellulose fiber and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2898623B1 JP2898623B1 (en) | 1999-06-02 |
| JPH11279943A true JPH11279943A (en) | 1999-10-12 |
Family
ID=13870644
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10085860A Expired - Fee Related JP2898623B1 (en) | 1998-03-31 | 1998-03-31 | Hygroscopic heat-generating cellulose fiber and method for producing the same |
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| Country | Link |
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| JP (1) | JP2898623B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014133963A (en) * | 2013-01-11 | 2014-07-24 | Kurabo Ind Ltd | Moisture-absorbing/releasing cellulose fiber and method for manufacturing the same |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001172866A (en) * | 1999-12-20 | 2001-06-26 | Toyobo Co Ltd | Hygroscopic and exothermic cellulose-based fiber product having excellent heat retaining property |
| CN100582334C (en) | 2003-08-14 | 2010-01-20 | 旭化成繊维株式会社 | Spun yarn, knitted article using the yarn and fiber product |
| JP7408311B2 (en) | 2019-07-31 | 2024-01-05 | 倉敷紡績株式会社 | Moisture-absorbing heat-generating fabric and moisture-absorbing heat-generating clothing using the same |
-
1998
- 1998-03-31 JP JP10085860A patent/JP2898623B1/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014133963A (en) * | 2013-01-11 | 2014-07-24 | Kurabo Ind Ltd | Moisture-absorbing/releasing cellulose fiber and method for manufacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2898623B1 (en) | 1999-06-02 |
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