JPH08337968A - Antimicrobial processing of cellulose-based fabric - Google Patents
Antimicrobial processing of cellulose-based fabricInfo
- Publication number
- JPH08337968A JPH08337968A JP14440395A JP14440395A JPH08337968A JP H08337968 A JPH08337968 A JP H08337968A JP 14440395 A JP14440395 A JP 14440395A JP 14440395 A JP14440395 A JP 14440395A JP H08337968 A JPH08337968 A JP H08337968A
- Authority
- JP
- Japan
- Prior art keywords
- fabric
- aminophosphazene
- antibacterial
- cellulose
- nitrogen
- 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.)
- Pending
Links
- 239000004744 fabric Substances 0.000 title claims abstract description 38
- 229920002678 cellulose Polymers 0.000 title abstract description 6
- 239000001913 cellulose Substances 0.000 title abstract description 6
- 238000012545 processing Methods 0.000 title abstract description 6
- 230000000845 anti-microbial effect Effects 0.000 title abstract 4
- 239000000835 fiber Substances 0.000 claims abstract description 37
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 6
- 230000000844 anti-bacterial effect Effects 0.000 claims description 25
- 239000003242 anti bacterial agent Substances 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000003672 processing method Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 abstract description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 12
- 239000000203 mixture Substances 0.000 abstract description 12
- 229920000742 Cotton Polymers 0.000 abstract description 4
- 239000004599 antimicrobial Substances 0.000 abstract 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000009472 formulation Methods 0.000 description 10
- 239000002759 woven fabric Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- -1 polyoxyethylene trimethyl ammonium chloride Polymers 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 4
- 239000004640 Melamine resin Substances 0.000 description 4
- 241000191967 Staphylococcus aureus Species 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 241000588748 Klebsiella Species 0.000 description 2
- 206010041925 Staphylococcal infections Diseases 0.000 description 2
- AKGZDINYLOSBTE-UHFFFAOYSA-N [(e)-n'-(diaminomethylideneamino)carbamimidoyl]azanium;chloride Chemical compound Cl.NC(=N)NN=C(N)N AKGZDINYLOSBTE-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 description 2
- 210000000170 cell membrane Anatomy 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000012258 culturing Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 208000015688 methicillin-resistant staphylococcus aureus infectious disease Diseases 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- YWMSPYAVKFABPD-UHFFFAOYSA-M (3,4-dichlorophenyl)methyl-dodecyl-dimethylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=C(Cl)C(Cl)=C1 YWMSPYAVKFABPD-UHFFFAOYSA-M 0.000 description 1
- HGVPAERCRRHYPS-UHFFFAOYSA-N 2-(3,5-dimethyl-1H-pyrazol-4-yl)-4-phenyl-1H-pyrimidin-6-one Chemical compound CC1=NNC(=C1C1=NC(=CC(=N1)C1=CC=CC=C1)O)C HGVPAERCRRHYPS-UHFFFAOYSA-N 0.000 description 1
- GINVCSKBOCDMBE-UHFFFAOYSA-N 2-chloro-1h-hexazine Chemical compound ClN1NN=NN=N1 GINVCSKBOCDMBE-UHFFFAOYSA-N 0.000 description 1
- QCQCHGYLTSGIGX-GHXANHINSA-N 4-[[(3ar,5ar,5br,7ar,9s,11ar,11br,13as)-5a,5b,8,8,11a-pentamethyl-3a-[(5-methylpyridine-3-carbonyl)amino]-2-oxo-1-propan-2-yl-4,5,6,7,7a,9,10,11,11b,12,13,13a-dodecahydro-3h-cyclopenta[a]chrysen-9-yl]oxy]-2,2-dimethyl-4-oxobutanoic acid Chemical compound N([C@@]12CC[C@@]3(C)[C@]4(C)CC[C@H]5C(C)(C)[C@@H](OC(=O)CC(C)(C)C(O)=O)CC[C@]5(C)[C@H]4CC[C@@H]3C1=C(C(C2)=O)C(C)C)C(=O)C1=CN=CC(C)=C1 QCQCHGYLTSGIGX-GHXANHINSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 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
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 241000191940 Staphylococcus Species 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical group [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229960000686 benzalkonium chloride Drugs 0.000 description 1
- UREZNYTWGJKWBI-UHFFFAOYSA-M benzethonium chloride Chemical compound [Cl-].C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 UREZNYTWGJKWBI-UHFFFAOYSA-M 0.000 description 1
- 229960001950 benzethonium chloride Drugs 0.000 description 1
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- CGMKPKRNUNDACU-UHFFFAOYSA-N carbamimidoyl(dodecyl)azanium;chloride Chemical compound Cl.CCCCCCCCCCCCN=C(N)N CGMKPKRNUNDACU-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- SXPWTBGAZSPLHA-UHFFFAOYSA-M cetalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SXPWTBGAZSPLHA-UHFFFAOYSA-M 0.000 description 1
- 229960000228 cetalkonium chloride Drugs 0.000 description 1
- 229960001927 cetylpyridinium chloride Drugs 0.000 description 1
- YMKDRGPMQRFJGP-UHFFFAOYSA-M cetylpyridinium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 YMKDRGPMQRFJGP-UHFFFAOYSA-M 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- JCALZGYNNQTXGP-UHFFFAOYSA-M dimethyl-[[4-(6-methylheptyl)phenyl]methyl]-[2-(2-phenoxyethoxy)ethyl]azanium chloride Chemical compound [Cl-].C(CCCCC(C)C)C1=CC=C(C[N+](C)(C)CCOCCOC2=CC=CC=C2)C=C1 JCALZGYNNQTXGP-UHFFFAOYSA-M 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920003176 water-insoluble polymer Polymers 0.000 description 1
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は，セルロース系繊維布帛
に耐久性のある抗菌性能を付与する加工方法に関するも
のである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a processing method for imparting durable antibacterial performance to a cellulosic fiber cloth.
【０００２】[0002]
【従来の技術】抗菌繊維の製造方法には，大別すると，
抗菌性の金属系無機微粒子を繊維の製造時に繊維に練り
混んで紡糸する方法と，製造された繊維に抗菌剤を含む
処理液を付与して熱処理する後加工方法がある。前者の
金属系無機微粒子の練り混み紡糸方法では，合成繊維ま
たは半合成繊維の紡糸原液へ抗菌性微粒子を混入して紡
糸する方法で製造され，この方法による抗菌繊維は，洗
濯耐久性に優れているが，抗菌剤が繊維表面に出てくる
のに時間がかかるため，抗菌効果の現れる時間が遅いと
いう問題があり，また，天然繊維に用いることはできな
いという問題がある。2. Description of the Related Art The methods for producing antibacterial fibers are roughly classified into
There are a method of kneading and spinning the antibacterial metal-based inorganic fine particles into the fiber at the time of producing the fiber, and a post-processing method of applying a treatment liquid containing an antibacterial agent to the produced fiber and heat-treating it. The former method of kneading and mixing metal-based inorganic fine particles is produced by mixing antibacterial fine particles into a spinning solution of synthetic fibers or semi-synthetic fibers and spinning. The antibacterial fibers produced by this method are excellent in washing durability. However, it takes a long time for the antibacterial agent to appear on the surface of the fiber, so that there is a problem that the antibacterial effect takes a long time to appear, and that it cannot be used for natural fibers.
【０００３】一方，後者の抗菌剤を含む処理液を繊維に
付与する後加工方法では，樹脂を介して抗菌剤を繊維の
表面に固定化するが，この場合，一般的にはメラミン樹
脂が用いられ，抗菌剤の単独使用に比べ抗菌性能の洗濯
耐久性は向上するが，メラミン樹脂からホルムアルデヒ
ドが遊離してくるという問題がある。On the other hand, in the latter post-processing method of applying a treatment liquid containing an antibacterial agent to the fiber, the antibacterial agent is immobilized on the surface of the fiber through a resin. In this case, a melamine resin is generally used. Although the antibacterial performance is improved in washing durability as compared with the case of using the antibacterial agent alone, there is a problem that formaldehyde is liberated from the melamine resin.
【０００４】[0004]
【発明が解決しようとする課題】本発明は，このような
現状に鑑みて行われたもので，セルロース系繊維布帛に
遊離ホルムアルデヒドが発生することのない性能と洗濯
耐久性の優れた抗菌性能を付与する加工方法を得ること
を目的とするものである。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it has an antibacterial performance with excellent free-formaldehyde generation and excellent washing durability in a cellulosic fiber cloth. The purpose is to obtain a processing method to be applied.
【０００５】[0005]
【課題を解決するための手段】本発明は，上記目的を達
成するもので，次の構成によりなるものである。すなわ
ち，本発明は，窒素を含有する抗菌剤とアミノホスファ
ゼン化合物の混合処理液をセルロース系繊維布帛に含浸
し，しかる後に乾燥，熱処理を行うことを特徴とするセ
ルロース系繊維布帛の抗菌加工方法を要旨とするもので
ある。以下，本発明を詳細に説明する。The present invention achieves the above object and has the following configuration. That is, the present invention provides an antibacterial processing method for a cellulosic fiber cloth, which comprises impregnating a cellulosic fiber cloth with a mixed treatment liquid of a nitrogen-containing antibacterial agent and an aminophosphazene compound, followed by drying and heat treatment. It is a summary. Hereinafter, the present invention will be described in detail.
【０００６】本発明で用いるセルロース系繊維布帛と
は，木綿，麻等の天然繊維，ビスコースレーヨン等の再
生繊維を主に用いた織物，編物，不織布等の布帛であっ
て，これらの天然繊維や再生繊維の混用率が３０％以上
のものをいう。もちろん，セルロース系繊維が１００％
であってもよい。混用率が３０％未満であると，抗菌剤
とセルロースとの架橋部分が少なくなり，洗濯耐久性の
ある抗菌性能をセルロース系繊維布帛に付与することが
できなくなる。The cellulosic fiber cloth used in the present invention is a cloth such as a woven fabric, a knitted fabric or a non-woven fabric mainly made of natural fibers such as cotton and hemp, and regenerated fibers such as viscose rayon. A mixture of recycled fibers and recycled fibers is 30% or more. Of course, 100% cellulosic fiber
It may be. When the mixing ratio is less than 30%, the cross-linking portion between the antibacterial agent and the cellulose becomes small, and it becomes impossible to impart the antibacterial performance with washing durability to the cellulosic fiber cloth.
【０００７】本発明では，上述のセルロース系繊維布帛
に窒素を含有する抗菌剤とアミノホスファゼン化合物の
混合処理液を含浸する。ここで用いる窒素を含有する抗
菌剤としては，塩化ベンザルコニウム，ポリオキシエチ
レントリメチルアンモニウムクロリド，塩化ベンゼトニ
ウム，塩化セチルピリジニウム，アルキルトリメチルア
ンモニウム塩，ｐ−イソオクチルフェノキシエトキシエ
チルジメチルベンジルアンモニウムクロリド，臭化フェ
ノドデシウム，セチルジメチルベンジルアンモニウムク
ロリド，（3,４−ジクロルベンジル）ドデシルジメチル
アンモニウムクロリド，アルキルジメチルエチルアンモ
ニウム塩，アルキルキノリニウム塩，アルキルアミドプ
ロピルジメチルベンジルアンモニウム塩，ジイソブチル
クレゾキシエトキシエチルベンジルアンモニウム塩等の
第４級アンモニウム塩，クロルヘキサジン，ドデシルグ
アニジン塩酸塩，ポリヘキサメチレンビグアニジン塩酸
塩，２−（3,５−ジメチルピラゾリル）−４−ヒドロキ
シ−６−フェニルピリミジン等を挙げることができる。
これらの抗菌剤の使用量は，目標とする抗菌性能により
異なるが，繊維重量に対して0.１〜１０重量％の範囲で
使用する。In the present invention, the above-mentioned cellulosic fiber cloth is impregnated with a mixed treatment liquid of an antibacterial agent containing nitrogen and an aminophosphazene compound. As the nitrogen-containing antibacterial agent used here, benzalkonium chloride, polyoxyethylene trimethyl ammonium chloride, benzethonium chloride, cetylpyridinium chloride, alkyl trimethyl ammonium salt, p-isooctylphenoxyethoxyethyl dimethylbenzyl ammonium chloride, bromide Phenododecium, cetyldimethylbenzylammonium chloride, (3,4-dichlorobenzyl) dodecyldimethylammonium chloride, alkyldimethylethylammonium salt, alkylquinolinium salt, alkylamidopropyldimethylbenzylammonium salt, diisobutylcrezoxyethoxyethylbenzylammonium salt Quaternary ammonium salts such as salts, chlorhexazine, dodecylguanidine hydrochloride, polyhexamethylene big Bleed hydrochloride salt, and 2- (3,5-dimethyl-pyrazolyl) -4-hydroxy-6-phenyl-pyrimidine, and the like.
The amount of these antibacterial agents used varies depending on the target antibacterial performance, but is used in the range of 0.1 to 10% by weight based on the weight of the fiber.
【０００８】本発明で用いるアミノホスファゼン化合物
は，一般式〔 ＮＰ（ＮＨ2)2 〕nで表され，通常はク
ロロホスファゼンとアンモニアから合成される。この方
法で合成されたアミノホスファゼン化合物は，塩化アン
モニウムを約５０重量％含有しているため，乾燥，熱処
理時に塩化アンモニウムが酸触媒として作用し，アミノ
ホスファゼン化合物の使用量が多くなると繊維布帛の強
力低下の原因となるので，望ましくはアミノホスファゼ
ン塩酸塩を用いるのが好ましい。アミノホスファゼン塩
酸塩は，クロロホスファゼンとアンモニアとを反応させ
て得られた反応生成物を５〜１０倍量の水に加えて溶か
し，この溶液に対して５〜７倍量のアルコールを徐々に
添加しながら攪拌し，析出する沈殿物を濾別して得るこ
とができる。アミノホスファゼン化合物の使用量は，抗
菌剤に対して１０〜１５０％の範囲で使用すればよい。The aminophosphazene compound used in the present invention is represented by the general formula [NP (NH 2 ) 2 ] n and is usually synthesized from chlorophosphazene and ammonia. Since the aminophosphazene compound synthesized by this method contains about 50% by weight of ammonium chloride, ammonium chloride acts as an acid catalyst during drying and heat treatment, and when the amount of aminophosphazene compound used is large, the strength of the fiber cloth is increased. It is preferable to use aminophosphazene hydrochloride because it causes a decrease. Aminophosphazene hydrochloride is a reaction product obtained by reacting chlorophosphazene with ammonia, and dissolved in 5 to 10 times the amount of water, and 5 to 7 times the amount of alcohol is gradually added to this solution. While stirring, the resulting precipitate can be obtained by filtration. The amount of the aminophosphazene compound used may be in the range of 10 to 150% with respect to the antibacterial agent.
【０００９】アミノホスファゼン塩酸塩を用いる場合
は，触媒としてアミノホスファゼン塩酸の等モル量の塩
酸またはリン酸を用いる。窒素を含有する抗菌剤とアミ
ノホスファゼン化合物の混合処理液をセルロース系繊維
布帛に含浸するには，通常の布帛の樹脂加工に用いるパ
ッダー等の樹脂加工装置を用いて含浸を行い，セルロー
ス系繊維布帛に付与する。When aminophosphazene hydrochloride is used, equimolar amounts of hydrochloric acid or phosphoric acid of aminophosphazene hydrochloric acid are used as a catalyst. To impregnate a cellulosic fiber cloth with a mixed treatment liquid of a nitrogen-containing antibacterial agent and an aminophosphazene compound, impregnation is carried out using a resin processing device such as a padder used for resin processing of ordinary cloth. Given to.
【００１０】窒素を含有する抗菌剤とアミノホスファゼ
ン化合物の混合処理液をセルロース系繊維布帛に含浸
後，乾燥し，１２０〜１８０℃で１〜５分間の熱処理を
行う。熱処理は，通常，ピンテンターを用いて行うとよ
い。本発明は，以上の構成よりなるものである。A cellulosic fiber cloth is impregnated with a mixed treatment liquid of an antibacterial agent containing nitrogen and an aminophosphazene compound, dried, and heat-treated at 120 to 180 ° C. for 1 to 5 minutes. The heat treatment should normally be performed using a pin tenter. The present invention has the above configuration.
【００１１】[0011]
【作用】本発明において，窒素を含有する抗菌剤とアミ
ノホスファゼン化合物の混合処理液をセルロース系繊維
布帛に含浸後，乾燥，熱処理を行うと，何故に洗濯耐久
性の優れた抗菌性能をセルロース系繊維布帛に付与する
ことができるのか，その理由は必ずしも明確ではない
が，本発明者は次のように推測している。In the present invention, when the cellulose fiber cloth is impregnated with the mixed treatment liquid of the nitrogen-containing antibacterial agent and the aminophosphazene compound, and then dried and heat-treated, the excellent antibacterial performance due to the excellent washing durability can be obtained. The reason why it can be added to the fiber cloth is not always clear, but the present inventors presume as follows.
【００１２】その１つは，窒素を含有する抗菌剤とアミ
ノホスファゼン化合物の混合処理液をセルロース系繊維
布帛に含浸後，乾燥，熱処理を行うと，アミノホスファ
ゼンが酸触媒によりアンモニアを脱離することによっ
て，抗菌剤の窒素を含め重縮合し，水に不溶のポリマー
が生成するので，洗濯耐久性の優れた抗菌性能をセルロ
ース系繊維布帛に付与することができるのであろうと推
測している。One of them is that when a mixed treatment liquid of an antibacterial agent containing nitrogen and an aminophosphazene compound is impregnated into a cellulosic fiber cloth, followed by drying and heat treatment, the aminophosphazene desorbs ammonia by an acid catalyst. It is presumed that, due to the polycondensation including nitrogen of the antibacterial agent, a water-insoluble polymer is produced, and thus the antibacterial performance with excellent washing durability can be imparted to the cellulosic fiber cloth.
【００１３】もう１つは，窒素を含有する抗菌剤とアミ
ノホスファゼン化合物の混合処理液をセルロース系繊維
布帛に含浸後，乾燥，熱処理を行うと，アミノホスファ
ゼン化合物のリン−窒素環が開環して，一端のリンと抗
菌剤の窒素が反応結合し，他端は酸触媒の作用によりセ
ルロースの水酸基とアミド交換反応を起こしてリン酸エ
ステルを生成する脱離付加反応により，抗菌剤が上記ア
ミノホスファゼン化合物を介してセルロース系繊維と強
固に結合するので，洗濯耐久性の優れた抗菌性能をセル
ロース系繊維布帛に付与することができるようになるの
であろうと推測している。Secondly, when the cellulose-based fiber cloth is impregnated with a mixed treatment liquid of a nitrogen-containing antibacterial agent and an aminophosphazene compound, and then dried and heat-treated, the phosphorus-nitrogen ring of the aminophosphazene compound is opened. The phosphorus on one end reacts with the nitrogen of the antibacterial agent, and the other end undergoes an amide exchange reaction with the hydroxyl group of cellulose by the action of an acid catalyst to produce a phosphoric acid ester. It is speculated that since it strongly binds to the cellulosic fiber through the phosphazene compound, it is possible to impart antibacterial performance with excellent washing durability to the cellulosic fiber cloth.
【００１４】セルロース系繊維に固定化された抗菌剤
は，陽イオン性を帯び，負に荷電した細菌の細胞膜に吸
着して細胞膜を破壊することにより，殺菌作用を示すも
のと推測される。It is presumed that the antibacterial agent immobilized on the cellulosic fibers exhibits a bactericidal action by being cationic and adsorbing to the cell membrane of a negatively charged bacterium to destroy the cell membrane.
【００１５】[0015]
【実施例】次に，本発明を実施例によってさらに具体的
に説明するが，実施例における布帛の性能の測定，評価
は，下記の方法で行った。EXAMPLES Next, the present invention will be described in more detail with reference to Examples. Measurement and evaluation of the performance of the fabrics in Examples were carried out by the following methods.
【００１６】（１）抗菌性 繊維製品衛生加工協議会が設定した菌数測定法に準じ
て，滅菌した液体ブイヨンに下記試験菌を懸濁させ，こ
の液を0.２ｇの試験片の上に0.２ミリリットル接種し，
温度３７℃で１８時間培養した後，取り出し，培養前後
の試験片上の生菌数を測定して，下記計算式により菌数
の増減比，増減値および増減値差を順次算出し，菌数増
減値差によって抗菌性を評価した。菌数増減値差が1.６
以上のとき，抗菌性ありと認められ，この値が大きいほ
ど抗菌性が良好であることを示す。 試験菌 次の菌株を適宜用いる。 Staphylococcus aureus ＦＤＡ ２０９ｐ（ＡＴＣＣ６
５３８Ｐ） Klebsiella pneummoooooniae（ＡＴＣＣ４３５２） Staphylococcus aureus ＩＩＤ １６７７（ＭＲＳＡ）(1) Antibacterial property The following test bacteria were suspended in a sterilized liquid broth according to the method for measuring the number of bacteria set by the Textile Products Sanitary Processing Council, and this liquid was placed on a 0.2 g test piece. Inoculate 0.2 ml,
After culturing at 37 ° C for 18 hours, take out, measure the number of viable bacteria on the test piece before and after culturing, and sequentially calculate the increase / decrease ratio, increase / decrease value and difference of increase / decrease value of the bacteria number by the following calculation formula. The antibacterial property was evaluated by the value difference. Difference in the number of bacteria is 1.6
In the above cases, antibacterial properties were recognized, and the larger this value is, the better the antibacterial properties are. Test strains Use the following strains as appropriate. Staphylococcus aureus FDA 209p (ATCC6
538P) Klebsiella pneummoooooniae (ATCC4352) Staphylococcus aureus IID 1677 (MRSA)
【００１７】 計算式Calculation formula
【数１】 [Equation 1]
【００１８】（２）洗濯繰り返し試験 ＪＩＳ Ｌ−１０４２ Ｆ−２法により洗濯を１０回行
うに際し，洗液に過酸化水素水３cc／リットルと過炭酸
ソーダ1.５ｇ／リットルを添加して行った。乾燥に際し
ては，タンブラーを用いて，５０℃で３０分間のタンブ
ル乾燥を行った。 （３）遊離ホルムアルデヒド量 ＪＩＳ Ｌ−１０９６ Ｂ法による。(2) Repeated washing test When washing was carried out 10 times according to the JIS L-1042 F-2 method, 3 cc / liter of hydrogen peroxide solution and 1.5 g / liter of sodium percarbonate were added to the washing solution. . At the time of drying, tumbling was performed at 50 ° C. for 30 minutes using a tumbler. (3) Free formaldehyde amount According to JIS L-1096 B method.
【００１９】実施例１ 木綿１００％の晒上がりの平織物（経糸３０ｓ／−，緯
糸３０ｓ／−；経糸密度９５本／吋，緯糸密度７１本／
吋）を用意し，これに下記処方１の処理液を含浸しマン
グルで絞液率６０％にて圧搾絞液後，１００℃で２分間
の乾燥を行い，続いて，ピンテンターを用いて１５０℃
で３分間の熱処理を行い，本発明の加工織物を得た。Example 1 A plain weave fabric made of 100% cotton (warp 30s /-, weft 30s /-; warp density 95 / inch, weft density 71 /
(Ichi) is prepared, impregnated with the treatment liquid of the following formulation 1 and squeezed and squeezed with a mangle at a squeezing rate of 60%, and then dried at 100 ° C for 2 minutes, and then 150 ° C using a pin tenter.
Was heat-treated for 3 minutes to obtain the processed fabric of the present invention.
【００２０】処方１ ニッカノン ＲＢ ４０ｇ／リットル （第四級アンモニウム系抗菌剤，日華化学工業株式会社
製） ＡＡ−１０００ １００ｇ／リットル （アミノホスファゼン化合物，日本曹達株式会社製）Formulation 1 Nikkanon RB 40 g / liter (quaternary ammonium antibacterial agent, manufactured by Nika Chemical Industry Co., Ltd.) AA-1000 100 g / liter (aminophosphazene compound, manufactured by Nippon Soda Co., Ltd.)
【００２１】本発明との比較のため，晒上がりの未加工
織物を採取し，これを比較例１とした。次に，本発明と
の比較のため，本実施例において処方１からアミノホス
ファゼン化合物のＡＡ−１０００を除く他は，本実施例
とまったく同一の方法により比較例２の加工織物を得
た。また，本発明との比較のため，本実施例において処
方１に代えて下記処方２の処理液を用いる他は，本実施
例とまったく同一の方法により従来法の比較例３の加工
織物を得た。For comparison with the present invention, a raw unbleached fabric was sampled and used as Comparative Example 1. Next, for comparison with the present invention, a processed woven fabric of Comparative Example 2 was obtained in the same manner as in this Example except that the aminophosphazene compound AA-1000 was omitted from Formulation 1 in this Example. Further, for comparison with the present invention, a processed fabric of Comparative Example 3 of the conventional method was obtained by the same method as in this Example except that the treatment liquid of the following Formulation 2 was used in place of Formulation 1 in this Example. It was
【００２２】処方２ ニッカノン ＲＢ ４０ｇ／リットル （第四級アンモニウム系抗菌剤，日華化学工業株式会社
製） Sumitex Resin Ｍ−３ ３０ｇ／リットル （メラミン樹脂，住友化学工業株式会社製） Sumitex Accelerator ＡＣＸ ３ｇ／リットル （触媒，住友化学工業株式会社製）Formulation 2 Nikkanon RB 40 g / liter (quaternary ammonium type antibacterial agent, manufactured by Nichika Chemical Industry Co., Ltd.) Sumitex Resin M-3 30 g / liter (melamine resin, manufactured by Sumitomo Chemical Co., Ltd.) Sumitex Accelerator ACX 3 g / Liter (catalyst, Sumitomo Chemical Co., Ltd.)
【００２３】本発明及び比較用の加工織物の抗菌性能等
を，試験菌体としてStaphylococcusaureus ＦＤＡ ２
０９ｐ（ＡＴＣＣ６５３８Ｐ）を用いて測定し，その結
果を合わせて表１に示した。The antibacterial performance and the like of the present invention and the processed fabrics for comparison were tested as Staphylococcus aureus FDA 2
09p (ATCC 6538P) was used for the measurement, and the results are also shown in Table 1.
【表１】 [Table 1]
【００２４】表１より明らかなごとく，本発明の加工織
物は，洗濯耐久性の優れた抗菌性能を有し，しかも遊離
ホルムアルデヒドを発生することもなかった。As is clear from Table 1, the processed woven fabric of the present invention has an excellent antibacterial performance with excellent washing durability and does not generate free formaldehyde.
【００２５】実施例２ ＡＡ−１０００（アミノホスファゼン化合物，日本曹達
株式会社製）１００ｇの粉体を５倍量の水に加えて溶解
し，この水溶液に対して５倍量のメタノールを徐々に添
加しながら攪拌し，析出した沈殿物を濾別，乾燥してア
ミノホスファゼン塩酸塩３０ｇを得た。これは，後述の
処方３で用いるものである。次に，綿５０％／ポリエス
テル５０％の混紡糸５０ｓ／−よりなる晒上がりの綾織
物（経糸密度１４４本／吋，緯糸密度７２本／吋）を用
意し，これに下記処方３の処理液を含浸し，マングルで
絞液率５０％にて圧搾絞液後，１００℃で２分間の乾燥
を行い，続いて，１６０℃で２分間の熱処理を行い，本
発明の加工織物を得た。Example 2 AA-1000 (aminophosphazene compound, manufactured by Nippon Soda Co., Ltd.) 100 g of powder was dissolved in 5 times amount of water, and 5 times amount of methanol was gradually added to this aqueous solution. While stirring, the deposited precipitate was separated by filtration and dried to obtain 30 g of aminophosphazene hydrochloride. This is used in prescription 3 described later. Next, a twill woven fabric (warp density 144 threads / inch, weft density 72 threads / inch) made of 50s / 50% cotton / 50% polyester mixed yarn 50s / -was prepared. After being squeezed and squeezed with a mangle at a squeezing rate of 50%, it was dried at 100 ° C. for 2 minutes and then heat-treated at 160 ° C. for 2 minutes to obtain a processed woven fabric of the present invention.
【００２６】処方３ Proxel ＩＢ ４０ｇ／リットル （ポリヘキサメチレンビグアニジン塩酸塩系抗菌剤，ゼ
ネカ株式会社製） アミノホスファゼン塩酸塩 ３０ｇ／リットル リン酸（８５％） ９ｇ／リットルFormulation 3 Proxel IB 40 g / l (Polyhexamethylene biguanidine hydrochloride antibacterial agent, manufactured by Zeneca Corporation) Aminophosphazene hydrochloride 30 g / l Phosphoric acid (85%) 9 g / l
【００２７】本発明との比較のため，晒上がりの未加工
織物を採取し，これを比較例４とした。次に，本発明と
の比較のため，本実施例において処方３からアミノホス
ファゼン塩酸塩とリン酸を除く他は，本実施例２とまっ
たく同一の方法により比較例５の加工織物を得た。For comparison with the present invention, a raw unbleached woven fabric was sampled and used as Comparative Example 4. Next, for comparison with the present invention, a processed woven fabric of Comparative Example 5 was obtained by the same method as in Example 2 except that aminophosphazene hydrochloride and phosphoric acid were removed from Formulation 3 in this example.
【００２８】また，本発明との比較のため，本実施例に
おいて処方３に代えて下記処方４の処理液を用いる他
は，本実施例とまったく同一の方法により従来法の比較
例６の加工織物を得た。 処方４ Proxel ＩＢ ４０ｇ／リットル （ポリヘキサメチレンビグアニジン塩酸塩系抗菌剤，ゼ
ネカ株式会社製） Sumitex Resin Ｍ−３ ３０ｇ／リットル （メラミン樹脂，住友化学工業株式会社製） Sumitex Accelerator ＡＣＸ ３ｇ／リットル （触媒，住友化学工業株式会社製）For comparison with the present invention, the processing of Comparative Example 6 of the conventional method was carried out by the same method as that of this Example except that the treatment liquid of the following Formulation 4 was used in place of Formulation 3 in this Example. A woven fabric was obtained. Prescription 4 Proxel IB 40 g / liter (polyhexamethylene biguanidine hydrochloride antibacterial agent, manufactured by Zeneca Corporation) Sumitex Resin M-3 30 g / liter (melamine resin, Sumitomo Chemical Co., Ltd.) Sumitex Accelerator ACX 3 g / liter ( Catalyst, manufactured by Sumitomo Chemical Co., Ltd.)
【００２９】本発明および比較用の加工織物の抗菌性能
等を，試験菌体として各々Staphylococcus aureus ＦＤ
Ａ ２０９ｐ（ＡＴＣＣ６５３８Ｐ），Klebsiella pne
umm-oooooniae(ＡＴＣＣ４３５２），Staphylococcus a
ureus ＩＩＤ １６７７（ＭＲＳＡ）を用いて測定し，
その結果を合わせて表２に示した。The antibacterial properties and the like of the present invention and the processed woven fabrics for comparison were tested as Staphylococcus aureus FD, respectively.
A 209p (ATCC6538P), Klebsiella pne
umm-oooooniae (ATCC4352), Staphylococcus a
ureus IID 1677 (MRSA),
The results are shown together in Table 2.
【００３０】[0030]
【表２】 [Table 2]
【００３１】表２より明らかなごとく，本発明の加工織
物は，洗濯耐久性の優れた抗菌性能を有し，しかも遊離
ホルムアルデヒドを発生することもなかった。As is clear from Table 2, the processed fabric of the present invention has an excellent antibacterial property with excellent washing durability and does not generate free formaldehyde.
【００３２】[0032]
【発明の効果】本発明方法によれば，遊離ホルムアルデ
ヒドが発生することのない性能と洗濯耐久性の優れた抗
菌性能をセルロース系繊維布帛に付与することができ
る。EFFECTS OF THE INVENTION According to the method of the present invention, the cellulosic fiber cloth can be provided with antibacterial performance which is free from generation of free formaldehyde and excellent in washing durability.
Claims (1)
ゼン化合物の混合処理液をセルロース系繊維布帛に含浸
し，しかる後に乾燥，熱処理を行うことを特徴とするセ
ルロース系繊維布帛の抗菌加工方法。1. An antibacterial processing method for a cellulosic fiber cloth, which comprises impregnating a cellulosic fiber cloth with a mixed treatment liquid of a nitrogen-containing antibacterial agent and an aminophosphazene compound, followed by drying and heat treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14440395A JPH08337968A (en) | 1995-06-12 | 1995-06-12 | Antimicrobial processing of cellulose-based fabric |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14440395A JPH08337968A (en) | 1995-06-12 | 1995-06-12 | Antimicrobial processing of cellulose-based fabric |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08337968A true JPH08337968A (en) | 1996-12-24 |
Family
ID=15361366
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14440395A Pending JPH08337968A (en) | 1995-06-12 | 1995-06-12 | Antimicrobial processing of cellulose-based fabric |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08337968A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10245777A (en) * | 1997-02-25 | 1998-09-14 | Barnhardt Mfg Co | Open and wet-processed intermediate natural fiber product having long-term antibacterial properties and suitable for use in final products, and method for producing the same |
| JPH11189978A (en) * | 1997-12-24 | 1999-07-13 | Toray Ind Inc | Polyester fiber structure and method for producing the same |
| KR100828023B1 (en) * | 2001-12-20 | 2008-05-08 | 주식회사 엘지생활건강 | Fabric softener composition |
| CN119121638A (en) * | 2024-09-14 | 2024-12-13 | 浙江大学 | Bacteria-responsive hemostatic and antibacterial cotton fabric and preparation method thereof |
-
1995
- 1995-06-12 JP JP14440395A patent/JPH08337968A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10245777A (en) * | 1997-02-25 | 1998-09-14 | Barnhardt Mfg Co | Open and wet-processed intermediate natural fiber product having long-term antibacterial properties and suitable for use in final products, and method for producing the same |
| JPH11189978A (en) * | 1997-12-24 | 1999-07-13 | Toray Ind Inc | Polyester fiber structure and method for producing the same |
| KR100828023B1 (en) * | 2001-12-20 | 2008-05-08 | 주식회사 엘지생활건강 | Fabric softener composition |
| CN119121638A (en) * | 2024-09-14 | 2024-12-13 | 浙江大学 | Bacteria-responsive hemostatic and antibacterial cotton fabric and preparation method thereof |
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