JPS591770A - Sterilizable cellulose fiber - Google Patents
Sterilizable cellulose fiberInfo
- Publication number
- JPS591770A JPS591770A JP11130882A JP11130882A JPS591770A JP S591770 A JPS591770 A JP S591770A JP 11130882 A JP11130882 A JP 11130882A JP 11130882 A JP11130882 A JP 11130882A JP S591770 A JPS591770 A JP S591770A
- Authority
- JP
- Japan
- Prior art keywords
- bactericidal
- cellulose fibers
- ions
- cation exchange
- cation
- 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
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- Apparatus For Disinfection Or Sterilisation (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
本発明は殺菌性を有するセルロース繊維に関するＯ
従来より繊維製品に微量の殺菌性化合物を付着させた殺
菌性繊維製語は知られている。しかし、これらは繊維に
固着させたものではないため当初は殺菌効果を有するも
のの、１． ２回の洗濯で簡単に脱落してしまい恒久的
な殺菌効果は得られないという欠点を有しており、その
後は毎回殺菌消毒あるいは殺菌剤付着をしなければなら
ないという問題があった。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to cellulose fibers having bactericidal properties. Bactericidal fibers have been known in the past, in which a trace amount of bactericidal compound is attached to a textile product. However, since these are not fixed to fibers, they initially have a bactericidal effect, but 1. It has the disadvantage that it easily falls off after two washes, and no permanent sterilizing effect can be obtained, and after that, it has to be sterilized or sterilized or coated with a sterilizing agent each time.
一方、従来より銀イオン、銅イオンならびに亜鉛イオン
は成る種の微生物に対して優れた殺菌作用を示すことは
よく知られており、しかもこれら殺菌性金属イオンは極
（微量でも殺菌作用を有し、従って極く微量の殺菌性金
属イオンを徐々に供給してやることができれば殺菌効果
は長期間にわたって持続させることが可能となる。On the other hand, it has been well known that silver ions, copper ions, and zinc ions have an excellent bactericidal effect against various types of microorganisms. Therefore, if extremely small amounts of bactericidal metal ions can be gradually supplied, the bactericidal effect can be sustained over a long period of time.
本発明者らはこのような殺菌性金属イオンの特性に注目
し、セルロース繊維に殺菌性金属イオンを結合させ、恒
久的な殺菌性を有するセルロース繊維を得るべく鋭意検
討の結果、本発明に至った。The present inventors paid attention to the characteristics of such bactericidal metal ions, and as a result of intensive studies to obtain cellulose fibers with permanent bactericidal properties by bonding bactericidal metal ions to cellulose fibers, the present invention was achieved. Ta.
即ち、本発明はアニオン性基含有蛍光直接染料で染色さ
れてなるカチオン吸着パラメーターが０．２以上である
カチオン交換能を有するセルロース繊維のカチオン交換
基の一部又は全部が銀イオン、銅イオン又は亜鉛イオン
を結合してなる殺菌性を有するセルロース繊維またはセ
ルロース繊維を含有する繊維製品にある。That is, in the present invention, some or all of the cation exchange groups of cellulose fibers having a cation adsorption parameter of 0.2 or more and having a cation exchange ability dyed with an anionic group-containing fluorescent direct dye are silver ions, copper ions, Cellulose fibers with bactericidal properties formed by bonding zinc ions or textile products containing cellulose fibers.
本発明の殺菌性繊維はカチオン交換繊維内部に存在する
アニオン性基と結合している殺菌性金属イオンが繊維表
面に極く微量ではあるが徐々に溶出し、これが優れた殺
菌性を示すものである。The bactericidal fiber of the present invention exhibits excellent bactericidal properties because the bactericidal metal ions bonded to the anionic groups present inside the cation exchange fibers are gradually eluted onto the fiber surface, albeit in very small amounts. be.
これに対し、通常のセルロース繊維については殺菌性金
属イオンが結合し難（、しかもその結合力が弱く、殺菌
性金属は容易に脱落し、恒久殺菌効果を示さない。On the other hand, with ordinary cellulose fibers, bactericidal metal ions are difficult to bind (and the binding force is weak, and bactericidal metals easily fall off, so they do not exhibit a permanent bactericidal effect.
本発明で用いるカチオン交換能を有するセルｏ−ス繊ｍ
ｃｖアニオン性基としては釧イオン。Cellulose fiber having cation exchange ability used in the present invention m
The cv anionic group is a sushi ion.
鋼イオ／又は亜鉛イオンが結合するものであればよく、
例えばスルホン酸基、カルボキシル基。Any material that binds steel ions/or zinc ions may be used.
For example, sulfonic acid group, carboxyl group.
ヒドロキシル基などがあげられるが、スルホン酸基、カ
ルボキシル基等の酸性基が好まシ（用いられる。Examples include hydroxyl groups, but acidic groups such as sulfonic acid groups and carboxyl groups are preferred.
本発明ｆ）カチオン交換能を有するセルロース繊維とは
カチオン吸着パラメーターが０．２以上である繊維であ
り、カチオン吸着パラメーターが０．２未満では恒久殺
菌性は付与できない。本発明のカチオン交換能を有する
セルロース繊維の製法は、セルロース繊維をセルロース
繊維に直接染着性を有する酸性基含有蛍光染料で処理す
るとセルロース繊維に結合した該染料の酸性基をカチオ
ン交換基として作用させることができ、カチオン交換能
を有する無色のセルロース繊維に転換することができる
。この場合、酸性基含有蛍光直接染料のセルロース繊維
への染着方法は通常の直接染料によるセルロース繊維の
染色法をそのまま使用することができ、浸染法。In the present invention f) Cellulose fibers having cation exchange ability are fibers having a cation adsorption parameter of 0.2 or more, and permanent bactericidal properties cannot be imparted when the cation adsorption parameter is less than 0.2. The method for producing cellulose fibers having cation exchange ability of the present invention is that when cellulose fibers are treated with an acidic group-containing fluorescent dye that can directly dye the cellulose fibers, the acidic groups of the dye bonded to the cellulose fibers act as cation exchange groups. It can be converted into colorless cellulose fibers with cation exchange ability. In this case, the method of dyeing the cellulose fibers with the acidic group-containing fluorescent direct dye can be the same as the usual method of dyeing cellulose fibers with direct dyes, and is the dip dyeing method.
パッドスチーム法、捺染法等を用いることができる０こ
のようにして得られるカチオン交換能を有するセルロー
ス繊維のカチオン吸着パラメーターは使用する蛍光染料
の染着量を多くするほど大きくなる傾向を示す。A pad steam method, a textile printing method, etc. can be used.The cation adsorption parameter of the thus obtained cellulose fibers having cation exchange ability tends to increase as the dyeing amount of the fluorescent dye used increases.
一方、本発明で使用する蛍光染料としてはセルロース繊
維と直接染着性を有するものであれはいずれでもよく、
例えばＣ，Ｉ ＦｌｕｏｒｅｓｃｅｎｔＢｒｌｇｈｔ（
ｎｇ Ａｇｅｎｔ １４ｓ ２２． ２４．３０．３２
゜３７．８４．８５，８６，８７，９０，１３４゜１５
３．１６６．１６７．１６８，１６９，１７３゜１７４
．１７５，１７６、 １７７などを用いることができる
。このようにして得られたカチオン交換能を有するセル
ロース繊維を硝酸銀、硫酸鋼、塩化銅、硫酸亜鉛、塩化
亜鉛等の殺菌性金属イオンを含む水溶液に浸漬処理する
ことにより殺菌性金属イオンが結合した殺菌性セルロー
ス繊維を得ることができる。On the other hand, the fluorescent dye used in the present invention may be any dye that can directly dye cellulose fibers.
For example, C,I FluorescentBrlght(
ng Agent 14s 22. 24.30.32
゜37.84.85, 86, 87, 90, 134゜15
3.166.167.168,169,173°174
．． 175, 176, 177, etc. can be used. The thus obtained cellulose fibers having cation exchange ability were immersed in an aqueous solution containing bactericidal metal ions such as silver nitrate, steel sulfate, copper chloride, zinc sulfate, and zinc chloride, thereby binding bactericidal metal ions. Sterilizable cellulose fibers can be obtained.
例えば、上記カチオン交換能を有するセルロース繊維を
硝酸銀を含有する水溶液中に浸漬すると繊維中の酸性基
と銀イオンとが結合し、銀する硝酸銀水溶液の濃度傘會
更により任意に調整することができる。本発明の殺菌性
繊維の殺菌効果は繊維中に含まれる殺菌性金属イオンの
溶出にもとづくものである。従って長期間使用した後、
再度殺菌性金属イオンを含む水溶液で処理することによ
り殺菌効果を再生させることが可能である。For example, when cellulose fibers having the above-mentioned cation exchange ability are immersed in an aqueous solution containing silver nitrate, the acidic groups in the fibers bond with silver ions, and the concentration of the aqueous silver nitrate solution can be adjusted as desired. . The bactericidal effect of the bactericidal fiber of the present invention is based on the elution of bactericidal metal ions contained in the fiber. Therefore, after long-term use,
It is possible to regenerate the bactericidal effect by treating again with an aqueous solution containing bactericidal metal ions.
本発明の殺菌性繊維は通常の繊維と同様に紡績２編織が
可能であり、必要に応じ通常の木綿繊維又は他種繊維と
混紡、交編、交織等をおこない殺菌性繊維製品を作るこ
とができ、セルロース繊維を混紡、交編、交織後の繊維
製品圧対し上記処理を行ない殺菌性繊維とすることもで
きる。このようにして得られた殺菌性繊維製品例えばソ
ックス、肌着等の一般衣料の外に病院用、カーペット、
カーテン等の分野でも利用価値はきわめて高い。The bactericidal fiber of the present invention can be spun, knitted and woven in the same way as normal fibers, and can be blended, knitted, interwoven, etc. with normal cotton fiber or other types of fibers to produce bactericidal fiber products, if necessary. It is also possible to make sterilizing fibers by subjecting cellulose fibers to the above-mentioned treatments on textile products after blending, inter-knitting, or inter-weaving. The sterilizing fiber products obtained in this way are used in general clothing such as socks and underwear, as well as for hospital use, carpets, etc.
It has extremely high utility value in fields such as curtains.
以下本発明を実施例によって説明するが、カチオン吸着
パラメーターならびに殺菌性の測定および洗濯は次の方
法で行なった。The present invention will be explained below with reference to Examples. Measurement of cation adsorption parameters and bactericidal properties and washing were carried out in the following manner.
■ カチオン吸着パラメーター
供試試料を次の条件でＣ，Ｉ ベーシックバイオレツ）
１で染色し、供試試料に対する染料の染着量（ｍ−ｍｏ
ｌ ／ｋｇ ｆｌｂｅｒ ）を測定し、次式によりカチ
オン吸着ノ（ラメ−ターを算出ｊ６゜力ｆオフ吸着）（
ラメ−ター（ｍ、ｍｏｌ／ｋＰｆｌｂｅｒ ） ＝供試
試料の染着量−コントロール試料の染着量＊コントロー
ル試料：供試試料の作成に当り使用した原試料
■ 染色条件
Ｃ，Ｉベーシックバイオレット１２０ ％ｏｗｆ酢酸
０．５％ｏｗｆ酢酸ソーダ
０°５％ｏｖｆ浴比
１：５０
温度Ｘ時間 ３０℃Ｘ３０分■ 殺菌性
供試試料を黄色ブドウ状球菌を植種した寒天培地上に置
き、３７℃で２４時間菌の培養を行ない試料周辺の黄色
ブドウ状球菌の生育の有無により殺菌効果を判定する。■ Cation adsorption parameters Test sample under the following conditions (C, I Basic Violet)
1 and the amount of dye (m-mo) dyed on the test sample.
l/kg flber), and calculate the cation adsorption rate (lameter) using the following formula:
Lameter (m, mol/kPflber) = Dyeing amount of test sample - Dyeing amount of control sample *Control sample: Original sample used to create test sample■ Staining conditions C, I Basic Violet 120% owf acetic acid 0.5%owf sodium acetate
0°5% ovf bath ratio
1:50 Temperature x Time 30°C x 30 minutes■ Sterilization Test sample was placed on an agar medium inoculated with Staphylococcus aureus, and the bacteria was cultured at 37°C for 24 hours to determine the growth of Staphylococcus aureus around the sample. The bactericidal effect is determined by the presence or absence of
（殺菌効果）
○：試料周辺での細菌の生育が認められずハローが発生
する。(Bactericidal effect) ○: No bacterial growth is observed around the sample and a halo occurs.
Δ：試料周辺にはノ１０−が発生しないが、試料表面で
の細菌の生育は認めもれな
ｖ１０
×：試料表面での細菌の生育が認められる。Δ: No 10- is not generated around the sample, but no bacterial growth is observed on the sample surface. v10 ×: Bacterial growth is observed on the sample surface.
■ 洗濯
家庭用電気洗濯機を用い、中性洗剤ザブ（化工石鹸社製
＞ Ｉ Ｐ／４３を含有する３０℃の水溶液中で１５分
間洗濯した後、流水洗を５分おこない、脱水、乾燥する
。繰り返し洗濯は上記操作を繰り返し実施する。■ Washing Using a household electric washing machine, wash for 15 minutes in an aqueous solution at 30°C containing the neutral detergent Zab (manufactured by Kakosoup Co., Ltd. > I P/43), then rinse under running water for 5 minutes, dehydrate, and dry. .Repeat washing is performed by repeating the above operation.
実施例−１
木綿１００％からなる目付１８０ Ｐ／ｒｒｌ の精
練した平織物を直接染着性を有する蛍光染料う
Ｈａｋｋｏｌ ＢＥ （Ｃ，Ｉ Ｆｌｕｏｒａｓｃｅｎ
ｔ Ｂｒｉｇｈｔｌｎｇ Ａｇｅｎｔ８５ 昭和化学
社製）０〜５．０％ｏｗｆ、芒硝４０％ｏｗｆを含有す
る６０℃の水溶液中に３０分間浸漬処理した後、水洗、
乾燥し、蛍光染料の染着量の異なる木綿織物を得た。引
続きこれら木綿織物を硝酸銀２０％ｏｗｆを含有する４
０℃の水溶液中に３０分間浸漬処理した後、水洗、脱水
、乾燥し、殺菌加工した木綿織物を得た。Example-1 A refined plain fabric with a basis weight of 180 P/rrl made of 100% cotton was dyed with Hakkol BE (C,I Fluorascen), a fluorescent dye with direct dyeability.
Brightlng Agent 85 (manufactured by Showa Kagaku Co., Ltd.) 0 to 5.0% OWF, immersed in an aqueous solution at 60°C containing 40% OWF of Glauber's salt for 30 minutes, and then washed with water.
After drying, cotton fabrics having different dyed amounts of fluorescent dye were obtained. These cotton fabrics were then treated with 4 containing 20% owf of silver nitrate.
After being immersed in an aqueous solution at 0° C. for 30 minutes, it was washed, dehydrated, and dried to obtain a sterilized cotton fabric.
上記の蛍光染料染着量の異なる木綿織物のカチオン吸着
パラメーターならびに殺菌加工した木綿織物の洗濯回数
と殺菌性の関係を測定し、次の結果を得た。The cation adsorption parameters of the cotton fabrics with different amounts of fluorescent dye dyeing were measured, as well as the relationship between the number of washings and the bactericidal properties of the sterilized cotton fabrics, and the following results were obtained.
上記の結果より比較例で示した如（直接染着性を有する
蛍光染料Ｈａｋｋｏｌ ＢＥ で処理しない木綿織物
は殺菌性を示さず、又Ｈａｋｋｏｌ ＢＫ を染着処
理した試料についてもＨａｋｋｏｌ ＢＫ の使用濃
度が小さく、染着量の小さいものは恒久殺菌性を示さな
い。この場合の恒久殺菌性はカチオン吸着パラメーター
と密接な関係があり、カチオン吸着パラメーターを０．
２以上にすると繰り返し洗濯を１０回行なった後でも優
れた殺菌性を示すことが判る。From the above results, as shown in the comparative example (cotton fabrics that are not treated with Hakkol BE, a fluorescent dye that has direct dyeability, do not exhibit sterilization properties, and samples that have been dyed with Hakkol BK, the concentration of Hakkol BK used is Small particles with a small amount of staining do not exhibit permanent bactericidal properties.Permanent bactericidal properties in this case are closely related to the cation adsorption parameter, and the cation adsorption parameter is set to 0.
It can be seen that when the number is 2 or more, excellent sterilizing properties are exhibited even after repeated washing 10 times.
実施例−２
木綿５０％、アクリル繊維ボンネルＶ１７Ｂ２ｄ（三菱
レイヨ／社製）５０チかうなる混紡糸を用いて作成した
天竺編物を直接染着性を有する蛍光染料Ｍｌｌｅｐｈｏ
ｒ ＢＳ （Ｃ，Ｉ ＦｌｕｏｒｅｓｃｅｎｔＢｒｌｇ
Ｊｎｇ Ａｇ＠ｎｔ ９０三井東圧社製）５％ｏｗｆ
。Example-2 A jersey knitted fabric made using 50% cotton and acrylic fiber Bonnel V17B2d (manufactured by Mitsubishi Rayo Co., Ltd.) 50-inch blended yarn was dyed with Mllepho, a fluorescent dye that has direct dyeability.
r BS (C,I FluorescentBrlg
Jng Ag@nt 90 Mitsui Toatsusha) 5% owf
.
芒硝４０％ｏｗｆを含有する６０℃の水溶液中に３０分
浸漬処理した後、水洗、乾燥し、カチオン吸着パラメー
ターを測定した結果０，５の値を得た。After being immersed in an aqueous solution at 60° C. containing 40% OWF of Glauber's salt for 30 minutes, the sample was washed with water and dried, and the cation adsorption parameter was measured, and a value of 0.5 was obtained.
引続き、この蛍光染料染着混紡編物を硫酸銅１０ ％
ｏｗｆを含有する４０℃の水溶液中に３０分間浸漬処理
した後、水洗、脱水、乾燥し、殺菌加工した木綿／アク
リル繊維混紡編物を得た。Subsequently, this fluorescent dye dyed blended knitted fabric was coated with 10% copper sulfate.
After being immersed in an aqueous solution containing owf at 40° C. for 30 minutes, the fabric was washed, dehydrated, dried, and sterilized to obtain a knitted cotton/acrylic fiber blend.
この編物の恒久殺菌性を知るため洗濯１０回行なった後
、殺菌性を測定した結果、試料周辺での黄色ブドウ状球
菌の生育は認められず優れた恒久殺菌性を有していた。In order to determine the permanent bactericidal properties of this knitted fabric, it was washed 10 times and its bactericidal properties were measured. As a result, no growth of Staphylococcus aureus was observed around the sample, indicating that it had excellent permanent bactericidal properties.
実施例−３
実施例−１で用いた木綿の平織物を反応性染料を用い黒
色に染色した後、直接染着性を有する蛍光染料Ｍｊｋｓ
ｐｈｏｒ ＭＸ （Ｃ，Ｉ ＦｌｕｏｒｅｓｃｅｎｔＢ
ｒｌｇＪｎｇ Ａｇｅｎｔ １７５ 三井東圧社製
）５％ｏｗｆ。Example-3 After dyeing the cotton plain fabric used in Example-1 black using a reactive dye, dyeing it with fluorescent dye Mjks that has direct dyeability.
phor MX (C,I FluorescentB
rlgJng Agent 175 (manufactured by Mitsui Toatsu) 5% owf.
芒硝４０％ｏｗｆを含有する６０℃の水溶液中で３０分
浸漬処理した後、水洗、脱水し、引続き塩化亜鉛１０％
ｏｗｆを含有する４０℃の水溶液中に３０分間浸漬した
後、水洗、脱水、乾燥し、殺菌加工した黒色に染色され
た木綿織物を得た。After being immersed for 30 minutes in an aqueous solution at 60°C containing 40% OWF of Glauber's salt, it was washed with water, dehydrated, and then treated with 10% zinc chloride.
After being immersed in an aqueous solution containing OWF at 40° C. for 30 minutes, it was washed, dehydrated, and dried to obtain a sterilized black-dyed cotton fabric.
この織物の恒久殺菌性を知るため洗濯１０回行なった後
、殺菌性を測定した結果、試料周辺での黄色ブドウ状球
菌の生育は認められず優れた恒久殺菌性を有していた。In order to determine the permanent bactericidal properties of this fabric, the fabric was washed 10 times and its bactericidal properties were measured. As a result, no growth of Staphylococcus aureus was observed around the sample, indicating that it had excellent permanent bactericidal properties.
特許出願人 三菱レイヨン株式会社代理人 弁理士
吉 沢 敏 夫Patent applicant Mitsubishi Rayon Co., Ltd. Agent Patent attorney Toshio Yoshizawa
Claims (1)
ン吸着パラメーターが０．２以上であるカチオン交換能
を有するセルロース繊維のカチオン交換基の一部又は全
部が釧イオン、銅イオン又は亜鉛イオンと結合してなる
殺菌性を有するセルロース繊維またはセルロース繊維を
含有する繊維製品。A part or all of the cation exchange groups of the cellulose fibers dyed with an anionic group-containing fluorescent direct dye and having a cation adsorption parameter of 0.2 or more have a cation exchange ability, and are bonded with snail ions, copper ions, or zinc ions. Cellulose fibers or textile products containing cellulose fibers have antibacterial properties.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11130882A JPS591770A (en) | 1982-06-28 | 1982-06-28 | Sterilizable cellulose fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11130882A JPS591770A (en) | 1982-06-28 | 1982-06-28 | Sterilizable cellulose fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS591770A true JPS591770A (en) | 1984-01-07 |
Family
ID=14557930
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11130882A Pending JPS591770A (en) | 1982-06-28 | 1982-06-28 | Sterilizable cellulose fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS591770A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6433272A (en) * | 1987-07-27 | 1989-02-03 | Asahi Chemical Ind | Cellulosic fiber having ion exchange capacity |
| CN103611366A (en) * | 2013-12-01 | 2014-03-05 | 苏州百海金属有限公司 | Bacteriostatic copper fiber air filtering material and preparation method thereof |
| JP2017155364A (en) * | 2016-03-01 | 2017-09-07 | 日本製紙株式会社 | Non-woven fabric |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5516946A (en) * | 1978-07-19 | 1980-02-06 | Mitsubishi Rayon Co | Acrylic fiber with sterilizing property |
| JPS5717108A (en) * | 1980-07-04 | 1982-01-28 | Mitsubishi Electric Corp | Potentiometer operating mechanism |
-
1982
- 1982-06-28 JP JP11130882A patent/JPS591770A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5516946A (en) * | 1978-07-19 | 1980-02-06 | Mitsubishi Rayon Co | Acrylic fiber with sterilizing property |
| JPS5717108A (en) * | 1980-07-04 | 1982-01-28 | Mitsubishi Electric Corp | Potentiometer operating mechanism |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6433272A (en) * | 1987-07-27 | 1989-02-03 | Asahi Chemical Ind | Cellulosic fiber having ion exchange capacity |
| CN103611366A (en) * | 2013-12-01 | 2014-03-05 | 苏州百海金属有限公司 | Bacteriostatic copper fiber air filtering material and preparation method thereof |
| CN103611366B (en) * | 2013-12-01 | 2015-04-01 | 苏州百海金属有限公司 | Bacteriostatic copper fiber air filtering material and preparation method thereof |
| JP2017155364A (en) * | 2016-03-01 | 2017-09-07 | 日本製紙株式会社 | Non-woven fabric |
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