JP6043624B2 - Antibacterial and antifungal fiber products and production method thereof - Google Patents
Antibacterial and antifungal fiber products and production method thereof Download PDFInfo
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- 239000000835 fiber Substances 0.000 title claims description 127
- 230000000844 anti-bacterial effect Effects 0.000 title claims description 72
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- 229940121375 antifungal agent Drugs 0.000 title claims description 48
- 238000004519 manufacturing process Methods 0.000 title claims description 20
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- 239000001648 tannin Substances 0.000 claims description 65
- 235000018553 tannin Nutrition 0.000 claims description 65
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- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- 239000003429 antifungal agent Substances 0.000 claims description 16
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- Agricultural Chemicals And Associated Chemicals (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
本発明は、洗濯耐久性を有する抗菌抗かび性繊維製品およびその製法に関するものである。 The present invention relates to an antibacterial and antifungal fiber product having washing durability and a method for producing the same.
近年、衛生や健康に対する意識の高まりから、衣料やタオル、寝具等、身の回りの繊維製品に、抗菌性や抗かび性を付与したものが多く出回っている。しかし、抗菌剤・抗かび剤の種類や繊維への処理方法によっては、繰り返しての使用や洗濯によって効果がすぐに消失してしまうものもあり、充分に消費者を満足させることのできるような、摩擦耐久性，洗濯耐久性に優れた抗菌抗かび性繊維製品の提供が、強く望まれている。 In recent years, with increasing awareness of hygiene and health, many textile products around us, such as clothing, towels and bedding, have been given antibacterial and antifungal properties. However, depending on the type of antibacterial agent and antifungal agent and the method of treating the fiber, the effect may disappear immediately after repeated use or washing, which can fully satisfy the consumer. It is strongly desired to provide antibacterial and antifungal fiber products having excellent friction durability and washing durability.
また、衛生環境が整えば整う程、メチシリン耐性ブドウ球菌（いわゆるＭＲＳＡ）やバンコマイシン耐性腸球菌（ＶＲＥ）といった、より耐性の強い菌が出現するため、加工技術の向上とともに、それら耐性の強い菌に対応した新しい抗菌剤、抗かび剤の開発が、要求されるようになっている。 In addition, as the sanitary environment is improved, more resistant bacteria such as methicillin-resistant staphylococci (so-called MRSA) and vancomycin-resistant enterococci (VRE) will appear. The development of new antibacterial and antifungal agents that are compatible is now required.
このような課題に応えるために、本出願人は、抗菌性能に優れ、しかも人体に対し安全なビス（２−ピリジルチオ）亜鉛１，１′−ジオキサイド（通称：ジンクピリチオン、以下「ＺＰＴ」と略す）を繊維に付与して洗濯耐久性をもたせる加工技術について研究を重ね、すでにいくつか出願している（特許文献１、２を参照）。 In order to respond to such problems, the present applicant has bis (2-pyridylthio) zinc 1,1′-dioxide (common name: zinc pyrithione, hereinafter abbreviated as “ZPT”) that is excellent in antibacterial performance and safe for the human body. ) Has been researched on the processing technology for imparting washing durability to fibers, and several applications have already been filed (see Patent Documents 1 and 2).
しかしながら、一連の研究を重ねるなかで、ポリエステル系繊維に対してはＺＰＴの吸着固定が充分になされ、耐久性の高いものが得られるのに対し、ポリアミド系繊維に対しては、ＺＰＴの吸着固定が不充分になりやすく、安定した洗濯耐久性を付与させることが困難であることが判明した。そして、抗菌性とともに抗かび性を発揮させるには、従来抗菌性が発揮されるとされてきた抗菌剤濃度よりも高い濃度で、抗菌剤を繊維に付着含有させることが必要であり、繰り返し洗濯によって、抗菌剤の含有割合が低下すると、抗菌性はある程度保つことができても、抗かび性が不充分となって、繊維品にかびが発生しやすくなり、問題となっている。 However, as a series of research is repeated, ZPT adsorption and fixation is sufficiently performed on polyester fibers, and a highly durable one is obtained, while ZPT adsorption and fixation is performed on polyamide fibers. Has been found to be insufficient, and it has been difficult to impart stable washing durability. And in order to exhibit antifungal properties as well as antibacterial properties, it is necessary to make the antibacterial agent adhere to the fiber at a concentration higher than the concentration of the antibacterial agent that has been considered to exhibit antibacterial properties, and washing repeatedly Thus, when the content ratio of the antibacterial agent is lowered, even if the antibacterial property can be maintained to some extent, the antifungal property becomes insufficient, and the fiber product tends to generate mold, which is a problem.
一方、ポリアミド系繊維に抗菌剤を吸着固定する技術として、例えば、ポリアミドと結合する官能基を有する抗菌剤を繊維に反応させ、さらにフィックス剤で固定する、というもの（特許文献３を参照）や、フィックス剤を繊維に反応させて固定し、そのフィックス剤の官能基に抗菌剤の官能基を反応させて固定する、という２段階プロセスを経由するもの（特許文献４を参照）が提案されている。 On the other hand, as a technique for adsorbing and fixing an antibacterial agent to a polyamide-based fiber, for example, an antibacterial agent having a functional group that binds to polyamide reacts with the fiber and is further fixed with a fixing agent (see Patent Document 3) or And a fixing agent that reacts and fixes to a fiber, and a functional group of the fixing agent reacts with a functional group of an antibacterial agent to fix it (see Patent Document 4). Yes.
しかし、ポリアミド系繊維やフィックス剤に対して結合する官能基をもたないＺＰＴに対し、これらの先行技術を適用することはできない。 However, these prior arts cannot be applied to ZPT that does not have a functional group bonded to a polyamide fiber or a fixing agent.
なお、ポリアミド系繊維と結合しうる官能基を有しない抗菌剤等を、樹脂等のバインダーを介して繊維表面もしくは繊維と繊維の間に物理的に付着させることが提案され、いくつか実用化されているが、バインダーを用いると、加工処理方法に制限があるという問題や、得られる繊維製品がごわごわした感じになって風合いが損なわれるという問題があるため、風合いが重視される衣料等への適用は好ましくない。 In addition, it has been proposed that an antibacterial agent that does not have a functional group capable of binding to a polyamide-based fiber is physically attached to the fiber surface or between the fibers via a binder such as a resin, and some have been put into practical use. However, when using a binder, there is a problem that the processing method is limited, and there is a problem that the texture is impaired due to the feeling that the resulting fiber product is stiff, so it is suitable for clothing etc. where texture is important Application is not preferred.
本発明は、このような事情に鑑みなされたもので、ＺＰＴによって洗濯耐久性のある優れた抗菌抗かび性が付与された繊維製品およびその製法の提供を、その目的とする。 The present invention has been made in view of such circumstances, and an object thereof is to provide a textile product to which excellent antibacterial and antifungal properties having washing durability are imparted by ZPT and a method for producing the same.
上記の目的を達成するため、本発明は、繊維中に、抗菌抗かび剤であるＺＰＴと、タンニン類とを含有するポリアミド系繊維を用いてなる繊維製品であって、上記ＺＰＴがポリアミド系繊維内に吸着されており、未洗濯時における上記抗菌抗かび剤の、繊維重量に対する含有割合（重量基準）を１とすると、４０℃の家庭洗濯（ＪＩＳ Ｌ０２１７−１０３に準拠）１０回後の抗菌抗かび剤の繊維重量に対する含有割合が、０．２以上に設定されている抗菌抗かび性繊維製品を第１の要旨とする。 In order to achieve the above object, the present invention provides a fiber product using a polyamide fiber containing ZPT which is an antibacterial and antifungal agent and tannins in the fiber, wherein the ZPT is a polyamide fiber. When the content ratio (weight basis) of the above antibacterial and antifungal agent when not washed is 1 with respect to the fiber weight, the antibacterial after 10 washings at 40 ° C. (based on JIS L0217-103) The first gist is an antibacterial and antifungal fiber product in which the content ratio of the antifungal agent to the fiber weight is set to 0.2 or more.
また、本発明は、そのなかでも、特に、上記ポリアミド系繊維の平均単糸繊度が０．１〜１０ｄｔｅｘであり、上記タンニン類の平均分子量が１，０００〜４０，０００である抗菌抗かび性繊維製品を第２の要旨とし、上記タンニン類が、１分子当たり平均３〜４００個のフェノール性水酸基を有するものである抗菌抗かび性繊維製品を第３の要旨とする。 In particular, the present invention is an antibacterial and antifungal property in which the average single yarn fineness of the polyamide fiber is 0.1 to 10 dtex and the average molecular weight of the tannins is 1,000 to 40,000. The second gist is a textile product, and the third gist is an antibacterial and antifungal textile product in which the tannins have an average of 3 to 400 phenolic hydroxyl groups per molecule.
そして、本発明は、上記第１の要旨である抗菌抗かび性繊維製品を製造する方法であって、抗菌抗かび剤であるＺＰＴと、タンニン類とを含有する処理液を調製する工程と、上記処理液にポリアミド系繊維を浸漬した状態で加熱処理し、上記ＺＰＴをポリアミド系繊維内に吸着させ、上記タンニン類の存在によって抜け止めする工程と、上記加熱処理されたポリアミド系繊維を脱液・乾燥する工程とを備えた抗菌抗かび性繊維製品の製法を第４の要旨とする。 And this invention is the method of manufacturing the antibacterial antifungal fiber product which is the said 1st summary, Comprising: The process of preparing the processing liquid containing ZPT which is an antibacterial antifungal agent, and tannins, Heat-treating the polyamide fiber in the treatment liquid, adsorbing the ZPT in the polyamide fiber and preventing the removal by the presence of the tannins, and dehydrating the heat-treated polyamide fiber The fourth gist is a method for producing an antibacterial and antifungal fiber product having a drying step.
また、本発明は、そのなかでも、特に、上記加熱処理における圧力が常圧であり、加熱温度が７０〜９０℃、加熱時間が５〜１２０分である抗菌抗かび性繊維製品の製法を第５の要旨とし、上記加熱処理における昇温時の温度勾配が、０．５〜５℃／分となるようにした抗菌抗かび性繊維製品の製法を第６の要旨とする。 In addition, the present invention includes, in particular, a method for producing an antibacterial and antifungal fiber product in which the pressure in the heat treatment is normal pressure, the heating temperature is 70 to 90 ° C., and the heating time is 5 to 120 minutes. The sixth gist is a method for producing an antibacterial and antifungal fiber product in which the temperature gradient at the time of temperature rise in the heat treatment is 0.5 to 5 ° C./min.
さらに、本発明は、それらのなかでも、特に、上記処理液におけるＺＰＴの濃度が０．００５〜０．４重量％であり、タンニン類の濃度が０．０２〜２．０重量％である抗菌抗かび性繊維製品の製法を第７の要旨とする。 Further, among these, the present invention is an antibacterial in which the concentration of ZPT in the treatment liquid is 0.005 to 0.4% by weight and the concentration of tannins is 0.02 to 2.0% by weight. The seventh gist is a method for producing an antifungal fiber product.
すなわち、本発明の抗菌抗かび性繊維製品は、抗菌剤として知られているＺＰＴが、タンニン類と組み合わせて用いられているため、従来、安定した洗濯耐久性を得ることが困難であったポリアミド系繊維に対して、非常に安定した、優れた洗濯耐久性を備え、長期にわたって良好な抗菌性と抗かび性を発揮することができる。 That is, in the antibacterial and antifungal fiber product of the present invention, since ZPT, which is known as an antibacterial agent, is used in combination with tannins, it has conventionally been difficult to obtain stable washing durability. It has very stable and excellent washing durability with respect to the fiber, and can exhibit good antibacterial and antifungal properties over a long period of time.
特に、繰り返しの洗濯等によって、繊維に対するＺＰＴの含有量が低下すると、抗菌性よりも先に抗かび性が消失し、湿度の高い環境下や水に濡れやすい環境下で、繊維製品にかびが発生しやすいという問題があったが、本発明の抗菌抗かび性繊維製品によれば、抗菌性とともに抗かび性が発揮されるのに充分なＺＰＴ量が、洗濯を繰り返した後もある程度保持されるため、長期にわたって繊維製品を衛生的に維持することができる。 In particular, when the content of ZPT in the fiber decreases due to repeated washing or the like, the antifungal property disappears before the antibacterial property, and the fiber product is moldy in a high humidity environment or an environment that is easily wet with water. However, according to the antibacterial and antifungal fiber product of the present invention, the amount of ZPT sufficient to exhibit antibacterial and antifungal properties is maintained to some extent even after repeated washing. Therefore, the textile product can be maintained hygienically for a long time.
なお、従来、ポリエステル系繊維等には充分に吸着固定されてその性能を発揮していたＺＰＴが、ポリアミド系繊維には、あまり吸着固定されず、吸着固定されても、脱落しやすく、その性能が不安定であったのに対し、本発明において、抗菌剤であるＺＰＴを、タンニン類と組み合わせると、非常に安定した洗濯耐久性を付与することができたのは、以下のような理由によると考えることができる。 Conventionally, ZPT, which has been sufficiently adsorbed and fixed to polyester fibers and so on, exhibits its performance, but it is not adsorbed and fixed to polyamide fibers very much. However, in the present invention, when ZPT, which is an antibacterial agent, was combined with tannins, very stable washing durability could be imparted for the following reasons. Can be considered.
すなわち、特にタンニン類等を用いなくても、ＺＰＴが充分に吸着固定されるポリエテテル系繊維１は、図１（ａ）に模式的に示すように、ポリマー分子が緻密かつ規則的に並んだ結晶領域１ａと、ポリマー分子が不規則で互いにランダムな隙間を有する非結晶領域１ｂとを備えており、これを、ＺＰＴ含有液に浸漬して加熱すると、図１（ｂ）に模式的に示すように、上記非結晶領域１ｂの隙間が広がり、その隙間にＺＰＴ２が取り込まれて吸着される。この隙間が、常温に戻ると再び狭くなってＺＰＴ２を固定するため、ＺＰＴ２が洗濯等で脱落せず、優れた洗濯耐久性を備え、長期にわたって良好な抗菌性と抗かび性を発揮することができる。
That is, the polyether fiber 1 in which ZPT is sufficiently adsorbed and fixed without using tannins or the like is a crystal in which polymer molecules are densely and regularly arranged as schematically shown in FIG. When the region 1a and the
一方、ポリアミド系繊維３は、図１（ｃ）に模式的に示すように、ポリエステル系繊維１と同様、結晶領域３ａと非結晶領域３ｂとを有しており、ＺＰＴ２は、ポリエステル系繊維１の場合と同様、非結晶領域３ｂの間隙に取り込まれて吸着し、常温に戻ることによって固定されるものの、非結晶領域３ｂのポリマー分子間の隙間が大きいため、図１（ｄ）に模式的に示すように、洗濯等で脱落してしまい、ポリエステル系繊維１の場合のように洗濯耐久性を備えることができず、長期にわたって良好な抗菌性と抗かび性を発揮することができない。
On the other hand, the
そこで、本発明では、フェノール性ヒドロキシ基を有し複雑な立体構造を有するタンニン類を、ＺＰＴ２と同時に、ポリアミド系繊維３に吸着させることにより、図１（ｅ）に示すように、非結晶領域３ｂに取り込まれたＺＰＴ２を、タンニン類４で塞いで抜け止めするようにしたのである。
Therefore, in the present invention, tannins having a phenolic hydroxy group and having a complicated three-dimensional structure are adsorbed on the
なお、ポリアミド系繊維等に染料を固定する際、フィックス剤としてタンニン類を用いることがよく知られているが、タンニン類が染料のフィックス剤として作用する場合は、繊維のアミド結合部に染料が結合し、その染料にタンニン類が結合して染料同士を架橋して染料の脱落を防止するものであり、本発明のように、ポリアミド系繊維に対してもタンニン類に対しても反応する官能基を有しないＺＰＴを、物理的に繊維間に閉じ込めた状態で、タンニン類のポリフェノール基とポリアミド繊維との結合を利用して、タンニン類を繊維間に固定することにより塞いで抜け止めする、という考え方は、本発明者らが初めて想到したものである。 It is well known that tannins are used as a fixing agent when fixing dyes to polyamide fibers and the like. However, when tannins act as a dye fixing agent, the dye is attached to the amide bond portion of the fiber. It binds and tannins bind to the dye to cross-link the dyes to prevent the dyes from dropping off. As in the present invention, the function reacts with both polyamide fibers and tannins. ZPT having no group is physically confined between the fibers, and the tannins are fixed between the fibers by using the bond between the polyphenol group of the tannins and the polyamide fiber, and are prevented from coming off. This idea was first conceived by the present inventors.
ちなみに、ポリアミド系繊維製品を製造する場合は、通常、染色処理を行うステップと、そのつぎに固定化（ＦＩＸ）処理を行うステップとがあり、また、最後に柔軟仕上げ等の仕上げ処理を行うステップを実施する場合もある。各ステップにおける処理は、それぞれ処理剤と繊維との結合を伴うため、別々に加工するステップを必要としている。 Incidentally, when producing a polyamide fiber product, there are usually a step of performing a dyeing process, a step of performing a fixing (FIX) process next, and a step of performing a finishing process such as a flexible finish. May be implemented. Since the treatment in each step involves the combination of the treatment agent and the fiber, a step for processing separately is required.
しかし、ＺＰＴとタンニン類を別々のステップで処理したのでは、充分な効果を発揮することができない。そこで、本発明の抗菌抗かび性繊維製品の製法においては、ＺＰＴとタンニン類とを混合した処理液中に、ポリアミド系繊維を浸漬し、その状態で加熱処理する、という同浴処理を行うこととし、洗濯耐久性に優れた本発明の抗菌抗かび性繊維製品を得るようにしたのである。この製法によれば、製造コストを低く抑えることができるという利点を有する。 However, if ZPT and tannins are processed in separate steps, sufficient effects cannot be exhibited. Therefore, in the method for producing the antibacterial and antifungal fiber product of the present invention, the same bath treatment is performed in which the polyamide fiber is immersed in a treatment liquid in which ZPT and tannins are mixed and heat-treated in that state. Thus, the antibacterial and antifungal fiber product of the present invention having excellent washing durability was obtained. This manufacturing method has the advantage that the manufacturing cost can be kept low.
そして、本発明の抗菌抗かび性繊維製品のなかでも、特に、上記ポリアミド系繊維の平均単糸繊度が０．１〜１０ｄｔｅｘであり、上記タンニン類の平均分子量が１，０００〜４０，０００である場合、あるいは上記タンニン類が、１分子当たり平均３〜４００個のフェノール性水酸基を有するものである場合は、とりわけ、ポリアミド系繊維に取り込まれたＺＰＴをタンニン類によって効果的に塞いで抜け止めすることにより、抗菌抗かび性の洗濯耐久性を高めることができ、好適である。 Among the antibacterial and antifungal fiber products of the present invention, in particular, the average single fiber fineness of the polyamide fiber is 0.1 to 10 dtex, and the average molecular weight of the tannins is 1,000 to 40,000. In some cases, or when the tannins have an average of 3 to 400 phenolic hydroxyl groups per molecule, the ZPT incorporated into the polyamide fiber is effectively blocked by the tannins to prevent slipping. By doing so, the antibacterial and antifungal washing durability can be enhanced, which is preferable.
また、本発明の製法のなかでも、特に、上記加熱処理における圧力が常圧であり、加熱温度が７０〜９０℃、加熱時間が５〜１２０分であると、ポリアミド系繊維へのＺＰＴおよびタンニン類の取り込みと固定が効率よく行われるため、加熱に要するエネルギーに無駄がなく好適である。 Further, among the production methods of the present invention, in particular, when the pressure in the heat treatment is normal pressure, the heating temperature is 70 to 90 ° C., and the heating time is 5 to 120 minutes, ZPT and tannin to the polyamide fiber Since it is efficiently taken in and fixed, energy required for heating is not wasted, which is preferable.
しかも、特に、上記加熱処理における昇温時の温度勾配が、０．５〜５℃／分となるようにすると、ポリアミド系繊維へのＺＰＴの取り込みが効果的に行われるため、ＺＰＴの繊維に対する含有量を多くすることができ、好適である。 In addition, in particular, when the temperature gradient at the time of temperature increase in the heat treatment is set to 0.5 to 5 ° C./min, ZPT incorporation into the polyamide-based fiber is effectively performed. The content can be increased, which is preferable.
そして、本発明の製法のなかでも、特に、上記処理液におけるＺＰＴの濃度が０．００５〜０．４重量％であり、タンニン類の濃度が０．０２〜２．０重量％である処理液を用いると、処理液中のＺＰＴとタンニン類とのバランスに優れ、どちらかが無駄に余ることがなく、経済的である。 Among the production methods of the present invention, in particular, the treatment liquid in which the concentration of ZPT in the treatment liquid is 0.005 to 0.4% by weight and the concentration of tannins is 0.02 to 2.0% by weight. Is excellent in the balance between ZPT and tannins in the treatment liquid, and either one is not wasted and is economical.
つぎに、本発明を実施するための形態について説明する。 Next, an embodiment for carrying out the present invention will be described.
まず、本発明の抗菌抗かび性繊維製品は、繊維中に、抗菌抗かび剤であるＺＰＴと、タンニン類とを含有するポリアミド系繊維からなる繊維製品である。 First, the antibacterial and antifungal fiber product of the present invention is a fiber product made of polyamide fiber containing ZPT which is an antibacterial and antifungal agent and tannins in the fiber.
上記繊維製品の形態としては、糸、編物、織物、不織等、各種の形態をあげることができる。そして、具体的な製品としては、例えば衣料品、寝装寝具、敷物、カーテン、屋内クロス等があげられ、特に、靴下、タイツ、スポーツウェア、アウトドア製品等に用いることが最適である。 Examples of the form of the fiber product include various forms such as yarn, knitted fabric, woven fabric, and non-woven fabric. Specific products include, for example, clothing, bedding, rugs, curtains, indoor cloths, etc., and are particularly suitable for use in socks, tights, sportswear, outdoor products, and the like.
上記繊維製品に用いられるポリアミド系繊維とは、アミド結合を有する重合体からなる繊維であればよく、例えばナイロン６、ナイロン６６、ナイロン６・１０、ナイロン１１、ナイロン８等があげられる。そして、なかでも、後述するタンニン類との相性の点で、ナイロン６６、ナイロン６が好適に用いられる。 The polyamide fiber used in the fiber product may be a fiber made of a polymer having an amide bond, and examples thereof include nylon 6, nylon 66, nylon 6 · 10, nylon 11, nylon 8, and the like. Among these, nylon 66 and nylon 6 are preferably used from the viewpoint of compatibility with tannins described later.
そして、上記ポリアミド系繊維の太さは、ＺＰＴを閉じ込めてタンニン類で塞ぐことを考慮すれば、その平均単糸繊度が０．１〜１０ｄｔｅｘであることが好適であり、なかでも０．５〜５ｄｔｅｘであることが最適である。 And the thickness of the said polyamide-type fiber is suitable that the average single yarn fineness is 0.1-10 dtex, when considering confining ZPT and plugging with tannins, Especially 0.5- It is optimal to be 5 dtex.
また、上記ポリアミド系繊維の繊維中に含有される、抗菌抗かび剤であるＺＰＴとは、下記の化学式（１）で示される化合物で、人体への安全性が高いとして、化粧品やシャンプーの分野において広く使用されているものである Further, ZPT, which is an antibacterial and antifungal agent, contained in the fiber of the polyamide fiber is a compound represented by the following chemical formula (1), and is considered to have high safety to the human body. Is widely used in
上記ＺＰＴは、その構造中に金属を含んでおり、非常に比重が大きいことから、安定した懸濁状態を保持させるには、平均粒径が０．１〜０．７μｍのものを用いることが好適であり、とりわけ０．３〜０．５μｍであることが好適である。そして、２μｍ以上の粒径のＺＰＴが全ＺＰＴに対し５重量％（以下「％」と略す）以下、好ましくは３％以下、さらに好ましくは１％以下となるよう粉砕されていることが好適である。 The ZPT contains a metal in its structure and has a very high specific gravity. Therefore, in order to maintain a stable suspended state, the ZPT having an average particle size of 0.1 to 0.7 μm should be used. It is preferable and it is especially preferable that it is 0.3-0.5 micrometer. It is preferable that the ZPT having a particle size of 2 μm or more is pulverized so as to be 5 wt% (hereinafter abbreviated as “%”) or less, preferably 3% or less, more preferably 1% or less with respect to the total ZPT. is there.
なお、上記ＺＰＴの平均粒径は、ＪＩＳ Ｒ１６２９に準拠してレーザ回折粒度分布測定装置を用いて測定される粒度分布において、累積５０％に相当するメジアン径として求められるものである。 The average particle diameter of the ZPT is obtained as a median diameter corresponding to a cumulative 50% in the particle size distribution measured using a laser diffraction particle size distribution measuring device in accordance with JIS R1629.
一方、上記ＺＰＴとともに繊維中に含有されるタンニン類は、植物に由来し、タンパク質、アルカロイド、金属イオンと反応し強く結合して難溶性の塩を形成する水溶性化合物の総称であり、多種多様なのものが存在している。また、植物由来のものを模して、人為的に製造された合成タンニンも、いくつか提案されている。これらのタンニンのうち、１種を単独で用いてもよいし、２種以上を併用してもよい。 On the other hand, tannins contained in fibers together with the above ZPT are generic names for water-soluble compounds that are derived from plants and react with proteins, alkaloids, and metal ions to form strongly insoluble salts. There is something like that. In addition, some synthetic tannins that have been artificially produced imitating those derived from plants have been proposed. Among these tannins, one type may be used alone, or two or more types may be used in combination.
そして、上記タンニン類を選択する場合、その平均分子量が１，０００〜４０，０００のものを用いることが好適であり、さらに好ましくは、平均分子量２，０００〜２０，０００である。すなわち、タンニン類の平均分子量が小さすぎると、膨潤した繊維の非結晶領域にとどまりにくく、逆に大きすぎると、非結晶領域に入り込みにくくなって、ＺＰＴを立体的に塞ぐ効果が低減するからである。 And when selecting the said tannin, it is suitable to use that whose average molecular weight is 1,000-40,000, More preferably, it is 2,000-20,000 average molecular weight. That is, if the average molecular weight of the tannins is too small, it will be difficult to stay in the amorphous region of the swollen fiber, and conversely if it is too large, it will be difficult to enter the amorphous region and the effect of sterically blocking the ZPT will be reduced. is there.
また、ポリアミド系繊維の繊維内にＺＰＴを閉じ込めた状態で繊維と確実に結合させるには、用いるタンニン類が、１分子当たり平均３〜４００個のフェノール性水酸基を有するものであることが好適である。すなわち、タンニン類が有するフェノール性水酸基の数が少なすぎると、上記ＺＰＴを閉じ込めて固定する効果が小さくなるおそれがあり、逆にフェノール性水酸基の数が多すぎると、ＺＰＴより先にタンニン類と繊維との間に結合が生成されてＺＰＴの吸着が妨げられるおそれがあるからである。 Further, in order to surely bond with the fiber in a state where the ZPT is confined in the fiber of the polyamide-based fiber, it is preferable that the tannin used has an average of 3 to 400 phenolic hydroxyl groups per molecule. is there. That is, if the number of phenolic hydroxyl groups possessed by tannins is too small, the effect of confining and fixing the ZPT may be reduced. Conversely, if the number of phenolic hydroxyl groups is too large, tannins and This is because a bond may be formed between the fibers and the adsorption of ZPT may be hindered.
このようなタンニン類としては、フェノールスルホン酸ホルムアルデヒド樹脂，ノボラック型樹脂スルホン化物，レゾール型樹脂メタンスルホン酸等のフェノール型合成タンニン、チオフェノール型合成タンニン、ジヒドロキシジフェニルスルホン型合成タンニン等があげられる。 Examples of such tannins include phenol-type synthetic tannins such as phenolsulfonic acid formaldehyde resin, novolak-type resin sulfonated products, and resole-type resin methanesulfonic acid, thiophenol-type synthetic tannins, dihydroxydiphenylsulfone-type synthetic tannins, and the like.
そして、本発明の抗菌抗かび性繊維製品は、そのポリアミド系繊維中に含有された抗菌抗かび剤であるＺＰＴの、未洗濯時における含有割合（繊維重量に対する含有割合、重量基準）を１とすると、４０℃の家庭洗濯（ＪＩＳ Ｌ０２１７−１０３に準拠）１０回後の抗菌抗かび剤の繊維重量に対する含有割合が、０．２以上に設定されているという特徴を有する。 The antibacterial and antifungal fiber product of the present invention has an antibacterial and antifungal agent ZPT, which is contained in the polyamide-based fiber, having a content ratio (content ratio with respect to fiber weight, based on weight) of 1 when not washed. Then, it has the characteristic that the content rate with respect to the fiber weight of the antibacterial antifungal agent after 40 times of 40 degreeC household washing (conforms to JIS L0217-103) is set to 0.2 or more.
すなわち、従来、ポリアミド系繊維への抗菌抗かび剤の洗濯耐久性は小さく、上記の洗濯条件下では、当初含有量の１０％残るか残らないかの耐久性しかなく、ごく少量でも抗菌効果を奏する抗菌剤によって抗菌効果こそ持続するものの、抗かび効果は消失する場合が多かったのに対し、本発明の繊維製品によれば、当初の抗菌抗かび剤含有量の２０％以上が含有保持されるため、抗菌抗かび効果が長く持続される。 That is, conventionally, the washing durability of the antibacterial and antifungal agent to the polyamide fiber is small, and under the above washing conditions, only 10% of the initial content remains or does not remain, and even a very small amount has an antibacterial effect. Although the antibacterial effect is sustained by the antibacterial agent produced, the antifungal effect often disappears, whereas according to the textile product of the present invention, 20% or more of the initial antibacterial antifungal agent content is retained. Therefore, the antibacterial and antifungal effect is sustained for a long time.
本発明の抗菌抗かび性繊維製品は、例えばつぎのようにして製造することができる。すなわち、まず、ＺＰＴを界面活性剤と水との存在下、ボールミル、ハンマーミル等の粉砕手段によって粉砕して攪拌することにより、ＺＰＴの水性懸濁液もしくは水性乳化液からなる分散液を得る。一方、ポリアミド系繊維を浸漬するための処理槽内に水を入れた後、上記ＺＰＴ分散液と、タンニン類とを、この水中に投入して、所定濃度のＺＰＴ、タンニン類の混合処理液を調製する。そして、この処理槽内に、ポリアミド系繊維を浸漬し、その状態で処理槽内を加熱して所定温度に昇温して所定時間保つことにより、ポリアミド系繊維に、ＺＰＴとタンニン類とを取り込ませる。そして、処理槽内からポリアミド系繊維を引き上げて脱液し、乾燥することにより、目的とする抗菌抗かび性繊維製品を得ることができる。 The antibacterial and antifungal fiber product of the present invention can be produced, for example, as follows. That is, first, ZPT is pulverized by a pulverizing means such as a ball mill or a hammer mill in the presence of a surfactant and water to obtain a dispersion composed of an aqueous suspension or aqueous emulsion of ZPT. On the other hand, after water is put into a treatment tank for immersing the polyamide fiber, the ZPT dispersion liquid and tannins are poured into the water, and a mixed treatment solution of ZPT and tannins having a predetermined concentration is added. Prepare. Then, the polyamide fiber is immersed in the treatment tank, and in this state, the treatment tank is heated to a predetermined temperature and kept for a predetermined time, thereby taking ZPT and tannins into the polyamide fiber. Make it. And the target antibacterial and antifungal fiber product can be obtained by pulling up the polyamide fiber from the treatment tank, draining it and drying it.
上記の製法によれば、すでに述べたとおり、ポリアミド系繊維の非結晶領域にＺＰＴが吸着され、タンニン類と繊維との結合によって、ＺＰＴが固定されるため、繰り返しの洗濯によってもＺＰＴが脱落しにくく、長期にわたって良好に抗菌抗かび性を発揮する、優れた抗菌抗かび性繊維製品を得ることができる。 According to the above manufacturing method, as already described, ZPT is adsorbed on the amorphous region of the polyamide-based fiber, and the ZPT is fixed by the combination of the tannins and the fiber. It is difficult to obtain an excellent antibacterial and antifungal fiber product that exhibits good antibacterial and antifungal properties over a long period of time.
なお、上記の製法において、ＺＰＴ分散液を調製する場合、ＺＰＴの濃度は、４〜８０％に設定することが好適である。すなわち、この範囲において、ＺＰＴ粒子が再び凝集することが少なく、また比較的長期にわたって安定した分散液状態を保つからである。 In the above production method, when preparing a ZPT dispersion, the concentration of ZPT is preferably set to 4 to 80%. That is, in this range, the ZPT particles are less likely to aggregate again and maintain a stable dispersion state for a relatively long period of time.
また、上記ＺＰＴ分散液のｐＨは、分散液を長期にわたって安定に保ち、繊維に対するＺＰＴの固定率を向上させるのに重要であり、通常、ｐＨを４〜１０の間、好ましくは５．５〜８．５、より好ましくは６〜８の間に調整することが好適である。ＺＰＴ分散液が上記範囲よりもアルカリ側にある場合には、酢酸、塩酸、リン酸等の酸を添加し、酸性側にある場合には、炭酸ナリトウム、水酸化ナトリウム等のアルカリを添加すればよい。 The pH of the ZPT dispersion is important for keeping the dispersion stable for a long period of time and improving the fixation rate of ZPT to the fiber. Usually, the pH is between 4 and 10, preferably 5.5. It is suitable to adjust between 8.5, more preferably between 6-8. If the ZPT dispersion is on the alkali side from the above range, add an acid such as acetic acid, hydrochloric acid or phosphoric acid. If the ZPT dispersion is on the acidic side, add an alkali such as sodium carbonate or sodium hydroxide. Good.
そして、上記ＺＰＴ分散液の調製に用いられる界面活性剤としては、脂肪酸せっけん、アルキルベンゼンスルホン酸塩、ナフタレンスルホン酸ホルマリン縮合物、ポリアクリル酸ナトリウム、リグニンスルフォン酸ナトリウム等の陰イオン界面活性剤、アルキルベンジルアンモニウム塩、アルキルアンモニウム塩等の陽イオン界面活性剤、長鎖アルキルアミノ酸、アルキルベタイン等の両性界面活性剤、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレン硬化ヒマシ油等の非イオン界面活性剤があげられ、これらのうち少なくとも一種の界面活性剤を、用途に応じて選択して用いることができる。 And as surfactant used for preparation of the above-mentioned ZPT dispersion, fatty acid soap, alkylbenzene sulfonate, naphthalene sulfonate formalin condensate, sodium acrylate, sodium lignin sulfonate, anionic surfactant, alkyl Cationic surfactants such as benzylammonium salts and alkylammonium salts, amphoteric surfactants such as long-chain alkyl amino acids and alkylbetaines, nonionic surfactants such as polyoxyethylene nonylphenyl ether and polyoxyethylene hydrogenated castor oil Of these, at least one surfactant can be selected and used according to the application.
上記界面活性剤の使用量は、通常、分散液全体に対し０．５〜１０％程度である。 The amount of the surfactant used is usually about 0.5 to 10% with respect to the entire dispersion.
また、上記ＺＰＴ分散液には、必要に応じて、増粘剤、凍結防止剤及び消泡剤等を加えてもよい。 Moreover, you may add a thickener, an antifreezing agent, an antifoamer, etc. to the said ZPT dispersion liquid as needed.
つぎに、上記ＺＰＴ分散液と、水と、タンニン類とを用いて、繊維処理用の混合処理液を調製するには、その処理液中においてＺＰＴが０．００５〜０．４％、なかでも、０．０１〜０．２％程度の濃度となるよう設定することが好適である。ＺＰＴが上記の範囲よりも少なすぎると繊維への処理が不充分となるおそれがあり、上記の範囲よりも多くしても、それ以上の効果は期待できず、経済的でないからである。 Next, in order to prepare a mixed treatment liquid for fiber treatment using the above ZPT dispersion liquid, water, and tannins, ZPT is 0.005 to 0.4% in the treatment liquid, It is preferable to set the concentration to about 0.01 to 0.2%. This is because if the ZPT is less than the above range, the treatment of the fiber may be insufficient, and if it exceeds the above range, no further effect can be expected and it is not economical.
そして、上記処理液中におけるタンニン類の濃度は、０．０２〜２．０％、なかでも０．０５〜０．７％程度の濃度となるよう設定することが好ましい。すなわち、上記の割合よりもタンニン類の割合が多いと製品の変色や風合い劣化を起こし、少ないとＺＰＴを繊維に固定化する効果が小さくなって、抗菌抗かび性が不充分となるおそれがあるからである。 And it is preferable to set the density | concentration of the tannins in the said processing liquid so that it may become a density | concentration of about 0.02-2.0%, especially 0.05-0.7%. That is, if the proportion of tannins is higher than the above proportion, discoloration and texture deterioration of the product will occur, and if it is less, the effect of fixing ZPT to the fiber will be reduced, and the antibacterial and antifungal properties may be insufficient. Because.
また、上記処理液中にポリアミド系繊維を浸漬して加熱する際の加熱温度は、６０℃以上１００℃未満、なかでも、７０〜９０℃に設定することが好適である。また、加熱時間は、５分以上１４０分未満、なかでも５〜１２０分に設定することが好適である。すなわち、加熱条件が、上記の範囲を外れると、繊維に対するＺＰＴの吸着固定が不充分となるおそれがあり、好ましくない。 Moreover, it is suitable to set the heating temperature at the time of immersing and heating the polyamide fiber in the treatment liquid to 60 ° C. or more and less than 100 ° C., particularly 70 to 90 ° C. The heating time is preferably set to 5 minutes or more and less than 140 minutes, particularly 5 to 120 minutes. That is, if the heating condition is out of the above range, ZPT adsorption / fixing to the fiber may be insufficient, which is not preferable.
そして、上記加熱処理における昇温時の温度勾配を、０．５〜５℃／分となるように設定することが好適である。すなわち、この温度勾配によれば、繊維へのＺＰＴの吸着とタンニン類による閉じ込めがうまく機能して、とりわけ優れた抗菌抗かび性の耐久性が得られるからである。 And it is suitable to set the temperature gradient at the time of temperature rising in the said heat processing so that it may become 0.5-5 degreeC / min. That is, according to this temperature gradient, the adsorption of ZPT to the fiber and the confinement by tannins function well, and particularly excellent antibacterial and antifungal durability can be obtained.
さらに、上記処理液へ繊維の浸漬は、常圧下で行ってもよいし、密閉容器を用いて加圧下で行ってもよく、本発明を適用しようとするポリアミド系繊維の形態に応じて、加工しやすい条件で行うことが好適である。ただし、浸漬浴を加熱するだけで充分にＺＰＴの吸着固定が行われるため、省エネルギーの点から、常圧で処理を行うことが好適である。 Furthermore, the fiber may be immersed in the treatment liquid under normal pressure, or under pressure using a sealed container, depending on the form of the polyamide fiber to which the present invention is applied. It is suitable to carry out on the conditions which are easy to do. However, since the ZPT is sufficiently adsorbed and fixed simply by heating the immersion bath, it is preferable to perform the treatment at normal pressure from the viewpoint of energy saving.
つぎに、本発明の実施例を、比較例と併せて説明する。ただし、本発明は、以下の実施例に限定されるものではない。 Next, examples of the present invention will be described together with comparative examples. However, the present invention is not limited to the following examples.
〔実施例１〜１９、比較例１，２〕
後記の表１〜表６に示すとおり、ポリアミド系繊維からなる糸の加工を行った。ただし、加工方法の種類は、常圧で浸漬槽に繊維を浸漬して取り出す「吸尽加工」と、図２に示すように、糸をチーズ状に巻回してパッケージ染色機等を用いて処理を行う「チーズ加工」の２種類とした。また、同じ「チーズ加工」であっても、図２に示すように、ステップ１において染色処理を行い、ステップ２において抗菌抗かび処理を行い、ステップ３において柔軟処理を行うという３段階処理を行う場合、ステップ１とステップ３を略して、ステップ２だけを行う場合、タンニン類を入れるステップを変える場合等、表に示すとおり条件を変化させた。そして、繊維の種類、処理液の種類、処理時の加熱条件等についても、表に示すとおり変化させた。
[Examples 1 to 19, Comparative Examples 1 and 2 ]
As shown in Tables 1 to 6 below, yarns made of polyamide fibers were processed. However, the types of processing methods are “exhaust processing” in which fibers are immersed in an immersion bath at normal pressure, and processing is performed using a package dyeing machine or the like by winding the yarn into cheese as shown in FIG. Two types of “cheese processing” are performed. Further, even in the same “cheese processing”, as shown in FIG. 2, a three-step process is performed in which a dyeing process is performed in step 1, an antibacterial and antifungal process is performed in
なお、繊維を浸漬するための処理液は、以下のようにして予め調製されたＺＰＴ分散液を水によって適宜希釈し、それに、以下に示すタンニン類を添加することによって調製した。 The treatment liquid for immersing the fibers was prepared by appropriately diluting a ZPT dispersion prepared in advance as described below with water and adding tannins shown below thereto.
＜ＺＰＴ分散液の調製＞
ＺＰＴ（アーチ・ケミカルズ社製、粉末状態、粒径ほぼ０．０２５ｍｍ）を２０重量部、ポリオキシエチレン硬化ヒマシ油（分散剤）を３重量部、ポリアクリル酸ソーダ（増粘剤）を０．５重量部、グリセリン（凍結防止剤）を２重量部、水を７４．５重量部用意し、ボールミル（ガラス製ボール使用）に仕込み、粉砕を行った。粉砕開始時点の液のｐＨは６．５であったが、１２時間粉砕した後のｐＨは１０．５となった。この時点で、ｐＨを調節するため酢酸を添加し、ｐＨを８．０に調節した。そして、得られた分散液中のＺＰＴの平均粒径は０．４μｍで、２μｍ以上の粒径のＺＰＴに対し０．５％であった。また、分散液中のＺＰＴ濃度は２０％であり、均一な分散状態を示した。この分散液の一部を１リットルの容器に移し、２４時間放置したが、極端な分離は認められなかった。
さらに、上記の方法に準じて、ＺＰＴの粉砕条件等を変更することによって、平均粒径が０．１μｍのＺＰＴ分散液と、平均粒径が０．７μｍのＺＰＴが分散する分散液とを調製した。
<Preparation of ZPT dispersion>
20 parts by weight of ZPT (manufactured by Arch Chemicals, powder state, particle size of approximately 0.025 mm), 3 parts by weight of polyoxyethylene hydrogenated castor oil (dispersant), and sodium acrylate (thickener) of 0. 5 parts by weight, 2 parts by weight of glycerin (freezing agent) and 74.5 parts by weight of water were prepared, charged in a ball mill (using glass balls), and pulverized. The pH of the liquid at the start of pulverization was 6.5, but the pH after pulverization for 12 hours was 10.5. At this point, acetic acid was added to adjust the pH and the pH was adjusted to 8.0. And the average particle diameter of ZPT in the obtained dispersion was 0.4 μm, which was 0.5% with respect to ZPT having a particle diameter of 2 μm or more. The ZPT concentration in the dispersion was 20%, indicating a uniform dispersion state. A portion of this dispersion was transferred to a 1 liter container and allowed to stand for 24 hours, but no extreme separation was observed.
Furthermore, according to the above method, by changing the pulverization conditions of ZPT, etc., a ZPT dispersion having an average particle size of 0.1 μm and a dispersion in which ZPT having an average particle size of 0.7 μm are dispersed are prepared. did.
＜タンニン類の種類＞
タンニン１：合成タンニン（商品名：ナイロンフィックス５０１、センカ社製）
〔数平均分子量：１３，０００〕
タンニン２：合成タンニン（試作品）
〔数平均分子量：１５，０００〕
タンニン３：タンニン酸（商品名：ハイフィックスＳＬ、大日本製薬社製）
〔数平均分子量：１，７００〕
<Types of tannins>
Tannin 1: Synthetic tannin (Product name: Nylon Fix 501, manufactured by Senka)
[Number average molecular weight: 13,000]
Tannin 2: Synthetic tannin (prototype)
[Number average molecular weight: 15,000]
Tannin 3: Tannic acid (trade name: HiFix SL, manufactured by Dainippon Pharmaceutical Co., Ltd.)
[Number average molecular weight: 1,700]
このようにして得られた処理品に吸着されたＺＰＴの含有量とタンニン類の含有量を測定するとともに、その抗菌抗かび性を評価した。また、所定回数の洗濯を繰り返した後のＺＰＴの含有量を測定するとともに、その抗菌抗かび性を評価した。それらの結果を、後記の表１〜表６に併せて示す。なお、ＺＰＴ、タンニン類の測定方法、抗菌抗かび性の評価方法は、以下に示すとおりである。 The content of ZPT adsorbed on the treated product thus obtained and the content of tannins were measured, and their antibacterial and antifungal properties were evaluated. Moreover, while measuring the content of ZPT after repeating predetermined washing | cleaning, the antibacterial and antifungal property was evaluated. The results are also shown in Tables 1 to 6 below. In addition, the measuring method of ZPT and tannins and the evaluation method of antibacterial and antifungal properties are as shown below.
＜ＺＰＴの含有量（未洗濯状態）Ｘ＞
得られた処理品０．１ｇを試料として取り出し、原子吸光法により、繊維中の亜鉛量を測定することにより、ＺＰＴの含有量Ｘを測定した。
<ZPT content (unwashed state) X>
The obtained treated product (0.1 g) was taken out as a sample, and the content X of ZPT was measured by measuring the amount of zinc in the fiber by the atomic absorption method.
＜ＺＰＴの含有量（１０回洗濯後）Ｘ′＞
得られた処理品を、ＪＩＳ Ｌ０２１７−１０３（４０℃の家庭洗濯）に準拠する洗濯方法によって洗濯することを１０回繰り返し、その後、上記と同様にして、ＺＰＴの含有量Ｘ′を測定した。
<ZPT content (after 10 washes) X '>
The obtained processed product was washed 10 times by a washing method in accordance with JIS L0217-103 (40 ° C. home washing), and then the ZPT content X ′ was measured in the same manner as described above.
＜抗菌性の評価＞
ＪＩＳ Ｌ１９０２に準拠する方法により、試験菌種として「黄色ブドウ球菌（Ｓｔａｐｈｙｌｏｃｏｃｃｕｓ ａｕｒｅｕｓ）」を用いて評価した。すなわち、まず、この試験菌種が懸濁した液体培地を、得られた処理品に接種して３７℃で２４時間培養した。そして、初期菌数と培養後の菌数の差を殺菌活性値とし、初期菌数より減少していることを意味する「０」以上を有効とした。なお、値が大きい程、抗菌性能が高いことを示している。
<Evaluation of antibacterial properties>
Evaluation was performed using “Staphylococcus aureus” as a test strain by a method based on JIS L1902. That is, first, a liquid medium in which the test bacterial species was suspended was inoculated into the obtained treated product and cultured at 37 ° C. for 24 hours. Then, the difference between the initial number of bacteria and the number of bacteria after culturing was defined as the bactericidal activity value, and “0” or more, which means that it was reduced from the initial number of bacteria, was effective. In addition, it has shown that antimicrobial performance is so high that a value is large.
＜抗かび性の評価＞
一般社団法人繊維評価技術協議会の定める「抗カビ性試験方法（繊技協法）」に準拠する方法により、試験菌種として「白癬菌（Ｔｒｉｃｈｏｐｈｙｔｏｎ ｍｅｎｔａｇｒｏｐｈｙｔｅ）」を用い、菌体内に含まれるＡＴＰ量の測定によって評価した。すなわち、まず、上記試験菌種の胞子が懸濁した液体培地を、得られた処理品に接種して２５℃で４２時間培養した。そして、培養後のＡＴＰ量を測定し、未処理綿繊維の同様の試験値（ＡＴＰ量）との対比を抗かび活性値として、未処理綿繊維の増殖値の１００分の１を表す「２」以上を有効とした。なお、値が大きい程、抗かび性能が高いことを示している。
<Evaluation of antifungal properties>
ATP contained in bacterial cells using “Trichophyton mentagrophyte” as a test strain by a method based on the “antifungal test method (textile technology cooperative method)” established by the Japan Textile Evaluation Technology Council It was evaluated by measuring the amount. That is, first, a liquid medium in which spores of the above-mentioned test bacterial species were suspended was inoculated into the obtained treated product and cultured at 25 ° C. for 42 hours. And the amount of ATP after culture | cultivation is measured, and contrast with the same test value (ATP amount) of untreated cotton fiber is made into antifungal activity value, and represents 1/100 of the proliferation value of untreated cotton fiber. The above is considered effective. In addition, it has shown that anti-mold performance is so high that a value is large.
上記の結果から、実施例品は、いずれも繊維に含有されるＺＰＴが、１０回洗濯後も、当初の量の２０％以上保持されており、抗菌抗かび性に優れていることがわかる。これに対し、比較例品は、抗菌抗かび性、特に抗かび性の低下が著しく、実用上好ましくないことがわかる。 From the above results, it can be seen that in all of the Example products, the ZPT contained in the fiber is retained 20% or more of the original amount even after 10 washes, and is excellent in antibacterial and antifungal properties. On the other hand, it can be seen that the comparative product is markedly deteriorated in antibacterial and antifungal properties, particularly in antifungal properties, and is not preferable in practice.
本発明は、抗菌抗かび性を有し、その抗菌抗かび性が洗濯耐久性に優れているポリアミド系繊維製品とその製法に利用することができる。 INDUSTRIAL APPLICABILITY The present invention can be used for a polyamide fiber product having antibacterial and antifungal properties, and the antibacterial and antifungal properties being excellent in washing durability, and a manufacturing method thereof.
２ ＺＰＴ
３ ポリアミド系繊維
４ タンニン類
2 ZPT
3
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