JPH08325844A - Antimicrobial fiber - Google Patents

Antimicrobial fiber

Info

Publication number
JPH08325844A
JPH08325844A JP12476595A JP12476595A JPH08325844A JP H08325844 A JPH08325844 A JP H08325844A JP 12476595 A JP12476595 A JP 12476595A JP 12476595 A JP12476595 A JP 12476595A JP H08325844 A JPH08325844 A JP H08325844A
Authority
JP
Japan
Prior art keywords
fiber
silver
based inorganic
hindered phenol
antimicrobial
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
Application number
JP12476595A
Other languages
Japanese (ja)
Inventor
Toshiyuki Nishio
俊幸 西尾
Masahiko Kimura
正彦 木村
Tasuku Yokomizo
資 横溝
Yukio Manabe
幸夫 真鍋
Eiji Tsukamoto
栄治 塚本
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unitika Ltd
Original Assignee
Unitika Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Unitika Ltd filed Critical Unitika Ltd
Priority to JP12476595A priority Critical patent/JPH08325844A/en
Publication of JPH08325844A publication Critical patent/JPH08325844A/en
Pending legal-status Critical Current

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  • Apparatus For Disinfection Or Sterilisation (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Artificial Filaments (AREA)

Abstract

PURPOSE: To obtain an antimicrobial fiber incorporated with a silver-based inorganic antimicrobial agent in combination with each specific benzotriazole compound and a hindered phenol compound, prevented from discoloration due to these ingredients during fiber production, processing or use, with antimicrobial effect as well as discoloration-preventive effect sustained even after subjected to laundering. CONSTITUTION: This antimicrobial fiber is incorporated with a silver-based inorganic antimicrobial agent, a benzotriazole compound of formula I (R<1> is H or a lower alkyl) and a hindered phenol compound of formula II (R<2> is a residue of hexamethylenediamine, triethylene glycol, 1,6-hexanediol or pentaerythritol; tB is t-butyl; (n) is an integer same as the valence number of R<2> ).

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は、着色が防止された銀系
無機抗菌剤を含有した抗菌性繊維に関するものである。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial fiber containing a silver-based inorganic antibacterial agent which prevents coloration.

【0002】[0002]

【従来の技術】従来、繊維中に抗菌剤を含有させた抗菌
性繊維は、種々提案されており、一部実用に供されてい
る。抗菌剤として最も広く使用されているものは、銀系
無機抗菌剤であり、例えば、銀イオンを担持させたリン
酸塩系抗菌剤、銀イオンを担持させたゼオライト系抗菌
剤、銀イオンを担持させたヒドロキシアパタイト焼成物
系抗菌剤等がある。
2. Description of the Related Art Conventionally, various antibacterial fibers containing an antibacterial agent have been proposed, and some of them have been put to practical use. The most widely used antibacterial agents are silver-based inorganic antibacterial agents, for example, phosphate-based antibacterial agents supporting silver ions, zeolite-based antibacterial agents supporting silver ions, and silver ion-supporting agents. There is a fired hydroxyapatite-based antibacterial agent.

【0003】ところで、このような銀系無機抗菌剤を含
有させた繊維は、繊維の製造や加工工程又は使用時に着
色しやすいという問題がある。
By the way, a fiber containing such a silver-based inorganic antibacterial agent has a problem that it is easily colored during the production, processing or use of the fiber.

【0004】この着色の問題を解決する方法として、特
開平6−158551号公報及び特開平6−272173号公報に
は、銀系無機抗菌剤を含有した繊維をベンゾトリアゾー
ルその他のアゾール化合物の溶液で処理する方法が提案
されている。しかし、この方法では、処理が煩雑であっ
たり、洗濯耐久性に乏しいといった問題があった。
As a method for solving this coloring problem, JP-A-6-158551 and JP-A-6-272173 disclose fibers containing a silver-based inorganic antibacterial agent in a solution of benzotriazole and other azole compounds. A method of handling has been proposed. However, this method has problems that the treatment is complicated and the washing durability is poor.

【0005】また、特開昭63−265958号公報には、抗菌
性ゼオライトと変色防止剤とを配合した抗菌性樹脂組成
物が開示さており、変色防止剤として、ベンゾトリアゾ
ール系化合物、オキザリックアシッドアニリド系化合
物、サリチル酸系化合物、シアノアクリレート系化合
物、ベンゾフェノン系化合物、ヒンダードアミン系化合
物、ヒンダードフェノール系化合物、リン系化合物、硫
黄系化合物及びヒドラジン系化合物が挙げられている。
この公報では、変色防止剤は、上記の化合物から選ばれ
た少なくとも1種の化合物を用いるとされているが、具
体的には2種以上の化合物を併用して例は示されていな
い。本発明者らが、このような樹脂組成物を溶融紡糸し
て繊維を製造することを試みたところ、上記のような変
色防止剤を単独で配合したものでは、十分な着色防止効
果が得られないことが分かった。
Further, Japanese Unexamined Patent Publication (Kokai) No. 63-265958 discloses an antibacterial resin composition containing an antibacterial zeolite and a discoloration preventive agent. As the discoloration preventive agent, a benzotriazole compound, oxalic Examples thereof include acid anilide compounds, salicylic acid compounds, cyanoacrylate compounds, benzophenone compounds, hindered amine compounds, hindered phenol compounds, phosphorus compounds, sulfur compounds and hydrazine compounds.
In this publication, at least one compound selected from the above compounds is used as the discoloration preventing agent, but specifically, no example is shown in which two or more compounds are used in combination. The inventors of the present invention tried to melt-spin such a resin composition to produce a fiber, and when the above discoloration-preventing agent alone was blended, a sufficient color-preventing effect was obtained. I found it wasn't.

【0006】[0006]

【発明が解決しようとする課題】本発明は、銀系無機抗
菌剤を含有させた繊維であって、繊維の製造や加工工程
又は使用時に着色することがなく、その効果が洗濯後も
持続する抗菌性繊維を提供しようとするものである。
DISCLOSURE OF THE INVENTION The present invention is a fiber containing a silver-based inorganic antibacterial agent, which is not colored during the production or processing of the fiber or during its use, and its effect is maintained even after washing. It is intended to provide antibacterial fibers.

【0007】[0007]

【課題を解決するための手段】本発明者らは、上記の課
題を解決するために鋭意検討の結果、特定のベンゾトリ
アゾール化合物とヒンダードフェノール化合物とを併用
することにより、この目的が達成されることを見出し、
本発明に到達した。
Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have achieved this object by using a specific benzotriazole compound and a hindered phenol compound in combination. To find out that
The present invention has been reached.

【0008】すなわち、本発明の要旨は、次のとおりで
ある。繊維中に銀系無機抗菌剤、下記式で表されるベ
ンゾトリアゾール化合物及び下記式で表されるヒンダ
ードフェノール化合物を含有させたことを特徴とする抗
菌性繊維。
That is, the gist of the present invention is as follows. An antibacterial fiber characterized by containing a silver-based inorganic antibacterial agent, a benzotriazole compound represented by the following formula, and a hindered phenol compound represented by the following formula in the fiber.

【化2】 ここで、R1 は水素又は低級アルキル基、R2 はヘキサ
メチレンジアミン、トリエチレングリコール、1,6−
ヘキサンジオール又はペンタエリスリトールの残基、t
Bはt−ブチル基を示し、nはR2 の価数と同じ整数を
示す。
Embedded image Here, R 1 is hydrogen or a lower alkyl group, R 2 is hexamethylenediamine, triethylene glycol, 1,6-
Hexanediol or pentaerythritol residue, t
B represents a t-butyl group, and n represents the same integer as the valence of R 2 .

【0009】以下、本発明について詳細に説明する。The present invention will be described in detail below.

【0010】本発明の繊維を構成するポリマーは、特に
限定されないが、溶融紡糸可能なものが好ましく、具体
例としては、ナイロン6、ナイロン66等のポリアミ
ド、ポリエチレンテレフタレート、ポリブチレンテレフ
タレート等のポリエステル、ポリエチレン、ポリプロピ
レン等のポリオレフィン及び熱可塑性ポリウレタン等が
挙げられる。
The polymer constituting the fiber of the present invention is not particularly limited, but those capable of melt spinning are preferable, and specific examples thereof include polyamides such as nylon 6 and nylon 66, polyesters such as polyethylene terephthalate and polybutylene terephthalate, and the like. Examples thereof include polyolefins such as polyethylene and polypropylene, and thermoplastic polyurethane.

【0011】本発明において用いられる銀系無機抗菌剤
としては、ゼオライト、ヒドロキシアパタイト、リン酸
ジルコニウム、リン酸チタン、チタン酸カリウム、シリ
カゲル、ガラス、モンモリロナイト等の銀イオン交換体
が挙げられる。
Examples of the silver-based inorganic antibacterial agent used in the present invention include silver ion exchangers such as zeolite, hydroxyapatite, zirconium phosphate, titanium phosphate, potassium titanate, silica gel, glass and montmorillonite.

【0012】銀系無機抗菌剤の配合量は、抗菌剤の種類
(銀イオン濃度)にもよるが、通常0.1〜10重量%、好
ましくは 0.5〜3重量%である。また、ベンゾトリアゾ
ール化合物の配合量は、銀系無機抗菌剤の重量の1/20
〜1/5、特に1/7.5 〜1/15が好ましく、ヒンダー
ドフェノール化合物の配合量は、ベンゾトリアゾール化
合物の重量の0.75〜5倍、特に1〜3倍が好ましい。
The amount of the silver-based inorganic antibacterial agent to be added depends on the kind of antibacterial agent (silver ion concentration), but is usually 0.1 to 10% by weight, preferably 0.5 to 3% by weight. The amount of the benzotriazole compound added is 1/20 of the weight of the silver-based inorganic antibacterial agent.
The amount of the hindered phenol compound is preferably 0.75 to 5 times, more preferably 1 to 3 times the weight of the benzotriazole compound.

【0013】銀系無機抗菌剤は、繊維全体に含有させて
もよいし、一部に含有させた複合繊維としてもよい。特
に、芯鞘複合繊維の芯部にのみ銀系無機抗菌剤を含有さ
せれば、製糸装置や織編機等の摩耗を防ぐことができて
好ましい。この場合、ベンゾトリアゾール化合物及びヒ
ンダードフェノール化合物は、芯部及び/又は鞘部に含
有させることができる。
The silver-based inorganic antibacterial agent may be contained in the whole fiber or in a part thereof as a composite fiber. In particular, it is preferable to include the silver-based inorganic antibacterial agent only in the core portion of the core-sheath composite fiber because it is possible to prevent abrasion of the yarn making device, the weaving machine, and the like. In this case, the benzotriazole compound and the hindered phenol compound can be contained in the core and / or the sheath.

【0014】本発明の繊維は、ポリマーに、銀系無機抗
菌剤、ベンゾトリアゾール化合物及びヒンダードフェノ
ール化合物を配合して、常法によって製糸することによ
って製造することができる。この場合、ポリマーチップ
と銀系無機抗菌剤等の添加剤とを混合しながら紡糸機に
供給して紡糸してもよいし、ポリマーチップと銀系無機
抗菌剤等の添加剤とを予め溶融混練してマスターチップ
化しておいて紡糸してもよい。
The fiber of the present invention can be produced by adding a silver-based inorganic antibacterial agent, a benzotriazole compound and a hindered phenol compound to a polymer and spinning the mixture by a conventional method. In this case, the polymer chips and additives such as silver-based inorganic antibacterial agents may be mixed and supplied to a spinning machine for spinning, or the polymer chips and additives such as silver-based inorganic antibacterial agents may be melt-kneaded in advance. It may be made into a master chip and then spun.

【0015】[0015]

【作用】本発明においては、銀イオンがベンゾトリアゾ
ール化合物とキレートを形成することにより着色が防止
されるものと推定される。また、本発明の繊維は、ベン
ゾトリアゾール化合物とヒンダードフェノール化合物と
を含有しているので、ヒンダードフェノール化合物によ
ってベンゾトリアゾール化合物の熱安定性が高められ、
溶融紡糸時にベンゾトリアゾール化合物が熱分解してし
まわないため、優れた着色防止性を示すものと認められ
る。さらに、本発明においては、着色防止剤が繊維中に
練り込まれているため、着色防止効果が洗濯後も持続す
る。
In the present invention, it is presumed that silver ions form a chelate with a benzotriazole compound to prevent coloring. Further, since the fiber of the present invention contains a benzotriazole compound and a hindered phenol compound, the hindered phenol compound enhances the thermal stability of the benzotriazole compound,
It is recognized that the benzotriazole compound does not thermally decompose during melt spinning, and thus exhibits excellent anti-coloring properties. Further, in the present invention, since the anti-coloring agent is kneaded into the fiber, the anti-coloring effect continues even after washing.

【0016】[0016]

【実施例】次に、実施例により本発明を具体的に説明す
る。なお、評価は、次の方法により行った。 (1) 抗菌性 繊維製品衛生加工協会SEK基準に準じ、黄色ブドウ状
球菌を用いる菌数測定法により抗菌性の評価を行った。
評価は、抗菌性繊維試料の菌数増加値の対数値から同種
の通常の繊維試料の菌数増加値の対数値を差し引いた値
により行った。試料としては、アクチノールR−100
(松本油脂製薬社製精練剤) を2g/リットル含有する
精練水中で30分間沸騰処理したもの(精練後)とこれを
JIS L-0217の103 の方法で10洗したもの(10洗後)を使
用した。 (2) 着色性 次の(a) 及び(b) の評価を行い、着色の程度により、次
の3段階でランクづけした。 〇:着色が認められない、△:少し着色が認められる、
×:着色が著しい。 (a) JIS L-1013法に従って、50時間光を照射した後の着
色の程度によって評価した。試料としては、上記と抗菌
性の評価と同様なものを使用した。 (b) 上記の精練後の繊維試料を塩素系漂白剤の水溶液に
浸漬したときの着色の程度によって評価した。
EXAMPLES Next, the present invention will be described in detail with reference to examples. The evaluation was performed by the following method. (1) Antibacterial property The antibacterial property was evaluated by a bacterial count method using Staphylococcus aureus according to the SEK standard of the Textile Products Sanitary Processing Association.
The evaluation was performed by the value obtained by subtracting the logarithmic value of the bacterial count increase value of the same type of ordinary fiber sample from the logarithmic value of the bacterial count increase value of the antibacterial fiber sample. As a sample, Actinol R-100
(Scouring agent manufactured by Matsumoto Yushi-Seiyaku Co., Ltd.) was boiled for 30 minutes in scouring water containing 2 g / liter (after scouring) and this
What was washed 10 times by the method of JIS L-0217 (after 10 washings) was used. (2) Colorability The following (a) and (b) were evaluated and ranked according to the degree of coloring in the following three stages. ◯: No coloring is observed, Δ: Some coloring is observed,
X: Coloring is remarkable. (a) According to JIS L-1013 method, the degree of coloring after irradiation with light for 50 hours was evaluated. As the sample, the same sample as used in the above evaluation of antibacterial property was used. (b) The fiber sample after the above refining was evaluated by the degree of coloring when immersed in an aqueous solution of chlorine bleach.

【0017】実施例1 ナイロン6チップに銀イオンを担持させたリン酸ジルコ
ニウムを1重量%、ベンゾトリアゾールAを0.01重量
%、N,N′−ヘキサメチレン−ビス(3,5−ジ−t
−ブチル−4−ヒトロキシ−ハイドロシンナマイドBを
0.01重量%添加して、常法によって溶融紡糸、延伸し
て、単糸繊度3デニールのナイロン6繊維を製造した。
Example 1 1% by weight of zirconium phosphate supporting silver ions on nylon 6 chips, 0.01% by weight of benzotriazole A, and N, N'-hexamethylene-bis (3,5-di-t).
-Butyl-4-humanroxy-hydrocinnamide B
0.01 wt% was added, and melt spinning and drawing were carried out by a conventional method to produce a nylon 6 fiber having a single yarn fineness of 3 denier.

【0018】比較例1 実施例1において、A及びBを添加しない以外は同様に
してナイロン6繊維を製造した。
Comparative Example 1 Nylon 6 fiber was produced in the same manner as in Example 1 except that A and B were not added.

【0019】比較例2 実施例1において、Bを添加しない以外は同様にしてナ
イロン6繊維を製造した。
Comparative Example 2 A nylon 6 fiber was produced in the same manner as in Example 1 except that B was not added.

【0020】実施例2 ナイロン6の代わりにポリエチレンテレフタレートを用
い、実施例1に準じてポリエステル繊維を製造した。
Example 2 Polyester fibers were produced in the same manner as in Example 1 except that polyethylene terephthalate was used instead of nylon 6.

【0021】比較例3 ナイロン6の代わりにポリエチレンテレフタレートを用
い、比較例1に準じてポリエステル繊維を製造した。
Comparative Example 3 Polyester fibers were produced in the same manner as in Comparative Example 1 except that polyethylene terephthalate was used instead of nylon 6.

【0022】比較例4 ナイロン6の代わりにポリエチレンテレフタレートを用
い、比較例2に準じてポリエステル繊維を製造した。
Comparative Example 4 Polyester fibers were produced according to Comparative Example 2 by using polyethylene terephthalate instead of nylon 6.

【0023】上記の実施例及び比較例で得られた繊維の
抗菌性及び着色性を評価した結果を表1に示す。
Table 1 shows the results of evaluation of the antibacterial properties and coloring properties of the fibers obtained in the above Examples and Comparative Examples.

【0024】[0024]

【表1】 [Table 1]

【0025】[0025]

【発明の効果】本発明によれば、銀系無機抗菌剤を含有
させた繊維であって、繊維の製造や加工工程又は使用時
に着色することがなく、その効果が洗濯後も持続する抗
菌性繊維が提供される。
Industrial Applicability According to the present invention, a fiber containing a silver-based inorganic antibacterial agent, which has no antibacterial property without being colored during the production, processing or use of the fiber, has its effect even after washing. Fibers are provided.

─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───

【手続補正書】[Procedure amendment]

【提出日】平成7年6月7日[Submission date] June 7, 1995

【手続補正1】[Procedure Amendment 1]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】0017[Correction target item name] 0017

【補正方法】変更[Correction method] Change

【補正内容】[Correction content]

【0017】実施例1 ナイロン6チップに銀イオンを担持させたリン酸ジルコ
ニウムを1重量%、ベンゾトリアゾールAを 0.1重量
、N,N′−ヘキサメチレン−ビス(3,5−ジ−t
−ブチル−4−ヒロキシ−ハイドロシンナマイドBを
0.1重量%添加して、常法によって溶融紡糸、延伸し
て、単糸繊度3デニールのナイロン6繊維を製造した。
Example 1 1% by weight of zirconium phosphate having silver ions supported on nylon 6 chips and 0.1 % by weight of benzotriazole A
% , N, N'-hexamethylene-bis (3,5-di-t
- butyl-4-arsenide de proxy - hydro cinnamate amide B
0.1% by weight was added, and melt spinning and drawing were carried out by a conventional method to produce nylon 6 fiber having a single yarn fineness of 3 denier.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 FI 技術表示箇所 D01F 1/10 D01F 1/10 6/90 301 6/90 301 6/92 301 6/92 301Q (72)発明者 真鍋 幸夫 京都府宇治市宇治戸ノ内5 ユニチカ株式 会社宇治工場内 (72)発明者 塚本 栄治 京都府宇治市宇治戸ノ内5 ユニチカ株式 会社宇治工場内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location D01F 1/10 D01F 1/10 6/90 301 6/90 301 6/92 301 6/92 301Q ( 72) Inventor Yukio Manabe 5 Uji-Tonouchi, Uji-shi, Kyoto Prefecture Unitika stock company Uji factory (72) Inventor Eiji Tsukamoto 5 Uji-Tonouchi, Uji-shi Kyoto prefecture Unitika Uji factory

Claims (1)

【特許請求の範囲】[Claims] 【請求項1】 繊維中に銀系無機抗菌剤、下記式で表
されるベンゾトリアゾール化合物及び下記式で表され
るヒンダードフェノール化合物を含有させたことを特徴
とする抗菌性繊維。 【化1】 ここで、R1 は水素又は低級アルキル基、R2 はヘキサ
メチレンジアミン、トリエチレングリコール、1,6−
ヘキサンジオール又はペンタエリスリトールの残基、t
Bはt−ブチル基を示し、nはR2 の価数と同じ整数を
示す。
1. An antibacterial fiber characterized by containing a silver-based inorganic antibacterial agent, a benzotriazole compound represented by the following formula, and a hindered phenol compound represented by the following formula in the fiber. Embedded image Here, R 1 is hydrogen or a lower alkyl group, R 2 is hexamethylenediamine, triethylene glycol, 1,6-
Hexanediol or pentaerythritol residue, t
B represents a t-butyl group, and n represents the same integer as the valence of R 2 .
JP12476595A 1995-05-24 1995-05-24 Antimicrobial fiber Pending JPH08325844A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP12476595A JPH08325844A (en) 1995-05-24 1995-05-24 Antimicrobial fiber

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP12476595A JPH08325844A (en) 1995-05-24 1995-05-24 Antimicrobial fiber

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EP1072698A1 (en) * 1999-07-21 2001-01-31 Vepetex B.V. Fibre, yarn and cable and method for manufacturing the same
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JP2013194080A (en) * 2012-03-16 2013-09-30 Teijin Ltd Flame-retardant polyester composition and flame-retardant polyester molded article
JP2016186135A (en) * 2015-03-27 2016-10-27 日本エクスラン工業株式会社 Color fastness fiber and fiber structure containing the fiber
CN106436292A (en) * 2016-12-18 2017-02-22 中南大学 Low-temperature pyrolysis and reduction preparation method for silver-series antibacterial fabric products
CN106436290A (en) * 2016-12-18 2017-02-22 中南大学 Method for preparing silver antibacterial agent textile by complexing aminoacetic acid and silver nitrate
CN106436291A (en) * 2016-12-18 2017-02-22 中南大学 Method for preparing silver-carrying carbon fibers by aminopropionic acid serving as reducing agent
CN106436292B (en) * 2016-12-18 2018-09-11 中南大学 A kind of silver system antibiotic fabric product low temperature pyrogenation reducing preparation method
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