JPH01104821A - Polyolefinic synthetic yarn having mildew-proofing property - Google Patents
Polyolefinic synthetic yarn having mildew-proofing propertyInfo
- Publication number
- JPH01104821A JPH01104821A JP26009087A JP26009087A JPH01104821A JP H01104821 A JPH01104821 A JP H01104821A JP 26009087 A JP26009087 A JP 26009087A JP 26009087 A JP26009087 A JP 26009087A JP H01104821 A JPH01104821 A JP H01104821A
- Authority
- JP
- Japan
- Prior art keywords
- mildew
- imidazole compound
- weight
- fiber
- yarn
- 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
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 67
- -1 imidazole compound Chemical class 0.000 claims abstract description 58
- 229920000098 polyolefin Polymers 0.000 claims abstract description 38
- WJCNZQLZVWNLKY-UHFFFAOYSA-N thiabendazole Chemical compound S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000835 fiber Substances 0.000 claims description 50
- 229920002994 synthetic fiber Polymers 0.000 claims description 26
- 239000012209 synthetic fiber Substances 0.000 claims description 26
- 230000000694 effects Effects 0.000 abstract description 22
- 238000009987 spinning Methods 0.000 abstract description 22
- 229920000642 polymer Polymers 0.000 abstract description 8
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract 2
- 239000004743 Polypropylene Substances 0.000 description 22
- 229920001155 polypropylene Polymers 0.000 description 21
- 239000000306 component Substances 0.000 description 12
- 239000002131 composite material Substances 0.000 description 10
- 239000004698 Polyethylene Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 229920000573 polyethylene Polymers 0.000 description 8
- 239000008358 core component Substances 0.000 description 5
- 239000000417 fungicide Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000000843 anti-fungal effect Effects 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 230000000855 fungicidal effect Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000567 combustion gas Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 230000005923 long-lasting effect Effects 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 1
- 241000228245 Aspergillus niger Species 0.000 description 1
- 241001515917 Chaetomium globosum Species 0.000 description 1
- 241000228153 Penicillium citrinum Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- JYZIHLWOWKMNNX-UHFFFAOYSA-N benzimidazole Chemical compound C1=C[CH]C2=NC=NC2=C1 JYZIHLWOWKMNNX-UHFFFAOYSA-N 0.000 description 1
- 238000009960 carding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000002973 irritant agent Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- YLGXILFCIXHCMC-JHGZEJCSSA-N methyl cellulose Chemical compound COC1C(OC)C(OC)C(COC)O[C@H]1O[C@H]1C(OC)C(OC)C(OC)OC1COC YLGXILFCIXHCMC-JHGZEJCSSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000001965 potato dextrose agar Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Multicomponent Fibers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Artificial Filaments (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は防黴性を有するポリオレフィン系合成繊維に関
する。本発明のポリオレフィン系合成繊維はカーペット
、寝具、衣料、衛生材料、フィルター等に使用される。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to polyolefin synthetic fibers having anti-mildew properties. The polyolefin synthetic fiber of the present invention is used for carpets, bedding, clothing, sanitary materials, filters, etc.
［従来の技術］
天然又は合成繊維に防黴性を付与するために、防黴剤の
溶液を繊維上にスプレーしたり、防黴剤の溶液に繊維を
含浸させることにより、繊維表面に防黴剤を塗布するこ
とが行なわれており、このような繊維の表面処理に用い
られる防黴剤として、ジンクビス（２−ピリジルチオ−
１−オキシド）、１０．１０’−オキシビスフェノキシ
アルシン、２．４．４’−トリクロロ−２′−ハイドロ
オキシジフェニルエーテル、ポリ−パラ−ビニルフェノ
ール等の化合物が用いられている。[Prior art] In order to impart anti-mildew properties to natural or synthetic fibers, anti-mildew properties are applied to the fiber surface by spraying a solution of an anti-mildew agent onto the fibers or impregnating the fibers with a solution of an anti-mildew agent. Zinc bis(2-pyridylthio-
Compounds such as 1-oxide), 10.10'-oxybisphenoxyarsine, 2.4.4'-trichloro-2'-hydroxydiphenyl ether, and poly-para-vinylphenol are used.
しかしながら、防黴剤を繊維表面に塗布する上記方法で
は、その後の水洗や洗濯等によって防黴剤が容易に脱落
してしまい、防黴剤の効力に持続性がないという欠点が
あった。また上記防黴剤のうちのあるもの、例えば１０
．１０’−オキシビスフェノキシアルシンは経時ととも
に黄変し、望ましくない繊維の着色化を引き起すという
欠点があった。However, the above-mentioned method of applying a fungicide to the fiber surface has the drawback that the fungicide is easily removed by subsequent washing with water or the like, and the effectiveness of the fungicide is not sustainable. Also, some of the above-mentioned fungicides, for example 10
．． 10'-oxybisphenoxyarsine has the disadvantage of yellowing over time, causing undesirable coloration of the fibers.
［発明が解決しようとする問題点］
従って本発明の目的は上記の従来技術の欠点を解消し、
すぐれな防黴効果を有するポリオレフィン系合成繊維を
提供することにある。[Problems to be Solved by the Invention] Therefore, the purpose of the present invention is to solve the above-mentioned drawbacks of the prior art,
An object of the present invention is to provide a polyolefin synthetic fiber having an excellent anti-mildew effect.
［問題点を解決するための手段］
上記の目的は、ポリオレフィン系合成繊維にイミダゾー
ル化合物を繊維重量に対し０．１〜５゜０重量％含有さ
せることにより達成された。[Means for Solving the Problems] The above object was achieved by adding an imidazole compound to the polyolefin synthetic fiber in an amount of 0.1 to 5.0% by weight based on the weight of the fiber.
従って本発明は、ポリオレフィン系合成繊維にイミダゾ
ール化合物を繊維重量に対し０．１〜５゜０重量％含有
させたことを特徴とする防黴性を有するポリオレフィン
系合成繊維である。Accordingly, the present invention provides a polyolefin synthetic fiber having mildew resistance, which is characterized in that the polyolefin synthetic fiber contains an imidazole compound in an amount of 0.1 to 5.0% by weight based on the weight of the fiber.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明において使用されるポリオレフィン系合成繊維用
の重合体としては、エチレン、プロピレン等のオレフィ
ンの単独重合によって得られる、ポリエチレン、ポリプ
ロピレン等のオレフィン重合体が代表例として挙げられ
るが、これ以外に、エチレンとプロピレンとの共重合体
も使用することができる。またエチレン及び／又はプロ
ピレンと他のコモノマーとの二元又は三元共重合体もポ
リオレフィンの有する基本的物性を保持しているもので
あれば、必要に応じて使用することができる。Typical examples of the polymer for polyolefin synthetic fibers used in the present invention include olefin polymers such as polyethylene and polypropylene obtained by homopolymerization of olefins such as ethylene and propylene, but in addition to these, Copolymers of ethylene and propylene can also be used. Furthermore, binary or ternary copolymers of ethylene and/or propylene and other comonomers can also be used as required, as long as they maintain the basic physical properties of polyolefins.
これらの重合体は単独でまたは２種以上を混合して繊維
化し、単一繊維とすることもでき、また２種以上を複合
して繊維化し、複合繊維とすることもできる。このよう
な複合繊維の一例として、鞘成分と芯成分とからなる、
いわゆる鞘芯型複合繊維を挙げることができる。繊維化
は、押出機を用いる通常の紡糸技術によって行なうのが
好ましい。These polymers can be used alone or in combination of two or more types to form a single fiber into a single fiber, or two or more types can be combined into a fiber to form a composite fiber. An example of such a composite fiber is one consisting of a sheath component and a core component.
Examples include so-called sheath-core type composite fibers. Fiberization is preferably carried out by conventional spinning techniques using an extruder.
本発明は、上記ポリオレフィン系合成繊維に防黴剤とし
てイミダゾール化合物を含有させたものであり、該イミ
ダゾール化合物としては、（イ）比較的に多量添加して
もポリオレフィン系合成繊維の紡糸が可能である、（ロ
）耐熱性にすぐれている、（ハ）比較的に安全性が高い
という特長を有する２−（４−チアゾリル）ベンズイミ
ダゾールを用いるのが最も好ましいが、上記（イ）。In the present invention, the above-mentioned polyolefin synthetic fiber contains an imidazole compound as an anti-mildew agent, and the imidazole compound (a) allows spinning of polyolefin synthetic fiber even if it is added in a relatively large amount. It is most preferable to use 2-(4-thiazolyl)benzimidazole, which has the following characteristics: (b) excellent heat resistance; and (c) relatively high safety.
（ロ）及び（ハ）の条件を満たすものであれば、他のイ
ミダゾール系防黴剤を用いても良い。Other imidazole-based fungicides may be used as long as they satisfy the conditions (b) and (c).
イミダゾール化合物のポリオレフィン系合成繊維への添
加は、該ポリオレフィン系合成繊維用の重合体にイミダ
ゾール化合物を練り込むことにより行なわれ、練り込み
後、イミダゾール化合物含有ポリオレフィン系重合体を
紡糸することとによ° リ、防黴性を有する本発明のポ
リオレフィン系合成繊維が得られる。なお鞘芯型複合繊
維の場合には、イミダゾール化合物を芯成分に添加させ
る必要はなく、鞘成分のみに添加すれば目的を達成する
。The imidazole compound is added to the polyolefin synthetic fiber by kneading the imidazole compound into the polymer for the polyolefin synthetic fiber, and after kneading the imidazole compound, the imidazole compound-containing polyolefin polymer is spun. Thus, the polyolefin synthetic fiber of the present invention having anti-mildew properties can be obtained. In the case of sheath-core type composite fibers, it is not necessary to add the imidazole compound to the core component, and the purpose can be achieved by adding it only to the sheath component.
本発明においてイミダゾール化合物の添加量は繊維重量
に対し０．１〜５．０重量％に限定される。その理由は
０．１重量％未満であると、防黴効果が十分でなく、特
に経時的な防黴効果の低下が認められ、また５、０重量
％を超えると、安定な紡糸が困難となり、繊維化できな
くなるからである。In the present invention, the amount of imidazole compound added is limited to 0.1 to 5.0% by weight based on the weight of the fiber. The reason for this is that if it is less than 0.1% by weight, the anti-mildew effect will not be sufficient, and in particular, the anti-mildew effect will deteriorate over time, and if it exceeds 5.0% by weight, stable spinning will become difficult. This is because it becomes impossible to form into fibers.
なお、本発明においては上述の如くイミダゾール化合物
の添加量を繊維重量に対し０．１〜５゜０重量％と規定
しているが、これは単一繊維の場合には全単一繊維重量
に対し０．１〜５．０重量％であることを意味し、また
鞘芯型複合繊維の場合には鞘成分の重量に対し０．１〜
５．０重量％であることを意味する。In addition, in the present invention, as mentioned above, the amount of the imidazole compound added is defined as 0.1 to 5% by weight based on the weight of the fiber, but in the case of a single fiber, this is based on the total weight of the single fiber. In the case of sheath-core composite fibers, it means 0.1 to 5.0% by weight based on the weight of the sheath component.
It means 5.0% by weight.
また例えば７ｄｅ以上の太い鞘芯型複合繊維の場合には
、イミダゾール化合物の添加量を鞘成分の重量に対し５
重量％以上とすることもできる。In addition, for example, in the case of thick sheath-core type composite fibers with a diameter of 7 de or more, the amount of imidazole compound added is 5% relative to the weight of the sheath component.
It can also be greater than % by weight.
本発明においては、前記イミダゾール化合物とともに、
低分子量ポリオレフィンをポリオレフィン系合成繊維に
添加すると、後掲の［作用］で述べるように繊維内部で
は防黴効果を発揮できないイミダゾール化合物を有効に
活用でき、ポリオレフィン系合成繊維の防黴効果の持続
性が更に向上する。このような低分子量ポリオレフィン
としては低分子量ポリエチレンや低分子量ポリプロピレ
ンが挙げられ、前者の低分子量ポリエチレンの場合、分
子量が９００〜４０００のものが、そして後者の低分子
量ポリプロピレンの場合、分子量２０００〜１５０００
のものが特に好ましい。In the present invention, together with the imidazole compound,
When low-molecular-weight polyolefin is added to polyolefin synthetic fibers, imidazole compounds, which cannot exhibit anti-mildew effects inside the fibers, can be effectively used, as described in [Actions] below, and the anti-mildew effect of polyolefin synthetic fibers can be sustained. further improves. Examples of such low molecular weight polyolefins include low molecular weight polyethylene and low molecular weight polypropylene; the former low molecular weight polyethylene has a molecular weight of 900 to 4000, and the latter low molecular weight polypropylene has a molecular weight of 2000 to 15000.
Particularly preferred are those.
本発明のポリオレフィン系合成繊維は、必要に応じて各
種成分を更に含有することができる。このような添加剤
としてジンクビス（２−ピリジルチオ−１−オキシド＞
、２，４．４’ −トリクロロ−２′−ハイドロオキシ
ジフェニルエーテル、酸化亜鉛等が挙げられる。The polyolefin synthetic fiber of the present invention can further contain various components as necessary. As such an additive, zinc bis(2-pyridylthio-1-oxide>
, 2,4.4'-trichloro-2'-hydroxydiphenyl ether, zinc oxide, and the like.
［作用］
本発明のポリオレフィン系合成繊維は、例えば２−（４
−チアゾリル）ベンズイミダゾールの如き、すぐれた防
黴性を有するイミダゾール化合物を練り込み等の手段に
よって繊維に含有させることにより得られたものである
ので、持続性のある防黴効果を示す。[Function] The polyolefin synthetic fiber of the present invention has, for example, 2-(4
Since it is obtained by incorporating an imidazole compound having excellent anti-mildew properties such as -thiazolyl)benzimidazole into the fiber by means such as kneading, it exhibits a long-lasting anti-mildew effect.
また必要に応じて低分子量ポリオレフィンを含有させる
と、イミダゾール化合物を有効に活用でき、防黴効果の
持続性が更に向上するが、これは下記の理由（ａ）及び
（ｂ）によるものと推定される。Furthermore, if a low molecular weight polyolefin is contained as necessary, the imidazole compound can be effectively utilized and the sustainability of the antifungal effect is further improved, but this is presumed to be due to the following reasons (a) and (b). Ru.
（ａ） イミダゾール化合物を含有するポリオレフィ
ン系合成繊維用重合体中に低分子量ポリオレフィンが添
加されていると、紡糸延伸時に、内部から外方に向けて
移行する性買を有する低分子量ポリオレフィンに同伴し
てイミダゾール化合物も移行して繊維内部よりも繊維表
面がイミダゾール化合物濃度が高いポリオレフィン系合
成繊維が得られる。(a) If a low molecular weight polyolefin is added to a polyolefin-based synthetic fiber polymer containing an imidazole compound, during spinning and drawing, it will be entrained in the low molecular weight polyolefin that has a sex bond that migrates from the inside to the outside. The imidazole compound also migrates, and a polyolefin synthetic fiber is obtained in which the imidazole compound concentration is higher on the fiber surface than in the inside of the fiber.
（ｂ） 低分子ｌポリオレフィンに同伴するイミダゾ
ール化合物の繊維内部より外方へ向けての移行は、ポリ
オレフィン繊維の製造後、使用時にも緩慢ではあるが行
なわれ、繊維表面からイミダゾール化合物が脱落等によ
り失われたとしても繊維表面でのイミダゾール濃度は急
激には低下しない。(b) The migration of the imidazole compound accompanying the low-molecular-weight polyolefin from the inside of the fiber to the outside occurs, albeit slowly, after the polyolefin fiber is manufactured and during use, and the imidazole compound is removed from the fiber surface, etc. Even if imidazole is lost, the concentration of imidazole on the fiber surface does not decrease rapidly.
「実施例］
以下、実施例により本発明をさらに説明するが、本発明
はこれらの実施例に限定されるものではない。"Examples" The present invention will be further explained below with reference to Examples, but the present invention is not limited to these Examples.
実施例１
一軸押出機と単一繊維用ノズル（ホール径０゜７ｍ、ホ
ール数３０）とからなる紡糸設備を使用し、結晶性ポリ
プロピレン（宇部興産（株）Ｓ１３０ＭＶ＞に２−（４
−チアゾリル）ベンズイミダゾール（以下ＴＢＩと略称
する）を結晶性ポリプロピレンの重量を基準にして０．
１，０．２゜０．５，１．０，５．０重量％添加し、紡
糸温度２４０℃、引取速度６００ｍ／ｍｉｎで紡糸し、
単糸デニール４５ｄｅの未延伸糸を得た。なお、紡糸時
の発煙はなく、紡糸時での糸切れは発生しなかった。得
られた未延伸糸を、試験延伸設備にて９０℃で４．５倍
延伸後、熱処理を行ない、単糸デニール１０ｄｅの延伸
糸を得な。Example 1 Using spinning equipment consisting of a single-screw extruder and a single fiber nozzle (hole diameter 0.7 m, number of holes 30), crystalline polypropylene (Ube Industries, Ltd. S130MV) was coated with 2-(4
-thiazolyl)benzimidazole (hereinafter abbreviated as TBI) based on the weight of the crystalline polypropylene.
1,0.2゜0.5,1.0,5.0% by weight was added, spinning was carried out at a spinning temperature of 240°C and a take-up speed of 600 m/min,
An undrawn yarn with a single yarn denier of 45 de was obtained. Note that there was no smoke during spinning, and no yarn breakage occurred during spinning. The obtained undrawn yarn was stretched 4.5 times at 90° C. in a test drawing facility and then heat treated to obtain a drawn yarn with a single yarn denier of 10 de.
この延伸糸を、厚さＩＭ、縦５０ｍｍ、横６０ｍｍの滅
菌したガラス板に５０ｍｍＸ５０ｎｗｎの面積に均一に
巻き付け、この試験片についてＪＩＳ Ｚ−２９１１
に基づく防黴テストを行った。This drawn yarn was uniformly wound around a 50 mm x 50 nwn area around a sterilized glass plate with a thickness of IM and a length of 50 mm and a width of 60 mm, and this test piece was tested according to JIS Z-2911.
We conducted an anti-mold test based on the following.
ＪＩＳ Ｚ−２９１１に基づく防黴テストの概要は以
下の通りである。The outline of the anti-mildew test based on JIS Z-2911 is as follows.
（１） テストに用いた黴は以下の４種の菌株である
。(1) The following four strains of mold were used in the test.
アスペルギルス ニゲル（Ａｓｐｅｒｇｉｌｌｕｓ ｎ
ｔｇｅｒ ）ＦＥＲＨＳ−１
ヘニシリウム シトリナム（Ｐｅｎｉｃｉｌｌｉｕｍｃ
ｉｔｒｉｎｕｍ） ＦＥＲ）ｌ Ｓ−５ケトミウム グ
ロボスム（Ｃｈａｅｔｏｍｉｕｍｇｌｏｂｏｓｕｍ）
ＦＥＲ）ｌ ５−１１ミロテシウム ベル力リア（Ｈｙ
ｒＯｔｈｅＣｉＵｍｖｅｒｒｕｃａｒｉａ） ＦＥＲＮ
Ｓ−１３（２） ポテトデキストローズ寒天培地で
それぞれ培養された上記４Ｎの黴のｍ株を湿潤剤添加殺
薯水に加えて４種の単一胞子懸濁液を調製し、次いでこ
れらの単一胞子懸濁液を等量ずつ混合して混合胞子懸濁
液を得る。Aspergillus niger
tger ) FERHS-1 Penicillium citrinum
itrinum) FER)l S-5 Chaetomium globosum
FER)l 5-11 Myrotesium Bell force rear (Hy
rOtheCiUmverrucaria) FERN
S-13 (2) Four types of single spore suspensions were prepared by adding the above 4N m strains of mold, each cultured on a potato dextrose agar medium, to wetting agent-added potato-killing water, and then these single spore suspensions were added. Mix equal volumes of single spore suspensions to obtain a mixed spore suspension.
（３） 次に上で得られた混合胞子懸濁液を試験片の
表面に均一にまきかけることにより試験片゛に黴の胞子
を接種し、２８℃で４週間培養する。(3) Next, the test piece is inoculated with mold spores by uniformly sprinkling the mixed spore suspension obtained above on the surface of the test piece, and cultured at 28°C for 4 weeks.
（４） 培養後、試験片を目視し、黴抵抗性を評価す
る。評価は試験片の接種した部分に菌子の発育が認めら
れない場合を「３ノ、試験片の接種した部分に認められ
る菌子の発育部分の面積が全面積の１／３以下の場合を
’２Ｊ、１／３を超える場合をｒ゛ｌＪとする。(4) After culturing, visually inspect the test pieces to evaluate mold resistance. The evaluation is ``3'' when no mycelium growth is observed on the inoculated part of the test piece, and ``2J'' when the area of the mycelial growth observed on the inoculated part of the test piece is less than 1/3 of the total area. , the case where it exceeds 1/3 is defined as r゛lJ.
第１表にこの防黴テストの結果を示す。同表よりＴＢＩ
を０．１〜５．０重量％含有させることにより、優れた
防黴効果が得られ、特に添加量が０．５〜５．０重量％
の時に防黴効果の経時的な低下もなく持続性に優れてい
ることが明らかである。Table 1 shows the results of this anti-mildew test. From the same table, TBI
An excellent anti-mildew effect can be obtained by containing 0.1 to 5.0% by weight, especially when the amount added is 0.5 to 5.0% by weight
It is clear that the antifungal effect does not deteriorate over time and has excellent sustainability.
またＴＢＩを０．２重量％添加した本発明の試料につい
て耐洗濯テストを行ない、ＴＢＩ無添加ポリプロピレン
繊維表面にＴＢＩを０．２重量％スプレー塗布した比較
試料と防黴効果を対比した。A washing resistance test was also conducted on the sample of the present invention to which 0.2% by weight of TBI had been added, and the anti-mildew effect was compared with a comparative sample in which 0.2% by weight of TBI was spray-coated on the surface of polypropylene fibers to which no TBI had been added.
この洗濯テストの条件は以下の通りである。The conditions for this washing test are as follows.
市販小型電気洗濯機使用
中性洗剤 １ｇ／ｌ
浴比 １ ： １００
（水１００ｇに対して試料１ｇ）
一回の洗濯サイクル
洗濯 ３０℃×５分間
水洗 １０分間
乾燥 ８０℃×１時間
第２表にこの洗濯テストの結果を示す。同表より、０．
２重量％のＴＢＩを繊維表面にスプレー塗布した比較品
が２回の洗濯により防黴効果の著しい低下が見られたの
に対し、同量のＴＢＩを繊維に添加した本発明品は５回
の洗濯後でも洗濯前と同一の防黴効果を維持しているこ
とが明らかである。Neutral detergent used in a commercially available small electric washing machine 1 g/l Bath ratio 1: 100 (1 g of sample to 100 g of water) One wash cycle Washing at 30°C for 5 minutes Washing in water for 10 minutes Drying at 80°C for 1 hour See Table 2 The results of this washing test are shown below. From the same table, 0.
The comparative product, in which 2% by weight of TBI was spray-coated on the fiber surface, showed a significant decrease in its anti-mildew effect after two washes, whereas the inventive product, in which the same amount of TBI was added to the fibers, was washed five times. It is clear that the same anti-mildew effect is maintained even after washing as before washing.
また本実施例１で得られたポリプロピレン繊維をプロパ
ンガスコンロの燃焼ガスにて１１０℃で４０分間処理し
たが、黄変等の変色がなく、元の状態が維持された。Furthermore, when the polypropylene fiber obtained in Example 1 was treated with combustion gas from a propane gas stove at 110° C. for 40 minutes, there was no discoloration such as yellowing, and the original state was maintained.
比較例Ｉ
ＴＢＩの添加量を本発明で規定された重量範囲の下限（
０，１重量％）に満たない０．０８重量％とじた以外は
実施例１と同様にしてＴＢＩ添加ポリプロピレン繊維を
得、この繊維について防黴テストを行なった。Comparative Example I The amount of TBI added was adjusted to the lower limit of the weight range specified in the present invention (
TBI-added polypropylene fibers were obtained in the same manner as in Example 1, except that 0.08% by weight (less than 0.1% by weight) was bound, and the anti-mildew test was conducted on this fiber.
防黴テストの結果は第１表に示すように防黴効果が不十
分であった。As shown in Table 1, the anti-mildew effect was insufficient.
比較例２
ＴＢＩの添加量を本発明で規定された重量範囲の上限（
５，０重量％）を超える６、０重量％とじた以外は実施
例１と同様にして紡糸を行なったが、６回／時間で単糸
切れが発生し、延伸時にも延伸切れが多発した。Comparative Example 2 The amount of TBI added was adjusted to the upper limit of the weight range specified in the present invention (
Spinning was carried out in the same manner as in Example 1 except that 6.0% by weight (over 5.0% by weight) was bound, but single yarn breakage occurred at 6 times/hour, and there were also many stretch breakages during stretching. .
本比較例２においては、安定な紡糸を行なうことができ
なかっなので、第１表に示す防黴効果を示すデータは、
参考程度のものである。In Comparative Example 2, stable spinning could not be performed, so the data showing the anti-mildew effect shown in Table 1 are as follows:
This is for reference only.
比較例３
実施例１で用いたＴＢＩの代りに、ジンクビス（２−ピ
リジルチオ−１−オキシド）０．３重量％を添加し、紡
糸を行ったが、紡糸時にノズル孔より刺激性ガスが発生
しな。又、得られた繊維について防黴テストを行ったと
ころ、第１表に示すように、防黴効果は十分ではなかっ
た。Comparative Example 3 Instead of TBI used in Example 1, 0.3% by weight of zinc bis(2-pyridylthio-1-oxide) was added and spinning was performed, but irritating gas was generated from the nozzle hole during spinning. Na. Furthermore, when the obtained fibers were subjected to an anti-mildew test, as shown in Table 1, the anti-mildew effect was not sufficient.
比較例４
実施例１で用いたＴＢＩの代りに１０．１０’−オキシ
ビスフェノキシアルシン０．３重量％を添加し紡糸を行
ない、得られた繊維について防黴テストを行なったが、
第１表に示すようにＴＢＩ程の防黴効果は得られなかっ
た。また、この繊維をプロパンガスコンロの燃焼ガスに
て１１０℃で４０分間処理したところ激しく黄変した。Comparative Example 4 Instead of the TBI used in Example 1, 0.3% by weight of 10.10'-oxybisphenoxyarsine was added and spun, and the resulting fiber was subjected to a mildew-proofing test.
As shown in Table 1, the anti-mildew effect was not as good as that of TBI. Further, when this fiber was treated with combustion gas from a propane gas stove at 110° C. for 40 minutes, it turned violently yellow.
実施例２
結晶性ポリプロピレン（宇部興産（株）Ｓ１３０ＭＶ＞
にＴＢＩを０．１重量％、更に低分子量ポリエチレン（
三井石油（株）ハイワックス１１０Ｐ、分子量１０００
）を０．２重量％添加した以外は実施例１と同様にして
紡糸、延伸し単糸デニール１０ｃｌｅの延伸糸を得た。Example 2 Crystalline polypropylene (Ube Industries, Ltd. S130MV>
0.1% by weight of TBI and further low molecular weight polyethylene (
Mitsui Oil Co., Ltd. Hiwax 110P, molecular weight 1000
) was added in an amount of 0.2% by weight, and the same procedure as in Example 1 was carried out to obtain a drawn yarn having a single yarn denier of 10 cle.
紡糸及び延伸はスムーズに行なうことができた。次に得
られた延伸糸について防黴テストを行なった。結果は第
３表 ゛に示す。同表より、低分子量ポリエチレンを添
加した本実施例２のポリプロピレン繊維は低分子量ポリ
エチレンを添加しない実施例１のポリプロピレン繊維よ
りも防黴効果に持続性があることが明らかである。Spinning and drawing could be carried out smoothly. Next, the obtained drawn yarn was subjected to a mildew-proofing test. The results are shown in Table 3. From the same table, it is clear that the polypropylene fiber of Example 2 to which low molecular weight polyethylene is added has a more durable anti-mildew effect than the polypropylene fiber of Example 1 to which low molecular weight polyethylene is not added.
実施例３
低分子量ポリオレフィンとして、実施例２の低分子量ポ
リエチレンの代りに、低分子量ポリプロピレン（三洋化
成（株）ビスコール６６０−Ｐ、分子量３０００）を用
いた以外は実施例２と同様にしてポリプロピレン繊維を
得、得られたポリプロピレン繊維について同様に防黴テ
ストを行なった。結果は第３表に示すように、実施例２
と同様の防黴効果が得られた。Example 3 Polypropylene fibers were produced in the same manner as in Example 2, except that low molecular weight polypropylene (Sanyo Kasei Co., Ltd. Viscol 660-P, molecular weight 3000) was used instead of the low molecular weight polyethylene of Example 2 as the low molecular weight polyolefin. The obtained polypropylene fibers were similarly tested for anti-mildew properties. The results are as shown in Table 3, Example 2
The same anti-mildew effect was obtained.
実施例４
一軸押出機２台と複合繊維用ノズル（ホール径０．６ｍ
ｍ）とから成る鞘芯型複合繊維紡糸設備を使用し、鞘成
分、芯成分ともに、結晶性ポリプロピレン（宇部興産（
株）８１３０ＭＶ＞とし、その両成分又は鞘成分のみに
ＴＢＩを０．２重量％添加し、紡糸温度２４０℃、引取
速度６６６ｍ／ｍｉｎで紡糸し単位デニール７ｄｅの未
延伸糸を得た。Example 4 Two single-screw extruders and a composite fiber nozzle (hole diameter 0.6 m
Using sheath-core type composite fiber spinning equipment consisting of
8130MV>, 0.2% by weight of TBI was added to both components or only the sheath component, and the yarn was spun at a spinning temperature of 240° C. and a take-up speed of 666 m/min to obtain an undrawn yarn with a unit denier of 7 de.
なお紡糸時での糸切れはなかった。得られた未延伸糸を
延伸設備にて９０℃で３．５倍延伸後、熱処理を行ない
単糸デニール２ｄｅの延伸糸を得た。There was no yarn breakage during spinning. The obtained undrawn yarn was stretched 3.5 times at 90° C. in a stretching facility, and then heat treated to obtain a drawn yarn with a single yarn denier of 2 de.
この延伸糸について防黴テストを行なった結果を第３表
に示す。同表よりポリプロピレン繊維の鞘成分にのみＴ
ＢＩを添加するだけで十分な効果が得られることが判明
した。Table 3 shows the results of an anti-mildew test performed on this drawn yarn. From the same table, T is applied only to the sheath component of polypropylene fibers.
It has been found that sufficient effects can be obtained simply by adding BI.
実施例５
芯成分として、実施例４で用いた結晶性ポリプロピレン
をＴＢＩ無添加で用い、また鞘成分として、実施例４で
用いた結晶性ポリプロピレンの代りに高密度ポリエチレ
ン（旭化成（株）サンチックＪ３１０）を用い、これに
ＴＢＩを０．２重量％添加した。上記芯成分と鞘成分と
を実施例４と同一の鞘芯型複合紡糸設備を用いて紡糸温
度２３０℃で紡糸して繊維化し同様に防黴テストを行な
った。結果は第４表に示すように優れた防黴効果が得ら
れた。Example 5 As a core component, the crystalline polypropylene used in Example 4 was used without adding TBI, and as a sheath component, high-density polyethylene (Santic J310, manufactured by Asahi Kasei Corporation) was used instead of the crystalline polypropylene used in Example 4. ), and 0.2% by weight of TBI was added thereto. The above core component and sheath component were spun into fibers using the same sheath-core type composite spinning equipment as in Example 4 at a spinning temperature of 230° C., and the anti-mildew test was conducted in the same manner. As shown in Table 4, an excellent anti-mildew effect was obtained.
又、この繊維をカード機にかけて目付２０ｇ／耐のウェ
ブを作り、巾３５０ｍ、速度５ ｍ／ｍｉｎの金網ベル
トに乗せ風温１３５℃、風速３ｍ／ｍｉｎの熱風を５秒
間吹き付けて得た熱Ｍ融着不織布について防黴テストを
行なった結果も第５表に示すように良好であった。In addition, this fiber was made into a web with a fabric weight of 20 g/proof by applying it to a carding machine, which was placed on a wire mesh belt with a width of 350 m and a speed of 5 m/min, and heated air was blown at a temperature of 135°C and a speed of 3 m/min for 5 seconds to obtain heat M. The anti-mildew test results for the fused nonwoven fabric were also good as shown in Table 5.
比較例５
芯成分として結晶性ポリプロピレンを、鞘成分として結
晶性ポリプロピレン又は高密度ポリエチレンを用い、こ
れらにＴＢＩを添加しなかった以外は実施例４と同様に
して２種の鞘芯型複合繊維を得、防黴テストを行なった
。結果は第４表に示すように防黴効果は全く認められな
かった。Comparative Example 5 Two types of sheath-core composite fibers were prepared in the same manner as in Example 4, except that crystalline polypropylene was used as the core component, crystalline polypropylene or high-density polyethylene was used as the sheath component, and TBI was not added to these. We conducted an anti-mold test. As shown in Table 4, no antifungal effect was observed at all.
また実施例５と同様にして得られた熱風融着不織布につ
いても防黴テストを行なったが、第５表に示すように防
黴効果は全く認められなかった。In addition, an anti-mildew test was also conducted on the hot-air fused nonwoven fabric obtained in the same manner as in Example 5, but as shown in Table 5, no anti-mildew effect was observed.
比較例６
鞘成分の結晶性ポリプロピレンにＴＢＩを６゜０重量％
添加した以外は実施例４と同様にして紡糸したところ、
糸切れが多発し紡糸不能であった。Comparative Example 6 6.0% by weight of TBI in crystalline polypropylene as sheath component
When spinning was carried out in the same manner as in Example 4 except that
Thread breakage occurred frequently and spinning was impossible.
（以下余白）
第）表
第３表
ＰＰ＝ポリプロピレン
第４表
第５表
ＰＥ＝ポリエチレン
［発明の効果］
本発明によればポリオレフィン系合成繊維に、すぐれた
防黴性を有するイミダゾール化合物の特定量を練り込み
等の手段により添加させることにより、持続性のある防
黴効果を有するポリオレフィン系合成繊維が得られた。(Left below) Table 3 PP = Polypropylene Table 4 Table 5 PE = Polyethylene [Effects of the Invention] According to the present invention, a specific amount of an imidazole compound having excellent anti-mildew properties is added to polyolefin synthetic fibers. By adding by means such as kneading, a polyolefin synthetic fiber having a long-lasting anti-mildew effect was obtained.
この合成繊維に必要に応じて低分子ポリオレフィンを更
に添加することにより、防黴効果の持続性は更に向上す
る。By further adding low-molecular-weight polyolefin to this synthetic fiber as needed, the durability of the antifungal effect is further improved.
Claims (3)
を繊維重量に対し０．１〜５．０重量％含有させたこと
を特徴とする防黴性を有するポリオレフィン系合成繊維
。(1) A polyolefin synthetic fiber having anti-mildew properties, characterized in that the polyolefin synthetic fiber contains an imidazole compound in an amount of 0.1 to 5.0% by weight based on the weight of the fiber.
ンズイミダゾールである、特許請求の範囲第１項記載の
ポリオレフィン系合成繊維。(2) The polyolefin synthetic fiber according to claim 1, wherein the imidazole compound is 2-(4-thiazolyl)benzimidazole.
請求の範囲第１項記載のポリオレフィン系合成繊維。(3) The polyolefin synthetic fiber according to claim 1, further containing a low molecular weight polyolefin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26009087A JPH01104821A (en) | 1987-10-15 | 1987-10-15 | Polyolefinic synthetic yarn having mildew-proofing property |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26009087A JPH01104821A (en) | 1987-10-15 | 1987-10-15 | Polyolefinic synthetic yarn having mildew-proofing property |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01104821A true JPH01104821A (en) | 1989-04-21 |
Family
ID=17343156
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26009087A Pending JPH01104821A (en) | 1987-10-15 | 1987-10-15 | Polyolefinic synthetic yarn having mildew-proofing property |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01104821A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4944901A (en) * | 1988-04-14 | 1990-07-31 | Kwok Lloyd A | Method of making dental copings |
| WO2007042416A1 (en) * | 2005-10-12 | 2007-04-19 | Ciba Specialty Chemicals Holding Inc. | Material having antibacterial and antifungal properties |
| WO2008046746A3 (en) * | 2006-10-16 | 2009-07-23 | Ciba Holding Inc | Acaricidal synthetic materials and articles made therefrom |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4980146A (en) * | 1972-12-05 | 1974-08-02 | ||
| JPS6225719B2 (en) * | 1984-09-07 | 1987-06-04 | Toray Industries |
-
1987
- 1987-10-15 JP JP26009087A patent/JPH01104821A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4980146A (en) * | 1972-12-05 | 1974-08-02 | ||
| JPS6225719B2 (en) * | 1984-09-07 | 1987-06-04 | Toray Industries |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4944901A (en) * | 1988-04-14 | 1990-07-31 | Kwok Lloyd A | Method of making dental copings |
| WO2007042416A1 (en) * | 2005-10-12 | 2007-04-19 | Ciba Specialty Chemicals Holding Inc. | Material having antibacterial and antifungal properties |
| JP2009513837A (en) * | 2005-10-12 | 2009-04-02 | チバ ホールディング インコーポレーテッド | Materials with antibacterial and antifungal properties |
| WO2008046746A3 (en) * | 2006-10-16 | 2009-07-23 | Ciba Holding Inc | Acaricidal synthetic materials and articles made therefrom |
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