JP2003096669A - Aquatic organism adhesion-preventing fiber material having excellent safety - Google Patents
Aquatic organism adhesion-preventing fiber material having excellent safetyInfo
- Publication number
- JP2003096669A JP2003096669A JP2001287999A JP2001287999A JP2003096669A JP 2003096669 A JP2003096669 A JP 2003096669A JP 2001287999 A JP2001287999 A JP 2001287999A JP 2001287999 A JP2001287999 A JP 2001287999A JP 2003096669 A JP2003096669 A JP 2003096669A
- Authority
- JP
- Japan
- Prior art keywords
- fiber material
- resin
- antifouling
- 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
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- Biological Depolymerization Polymers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Multicomponent Fibers (AREA)
- Farming Of Fish And Shellfish (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
【0001】[0001]
【発明が属する技術分野】本発明は、海水や淡水に長期
間接触して使用された時に、水棲生物の付着が極めて少
ない繊維に関し、特に、水産資材として加工する場合や
取り扱う場合に安全性に優れた繊維材料に関する。TECHNICAL FIELD The present invention relates to a fiber which has very little attachment of aquatic organisms when it is used in contact with seawater or fresh water for a long period of time, and particularly when it is processed or handled as a marine product and is safe. Regarding excellent fiber materials.
【0002】[0002]
【従来の技術】海水や淡水中で長期間使用される繊維製
品としては、例えば漁業用定置網、養殖魚介類用生け簀
網等の水産用繊維製品;航路浮標、灯浮標、ブイ等の係
留に使用されるロープ;土木用に使用される汚濁防止繊
維幕等がある。これらの繊維製品は、海水や淡水に長期
間接触するうちに、その表面に種々の付着性水棲生物、
例えばアオサや珪藻等の藻類、イソギンチャクやヒドロ
虫等の腔腸動物、イソカイメン等の海綿動物、カサネカ
ンザシ、ヒトエカンザシ等の環形動物、フサコケムシ、
ホンダワラコケムシ等の触手動物、アカフジツボ等の節
足動物、シロボヤ、ユウレイボヤ等の原索動物、ムラサ
キイガイ、ホトトギスガイ等の軟体動物が付着、生息す
る。2. Description of the Related Art Textile products used for a long period of time in seawater or freshwater include, for example, fixed nets for fisheries, fish nets for farmed fish and shellfish, etc .; used for mooring nautical buoys, light buoys, buoys, etc. Rope used; There is a pollution control fiber curtain used for civil engineering. These textiles are exposed to various adherent aquatic organisms on their surface during long-term contact with seawater or freshwater.
For example, algae such as sea bream and diatoms, coelenterates such as sea anemones and hydrozoa, sponges such as sea sponges, annelids such as Kasane kanzaku, human kanzaku, Fusokomushi,
Tactile objects such as the horned beetle, arthropods such as the barnacles, protozoa such as the white oyster and the sea urchin, and molluscs such as the mussels and the mussels attach to and inhabit.
【0003】そして、水棲生物の付着によって、例えば
定置網では重量増加に伴う網の沈下、水流抵抗増大によ
る網の流失、接触・屈曲による網の破損、捕獲した魚介
類の損傷等の問題が生じている。また、生け簀網の場合
は、水の流通性低下による酸素欠乏、寄生虫病の発生源
となり、大きな障害を来たしている。Due to the attachment of aquatic organisms, for example, in a fixed net, problems such as net subsidence due to increase in weight, net loss due to increased water flow resistance, net damage due to contact / bending, and damage to captured seafood occur. There is. In the case of cage nets, it becomes a source of oxygen deficiency and parasitic diseases due to the reduced flowability of water, which is a major obstacle.
【0004】海水や淡水に接触して使用される定置網や
養殖生け簀等は、上記のような水棲生物の付着を防止す
るための対策として、トリブチルスズオキシド、トリフ
ェニルスズオキシド、トリフェニルスズアセテート、ト
リフェニルスズクロライド等の有機スズ化合物や、銅、
銀、亜鉛、ニッケルなどの金属やその化合物、または窒
素硫黄系、ハロゲン系等の有機化合物を含有させた塗料
を塗布する方法が広く知られている。しかしながら、防
汚塗料を処理する際に、防汚成分自体や有機溶媒に起因
する激しい不快臭、刺激臭を伴い、更に作業者の健康を
害するという問題があり、塗料塗布が不要で、防汚効果
が長期間持続する製品が強く要望されている。Stationary nets, aquaculture cages, etc. used in contact with seawater or freshwater are tributyltin oxide, triphenyltin oxide, triphenyltin acetate, triphenyltin acetate, triphenyltin acetate, triphenyltin acetate and triphenyltin acetate as measures to prevent the aquatic organisms from adhering. Organotin compounds such as phenyltin chloride, copper,
A method of applying a coating material containing a metal such as silver, zinc or nickel or a compound thereof, or a nitrogen-sulfur-based or halogen-based organic compound is widely known. However, when treating the antifouling paint, there is a problem that it causes a severe unpleasant odor and an irritating odor caused by the antifouling component itself and the organic solvent and further impairs the health of workers. There is a strong demand for products that have long-lasting effects.
【0005】そこで、本願出願人は、上記のような弊害
を防止する手段として、ピリジン−トリフェニルボラン
またはその誘導体(以下防汚剤と称する場合もある)を
含有する熱可塑性樹脂からなる水産資材を提案し(特開
平2000−344605号公報)、これにより従来の
ような作業者の健康面の問題は改善されている。Therefore, the applicant of the present invention, as a means for preventing the above-mentioned harmful effects, is a marine product made of a thermoplastic resin containing pyridine-triphenylborane or a derivative thereof (hereinafter sometimes referred to as an antifouling agent). (Japanese Patent Laid-Open No. 2000-344605), which improves the problem of the conventional health of workers.
【0006】[0006]
【発明が解決しようとする課題】本発明の目的は、上記
の従来技術に対してさらに人体に対する安全性が高く、
耐久性があり、水棲生物の付着を長期に亘って防止でき
る繊維及び繊維製品を提供することにある。DISCLOSURE OF THE INVENTION The object of the present invention is that the human body is more safe than the above-mentioned prior art,
An object of the present invention is to provide a fiber and a fiber product which are durable and can prevent adhesion of aquatic organisms for a long period of time.
【0007】[0007]
【課題を解決するための手段】すなわち、本発明は、ピ
リジン−トリフェニルボランまたはその誘導体を含有す
る熱可塑性樹脂成分と該樹脂成分を覆う生分解性樹脂成
分とから構成される海棲生物付着防止性繊維材料であ
り、該繊維材料とは、具体的には、ピリジン−トリフェ
ニルボランまたはその誘導体を含有する熱可塑性樹脂成
分を芯成分とし、生分解性樹脂成分を鞘成分とする芯鞘
型複合繊維や最表面に生分解性樹脂成分が存在し、その
下層にピリジン−トリフェニルボランまたはその誘導体
を含有する熱可塑性樹脂成分が存在し最内層の芯糸を被
覆している樹脂被覆糸である。Means for Solving the Problems That is, the present invention relates to the attachment of marine organisms composed of a thermoplastic resin component containing pyridine-triphenylborane or a derivative thereof and a biodegradable resin component covering the resin component. The fiber material is a preventive fiber material, and specifically, the fiber material is a core-sheath containing a thermoplastic resin component containing pyridine-triphenylborane or a derivative thereof as a core component and a biodegradable resin component as a sheath component. -Type composite fiber or a biodegradable resin component on the outermost surface, a thermoplastic resin component containing pyridine-triphenylborane or a derivative thereof on the lower layer, and a resin-coated yarn that coats the innermost core yarn Is.
【0008】本発明で使用されるピリジン−トリフェニ
ルボランは、下記に示した構造を有するものであるが、
本発明においては該化合物の誘導体も使用することがで
き、例えば米国特許第3211679号明細書に記載さ
れているような、3−ブロモピリジン−トリフェニルボ
ラン等のハロゲン置換ピリジン−トリフェニルボラン、
4−メチルピリジン−トリフェニルボラン、4−エチル
−トリフェニルボラン等の低級アルキル置換ピリジン−
トリフェニルボランを挙げることができる。The pyridine-triphenylborane used in the present invention has the structure shown below.
In the present invention, a derivative of the compound can also be used, for example, a halogen-substituted pyridine-triphenylborane such as 3-bromopyridine-triphenylborane as described in U.S. Pat. No. 3,211,679,
4-Methylpyridine-triphenylborane, lower alkyl-substituted pyridine such as 4-ethyltriphenylborane-
Mention may be made of triphenylborane.
【0009】[0009]
【化1】 [Chemical 1]
【0010】かかる化合物の熱可塑性樹脂への含有量
は、水棲生物の付着防止効果を考慮して、0.1〜30
質量%の範囲であることが好ましい。含有量を多くして
も効果の向上は認められず、また少なすぎても効果は奏
されない。より好ましい含有量は3〜10質量%の範囲
である。The content of such a compound in the thermoplastic resin is 0.1 to 30 in consideration of the effect of preventing adhesion of aquatic organisms.
It is preferably in the range of mass%. Even if the content is increased, the effect is not improved, and if it is too small, the effect is not exhibited. A more preferable content is in the range of 3 to 10% by mass.
【0011】上述の防汚剤を含有する熱可塑性樹脂とし
ては特に制限はないが、例えば、ポリエステルとして
は、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、ポリヘキサメチレンテレフタレートなどのポ
リエステルを用いることができ、ポリヘキサメチレンテ
レフタレートを使用することが強度、融点、溶融粘度の
点で好ましい。とくに、これを第3成分で共重合した変
性ポリヘキサメチレンテレフタレートをジオール成分ま
たは酸成分で共重合した変性ポリエステルであること
が、防汚剤の熱安定性、及び製織を行う際の耐磨耗性の
点で好ましい。The thermoplastic resin containing the antifouling agent is not particularly limited, but for example, polyester such as polyethylene terephthalate, polybutylene terephthalate and polyhexamethylene terephthalate can be used. It is preferable to use methylene terephthalate in terms of strength, melting point and melt viscosity. In particular, the modified polyester obtained by copolymerizing modified polyhexamethylene terephthalate with a third component with a diol component or an acid component is used as a modified polyester, because the antifouling agent has thermal stability and abrasion resistance during weaving. It is preferable in terms of sex.
【0012】該ポリエステルを変性させるジオール成分
とは、エチレングリコール、ジエチレングリコール、
1,4−ブタンジオール、ネオペンチルグリコール、シ
クロヘキサン−1,4−ジメタノール、ポリエチレング
リコール、ポリテトラメチレングリコール等であり、ま
た、酸成分とはイソフタル酸、ナフタレン−2,6−ジ
カルボン酸、フタル酸、α,β−(4−カルボキシフェ
ノキシ)エタン、4,4−ジカルボキシジフェニル、5
−ナトリウムスルホイソフタル酸などの芳香族ジカルボ
ン酸、もしくはアジピン酸、セバシン酸などの脂肪族ジ
カルボン酸、またはこれらのエステル類であり、その変
性率は特に限定されないが、酸成分およびジオール成分
ともに50モル%以下の割合で使用することが望ましい。The diol component for modifying the polyester is ethylene glycol, diethylene glycol,
1,4-butanediol, neopentyl glycol, cyclohexane-1,4-dimethanol, polyethylene glycol, polytetramethylene glycol and the like, and the acid component is isophthalic acid, naphthalene-2,6-dicarboxylic acid, phthalate. Acid, α, β- (4-carboxyphenoxy) ethane, 4,4-dicarboxydiphenyl, 5
An aromatic dicarboxylic acid such as sodium sulfoisophthalic acid, or an aliphatic dicarboxylic acid such as adipic acid or sebacic acid, or an ester thereof, and the modification ratio is not particularly limited, but both the acid component and the diol component are 50 mol. It is desirable to use at a ratio of less than%.
【0013】また、該変性ポリエステルは、融点が15
0℃以下、溶融粘度が10000ポイズ以下(160
℃、キャピラリー長10mm、キャピラリー径1mm、剪断
速度1000sec-1の条件)であることが望ましい。融
点が150℃を越える場合には、熱溶融による上述の防
汚剤との混練、紡糸、成形の各工程で180℃を越えて
熱をかける必要が生じ、それにより防汚剤が気化または
分解して最終製品の防汚効果が低下してしまう場合があ
る。また溶融粘度も、あまり高過ぎると混練、紡糸、成
形の各工程で180℃以上の剪断熱が生じ、上述の防汚
剤の気化や分解を招く場合がある。従って、より好まし
い融点は140℃以下、溶融粘度は2000〜5000
ポイズの範囲である。The modified polyester has a melting point of 15
0 ° C or less, melt viscosity of 10,000 poise or less (160
C., capillary length 10 mm, capillary diameter 1 mm, shear rate 1000 sec.sup.- 1 ) are desirable. When the melting point is higher than 150 ° C, it is necessary to apply heat over 180 ° C in each step of kneading, spinning, and molding with the above-mentioned antifouling agent by heat melting, whereby the antifouling agent vaporizes or decomposes. As a result, the antifouling effect of the final product may decrease. Further, if the melt viscosity is too high, shear heat insulation at 180 ° C. or higher may occur in each step of kneading, spinning, and molding, which may cause vaporization or decomposition of the antifouling agent. Therefore, a more preferable melting point is 140 ° C. or lower, and a melt viscosity is 2000 to 5000.
It is a range of poise.
【0014】変性ポリエステルの中には融点が高いもの
があるが、この場合には融点降下剤としてポリブテン、
液状ポリエステル等の中分子ポリマーを使用することが
できる。該融点降下剤の添加量は、融点が150℃以下
に下がる程度に、また溶融粘度が10000ポイズ以下
に下がる程度の量を添加させれば、特に限定されるもの
ではないが、樹脂組成物中の変性ポリエステルに対して
20質量%以下の割合で含有させておくことが好まし
い。Some modified polyesters have a high melting point. In this case, polybutene, a melting point depressant,
A medium molecular weight polymer such as liquid polyester can be used. The addition amount of the melting point depressant is not particularly limited as long as the melting point is reduced to 150 ° C. or lower and the melt viscosity is reduced to 10,000 poise or lower. It is preferable that the modified polyester is contained in an amount of 20% by mass or less.
【0015】本発明で使用される生分解性樹脂とは、全
部または一部が生物によって崩壊するものを指し、単独
樹脂もしくは樹脂混合物でもよい。生分解性樹脂として
は、例えば、ポリ3−ヒドロキシ酪酸、3−ヒドロキシ
酪酸−3−ヒドロキシ吉草酸共重合体、ポリビニルアル
コール、エチレン変性ポリビニルアルコール、ポリγ−
メチル−L−グルタメート、ポリε−カプロラクトン、
ポリエチレンサクシネート、ポリブチレンサクシネー
ト、ポリ乳酸、ポリリンゴ酸、デンプン、セルロース、
キチン・キトサン、グルテン、ゼラチン、ケラチン、コ
ラーゲン、天然ゴム等を挙げることができる。これらの
樹脂は、本発明の効果を大幅に損なわない範囲におい
て、ポリウレタン、ポリメタクリレート、ポリエチレ
ン、ポリスチレン等の非生分解性樹脂、及び分散剤、可
塑剤、顔料等と適宜混合してコンパウンドとして使用す
ることもできる。The biodegradable resin used in the present invention refers to a resin which is wholly or partially decomposed by organisms, and may be a single resin or a resin mixture. Examples of the biodegradable resin include poly-3-hydroxybutyric acid, 3-hydroxybutyric acid-3-hydroxyvaleric acid copolymer, polyvinyl alcohol, ethylene-modified polyvinyl alcohol, polyγ-
Methyl-L-glutamate, poly ε-caprolactone,
Polyethylene succinate, polybutylene succinate, polylactic acid, polymalic acid, starch, cellulose,
Examples thereof include chitin / chitosan, gluten, gelatin, keratin, collagen and natural rubber. These resins are used as a compound by appropriately mixing them with a non-biodegradable resin such as polyurethane, polymethacrylate, polyethylene, polystyrene, and a dispersant, a plasticizer, a pigment, etc. within a range that does not significantly impair the effects of the present invention. You can also do it.
【0016】次に、本発明の繊維材料の製造方法につい
て説明する。防汚剤を含有する熱可塑性樹脂成分を芯成
分とし、生分解性樹脂を鞘成分とする芯鞘型複合繊維を
製造する為には、いわゆる二軸混練押出機を用い、防汚
剤と熱可塑性樹脂及び必要に応じ改質剤、添加剤を均一
に溶融混練し、また、別の押出機にて生分解性樹脂を溶
融し、これらの溶融ポリマー流を芯鞘型複合紡糸装置に
て合流させて、生分解性樹脂が鞘成分になるように複合
紡糸ノズルから押し出して繊維化することができる。な
お、繊維の断面形状は、円形、異形、中空型のいずれで
もよい。Next, the method for producing the fiber material of the present invention will be described. To produce a core-sheath type composite fiber having a thermoplastic resin component containing an antifouling agent as a core component and a biodegradable resin as a sheath component, a so-called twin-screw kneading extruder is used, A plastic resin and, if necessary, a modifier and an additive are uniformly melt-kneaded, and the biodegradable resin is melted by another extruder, and these molten polymer streams are combined by a core-sheath type composite spinning device. Then, the biodegradable resin can be extruded from the composite spinning nozzle so as to be a sheath component and made into fibers. The cross-sectional shape of the fiber may be any of circular shape, irregular shape, and hollow type.
【0017】また樹脂被覆糸とする場合は、該熱可塑性
樹脂、生分解性樹脂をそれぞれ溶媒に溶解して芯糸表面
に塗布する方法があるが、本発明においては、二軸混練
機を使用して、防汚剤を含有する熱可塑性樹脂をを均一
に溶融混練し、溶融押出被覆法によって芯糸に防汚剤含
有熱可塑性樹脂を被覆させ、ついで、生分解性樹脂によ
りさらに被覆をすることにより製造することができる。
樹脂被覆糸に使用される芯糸の素材は合成繊維、再生繊
維、天然繊維、金属繊維、ガラス繊維、炭素繊維等から
選ばれるが、融点、軟化点、または分解点が上述の防汚
剤含有樹脂よりも50℃以上高いものであることが好ま
しい。芯糸の形態は特に限定されるものではなく、モノ
フィラメント、マルチフィラメント、ステープル等を問
わず、さらにこれらからなる合撚糸等も必要に応じて用
いることができる。In the case of using resin-coated yarn, there is a method of dissolving the thermoplastic resin and the biodegradable resin in a solvent and coating them on the surface of the core yarn. In the present invention, a biaxial kneader is used. Then, the thermoplastic resin containing the antifouling agent is uniformly melt-kneaded, and the core yarn is coated with the antifouling agent-containing thermoplastic resin by the melt extrusion coating method, and then further coated with the biodegradable resin. It can be manufactured.
The material of the core yarn used for the resin-coated yarn is selected from synthetic fiber, recycled fiber, natural fiber, metal fiber, glass fiber, carbon fiber, etc., but the melting point, softening point, or decomposition point contains the antifouling agent described above. It is preferably higher than the resin by 50 ° C. or more. The form of the core yarn is not particularly limited, and monofilaments, multifilaments, staples and the like may be used, and a plied yarn or the like made of these may be used as necessary.
【0018】本発明の繊維材料の表面に生分解性樹脂を
付与する方法は、特に限定されないが、付与する生分解
性樹脂コンパウンドが熱可塑性の場合は、上記のような
芯鞘型複合紡糸法や溶融被覆法による樹脂被覆糸の製造
技術を利用することができる。また、生分解性樹脂コン
パウンドが水溶性、もしくは水懸濁性の場合は、防汚剤
を含有する熱可塑性樹脂からなる繊維または樹脂被覆糸
を、生分解性樹脂水溶液に対してディップ・アンド・ニ
ップ方式で付与することができる。溶媒に溶解させた溶
液、または高粘度ゾルの場合も同様である。また、防汚
剤を含有する繊維や樹脂被覆糸が、既にネット、メッシ
ュ、織物の形態に加工されている場合であってもディッ
プ・アンド・ニップ方式で生分解性樹脂を付与すれば、
本発明の効果は当然達せられるものである。生分解性樹
脂による被覆層の厚みは特に限定されないが、薄すぎる
と防汚剤の過度の滲出を紡糸することが困難であるの
で、好ましくは、1μm〜100μmであることが望ま
しい。The method of applying the biodegradable resin to the surface of the fiber material of the present invention is not particularly limited, but when the biodegradable resin compound to be applied is thermoplastic, the core-sheath composite spinning method as described above is used. It is possible to use a technique for producing a resin-coated yarn by a melt coating method or a melt coating method. Further, when the biodegradable resin compound is water-soluble or water-suspendable, fibers or resin-coated yarn made of a thermoplastic resin containing an antifouling agent are dipped and dipped into the biodegradable resin aqueous solution. It can be applied by a nip method. The same applies to a solution dissolved in a solvent or a high-viscosity sol. Further, if a fiber or resin-coated yarn containing an antifouling agent is already processed into a net, mesh or woven form, if a biodegradable resin is applied by the dip and nip method,
The effects of the present invention can of course be achieved. The thickness of the coating layer of the biodegradable resin is not particularly limited, but if it is too thin, it is difficult to spin excessive leaching of the antifouling agent, and therefore it is preferably 1 μm to 100 μm.
【0019】本発明の繊維材料は、その表面に生分解性
樹脂が存在しており、内部の防汚剤含有樹脂を全体的に
覆っているため、該防汚剤は繊維材料表面に過剰に滲出
することなく、本発明の繊維材料を加工又は使用する場
合に、手、腕などに与える危険性が低く抑制されたもの
である。具体的には、後述する方法で求められる「ワイ
ピング付着量」は、本発明の繊維材料について2.5μ
g/cm2以下、特に0.25μg/cm2以下である。
本発明の繊維材料について、モルモットを用いた皮膚感
作性試験を行った結果では、ワイピング付着量が0.2
5〜2.5μg/cm2の範囲であれば、本発明の繊維
材料を素手で触れた場合の皮膚かぶれが起こる危険性は
10〜20%、0.25μg/cm2以下であれば危険
性は10%以下で安全領域であった。In the fiber material of the present invention, the biodegradable resin is present on the surface thereof and entirely covers the resin containing the antifouling agent inside, so that the antifouling agent is excessively applied to the surface of the fiber material. When the fiber material of the present invention is processed or used without exuding, the risk of giving it to hands, arms, etc. is suppressed to a low level. Specifically, the “wiping adhesion amount” obtained by the method described below is 2.5 μm for the fiber material of the present invention.
g / cm 2 or less, especially 0.25μg / cm 2 or less.
The fiber material of the present invention was subjected to a skin sensitization test using a guinea pig, and as a result, a wiping adhesion amount was 0.2.
Be in the range of 5~2.5μg / cm 2, risk of skin irritation when the fiber material of the present invention mentioned with bare hands occurs 10-20% risk if 0.25 [mu] g / cm 2 or less Was below 10% in the safe area.
【0020】[0020]
【実施例】以下、実施例により本発明を詳述するが、本
発明はこれら実施例により何等限定されるものではな
い。尚、実施例中の各評価は、以下の方法により評価さ
れたものである。The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. The evaluations in the examples are evaluated by the following methods.
【0021】・繊維への水棲生物付着状況
糸条を合糸して約10000dtexとし、これを諸撚(下
撚S200T/M、上撚Z100T/M)にして約20000
dtexの諸撚糸を得た。これを用いて1目5cmの蛙又結
節網を作製し、50cm×50cmの銅枠に取り付け、
和歌山県白浜の海中に水深1mの位置で懸垂し、経時的
に生物の付着状況を観察し、次の5段階で評価した。
判定基準
5:生物の付着が全く観察されなかった。
4:対象物の表面全体の10%程度に生物の付着が認め
られた。
3:対象物の表面全体の20%程度に生物の付着が認め
られた。
2:対象物の表面全体の50%程度に生物の付着が認め
られた。
1:対象物の表面全体に生物の付着が見られた。A state where aquatic organisms adhere to the fiber The yarn is combined into about 10,000 dtex, which is then twisted (bottom twist S200T / M, top twist Z100T / M) to about 20,000.
We obtained plied yarn of dtex. Using this, make a frog or knot net with a size of 5 cm and attach it to a copper frame of 50 cm x 50 cm.
Suspended at a depth of 1 m in the sea of Shirahama, Wakayama Prefecture, the state of attachment of organisms was observed over time, and the following 5 grades were evaluated. Criterion 5: No attachment of organisms was observed. 4: Approximately 10% of the entire surface of the object was found to have organisms attached. 3: Attachment of organisms was recognized on about 20% of the entire surface of the object. 2: Approximately 50% of the entire surface of the object was found to have organisms attached. 1: Adhesion of organisms was found on the entire surface of the object.
【0022】・ワイピング付着量
試料となる繊維材料を25℃の恒温室で30日間保管し
た後、繊維材料表面を、白地・薄手・綿100%の手袋
をはめた手で、中程度の力で約30cm/秒の速さで1
5秒間擦り、手袋をメタノールで1時間振とう・抽出
し、高速液体クロマトグラフィーで分析。手袋に付着し
た防汚成分量から、糸条表面に存在する防汚成分量を換
算・定量した。なお、試料が繊維糸条の状態にある場合
は、ボビンに巻いた状態で本分析を行い、布帛の状態に
ある場合は、布帛をそのままの状態で分析する。After the fibrous material to be used as a sample for wiping is stored in a thermostatic chamber at 25 ° C. for 30 days, the surface of the fibrous material is white background, thin, and a hand with gloves made of 100% cotton with moderate force. 1 at a speed of about 30 cm / sec
Rub for 5 seconds, shake and extract gloves for 1 hour with methanol, and analyze by high performance liquid chromatography. The amount of the antifouling component present on the yarn surface was converted and quantified from the amount of the antifouling component attached to the gloves. When the sample is in the state of fiber yarn, the main analysis is performed in the state of being wound on a bobbin, and when the sample is in the state of cloth, the fabric is analyzed as it is.
【0023】実施例1
イソフタル酸10モル%変性ポリヘキサメチレンテレフ
タレートにピリジン−トリフェニルボランを10質量
%、平均分子量3000のポリブテン(出光石油化学社
製:2000H)を6質量%、カーボンよりなる黒色顔
料を0.4質量%含有させ、熱溶融樹脂被覆装置を用い
て、500d/96f、120t/m片撚のポリエチレ
ンテレフタレートフィラメント(クラレ製)100質量
部に対し、200質量部被覆し、1500dの防汚性樹
脂被覆糸を得た。これに、重合度500、鹸化度73モ
ル%、メルトフローレート5g/10分(210℃、2
160g荷重)のポリビニルアルコール(クラレ製:ポ
バールCP1000)を、同様の熱溶融樹脂被覆装置を
用いて防汚性樹脂被覆糸に対し15質量%被覆し、生分
解性樹脂被覆防汚性糸条を得た。これについて水棲生物
付着試験を行い、ワイピング付着量を測定した。海中浸
漬1ヶ月目から充分な防汚効果を示し、ワイピング付着
量は0.08μg/cm2で安全性も充分満足できるレ
ベルであった。Example 1 10% by mass of isophthalic acid-modified polyhexamethylene terephthalate, 10% by mass of pyridine-triphenylborane, 6% by mass of polybutene having an average molecular weight of 3000 (manufactured by Idemitsu Petrochemical Co., Ltd .: 2000H), carbon black Using 0.4% by mass of the pigment, and using a hot-melt resin coating device, 200 parts by mass of 100 parts by mass of 500 d / 96f, 120 t / m single twisted polyethylene terephthalate filament (manufactured by Kuraray) were coated, and 1500 d of 1500 d An antifouling resin-coated yarn was obtained. A polymerization degree of 500, a saponification degree of 73 mol%, a melt flow rate of 5 g / 10 minutes (210 ° C., 2
Using a similar hot-melt resin coating device, polyvinyl alcohol (160 g load) polyvinyl alcohol (made by Kuraray: POVAL CP1000) was coated on the antifouling resin coated yarn in an amount of 15% by mass to obtain a biodegradable resin coated antifouling yarn. Obtained. An aquatic organism adhesion test was performed on this, and the wiping adhesion amount was measured. From the first month of immersion in the sea, a sufficient antifouling effect was exhibited, and the amount of adhering wiping was 0.08 μg / cm 2 , which was a level that was sufficiently satisfactory for safety.
【0024】[0024]
【表1】 [Table 1]
【0025】実施例2
実施例1の防汚性樹脂被覆糸に、分子量5×104のポ
リε−カプロラクトン(ダイセル化学社製:プラクセル
H5:登録商標)を熱溶融樹脂被覆装置を用いて20質
量%被覆し、生分解性樹脂被覆防汚性糸条を得た。これ
について水棲生物付着試験を行い、ワイピング付着量を
測定した。海中浸漬1ヶ月目から防汚効果を示し、ワイ
ピング付着量は2.52μg/cm 2で安全性も満足で
きるレベルであった。Example 2
The antifouling resin-coated yarn of Example 1 had a molecular weight of 5 × 10 5.FourPo
Li-caprolactone (manufactured by Daicel Chemical Industries: Praxel)
H5: registered trademark) with a hot-melt resin coating device
The coating was performed in an amount of 0.5% to obtain a biodegradable resin-coated antifouling yarn. this
Aquatic organism adhesion test to determine the amount of wiping adherence
It was measured. Shows antifouling effect from the 1st month of submersion in the sea,
Ping adhesion is 2.52 μg / cm 2And safety is satisfied
It was a good level.
【0026】実施例3
実施例1の防汚性樹脂被覆糸に、ポリブチレンサクシネ
ート(昭和高分子製:ビオノーレ#1000:登録商
標、PBSU)を熱溶融樹脂被覆装置を用いて20質量%被
覆し、生分解性樹脂被覆防汚性糸条を得た。これについ
て水棲生物付着試験を行い、ワイピング付着量を測定し
た。海中浸漬1ヶ月目から防汚効果を示し、ワイピング
付着量は0.75μg/cm 2で安全性も満足できるレ
ベルであった。Example 3
Polybutylene succine was added to the antifouling resin-coated yarn of Example 1.
Toh (Showa High Polymer Co., Ltd .: Bionore # 1000: registered trader
20% by mass of the target (PBSU) using a hot-melt resin coating device.
Covered to obtain a biodegradable resin-coated antifouling yarn. About this
Aquatic organism adhesion test to measure the amount of wiping adherence
It was Wiping, showing antifouling effect from the 1st month of immersion in the sea
Adhesion amount is 0.75 μg / cm 2To ensure safety
It was a bell.
【0027】実施例4
実施例1の防汚性樹脂被覆糸に、ヒドロキシ吉草酸共重
合化率12%の3−ヒドロキシ酪酸−3−ヒドロキシ吉
草酸共重合体(ゼネカ製:バイオポールD600G、登
録商標、PHB-PHV)を熱溶融樹脂被覆装置を用いて20
質量%被覆し、生分解性樹脂被覆防汚性糸条を得た。こ
れについて水棲生物付着試験を行い、ワイピング付着量
を測定した。海中浸漬1ヶ月目から防汚効果を示し、ワ
イピング付着量は1.83μg/cm2で安全性も満足
できるレベルであった。Example 4 A 3-hydroxybutyric acid-3-hydroxyvaleric acid copolymer having a hydroxyvaleric acid copolymerization rate of 12% was added to the antifouling resin-coated yarn of Example 1 (manufactured by Zeneca: Biopol D600G, registered. Trademark, PHB-PHV) 20 using a hot melt resin coating device
Mass% coating was performed to obtain a biodegradable resin-coated antifouling yarn. An aquatic organism adhesion test was performed on this, and the wiping adhesion amount was measured. From the first month of immersion in the sea, the antifouling effect was exhibited, and the amount of adhering wiping was 1.83 μg / cm 2 , which was a level with satisfactory safety.
【0028】実施例5
実施例1の防汚性樹脂被覆糸に、デンプン・変性ポリビ
ニルアルコールポリマーアロイ(日本合成化学製:マタ
ービーAF10H、登録商標、St-PVA)を熱溶融樹脂被
覆装置を用いて20質量%被覆し、生分解性樹脂被覆防
汚性糸条を得た。これについて水棲生物付着試験を行
い、ワイピング付着量を測定した。海中浸漬1ヶ月目か
ら防汚効果を示し、ワイピング付着量は2.24μg/
cm2で安全性も満足できるレベルであった。Example 5 Starch-modified polyvinyl alcohol polymer alloy (Matterby AF10H, registered trademark, St-PVA, manufactured by Nippon Synthetic Chemical Industry) was applied to the antifouling resin-coated yarn of Example 1 using a hot-melt resin coating device. 20% by mass was coated to obtain a biodegradable resin-coated antifouling yarn. An aquatic organism adhesion test was performed on this, and the wiping adhesion amount was measured. Shows antifouling effect from the 1st month of submersion in the sea, and the wiping adhesion amount is 2.24μg /
The safety was at a level of 2 cm2.
【0029】実施例6
実施例1の防汚性樹脂被覆糸に、重合度1700、鹸化
度88モル%のポリビニルアルコール(クラレ製:クラ
レポバール217)10質量%、ポリウレタンエマルジ
ョン(日本ゼオン製:ニッポールSX1706、登録商
標、Em)5質量%の水溶液を、ディッピングマシンを用
い、ディップ・ニップ方式にて、乾燥質量当り5質量%
被覆し、生分解性樹脂被覆防汚性糸条を得た。これにつ
いて水棲生物付着試験を行い、ワイピング付着量を測定
した。海中浸漬1ヶ月目から防汚効果を示し、ワイピン
グ付着量は0.23μg/cm2で安全性も充分満足で
きるレベルであった。Example 6 10% by weight of polyvinyl alcohol (Kuraray: Kuraray Poval 217) having a degree of polymerization of 1700 and a saponification degree of 88 mol% was added to the antifouling resin-coated yarn of Example 1 and a polyurethane emulsion (Nippon, Nippon Zeon). SX1706, registered trademark, Em) 5% by mass aqueous solution by dipping machine using dipping machine, 5% by mass per dry mass
The coating was performed to obtain a biodegradable resin-coated antifouling yarn. An aquatic organism adhesion test was performed on this, and the wiping adhesion amount was measured. From the first month of submersion in the sea, the antifouling effect was exhibited, and the amount of adhering wiping was 0.23 μg / cm 2 , which was a level that was sufficiently satisfactory for safety.
【0030】比較例1
実施例1の防汚性樹脂被覆糸に、非生分解性樹脂のイソ
フタル酸10モル%変性ポリヘキサメチレンテレフタレ
ートを熱溶融樹脂被覆装置を用いて20質量%被覆し
た。これについて水棲生物付着試験を行い、ワイピング
付着量を測定した。ワイピング付着量は0.12μg/
cm2で安全性は満足できるレベルであったが、防汚効
果を全く示さなかった。Comparative Example 1 The antifouling resin coated yarn of Example 1 was coated with 20% by mass of a non-biodegradable resin, isophthalic acid 10 mol% modified polyhexamethylene terephthalate, using a hot melt resin coating device. An aquatic organism adhesion test was performed on this, and the wiping adhesion amount was measured. Wiping adhesion is 0.12μg /
Although the safety was satisfactory at cm 2, it did not show any antifouling effect.
【0031】比較例2
実施例1の防汚性樹脂被覆糸を、生分解性樹脂を被覆せ
ずに、水棲生物付着試験を行い、ワイピング付着量を測
定した。防汚効果は充分であったが、ワイピング付着量
は88μg/cm2で、安全性が不十分であった。Comparative Example 2 The antifouling resin-coated yarn of Example 1 was subjected to an aquatic organism adhesion test without coating the biodegradable resin, and the wiping adhesion amount was measured. Although the antifouling effect was sufficient, the wiping adhesion amount was 88 μg / cm 2 , and the safety was insufficient.
【0032】比較例3
実施例1の方法で防汚成分を含有しない樹脂被覆糸を作
製し、水棲生物付着試験を行い、ワイピング付着量を測
定した。海中浸漬1ヶ月目で旺盛な生物付着が認められ
た。Comparative Example 3 A resin-coated yarn containing no antifouling component was prepared by the method of Example 1, and an aquatic organism adhesion test was conducted to measure the wiping adhesion amount. Vigorous biofouling was observed at the first month of immersion in the sea.
【0033】[0033]
【発明の効果】本発明の繊維、及び繊維製品は、水棲生
物の付着が全く無く、且つ人体に接触しても安全な水産
資材の提供を可能にできるものである。INDUSTRIAL APPLICABILITY The fiber and the fiber product of the present invention are capable of providing a marine product which has no aquatic organisms attached thereto and is safe even when it comes into contact with the human body.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 FI テーマコート゛(参考) A01N 55/08 A01N 55/08 D01F 8/04 ZBP D01F 8/04 ZBPZ D06M 15/333 D06M 15/333 Fターム(参考) 2B104 CC28 CG17 2B106 AA08 HA16 4H011 AA02 AD01 BA01 BB16 BC18 BC19 DA10 DD01 DH02 DH04 DH05 DH06 DH08 DH10 4L033 AA07 AB03 AC10 AC15 BA57 CA45 CA46 CA55 CA56 4L041 BA02 BA05 BA21 BD20 CB16 CB28 DD03 DD21 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) A01N 55/08 A01N 55/08 D01F 8/04 ZBP D01F 8/04 ZBPZ D06M 15/333 D06M 15/333 F Terms (reference) 2B104 CC28 CG17 2B106 AA08 HA16 4H011 AA02 AD01 BA01 BB16 BC18 BC19 DA10 DD01 DH02 DH04 DH05 DH06 DH08 DH10 4L033 AA07 AB03 AC10 AC15 BA57 CA45 CA46 CA55 CA56 4L041 BA02 BA16 BA21 BD20 DD
Claims (4)
の誘導体を含有する熱可塑性樹脂成分と該樹脂成分を覆
う生分解性樹脂成分とから構成される海棲生物付着防止
性繊維材料。1. A marine organism adhesion preventing fiber material comprising a thermoplastic resin component containing pyridine-triphenylborane or a derivative thereof and a biodegradable resin component covering the resin component.
ランまたはその誘導体を含有する熱可塑性樹脂成分を芯
成分とし、生分解性樹脂成分を鞘成分とする芯鞘型複合
繊維である請求項1に記載の繊維材料。2. The core-sheath type composite fiber having a thermoplastic resin component containing pyridine-triphenylborane or a derivative thereof as a core component and a biodegradable resin component as a sheath component, in the fiber material. The described fiber material.
おり、被覆樹脂層の最表面には生分解性樹脂成分が存在
し、その下層にピリジン−トリフェニルボランまたはそ
の誘導体を含有する熱可塑性樹脂成分が存在し最内層の
芯糸を被覆していることを特徴とする請求項1に記載の
繊維材料。3. The fiber material is in the form of a resin-coated yarn, a biodegradable resin component is present on the outermost surface of the coating resin layer, and pyridine-triphenylborane or its derivative is contained in the lower layer. The fiber material according to claim 1, wherein a thermoplastic resin component is present and covers the innermost core yarn.
維材料からなる水産資材。4. A marine product comprising the fiber material according to any one of claims 1 to 3.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2001287999A JP2003096669A (en) | 2001-09-21 | 2001-09-21 | Aquatic organism adhesion-preventing fiber material having excellent safety |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2001287999A JP2003096669A (en) | 2001-09-21 | 2001-09-21 | Aquatic organism adhesion-preventing fiber material having excellent safety |
Publications (1)
Publication Number | Publication Date |
---|---|
JP2003096669A true JP2003096669A (en) | 2003-04-03 |
Family
ID=19110715
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2001287999A Pending JP2003096669A (en) | 2001-09-21 | 2001-09-21 | Aquatic organism adhesion-preventing fiber material having excellent safety |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2003096669A (en) |
-
2001
- 2001-09-21 JP JP2001287999A patent/JP2003096669A/en active Pending
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