JP3899405B2 - Eating damage inhibitor, eating damage control material containing this eating damage inhibitor, and method for producing the same - Google Patents

Description

【００４７】
表１において、ＴＨＦＡはテトラヒドロフルフリルアクリレート、ＩＢＸＭはイソボルニルメタクリレート、５１２Ａはジシクロペンテニルオキシエチルアクリレートである。
表１から、モノマーが異なっても羊毛に対するグラフト加工が良好に進むこと、また、モノマー濃度を増加することで羊毛への加工率が増大することが確かめられた。
以下の実施例では、これらのグラフトモノマーの他に、ＩＢＸＡ：イソボルニルアクリレート、ＴＨＦ：テトラヒドロフルフリルメタクリレート、５１１Ａ：ジシクロペンテニルアクリレート等も使用した。
【００４８】
＜銀付着、銅付着繊維＞
メタクリル酸の銀塩又は銅塩を用いて上記脱脂羊毛をグラフト加工した。すなわち、羊毛繊維へのグラフト加工は、２.５％ｏｗｆの過硫酸ナトリウム、８５％蟻酸(２ｍＬ/Ｌ)、及び４０％ｏｗｆのメタクリル酸の銀塩又は銅塩を含み、さらにモノマー重量に対して１２％の乳化剤を加えて調製した混合溶液中に羊毛繊維を浸漬し（浴比１:２０）、加熱処理することにより行った。常温から８０℃まで２０分間で昇温した後、４０分間、同温度を保持して反応を進めた。反応終了後、水洗いし、ノイゲンＨＣ(１ｍＬ/Ｌ)を添加した混合溶液中で、７０℃、２０分間還元洗浄を行った。水洗いし、風乾した後、標準状態(２０℃、６５％ＲＨ)で調湿させて金属含有加工羊毛繊維を作製した。かくして、銀、銅を含むグラフト加工羊毛を調製できた。
また、グラフト加工液に重合開始剤を加えることなく、また、グラフト加工液を加熱することなく、室温で脱脂羊毛を３０分浸漬し、取り出して水洗いすることで銅付着、あるいは銀付着羊毛を調製した。
【００４９】
＜各種染料による染色方法＞
クリキュラ色素：
野蚕由来でインドネシア産のクリキュラ繭２０ｇを１,０００ｍｌの水で９０℃、１時間煮出した後、煮出し水溶液をまず濾紙で、続いてポーラスサイズが５μｍ、１.２μｍのミクロフィルターで濾過した。濾過したクリキュラ繭抽出色素(以下、単に「クリキュラ色素」又は「クリキュラ」と称す。)を含む液をクリキュラ染色液とし、このクリキュラ染色液に酢酸を添加してｐＨ４.５に調整したクリキュラ染色浴で羊毛布を８５℃で１時間染色した。
【００５０】
ラックダイ、五倍子、カテキュー、赤キャベツ、紫根：
これらの染色剤としては、各植物より色素成分を抽出し、濃縮液体化した液体植物染料（市販品、田中直染料店製）を用いた。各染色剤を上記クリキュラ色素と同じ方法で濾過後吸光度測定に使用すると共に、２０％ｏｗｆの植物染料を含む水溶液を弱酸性（ｐＨ５〜６）とし、この染料液を用いて、浴比１:５０倍に設定し、羊毛布を６０℃で１時間染色した。
【００５１】
コチニール、キハダ：
コチニール、キハダ（市販品、田中直染料店製）を、それぞれ、羊毛重量の２０％ｏｗｆ、５０％ｏｗｆ使用し、浴比を１:５０に設定し、沸騰水中で３０分間煮出し、熱いうちに漉して一番染液を採った。再びコチニールとキハダに水を加えて最初と同じ要領で二番染液を得た。これらの染液を合併して冷えるまで静置後、染色浴を先ず濾紙で、続いてポーラスサイズが５μｍのミクロフィルターで濾過した。濾液に羊毛布の目方の５０倍になるように温湯水と酢酸３％とを添加して、羊毛布を６０℃で１時間染色した。
【００５２】
藍：
インド藍液（市販品、田中直染料店製）を用いてメーカー推奨の飽和染法に準じて羊毛布を染色した。
化学染料：
直接染料C.I. Direct Black 51(Kayaku Direct Fast Black conc.)５％ｏｗｆ、無水硫酸ナトリウム３０％ｏｗｆの染色溶液中で羊毛布を９０℃で１時間染色した。
【００５３】
＜コチニールの抽出及び染色方法＞
コチニールは次のようにして２回の熱水抽出を行い、この抽出液を染色浴として用いた。
コチニール５０ｇを含む水１０００ｍＬを２０分間沸騰させたものをステンレス製の篩（サイズ：２００メッシュ）で濾過して第一抽出液とした。濾別したコチニールに新たに水４００ｍＬを加えて２０分間煮沸したものを同様にステンレス製の篩（サイズ：２００メッシュ）で濾過して第二抽出液とした。次に、第一抽出液と第二抽出液とを混合し、この混合水溶液を濾紙及びミクロフィルターで濾過して不純物のない染色浴を濾別した。これに水３００ｍＬを加えて全量３０００ｍＬのコチニール染色浴を調製した。
【００５４】
被処理試料（羊毛）を上記コチニール染色浴に入れ、染色浴温度を室温から９８℃まで４０分かけて昇温し、９８℃で１時間処理して試料を染色した。染色終了後、染色浴を自然放冷して室温にしてから試料を取り出し、水洗後、室温で乾燥させた。
＜ウコンの抽出及び染色方法＞
ウコン色素は、（資）比嘉製茶の市販品「春ウコン」を抽出することで調製した。ウコンの抽出及び染色は、上記コチニールの抽出と染色方法に準じて行った。
【００５５】
＜媒染方法＞
アルミ媒染は、被処理試料（羊毛）を２ｇ/Ｌ焼きミョウバン水溶液で処理して行った。銅媒染は２ｇ/Ｌ酢酸銅水溶液、鉄媒染は５ｍＬ/５００ｍＬ木酢酸鉄水溶液、チタン媒染は５ｍＬ/５００ｍＬチタン媒染水溶液、クロム媒染は５％クロムミョウバン水溶液を用いて行った。いずれの媒染処理の温度と時間も６０℃、３０分であった。
＜含金染料による染色＞
含金染料として、Kayakalan Blue Black RL又はKayakalan Black 2RLを用いた。１ｇ/Ｌ濃度の染料を用い、１時間、９８℃処理することにより染色した。直接染料(Kayaku Direct Fast Black conc.)による染色は、濃度１ｇ/Ｌの染料を含む染色浴で１時間、９８℃処理することにより染色した。
【００５６】
＜クリキュラ絹糸の調製＞
濃度１２ｇ/Ｌの炭酸ナトリウム水溶液１,０００ｍＬに袋詰めしたクリキュラ繭８.５６ｇを入れ、１３０℃で２時間精練した。精練後の重量は６.４１ｇ（練減率２５.１％）であった。
次に、このクリキュラ繭を９０℃、１時間水抽出した。続いて、クリキュラ繭をソックスレー抽出器によりエチルアルコールで５時間抽出した。
ラボ・オートクレーブ（三洋 MLS-3780）を用いて、クリキュラ繭６２.４５ｇを１２０℃で１時間処理し、更に１３０℃で１時間処理した。処理後の重量は５２.６１ｇ（重量減少率１５.７６％）であった。このようにして精練したクリキュラ絹糸を調製し、試験に供した。
【００５７】
（実施例１）グラフト加工羊毛の食害実験
グラフトモノマーとしてＩＢＸＭ、ＴＨＦＡ、５１２Ａを用い、次のようにしてグラフト加工した羊毛を製造した。ニューカルゲン１５１５−２Ｈ（商品名、竹本油脂(株)製非イオン／アニオン混合界面活性剤）６重量％を含む水溶液に希薄蟻酸を加えてｐＨ２.５に調整した後、所定濃度のＩＢＸＭ、ＴＨＦＡ、又は５１２Ａを加え、さらに重合開始剤として所定量の過硫酸アンモニウムを上記脱脂羊毛とグラフトモノマーとの合計重量に対し１.８％ｏｗｆ加えてグラフト加工液を調製した。グラフト加工液の浴比を１：１５とし、羊毛を浸漬し、２５℃から８０℃まで４５分かけて昇温し、８０℃で６０分加熱処理した。処理後、ノイゲンＨＣ（商品名、第一工業製薬(株)製非イオン界面活性剤）１０％を含む水溶液で８５℃で３０分洗浄し、１０５℃で２時間乾燥した。
なお、一部の試料加工用のグラフトモノマー濃度は前記表１に示した。
【００５８】
このようにしてＩＢＸＭ、ＴＨＦＡ、５１２Ａでグラフト加工した結果、加工率がそれぞれ１４％、３２％、２３％のグラフト加工羊毛を調製できた。なお、メタクリル酸の銅塩、銀塩でグラフト加工しても加工率は０.２％程度であった。
一個の小プラスチック培養器に１０匹のヒメマルカツオブシムシと１種類の被検用試料を入れた「個別法」により、一週間毎に４週間まで食害試験を行った。なお、ヒメマルカツオブシムシの若齢幼虫(３齢と４齢)を小プラスチック培養器に１０匹を入れ、これをインキュベーター(温度２４±１℃)内に保管して４週間食害試験を続けた。試験は同一試料につき２回反復試験を行い、１週間毎に試料重量を秤量し、平均値をとり食害割合を算出した。得られた食害割合を表２に示す。
【００５９】
表２中の試料の項において、対照区とは、未処理未加工の脱脂羊毛を意味し、ＩＢＸＭ、ＴＨＦＡ及び５１２Ａはそれぞれ、ＩＢＸＭ、ＴＨＦＡ及び５１２Ａを用いてグラフト加工した羊毛を意味し、銅とは、メタクリル酸の銅塩でグラフト加工した羊毛を意味し、また、ＩＢＸＭ／銅及びＴＨＦＡ／銅はそれぞれ、ＩＢＸＭ及びＴＨＦＡでグラフト加工した羊毛にさらに第二段階でメタクリル酸の銅塩でグラフト加工した羊毛を意味する。それぞれの試料に対して食害試験を２回繰り返し、その結果の平均値を表２に示す。
【００６０】
（表２）

【００６１】
表２から明らかなように、ＩＢＸＭ、ＴＨＦＡ、５１２Ａでグラフト加工した羊毛をヒメマルカツオブシムシはほとんど食害せず（食害割合はほぼ０％）、グラフト加工により食害制御素材を製造できることが確認された。また、ＩＢＸＭ及びＴＨＦＡでグラフト加工した羊毛を引き続いてメタクリル酸の銅塩でグラフト加工すると１００％の食害抑制効果が得られた。また、メタクリル酸の銅塩でグラフト加工した羊毛も、対照区の場合と比べて食害被害を受けないことがわかる。
なお、メタクリル酸の銅塩の代わりにその銀塩、亜鉛塩、コバルト塩、クロム塩等、アクリル酸の銅塩、銀塩、亜鉛塩、コバルト塩、クロム塩等を用いても同様な結果が得られた。また、羊毛のかわりに家蚕繭糸、野蚕繭糸、セリシン繭や、精練処理前の家蚕、野蚕、繭糸に対して上記と同様にグラフト加工した試料を用いて行った食害試験の場合も、羊毛の場合と同様に食害抑制効果が認められた。
【００６２】
（実施例２）グラフト加工羊毛の機械的特性変化
実施例１に従ってＩＢＸＭ、ＴＨＦＡでグラフト加工した羊毛についての機械的特性変化を、グラフト加工の前後で繊維製品の強度・伸度が劣化するか否かを評価した。得られた結果を表３に示す。
【００６３】
（表３）

表３から明らかなように、羊毛にグラフト加工を施しても、グラフト加工前後における羊毛の強度、伸度の劣化程度は軽微であり、機械的実用性能が劣悪と成らないことが実証された。
【００６４】
（実施例３）個別法による染色羊毛の食害試験
第一段階の処理として脱脂羊毛をコチニール染料で染色し、その後、各種の色相に発色させるための第２段階の処理として、種々な金属イオンで媒染処理した羊毛、あるいは含金染料や直接染料で染色した羊毛について、その食害割合を次に記載する方法で調べた。一個の小プラスチック培養器に１０匹のヒメマルカツオブシムシと一種類の被検用試料を入れた「個別法」により、一週間毎に４週間迄食害試験を行った。食害割合は、試験開始後、２、３、４週間目の試料重量変化から求めた。得られた結果を表４に示す。
【００６５】
（表４）

【００６６】
表４中、コチニール染とは、コチニールを染料に用いて染めた羊毛を意味する。コチニール染＋Ａｌとは、コチニールで羊毛を染色した後、焼きミョウバン水溶液を用いて媒染処理した試料を意味する。以下、同様に、コチニール染＋Ｃｕ、Ｆｅ、Ｔｉ、Ｃｒは、焼きミョウバン水溶液の代わりに、酢酸銅水溶液、木酢酸水溶液、チタン媒染水溶液、クロムミョウバン水溶液を用いて媒染染色した羊毛を意味する。また、Kayakalan Blue Black RL、Kayakalan Black 2RL、Kayaku Black conc.はそれぞれ、脱脂羊毛を、含金染料であるKayakalan Blue Black RL若しくはKayakalan Black 2RL、又は直接染料Kayaku Direct Fast Black conc.で染色しただけの羊毛を意味する。
【００６７】
表４において、コチニール染＋Ａｌ、コチニール染＋Ｃｕ、コチニール染＋Ｆｅ、コチニール染＋Ｔｉ、コチニール染＋Ｃｒの場合の媒染処理条件の概要、及び含金染料染め、直接染料染めの条件の概要は次の通りである。
Ａｌ媒染剤としてはアルミみょうばんを用いた：２ｇ/Ｌで６０℃、３０ｍｉｎ.
Ｃｕ媒染剤としては酢酸銅を用いた：２ｇ/Ｌで６０℃、３０ｍｉｎ.
Ｆｅ媒染剤としては木酢酸鉄を用いた：５ｃｃ/５００ｃｃで６０℃、３０ｍｉｎ.
Ｔｉ媒染剤としてはチタン媒染液を用いた：５ｃｃ/５００ｃｃで６０℃、３０ｍｉｎ.
Ｃｒ媒染剤としてはクロムみょうばんを用いた：５％溶液で６０℃、３０ｍｉｎ.
また、Kayakalan Blue Black RL、Kayakalan Black 2RL、Kayaku Direct Fast Black conc.)等の含金染料で羊毛を染色した。０.１％の含金染料を使用し、沸騰水中で１時間染色処理を行った。
表４から明らかなように、含金染料、直接染料で染色した羊毛は、対象区に比べて食害抑制効果があった。
【００６８】
（実施例４）一括法による染色羊毛の食害試験
実施例３で用いたものと同じ試料の食害割合を「一括法」で評価した。
１０種類の被検試料を一個の大型プラスチック培養器にほぼ一定の距離を隔てて配位する「一括法」により食害試験を行った。なお、この大型プラスチック培養器に１００匹のヒメマルカツオブシムシ幼虫を入れて食害時間が４週間になるまで食害試験を行った。食害割合は、試験開始後、３、４週間目の試料重量変化から計算して求めた。得られた結果を表５に示す。
【００６９】
（表５）

表５から明らかなように、含金染料及び直接染料で染色した羊毛が最も食害抑制効果がよかった。
【００７０】
（実施例５）天然染料で染着した染色羊毛の食害試験
各種染料(クリキュラ、ラックダイ、コチニール、五倍子、カテキュー、赤キャベツ、紫根、藍、キハダ、直接染料C.I. Direct Black 5)で染色した脱脂羊毛のヒメマルカツオブシムシに対する食害割合を調べた。小プラスチック培養器に被検用試料と１０匹のヒメマルカツオブシムシ幼虫とを入れた個別法により、一週間毎に４週間迄、食害試験を行った。表６中、ＩＢＸＭ／赤キャベツ及び５１２Ａ／赤キャベツは、それぞれ、実施例１の方法で羊毛をグラフト加工した後、実施例５と同様の方法で赤キャベツで染色加工した試料を意味する。食害割合は、試験開始後、１、２、３、４週間目の試料重量変化から計算して求めた。得られた結果を表６に示す。また、被染物の色相も表６に示す。
【００７１】
（表６）

【００７２】
表６から明らかなように、未加工未処理羊毛（対象区）は、食害試験１週間の時間経過までの食害量は低いが、２週間目あたりから食害量が次第に急激に増加するようになり、４週間でサンプルの７０％以上が食べ尽くされた。紫根で染色した羊毛に対するヒメマルカツオブシムシの食害量は多く、食害試験４週間で６０％程度の食害量となった。クリキュラ、ラックダイ、コチニール、五倍子、アテキュー、赤キャベツ、藍、キハダ等の天然染料で染色した羊毛の食害割合は低く、経過時間４週間の食害割合はいずれも１５％程度前後であり、また、化学染料で染色した羊毛の食害割合は約３０％であった。また、ＩＢＸＭ、５１２Ａでグラフト加工した羊毛を更に赤キャベツで染色することにより、食害抑制効果が実質的に１００％発現するに至った。
【００７３】
（実施例６）家蚕繭糸の食害試験
グラフトモノマーとして５１２Ａを用い、実施例１と同様の方法でグラフト加工した家蚕繭糸について食害試験を行った。食害割合は、試験開始後、１、２、３、４週間目の試料重量変化から計算して求めた。得られた結果を表７に示す。
（表７）

【００７４】
表７から明らかなように、未加工家蚕繭糸は、食害試験の経過１週間以内での食害割合は低いが、２週間目あたりから食害割合が次第に急激に増加するようになり、４週間でサンプルの７０％以上が食べ尽くされた。これに対して、本発明によるグラフト加工した家蚕繭糸の食害割合は著しく軽微で、４週間経過後でも１０％以下であり、グラフト加工により家蚕繭糸の食害被害が著しく減少したことがわかる。
【００７５】
（実施例７）カテキン、タンニン酸を含む試料の食害試験
黒系の直接染料（C.I. Direct Black 51(Kayaku Direct Fast Black conc.)で羊毛を染色する際、カテキン、タンニン酸を染色浴に加えて染色することで、食害抑制機能を持つ素材が調製できるかどうかを検討した。なお、用いたタンニン酸は和光純薬工業株式会社製の商品であり、また、カテキンは和光純薬工業株式会社製の商品である。
試料番号と試料の調製方法とを表８にまとめて示す。
【００７６】
（表８）

【００７７】
次に、表８に記載した染色加工羊毛の食害試験を行った。すなわち、プラスチック容器にヒメマルカツオブシムシ１０匹と各試料とを入れ、個別法により食害試験を行った。１試料につき５回の繰り返し試験を行い、得られた食害割合の平均値を表９に示す。
【００７８】
（表９）

【００７９】
表９から明らかなように、(１)タンニン酸、カテキンがヒメマルカツオブシムシの食害抑制効果を持つこと、また、(２)タンニン酸、カテキンを含む染色浴で染色しても、又は(３)通常の工程で染色した後、後処理としてタンニン酸、カテキン水溶液で処理しても、食害抑制効果を持つことが分かった。
【００８０】
（実施例８）スプレー処理
実施例１で用いた各グラフト加工水溶液をスプレー装置で脱脂羊毛表面にスプレーした。室温で乾燥したものについて食害試験を行ったところ、実施例１と同様に各試料の食害割合は著しく低下することが確かめられた。
【００８１】
（実施例９）耐久性と食害試験。
実施例１で作製したＩＢＸＭによるグラフト加工羊毛、ＴＨＦＡによるグラフト加工羊毛、５１２Ａによるグラフト加工羊毛を、ＪＩＳ規格の洗濯試験（ＪＩＳ Ｌ１０４５）に準じ、石鹸を主剤とする試験液で洗濯した。洗濯試験後の各種グラフト加工羊毛の食害試験を行ったところ、表２に記載した食害割合と同一の値であり、洗濯により食害特性が変化することはなかった。
【００８２】
（実施例１０）亜鉛付着羊毛の食害抑制効果
実施例１で使用したメタクリル酸の銅塩の代わりにメタクリル酸の亜鉛塩でグラフト加工した羊毛の食害割合は、メタクリル酸の銅塩で加工した羊毛とほぼ同一の値となった。
上記実施例では、処理試料として繊維が太めでグラフト加工が施しやすい羊毛、家蚕繭糸について実施したが、素材として羊毛のみに限定されるものではなく、その他に、野蚕繭糸や、これらの繭糸からセリシンを除去した絹フィブロイン繊維を用いた場合であっても、また、精練処理前の家蚕繭糸、野蚕繭糸等を用いた場合であっても同様の食害抑制効果が得られた。
【００８３】
【発明の効果】
本発明の食害抑制剤によれば、特定の（メタ）アクリル酸誘導体及び／又はその重合体、又は特定の（メタ）アクリル酸誘導体の金属塩を有効成分として含んでいるので、食害昆虫に対して優れた食害抑制機能を発揮することができる。
本発明の食害抑制素材によれば、グラフトモノマーとして、上記特定の物質を用いて天然タンパク質繊維及び繊維製品をグラフト加工しているので、繊維害虫による食害割合を軽減し、繊維及び繊維製品に対する食害昆虫からの被害を防ぐことが可能となる。しかも、グラフト加工に伴い繊維製品の機械的特性はほぼ未加工時のままであり、未加工時の特性を大幅に低下させることはない。また、人畜に有害な防虫、殺虫剤、昇華性防虫剤、防除剤を用いて繊維害虫を避ける従来の技術とは異なり、本発明の食害抑制素材は、人畜に無害であり、繊維製品と接しても、繊維製品にシミをつけたり、繊維製品の色合いを変色させたりする危険性は全くない。
【００８４】
また、本発明の食害抑制素材は、上記グラフトモノマーの水分散液又は溶媒分散液中に天然タンパク質繊維及び繊維製品浸漬することによっても、また、これらの液を用いてスプレー方式等で天然タンパク質繊維及び繊維製品を処理することによっても製造でき、優れた食害抑制機能を有する発現することができる。このグラフト加工した素材は耐洗濯性に優れ、洗濯後も食害抑制効果は減退することはなく、長時間持続する。
本発明によれば、グラフト加工率を制御することで素材の食害抑制程度を変えることもできる。
【００８５】
さらに、本発明によれば、従来公知の染料の染色浴にタンニン酸、カテキン等の食害制御物質を含ませて天然タンパク質繊維及び繊維製品を染色することにより、又は従来公知の染料でこの繊維及び繊維製品を染色した後、染料を繊維及び繊維製品中に固定させる目的で金属水溶液に浸漬する媒染処理を行うことにより、繊維及び繊維製品に対する食害昆虫からの被害を防ぐことができる。
本発明によれば、処理される素材として、羊毛の他に、家蚕繭糸、野蚕繭糸や、これらの繭糸からセリシンを除去した絹フィブロイン繊維を用いた場合であっても、また、精練処理前の家蚕繭糸、野蚕繭糸等を用いた場合であっても同様の食害抑制効果が得られる。
【００８６】
本発明の食害抑制機能を持つ素材は、食害抑制機能の効果の耐久性に優れたものであるので、例えば、肌着、シャツ、ブラウス、パジャマ等の衣料品、寝装具、タオル、ハンカチ、包帯等の各種食害抑制機能を持つ製品として、或いはマット、シート、綿体、粉砕体等の食害抑制機能性製品の素材として好適なものである。
また、本発明の食害抑制機能を持つ素材は、衣料分野はもとより、農業、園芸分野においても利用できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a food damage inhibitor for preventing damage caused by pests that mainly damage fibers and textile products, a food damage suppressing material containing the food damage inhibitor, and a method for producing the food damage suppressing material.
[0002]
[Prior art]
Many fiber pests are alive around us, feeding on precious fiber products and significantly deteriorating product quality. Such fiber pests grow by feeding on dry foods such as clothes, insects, carcasses of small animals, dried fish, dried meat, brown rice, and wheat.
In order to understand the actual state of damage, the following is general knowledge about fiber insects and damage. Insects that harm wool fibers, wool fiber products, silk protein fibers, silk protein fiber products, etc. include Coleoptera cutworms, Dromedary cutworms, and lobsters of the family Lepidoptera, Chiropodidae. Of these, the cutlet worms and the common cutlet worms will be mainly described below.
[0003]
Katsuobushimushi and Himemarukatsuobushimushi:
Cut wig beetles are adults with a body length of about 4 mm, and their body colors are reddish brown to black brown. The larva has a body length of about 9 mm, and its body color is yellowish brown to brown.
Himemaru cutworm is an adult and has a body length of about 2.5 mm. Its body color is yellow and white, and it is characterized by brown spots. The larva has a body length of about 4 mm, and its body color is dark brown to black brown.
[0004]
Cut wig beetles and common cut wig beetles usually occur once a year and overwinter with larvae. It hatches in March to May and becomes an adult in May to June. The larval period for both is 300 days. Larvae infiltrate the perishables and the gaps in the storage, etc., sleep, and go through the year. During the period of the larvae, you do not continue to eat clothes. The amount of food eaten by Hime Marukatsu Oshimushi will gradually decrease from around September. When the common cutlet worm grows actively, it will increase by 2 to 3 times its weight per week.
[0005]
Feeding damage by larvae of cutworms and longhorn beetles:
Insects such as cutlet worms and long-horned beetles are serious problems because they seriously damage wool products. In addition to wool, animal fiber products such as silk, skin products and fur, dried animal foods such as dried fish, and animal products and insect specimens are known as prey to these insects. Cereals and seeds are also damaged by food damage.
In order to control such insects, it is important to take care not to enter adult insects, although they are passive. In other words, only the larvae eat the clothes, and adults appear in the field from spring and lay eggs in the fall. Therefore, it is necessary to consider not bringing adults indoors.
[0006]
In general, basic control measures against insects can be broadly divided into the following three types. (1) Measures to suppress the generation of pests, (2) Measures to eliminate pests, (3) Measures to suppress pest damage.
Pest control:
Since clothes are preferably damaged by soiled parts, it is desirable to store textile products after dry cleaning after use. Insect repellents such as naphthalene and paradichlorobenzene are effective for prevention of food damage, and organic phosphorus powders and oil sprays are effective for pesticide control, but the target (clothing and food) Sufficient attention should be paid to quality control.
[0007]
Since the above-mentioned insect repellent is an active ingredient that becomes a gas and evaporates in the air to kill pests, it may have an adverse effect on the human body. It is necessary to reduce the amount of use as much as possible and to ventilate the room air when changing clothes.
How to control fiber pests:
Control methods against fiber pests can be broadly classified into the following two types. (1) Chemical control method using insecticide / insecticide, (2) Low temperature / high temperature treatment, and physical control method using oxygen scavenger. In the case of chemical control methods, safety to human livestock must be considered with priority, and it is necessary to consider the environment, material, sealing degree, application amount, and economic efficiency of the place of use.
[0008]
Sublimable insect repellents such as paradichlorobenzene, naphthalene, camphor, etc. may dissolve the synthetic resin in the storage container, and may deteriorate the polyvinyl chloride or lose the gloss of gold or silver thread. It is necessary to be careful. In addition, when multiple different sublimable insect repellents such as paradichlorobenzene and camphor are used at the same time, they may melt and leave stains on the clothing.
Transpirant insecticides and smoking insecticides can usually turn yellow when applied directly to white products. In addition, fumigant insecticides such as methyl bromide and aluminum phosphide are harmful to human livestock.
[0009]
[Problems to be solved by the invention]
Therefore, unlike conventional insect repellents and insecticides, it does not adversely affect the health of human animals, and it is not necessary to pay special attention when using it, and it is efficient and economical. In particular, fiber pest control technology that suppresses food damage or the development of materials that keep fiber insects away is desired, but no satisfactory technology has yet been proposed.
[0010]
As a solution to the above problem, it is conceivable to develop a technique for processing the fiber material itself so as to keep the fiber pests away. For example, to develop a fiber material that has been grafted with a specific monomer, that is, to search for a processing agent that does not deteriorate the mechanical properties of the fiber material before and after the grafting process and that can suppress food damage, and to process reagents It is conceivable to develop a technology for processing materials using slag.
The problem of the present invention is to solve the problems of the prior art, provide a food damage inhibitor exhibiting an excellent food damage control effect against insects that eat, and fibers and textile products having a food damage control effect excellent in durability. An object of the present invention is to provide a food damage control material and a method for producing the material.
[0011]
[Means for Solving the Problems]
  The inventors of the present invention have been diligently carrying out basic research for imparting a novel food injury-suppressing property that is not inherent to natural proteins by processing natural proteins with graft monomers. As a result, natural proteins grafted with (meth) acrylic acid derivatives with unique molecular side chains, Have damage to fiberThe inventors have found that the insect damage-inhibiting effect of insect-damaging insects is expressed, and have completed the present invention.
[0012]
  Of the present inventionHas damage to fiberThe insect damage inhibitor for insect insects is represented by the following general formula [I]:
CH₂ = C (R) COOXY [I]
(However, in general formula [I],
  R is H or CH_ThreeAnd
  X is (CH₂)_aO_b(a is 0-4, b is 0 or 1),
  Y is (1) (CF₂)_cA fluorinated alkyl group represented by Z (c is 1 to 10, Z is H or F),
     (2) Tetrahydrofurfuryl group, or
     (3) Tricyclo [5,2,1,0^2,6] A decanyl group or a decenyl group. )
A (meth) acrylic acid derivative represented by: a polymer thereof, or a combination of the derivative and the polymer, or
  The following general formula [II]:
                CH₂ = C (R) COOZ [II]
(In the general formula [II], R is H or CH._ThreeAnd Z isSelected from iron, silver, copper, zinc, cobalt, and chromiumIt is a metal. )
A metal salt of a (meth) acrylic acid derivative represented by:
  (Meth) acrylic acid derivative represented by general formula [I], a polymer thereof, or a combination of the derivative and the polymer, and a metal of (meth) acrylic acid derivative represented by general formula [II] Mixture with salt
Is an active ingredient. In the present specification, the (meth) acrylic acid derivative means an acrylic acid derivative and a methacrylic acid derivative.
[0013]
  ThisInsect damage inhibitors of the mosquitoes can avoid the damage caused by insects selected from Coleoptera, Coleoptera, and Lepidoptera (Lepidoptera: Noctuidae)The
[0014]
  The damage control material for insects having damage to the fiber of the present invention is a damage control material comprising a fiber or a fiber product to which the above-mentioned damage control agent is attached.The fiber or textile product is a silk protein fiber containing catechin or tannic acid andfiberIt is a natural protein fiber or fiber product selected from products and wool keratin fibers and fiber products.
  The catechin or tannic acid has a concentration of 0 for the natural protein fiber or fiber product. . After dyeing in a dye bath containing 5 to 3% catechin or tannic acid, or after dyeing the fiber or fiber product in a dye bath not containing catechin or tannic acid, the concentration is 0. . It is characterized by being included in the fiber or fiber product by dipping in an aqueous solution of 5 to 3% catechin or tannic acid and mordant treatment..
[0015]
  According to the present invention, there is provided a method for producing an insect damage-inhibiting material against insect insects having an insect damage to a fiber, wherein the agent for preventing damage to insects is a natural protein fiber or fiber product selected from silk protein fibers and fiber products and wool keratin fibers and fiber products. Concentration of anti-corrosion material is 0 . After dyeing in a dyeing bath containing 5 to 3% catechin or tannic acid, or after dyeing this food damage suppressing material in a dyeing bath not containing catechin or tannic acid, the concentration is 0. . It is characterized by being dipped in an aqueous solution of 5-3% catechin or tannic acid and mordanted..
[0016]
  Of the present inventionAgainst insects that have fiber damageThe manufacturing method of the food damage control materialAlso,The above-mentioned food damage inhibitorA natural protein fiber or fiber product grafted with an active ingredient of the above, wherein the concentration of a food damage inhibiting material comprising a natural protein fiber or fiber product selected from silk protein fiber and fiber product and wool keratin fiber and fiber product is 0 . After dyeing in a dyeing bath containing 5 to 3% catechin or tannic acid, or after dyeing the food damage suppressing material in a dyeing bath not containing catechin or tannic acid, the concentration is 0. . It is characterized by being dipped in an aqueous solution of 5-3% catechin or tannic acid and mordanted..
[0017]
DETAILED DESCRIPTION OF THE INVENTION
Examples of the material that is the target of the food damage suppressing material of the present invention include silk protein derived from silkworm, wool fiber of animal protein, keratin fiber, and the like as the organic polymer.
According to the present invention, silkworm-derived silk protein and wild silkworm-derived silk protein can be used. For example, silk fibers derived from rabbits (Rabbit raw silk (raw silk)), silk fibers derived from Kuwako of the relative species, silkworms derived from wild silkworms, silkworms, sunflowers, Eli silkworms, mug silkworms (wild silk raw silk) Silk fibroin fibers obtained by scouring raw silk can also be used.
[0018]
Rabbit larvae and wild moth larvae mature and are spun out to produce spider silks, which are peeled off in layers when opened with hands. This is called a soot layer and can be used in the present invention. The surface of the cocoon yarn constituting the cocoon layer is covered with glue-like sericin, and the cocoon yarn is continuously taken out from the cocoon layer, and the raw yarn is obtained by spinning a plurality of cocoon yarns in the spinning process. In order to obtain silk fibroin fiber, silk sericin may be removed by scouring treatment. In the case of silkworm silk, for example, silk sericin is removed by boiling with an alkaline solution such as sodium carbonate, and in the case of silkworm silk, for example, silk heat treated with a mixed solution such as sodium metasilicate and sodium carbonate, ethylenediaminetetraacetic acid. Sericin is removed to form silk fibroin fibers.
[0019]
Further, in the present invention, a silk nonwoven fabric in which silk fibroin fibers cut into fine pieces are randomly assembled can be used.
Further, natural organic polymers such as wool keratin can be used as protein fibers other than silk. The wool keratin fiber used by this invention can be prepared as follows, for example. The pigment and fat contained in Merino wool (64'S) are removed by treating with a Soxhlet extractor for 2.5 hours using a mixed solution of benzene-ethanol (50/50 (volume%)), A wool fiber used in the present invention is prepared.
The shape of silk, wool or the like used in the present invention is not particularly limited, and may be, for example, a fiber, a woven fabric, a knitted fabric, a nonwoven fabric, a fiber composite, or a powder.
[0020]
According to the present invention, it is possible to manufacture a material capable of treating an object to be treated by the following seven methods and suppressing food damage from insects.
(1) A method of grafting with a graft monomer which is a (meth) acrylic acid derivative represented by the above general formula [I].
(2) A method of grafting with a graft monomer which is a metal salt of a (meth) acrylic acid derivative represented by the above general formula [II].
(3) A method of dyeing a material that has not been processed by the above method (1) or (2) or a processed material with a natural dye.
(4) The material not processed by the above method (1) or (2) or the processed material is dyed with a general dye or an animal dye such as cochineal, and is immersed in an aqueous solution containing metal ions to be mordanted. how to.
[0021]
(5) A method of dyeing a material that has not been processed by the above method (1) or (2) or a processed material with a metal-containing dye.
(6) A method of dyeing in a dyeing bath to which catechin or tannic acid is added in addition to a dye when dyeing a material not processed by the above method (1) or (2) or a processed material.
(7) A method in which a material not processed by the above method (1) or (2) or a processed material is dyed with a general dye and then mordanted with an aqueous solution of catechin or tannic acid.
(8) A method of immersing a material that has not been processed or processed by the above method (1) or (2) in an aqueous solution of catechin or tannic acid.
[0022]
The method for producing a food damage suppression material by the above method will be described in detail below.
When producing the food damage control material by the method of (1):
Specific examples of the (meth) acrylic acid derivative represented by the general formula [I] include, for example, trifluoroethyl acrylate, trifluoroethyl methacrylate, octafluoropentyl acrylate, octafluoropentyl methacrylate, and tridecafluorooctyl methacrylate. , Heptadecafluorodecyl acrylate, heptadecafluorodecyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, phenoxyethyl methacrylate, isobornyl acrylate, isobornyl methacrylate, norbornyl acrylate, norbornyl methacrylate, Tricyclo [5,2,1,0^2,6] Decanyl acrylate, tricyclo [5,2,1,0^2,6] Decanyl methacrylate, tricyclo [5,2,1,0^2,6] Decenyl acrylate, tricyclo [5,2,1,0^2,6] Decenyloxyethyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, etc. may be mentioned, and these may be used alone or in combination of two or more.
[0023]
Examples of the metal salt of the (meth) acrylic acid derivative represented by the general formula [II] include silver salt of methacrylic acid, copper salt, iron salt, zinc salt, and the like, and silver salt of acrylic acid, copper salt, An iron salt, a zinc salt, etc. are mentioned, These may be used independently or may be used in combination of 2 or more type.
In the present embodiment, a (meth) acrylic acid derivative having excellent graft polymerizability will be described below as an example.
The food damage inhibitor of the present invention may be composed of only these (meth) acrylic acid derivatives as active ingredients, or may be in the form of a solution in which these (meth) acrylic acid derivatives are dissolved in water, alcohol or the like. In addition, when the (meth) acrylic acid derivative is hardly soluble, it may be in the form of a dispersion obtained by dispersing the (meth) acrylic acid derivative in water, alcohol or the like with a dispersant.
When the form of the food damage inhibitor of the present invention is liquid, the food damage control function is imparted to the product such as fiber by immersing the product such as fiber or applying and adhering the product. In addition, by using a method such as coating or spraying, it is possible to easily impart the damage prevention functionality to secondary products such as residential building materials and furniture that are difficult to dip.
[0024]
In addition, since the (meth) acrylic acid derivative represented by the general formula [I] used in the present invention has a carbon-carbon double bond and has polymerizability, the (meth) acrylic acid derivative remains as it is. It can be applied to the treated product and then polymerized, or a polymer of (meth) acrylic acid derivative or an active ingredient composed of this monomer and polymer may be applied to the treated product. Good. The polymer may be a copolymer of an unsaturated compound copolymerizable with a (meth) acrylic acid derivative. In addition, the corrosion inhibitor containing the polymer of a (meth) acrylic acid derivative can also give the corrosion inhibitory effect to resin itself by kneading | mixing, mixing, etc. with resin which consists of a well-known organic polymer. .
[0025]
Any known method can be used for the polymerization of the (meth) acrylic acid derivative. For example, the (meth) acrylic acid derivative contains an arbitrary polymerization initiator such as ammonium persulfate and a surfactant, and further grafted. In order to increase the efficiency of polymerization, a method of heat polymerization in an aqueous system acidified with an acid or the like can also be used.
The food damage suppressing agent of the present invention exhibits an excellent food damage suppressing effect on insects that damage food, and can impart a food damage suppressing effect to various products including resin products, and in particular, the food damage suppressing effect of the present invention. A fiber or a fiber product to which a (meth) acrylic acid derivative represented by the general formula [I] and / or a polymer thereof is attached, which is an active ingredient having an active ingredient, is useful as a fiber or a fiber product having a food damage inhibiting function. It is.
[0026]
The grafting process for producing the food damage inhibiting material according to the present invention is usually performed as follows.
In an aqueous dispersion obtained by dispersing a graft monomer (general formulas [I] and [II]) with a surfactant, natural protein fibers or fiber products are placed, and if desired, a polymerization initiator is added to perform graft polymerization. Let it be done. Any polymerization initiator can be used as long as it is a radical catalyst that generates a radical that serves as a base for graft polymerization on the protein. For example, ammonium persulfate is used in order to prevent deterioration in fiber characteristics. preferable. The amount of monomer that can be introduced into a natural protein depends on the graft processing rate (hereinafter simply referred to as “processing rate”), and the amount of monomer used, that is, the processing rate, is determined by the amount of graft monomer used, processing temperature, processing time, and processing rate. Depending on the type of protein to be prepared, etc., it can be adjusted as desired.
[0027]
Specific examples of processing conditions for grafting are as follows.
In a solution containing a predetermined amount of the graft monomer, a graft polymerization initiator (for example, sodium persulfate 2.5% owf), formic acid (for example, 2 mL / L 85% formic acid), a predetermined amount (for example, 12 wt%) emulsifier is added to obtain a mixed solution, and natural protein fibers are immersed in the solution (for example, a bath ratio of 1:20) and grafted. Using a thermostat or an overmeier type dyeing tester (sealed type), etc., the temperature of the grafting solution is raised from room temperature to 80 ° C. over 20 minutes, for example, and then the reaction is carried out for 40 minutes. Proceed. After completion of the reaction, the protein fiber was washed with water, and Neugen HC (1 mL / L: trade name, nonionic surfactant manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added to the aqueous hydrosulfite sodium solution (1 g / L). In the mixed solution, reduction cleaning is performed at 70 ° C. for 20 minutes. After washing with water, air-drying, and then conditioning in a standard state (20 ° C., 65% RH) to prepare a grafted fiber sample.
[0028]
In the present invention, as described above, by performing grafting with a grafting reagent having an effect of suppressing damage to food, a function of suppressing damage to food can be imparted to natural protein fibers and fiber products such as silk and wool. In addition, as shown below, in order to develop colors in various colors following the first stage of dyeing wool with a dye, the dyed wool is immersed in a metal ion-containing aqueous solution and heated. It is also possible to prepare a food damage suppression material by performing a two-stage process. In this case, the wool or the like may be processed as in (1) or may not be processed.
[0029]
When manufacturing the food damage control material by method (2):
For example, silver salt, copper salt, zinc salt, cobalt salt, chromium salt of methacrylic acid, silver salt of acrylic acid, copper salt, zinc salt, cobalt salt, chromium salt, etc. {Circle around (1)} The material for controlling food damage can be produced by grafting natural protein fibers or fiber products by the method as described above.
[0030]
When manufacturing the food damage control material by the method of (3):
(1) A material that has not been processed or processed by the above method (1) or (2) is dyed with the extracted curcula extract pigment from the wild curdula.
(2) Dye a raw material or a processed raw material with a plant dye, rack die, pentaploid, catechu, red cabbage, purple root, which has not been processed by the above method (1) or (2).
(3) A material not processed or processed by the method (1) or (2) is dyed with cochineal or yellowfin that is an animal-derived pigment.
In order to stain a sample with a natural pigment derived from a plant, a staining bath containing 10 to 80% owf of pigment is used, and a dilute aqueous solution of acetic acid is added to the staining bath to adjust the pH of the staining bath to 5 to 6. And a dyeing treatment may be performed at a bath ratio of 1:50 at 40 to 70 ° C., preferably 55 to 65 ° C. for 1 hour.
As the natural pigment in the present invention, cochineal was mainly used because it focused on protein fibers such as wool and silk, and improved weather resistance.
[0031]
Graft processing sample:
The material having a function of inhibiting damage according to the present invention is obtained by grafting a (meth) acrylic acid derivative represented by the general formula [I] and / or a polymer thereof onto fibers and fiber products by graft processing. As mentioned above, examples thereof include silk fibers such as rabbits and wild silk, and animal protein fibers such as wool fibers, with silk fibers and wool fibers being particularly preferred. The form of the fiber may be any of fabrics such as cotton, yarn, woven fabric, knitted fabric, and non-woven fabric, or fiber products made of these yarn and fabric.
In the raw material having a food damage suppressing function of the present invention, the (meth) acrylic acid derivative and / or the polymer thereof is firmly attached to the surface and / or the interior of the fiber to be treated by graft polymerization, so that the food damage suppressing effect is further improved. This is preferable for a long time.
[0032]
The fiber etc. which are the raw materials with a feeding damage suppression function of this invention are manufactured by the following method.
That is, it is produced by subjecting the fiber to be treated to adhesion treatment with a solution or dispersion of a (meth) acrylic acid derivative represented by the general formula [I] and / or a polymer thereof.
The solution or dispersion of the (meth) acrylic acid derivative and / or polymer thereof is an aqueous solution if the (meth) acrylic acid derivative and / or polymer thereof is water-soluble, an alcohol solution or water if it is alcohol-soluble. If it is insoluble, an aqueous dispersion dispersed with a dispersant such as a surfactant is preferred from the viewpoint of increasing the efficiency of graft polymerization.
[0033]
As a method for the adhesion treatment, a solution or dispersion of a (meth) acrylic acid derivative and / or a polymer thereof is used as a treatment liquid, (a) a treatment initiator is present in the treatment liquid and the fiber to be treated is immersed, A treatment method in which a (meth) acrylic acid derivative and / or a polymer thereof is graft-polymerized on the fiber, and (b) a method in which the fiber to be treated is adhered and treated in a treatment solution are used. In addition, (c) a method of applying or spraying the treatment liquid on the fiber and drying it may be used. Among these methods, in particular, the method (a) is a fiber material having a more effective (meth) acrylic acid derivative and / or polymer thereof attached to the fiber to be treated and having an excellent food damage control effect. Is obtained, and the deterioration of the fiber characteristics is slight. In particular, when silk fiber or wool fiber is used as the fiber to be treated, the method (a) is an effective method.
[0034]
As the polymerization initiator in the method (a), any catalyst can be used as long as it is a radical catalyst that generates radicals serving as a base for graft polymerization on the fiber, and ammonium persulfate is preferably used in terms of not deteriorating fiber properties. . In the method (b), after immersing, the treated product may be washed with water if necessary and dried by heating or immersed under heating. In the method (c), It may be dried.
The conditions such as the amount of the (meth) acrylic acid derivative and / or polymer thereof used in the treatment liquid, the treatment temperature, and the treatment time in the adhesion method of (a), (b) or (c) are as follows. It can be changed as appropriate depending on the type, the degree of imparting the damage prevention function, the use of the fiber having the damage prevention function, and the like. The amount of the (meth) acrylic acid derivative and / or polymer thereof adhering to the fiber is generally at least 0.01% by weight as the processing rate in order to exert the effect of excellent food damage control functionality. Preferably, it may be 5% by weight or more. The upper limit of the adhesion amount may be appropriately selected in consideration of the manufacturing cost and the like.
[0035]
When manufacturing the food damage control material by the method of (4):
Examples of metal ions used for mordanting include ions such as Al, Cu, Fe, Ti, Cr, etc. In order to mordant with these metal ions, copper acetate, iron pyroacetate, titanium mordant, aluminum alum, chromium What is necessary is just to process using alum etc. The metal ion concentration of this aqueous solution containing metal ions is 1 to 15 g / L, preferably 1 to 5 g / L. Degreased wool or grafted defatted wool is immersed in this metal ion-containing aqueous solution, and heat treatment is performed at 40 ° C. to 80 ° C., preferably 55 to 75 ° C. for 30 minutes to 2 hours.
[0036]
When producing the food damage control material by the method of (5):
By dyeing defatted wool or grafted defatted wool with a metal-containing dye containing metal ions such as Cr, Cu, Co, etc., a food damage control material can be produced.
The concentration of the metal-containing dye is generally 2-3%, preferably 0.1-0.5%, more preferably 0.05-0.2%. For example, the following metal-containing dyes can be used.
Cr-complex dyes:
Acid Black 54 (CI = 14885), Acid Black 124 (CI = 15900), Acid Red 184 (CI = 1 5685), Acid Red 187 (CI = 16265), Acid Blue 193 (CI = 15707), Acid Violet 58 ( CI = 16260), Acid Blue 234 (Kayakalan Blue Black RL), and Acid Black 155 (Kayakalan Black 2RL)
Co-complex dyes:
Acid Brown 86 (CI = 17620), Acid Blue 42 (CI = 17255), Acid Violet 91 (CI = 1 5681), and Direct Violet 46 (CI = 17595).
Cu-complex dyes:
Direct Yellow 88, Direct Blue 165, and Direct Green 80.
[0037]
When manufacturing the food damage control material by the method of (6):
By subjecting the fiber or fiber product or the grafted fiber or fiber product to a dyeing bath containing a general dye to which catechin or tannic acid is added, a food damage suppressing material can be produced. The concentration of catechin and tannic acid contained in this dyeing bath is 0.5 to 3% owf, preferably 1 to 2% owf.
[0038]
When manufacturing the food damage control material by the method of (7):
After the fiber or fiber product or the grafted fiber or fiber product is dyed with a general dye, a damaging treatment with an aqueous solution of catechin or tannic acid can be used to produce a food damage inhibiting material. The concentration of catechin and tannic acid is 0.5 to 3% owf, preferably 1 to 2% owf.
When manufacturing the food damage control material by the method of (8):
The material for inhibiting damage to food can be produced by immersing a fiber or fiber product or a grafted fiber or fiber product in a catechin aqueous solution or tannic acid aqueous solution of 1 to 10% owf, preferably 2 to 5% owf.
In addition, it turned out that the raw material grafted with the acrylic acid derivative is less susceptible to damage than the raw material grafted with the methacrylic acid derivative if the processing rate is the same. However, there was no significant difference in the damage ratio of the materials grafted with the metal salt of acrylic acid derivative and the metal salt of methacrylic acid derivative.
[0039]
【Example】
EXAMPLES Hereinafter, although an Example and a manufacture example are given and this invention is demonstrated in detail, this invention is not limited to these examples. In addition, the definition of the damage insect and the damage rate used in the damage test prior to the examples is shown below. Also, the fiber to be treated used in the examples, grafting to this fiber, dyeing method and the like will be described. The physical property value of the processed fiber was determined by the following method.
[0040]
<Eating insects>
Larvae (3, 4) collected from submerged silkworm larvae grown from dry cocoons as feed from dry cloth storage bags stored in the cocoon warehouse of the former Silkworm Insect Agriculture Research Institute Aged) was cultivated for 1 year in an incubator (Sanyo Electric Co., Ltd., MIR-153) at 25 ° C. and humidity 70-80% RH. Larva larvae were used as insect insects.
[0041]
<Eating damage ratio>
The eating damage test by Hime Marukatsu Oshimushi was conducted as follows.
A feeding damage test was carried out by the “collective method” in which the larvae and a plurality of samples were placed in the rearing container, and the “individual method” in which the larvae and a single sample were placed in the rearing container. In this batch test, a Petri dish (No. 639 102) manufactured by Greiner was used as a plastic container (diameter 154 mmφ, height 20 mm). In the test by the individual method, a small Petri dish (diameter 55 mmφ, height 15 mm) manufactured by Kord-Volmark was used. A test sample and a certain headed sword beetle of the same size and age were placed in a Petri dish, and a food damage test was performed in an environment where light was shielded, and the food damage was observed for a predetermined period. That is, after starting the damage test, the damage ratio was examined by the following formula while weighing the sample amount with a chemical balance every week from 1 to 4 weeks.
[0042]
Eating damage ratio (%) = [(Wa−Wb) / Wa] × 100
Wa: Weight of the test sample before the damage test
Wb: Weight of test sample after eating damage test
[0043]
<Processed fiber>
Merino wool (64'S) was used as the fiber to be treated. Before grafting the wool sample, in order to remove impurities such as pigments and fats contained in the sample, a soxhlet extractor is used with a mixed solvent of benzene-ethanol (50/50 (volume%)). After 5 hours of treatment, defatted wool was prepared.
[0044]
<Grafting to treated fiber>
After adjusting the pH to 3.0 by adding dilute formic acid to an aqueous solution containing 6% by weight of Neukalgen 1515-2H (trade name, nonionic / anionic mixed surfactant manufactured by Takemoto Yushi Co., Ltd.) In addition, a predetermined amount of ammonium persulfate (APS) as a polymerization initiator was added to the total weight of the defatted wool and the graft monomer by 1.8% owf to prepare a graft processing solution. The bath ratio of the grafting solution was 1:15, wool was immersed, the temperature was raised from 25 ° C to 80 ° C over 45 minutes, and heat treatment was performed at 80 ° C for 60 minutes. After the treatment, it was washed with an aqueous solution containing 10% Neugen HC (trade name, non-ionic surfactant manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) at 85 ° C. for 30 minutes and dried at 105 ° C. for 2 hours. Table 1 shows the relationship between the graft processing conditions and the obtained processing rate.
[0045]
In addition, the processing rate of the sample to be processed when the graft polymerization was performed was obtained by the following equation.
Processing rate (%) = (B−A) / A × 100
In the above formula, A represents the weight of the sample before graft polymerization, and B represents the weight of the sample after graft polymerization. Each sample weight was measured after drying at 105 ° C. for 2 hours.
[0046]
(Table 1)

[0047]
In Table 1, THFA is tetrahydrofurfuryl acrylate, IBXM is isobornyl methacrylate, and 512A is dicyclopentenyloxyethyl acrylate.
From Table 1, it was confirmed that even if the monomers were different, the grafting process to wool progressed well, and that the processing rate to wool increased by increasing the monomer concentration.
In the following examples, IBXA: isobornyl acrylate, THF: tetrahydrofurfuryl methacrylate, 511A: dicyclopentenyl acrylate, and the like were used in addition to these graft monomers.
[0048]
<Silver adhesion, copper adhesion fiber>
The defatted wool was grafted using a silver salt or copper salt of methacrylic acid. That is, the grafting process to wool fiber includes 2.5% owf sodium persulfate, 85% formic acid (2 mL / L), and 40% owf methacrylic acid silver salt or copper salt, Then, wool fibers were dipped in a mixed solution prepared by adding 12% emulsifier (bath ratio 1:20) and heat-treated. After raising the temperature from room temperature to 80 ° C. over 20 minutes, the reaction was allowed to proceed for 40 minutes while maintaining the same temperature. After completion of the reaction, the mixture was washed with water and reduced and washed at 70 ° C. for 20 minutes in a mixed solution to which Neugen HC (1 mL / L) was added. After washing with water and air-drying, the moisture was adjusted in a standard state (20 ° C., 65% RH) to prepare a metal-containing processed wool fiber. Thus, grafted wool containing silver and copper could be prepared.
Also, without adding a polymerization initiator to the grafting solution, and without heating the grafting solution, defatted wool is soaked for 30 minutes at room temperature, taken out and washed with water to prepare copper-attached or silver-attached wool. did.
[0049]
<Dyeing method with various dyes>
Cricula pigment:
After 20 g of Indonesian crikula koji derived from samurai was boiled with 1,000 ml of water at 90 ° C. for 1 hour, the boiled aqueous solution was first filtered with filter paper, followed by a microfilter with a porous size of 5 μm and 1.2 μm. A liquid containing a filtered cricula koji extract dye (hereinafter simply referred to as “cricula dye” or “cricula”) is used as a clicula dyeing liquid, and acetic acid is added to the cricula dyeing liquid to adjust the pH to 4.5. The woolen fabric was dyed at 85 ° C. for 1 hour.
[0050]
Rack die, quintuplet, catechu, red cabbage, purple root:
As these dyeing agents, liquid plant dyes (commercial products, manufactured by Nanaka Tanaka Dye Store) obtained by extracting pigment components from each plant and concentrating them into liquids were used. Each dyeing agent is used for absorbance measurement after filtration in the same manner as the above-mentioned clicula pigment, and an aqueous solution containing 20% owf of plant dye is made weakly acidic (pH 5-6), and using this dye solution, a bath ratio of 1: The woolen cloth was dyed at 60 ° C. for 1 hour.
[0051]
Cochineal, Kihada:
Cochineal and yellowfin (commercial product, manufactured by Tanaka Nao Dye Store), 20% owf and 50% owf of the weight of wool, respectively, bath ratio set to 1:50, boiled in boiling water for 30 minutes, while hot I hesitantly took the most dye. Again, water was added to cochineal and yellowfin to obtain a second dyeing solution in the same manner as the first. After these dye solutions were combined and allowed to cool, the dyeing bath was first filtered with filter paper and then with a microfilter having a porous size of 5 μm. Hot water and 3% acetic acid were added to the filtrate so as to be 50 times the size of the woolen cloth, and the woolen cloth was dyed at 60 ° C. for 1 hour.
[0052]
Ai:
Wool cloth was dyed using Indian indigo liquor (commercial product, manufactured by Nanaka Tanaka Dye Store) according to the manufacturer's recommended saturated dyeing method.
Chemical dyes:
Direct dye C.I. Direct Black 51 (Kayaku Direct Fast Black conc.) A wool cloth was dyed at 90 ° C. for 1 hour in a dyeing solution of 5% owf and anhydrous sodium sulfate 30% owf.
[0053]
<Cochineal extraction and staining method>
Cochineal was subjected to hot water extraction twice as follows, and this extract was used as a staining bath.
A solution obtained by boiling 1000 mL of water containing 50 g of cochineal for 20 minutes was filtered through a stainless steel sieve (size: 200 mesh) to obtain a first extract. A solution obtained by adding 400 mL of water to the filtered cochineal and boiling it for 20 minutes was similarly filtered through a stainless steel sieve (size: 200 mesh) to obtain a second extract. Next, the 1st extract and the 2nd extract were mixed, this mixed aqueous solution was filtered with the filter paper and the micro filter, and the dyeing bath without an impurity was separated by filtration. To this, 300 mL of water was added to prepare a 3000 mL total cochineal dyeing bath.
[0054]
The sample to be treated (wool) was placed in the above-mentioned cochineal dyeing bath, the dyeing bath temperature was raised from room temperature to 98 ° C. over 40 minutes, and the sample was dyed by treatment at 98 ° C. for 1 hour. After completion of the dyeing, the dyeing bath was naturally allowed to cool to room temperature, and then the sample was taken out, washed with water, and dried at room temperature.
<Turmeric extraction and staining method>
The turmeric pigment was prepared by extracting a commercial product “Spring Turmeric” from Higa tea. Turmeric extraction and staining were performed in accordance with the above-described extraction and staining method for cochineal.
[0055]
<Mordant method>
The aluminum mordanting was performed by treating the sample to be treated (wool) with a 2 g / L baked alum aqueous solution. Copper mordanting was performed using a 2 g / L copper acetate aqueous solution, iron mordanting using 5 mL / 500 mL wood iron acetate aqueous solution, titanium mordanting using 5 mL / 500 mL titanium mordanting aqueous solution, and chromium mordanting using 5% chrome alum aqueous solution. The temperature and time of any mordant treatment were 60 ° C. and 30 minutes.
<Dyeing with gold-containing dyes>
As the metal-containing dye, Kayakalan Blue Black RL or Kayakalan Black 2RL was used. It dye | stained by processing at 98 degreeC for 1 hour using the dye of a 1g / L density | concentration. Dyeing with direct dye (Kayaku Direct Fast Black conc.) Was performed by treating at 98 ° C. for 1 hour in a dye bath containing a dye having a concentration of 1 g / L.
[0056]
<Preparation of Cricula Silk>
8.56 g of cricula koji packed in 1,000 mL of an aqueous sodium carbonate solution having a concentration of 12 g / L was added and scoured at 130 ° C. for 2 hours. The weight after scouring was 6.41 g (kneading reduction rate 25.1%).
Next, this cricula koji was extracted with water at 90 ° C. for 1 hour. Subsequently, cricula koji was extracted with ethyl alcohol for 5 hours using a Soxhlet extractor.
Using a laboratory autoclave (Sanyo MLS-3780), 62.45 g of crucible koji was treated at 120 ° C. for 1 hour, and further treated at 130 ° C. for 1 hour. The weight after the treatment was 52.61 g (weight reduction rate 15.76%). A cricula silk thread scoured in this way was prepared and used for testing.
[0057]
(Example 1) Graft damage experiment of grafted wool
Using IBXM, THFA, 512A as a graft monomer, grafted wool was produced as follows. After adjusting the pH to 2.5 by adding dilute formic acid to an aqueous solution containing 6% by weight of Neucalgen 1515-2H (trade name, non-ionic / anionic mixed surfactant manufactured by Takemoto Oil & Fats Co., Ltd.), IBXM and THFA at a predetermined concentration Alternatively, 512A was added, and a predetermined amount of ammonium persulfate as a polymerization initiator was added at 1.8% owf based on the total weight of the defatted wool and the graft monomer to prepare a graft processing solution. The bath ratio of the grafting solution was 1:15, wool was immersed, the temperature was raised from 25 ° C. to 80 ° C. over 45 minutes, and heat treatment was performed at 80 ° C. for 60 minutes. After the treatment, it was washed with an aqueous solution containing 10% Neugen HC (trade name, non-ionic surfactant manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) at 85 ° C. for 30 minutes and dried at 105 ° C. for 2 hours.
The graft monomer concentrations for some sample processing are shown in Table 1 above.
[0058]
As a result of grafting with IBXM, THFA, and 512A in this manner, grafted wool having processing rates of 14%, 32%, and 23%, respectively, could be prepared. The processing rate was about 0.2% even when grafting with methacrylic acid copper salt or silver salt.
According to the “individual method” in which 10 small brown beetles and one kind of test sample were placed in one small plastic incubator, a food damage test was conducted every week for up to 4 weeks. In addition, 10 young larvae (3rd and 4th instar) of Himemarukatobushimushi were placed in a small plastic incubator and stored in an incubator (temperature 24 ± 1 ° C.), and the feeding damage test was continued for 4 weeks. The test was repeated twice for the same sample, the sample weight was weighed every week, the average value was taken, and the damage ratio was calculated. Table 2 shows the obtained damage ratio.
[0059]
In the section of the sample in Table 2, the control group means untreated unprocessed defatted wool, IBXM, THFA and 512A mean the wool grafted with IBXM, THFA and 512A, respectively, copper Means wool grafted with a copper salt of methacrylic acid, and IBXM / copper and THFA / copper are grafted with a copper salt of methacrylic acid in a second stage on wool grafted with IBXM and THFA, respectively. It means processed wool. The eating damage test was repeated twice for each sample, and the average value of the results is shown in Table 2.
[0060]
(Table 2)

[0061]
As is apparent from Table 2, it was confirmed that the silkworm cutworm which was grafted with IBXM, THFA and 512A hardly caused damage (the damage ratio was almost 0%), and that the damage control material could be produced by grafting. In addition, when the wool grafted with IBXM and THFA was subsequently grafted with a copper salt of methacrylic acid, a 100% feeding damage suppressing effect was obtained. It can also be seen that the wool grafted with the copper salt of methacrylic acid is not damaged by damage compared to the control group.
Similar results can be obtained by using silver salt, zinc salt, cobalt salt, chromium salt, etc. instead of methacrylic acid copper salt, acrylic acid copper salt, silver salt, zinc salt, cobalt salt, chromium salt, etc. Obtained. Also, in the case of wool, in the case of wool damage test using rabbits, wild silks, sericin silkworms, and pre-scouring rabbits, wild silkworms, silkworms as well as grafted samples as above. In the same manner as above, the effect of suppressing food damage was observed.
[0062]
(Example 2) Change in mechanical properties of grafted wool
The change in mechanical properties of wool grafted with IBXM and THFA according to Example 1 was evaluated as to whether the strength and elongation of the fiber product deteriorated before and after the grafting. The obtained results are shown in Table 3.
[0063]
(Table 3)

As is apparent from Table 3, even when the wool was grafted, the degree of degradation of the strength and elongation of the wool before and after the grafting was slight, and it was proved that the mechanical practical performance was not deteriorated.
[0064]
(Example 3) Eating damage test of dyed wool by individual method
As a first step treatment, defatted wool is dyed with a cochineal dye, and then as a second step treatment for developing various hues, wool mordanted with various metal ions, or a metal-containing dye or direct dye About the dyed wool, the damage ratio was investigated by the method described below. According to the “individual method” in which 10 small brown beetles and one kind of test sample were placed in one small plastic incubator, a food damage test was conducted every week for up to 4 weeks. The eating damage ratio was determined from the change in sample weight at 2, 3, and 4 weeks after the start of the test. Table 4 shows the obtained results.
[0065]
(Table 4)

[0066]
In Table 4, “cochineal dyeing” means wool dyed using cochineal as a dye. Cochineal dye + Al means a sample that is dyed with wool using cochineal and then mordanted with a baked alum aqueous solution. Hereinafter, similarly, cochineal dye + Cu, Fe, Ti, Cr means wool dyed by mordanting using a copper acetate aqueous solution, a phytoacetic acid aqueous solution, a titanium mordanting aqueous solution, or a chrome alum aqueous solution instead of the baked alum aqueous solution. In addition, Kayakalan Blue Black RL, Kayakalan Black 2RL, and Kayaku Black conc. Are each obtained by dyeing defatted wool with a metal-containing dye, Kayakalan Blue Black RL or Kayakalan Black 2RL, or the direct dye Kayaku Direct Fast Black conc. It means wool.
[0067]
In Table 4, the outline of the mordanting conditions in the case of cochineal dyeing + Al, cochineal dyeing + Cu, cochineal dyeing + Fe, cochineal dyeing + Ti, cochineal dyeing + Cr, and the outline of the conditions of metal dyeing dyeing and direct dyeing are as follows. is there.
Aluminum alum was used as the Al mordant: 2 g / L at 60 ° C., 30 min.
Copper acetate was used as the Cu mordant: 2 g / L at 60 ° C., 30 min.
Wood Fe-acetate was used as Fe mordant: 5 cc / 500 cc, 60 ° C., 30 min.
A titanium mordant was used as the Ti mordant: 5 cc / 500 cc, 60 ° C., 30 min.
Chromium alum was used as the Cr mordant: 5% solution at 60 ° C., 30 min.
In addition, wool was dyed with a metal-containing dye such as Kayakalan Blue Black RL, Kayakalan Black 2RL, Kayaku Direct Fast Black conc.). Using 0.1% gold-containing dye, dyeing treatment was performed in boiling water for 1 hour.
As is apparent from Table 4, wool dyed with a metal-containing dye and a direct dye had a food damage-suppressing effect as compared with the target area.
[0068]
(Example 4) Eating damage test of dyed wool by batch method
The damage rate of the same sample as that used in Example 3 was evaluated by the “batch method”.
The feeding damage test was conducted by the “collective method” in which 10 kinds of test samples were coordinated to one large plastic incubator at a substantially constant distance. Incidentally, 100 large brown beetle larvae were placed in this large plastic incubator, and the feeding damage test was conducted until the feeding damage time reached 4 weeks. The eating damage ratio was calculated from the sample weight change at 3 and 4 weeks after the start of the test. The results obtained are shown in Table 5.
[0069]
(Table 5)

As is clear from Table 5, wool dyed with metal-containing dyes and direct dyes was most effective in inhibiting damage.
[0070]
(Example 5) Eating damage test of dyed wool dyed with natural dye
The rate of feeding damage of defatted wool against the brown beetle was examined with various dyes (cricula, lacquer, cochineal, pentaploid, catechu, red cabbage, purple root, indigo, yellowfin, direct dye C.I. Direct Black 5). The feeding damage test was conducted every week for up to 4 weeks by an individual method in which a test sample and 10 euglena larvae were placed in a small plastic incubator. In Table 6, IBXM / red cabbage and 512A / red cabbage each mean a sample dyed with red cabbage in the same manner as in Example 5 after grafting wool by the method of Example 1. The eating damage ratio was calculated from the sample weight change at 1, 2, 3, and 4 weeks after the start of the test. The results obtained are shown in Table 6. Table 6 also shows the hues of the objects to be dyed.
[0071]
(Table 6)

[0072]
As is clear from Table 6, the amount of damage to raw unprocessed wool (target zone) was low until the first week of the damage test, but the amount of damage gradually increased from around the second week. Over four weeks, over 70% of the sample was consumed. The amount of damage caused by the brown pine wigworm on the wool dyed with purple root was large, and the amount of damage was about 60% after 4 weeks of the damage test. The damage rate of wool dyed with natural dyes such as clicula, lacquer, cochineal, pentaploid, atekyu, red cabbage, indigo, yellowfin, etc. is low, and the damage rate after 4 weeks is around 15%. The damage ratio of wool dyed with dye was about 30%. Moreover, the wool damage grafted with IBXM, 512A was further dyed with red cabbage, so that the effect of inhibiting damage to food was substantially 100%.
[0073]
(Example 6) Eating damage test of rabbit yarn
Using 512A as a grafting monomer, the rabbit silkworm grafted by the same method as in Example 1 was subjected to a feeding damage test. The eating damage ratio was calculated from the sample weight change at 1, 2, 3, and 4 weeks after the start of the test. Table 7 shows the obtained results.
(Table 7)

[0074]
As can be seen from Table 7, the raw rabbit silkworm has a low rate of damage within 1 week of the damage test, but the damage rate gradually increased from around the second week, and the sample was taken at 4 weeks. More than 70% of them were eaten up. On the other hand, the damage ratio of the rabbit yarn grafted according to the present invention is extremely small, and is 10% or less even after 4 weeks, and it can be seen that the damage damage of the rabbit yarn is significantly reduced by grafting.
[0075]
(Example 7) Eating damage test of sample containing catechin and tannic acid
When dyeing wool with black direct dye (CI Direct Black 51 (Kayaku Direct Fast Black conc.)), Can catechin and tannic acid be added to the dyeing bath and dyed to prepare a material with a food damage control function? Note that tannic acid used is a product manufactured by Wako Pure Chemical Industries, Ltd., and catechin is a product manufactured by Wako Pure Chemical Industries, Ltd.
Table 8 summarizes the sample numbers and sample preparation methods.
[0076]
(Table 8)

[0077]
Next, the feeding damage test of the dyed processed wool described in Table 8 was performed. That is, 10 specimens of each of them were placed in a plastic container and each sample was subjected to a food damage test by an individual method. Table 9 shows the average value of the percentage of damage caused by repeating the test five times for each sample.
[0078]
(Table 9)

[0079]
As is clear from Table 9, (1) tannic acid and catechin have an effect of inhibiting the damage of rotifer, and (2) dyeing in a dye bath containing tannic acid and catechin, or (3) normal It was found that, even after treatment with tannic acid or an aqueous catechin solution as a post-treatment after dyeing in this step, it has an effect of suppressing damage to food.
[0080]
(Example 8) Spray treatment
Each graft processing aqueous solution used in Example 1 was sprayed on the defatted wool surface with a spray device. When the food damage test was performed on those dried at room temperature, it was confirmed that the food damage ratio of each sample was remarkably reduced as in Example 1.
[0081]
(Example 9) Durability and damage test.
The grafted wool by IBXM, the grafted wool by THFA, and the grafted wool by 512A prepared in Example 1 were washed with a test liquid containing soap as a main component according to a JIS standard washing test (JIS L1045). When the eating damage test of various graft-processed wool after the washing test was conducted, the values were the same as the eating damage ratio shown in Table 2, and the eating damage characteristics were not changed by washing.
[0082]
(Example 10) Inhibition effect of zinc-fouling wool
The damage ratio of the wool grafted with the zinc salt of methacrylic acid instead of the copper salt of methacrylic acid used in Example 1 was almost the same as that of the wool processed with the copper salt of methacrylic acid.
In the above examples, wool and rabbit yarns with thick fibers and easy grafting were used as the treated samples. However, the material is not limited to wool only. In addition, wild silk yarns and sericin from these silk yarns are used. Even when the silk fibroin fiber from which the cocoon was removed was used, and even when rabbit silk, wild silk yarn, etc. before the scouring treatment were used, the same effect of suppressing damage to food was obtained.
[0083]
【The invention's effect】
According to the food damage inhibitor of the present invention, it contains a specific (meth) acrylic acid derivative and / or a polymer thereof, or a metal salt of a specific (meth) acrylic acid derivative as an active ingredient. In addition, it can exhibit an excellent food damage control function.
According to the food damage inhibiting material of the present invention, natural protein fibers and fiber products are grafted using the above-mentioned specific substances as graft monomers, so that the rate of damage caused by fiber pests is reduced and the food damage to the fibers and fiber products is reduced. It is possible to prevent damage from insects. In addition, the mechanical properties of the fiber product remain almost unprocessed with the grafting process, and the properties when not processed are not significantly reduced. Also, unlike conventional techniques that avoid fiber pests by using insecticides, insecticides, sublimation insecticides and control agents that are harmful to human livestock, the food damage control material of the present invention is harmless to human livestock and is in contact with textile products. However, there is no danger of smearing the textile or changing the color of the textile.
[0084]
Further, the food damage inhibiting material of the present invention can be obtained by immersing the natural protein fiber and the fiber product in the aqueous dispersion or solvent dispersion of the graft monomer, or by using these liquids in a spray method or the like. In addition, it can also be produced by treating a textile product, and can be expressed having an excellent ability to suppress food damage. This grafted material is excellent in washing resistance, and the effect of inhibiting damage after washing is not diminished and lasts for a long time.
According to the present invention, it is also possible to change the degree of damage prevention of the material by controlling the grafting rate.
[0085]
Further, according to the present invention, the fiber and the fiber product are dyed by adding a food damage controlling substance such as tannic acid or catechin to a dye bath of a conventionally known dye, or with a conventionally known dye. After dyeing the fiber product, the mordanting treatment of immersing the dye in the metal aqueous solution for the purpose of fixing the dye in the fiber and the fiber product can prevent damage to the fiber and the fiber product from insects.
According to the present invention, in addition to wool, rabbit silk, wild silk thread, and silk fibroin fiber from which sericin has been removed from these silk threads are used as a material to be treated. Even when rabbit yarn, wild silk yarn or the like is used, the same effect of suppressing damage to food can be obtained.
[0086]
Since the material having the food damage suppression function of the present invention is excellent in durability of the effect of the food damage suppression function, for example, clothing such as underwear, shirts, blouses, pajamas, bedding, towels, handkerchiefs, bandages, etc. It is suitable as a product having various food damage control functions or as a material for food damage control functional products such as mats, sheets, cotton bodies, and pulverized bodies.
Moreover, the raw material with the food damage suppression function of the present invention can be used not only in the clothing field but also in the agriculture and horticulture fields.

Claims (6)

The following general formula [I]:
CH ₂ = C (R) COOXY [I]
(However, in general formula [I],
R is H or CH ₃
X is _{(CH 2) a O b (} a is 0 to 4, b is 0 or 1.),
Y is a fluorinated alkyl group represented by (1) (CF ₂ ) _c Z (c is 1 to 10, Z is H or F),
(2) a tetrahydrofurfuryl group, or (3) a tricyclo [5,2,1,0 ^2,6 ] decanyl group or a decenyl group. )
A (meth) acrylic acid derivative represented by the following formula, a polymer thereof, a combination of the derivative and the polymer, or the following general formula [II]:
CH ₂ = C (R) COOZ [II]
(In the general formula [II], R is H or CH ₃ , and Z is a metal selected from iron, silver, copper, zinc, cobalt, and chromium .)
A metal salt of a (meth) acrylic acid derivative represented by: or a (meth) acrylic acid derivative represented by the general formula [I], a polymer thereof, or a combination of the derivative and the polymer, and a general formula An inhibitor of insect damage to insects having insect damage to fibers, characterized by comprising a mixture with a metal salt of a (meth) acrylic acid derivative represented by [II] as an active ingredient. The insect damage-inhibiting agent for insects having an insect damage to fibers according to claim 1 , wherein the insect damage insect is an insect selected from the order Coleoptera: Coleoptera: Coleoptera: Bombycidae, and: . 3. A material for controlling food damage comprising a fiber or a fiber product to which the food damage inhibitor according to claim 1 is attached, wherein the fiber or fiber product contains silk protein fiber and fiber product containing catechin or tannic acid, and wool keratin fiber. And a natural protein fiber selected from textile products or a textile product, a material for controlling damage to insects having damage to fibers . The catechin or tannic acid, wherein the natural protein fibers or concentration textiles 0. Either stained with dye bath containing 5-3% of catechin or tannic acid, or does not contain a catechin or tannic acid the fibers or fiber products after staining with the dye bath, the concentration 0. claim 3, characterized in that it has to be contained in the fibers or fiber products by 5-3% of immersion to mordant treatment in an aqueous solution of catechin or tannic acid A material for controlling damage to insects having damage to the fibers described above . Claim 1 or 2 predation inhibitor according silk protein fibers and textiles, as well as the concentration of insect damage suppression material comprising by adhering to the natural protein fibers or fiber products selected from wool keratin fibers and textiles from 0.5 to 3 % of either stained with catechin or dyeing bath containing tannic acid, or the insect damage suppression material after staining with a dye bath containing no catechin or tannic acid concentration 0. an aqueous solution of 5-3% of catechin or tannic acid A method for producing a material for controlling damage to insects having a damage to fibers, characterized by dipping and mordanting . A natural protein fiber or fiber product grafted with an active ingredient of the food damage inhibiting agent according to claim 1 or 2 , wherein the protein is selected from silk protein fiber and fiber product and wool keratin fiber and fiber product. predation suppression material consisting of the product concentration 0. either stained with dye bath containing 5-3% of catechin or tannic acid, or after staining the insect damage suppression material in the dyebath containing no catechin or tannic acid concentration 0 A method for producing a food damage-suppressing material for insects having a food damage to fibers, characterized by immersing in an aqueous solution of 5-3% catechin or tannic acid and mordant treatment .