WO2007004389A1 - Anti-bacterial film - Google Patents

Anti-bacterial film Download PDF

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Publication number
WO2007004389A1
WO2007004389A1 PCT/JP2006/311749 JP2006311749W WO2007004389A1 WO 2007004389 A1 WO2007004389 A1 WO 2007004389A1 JP 2006311749 W JP2006311749 W JP 2006311749W WO 2007004389 A1 WO2007004389 A1 WO 2007004389A1
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WIPO (PCT)
Prior art keywords
isothiocyanate
film
antibacterial
shellac
ester
Prior art date
Application number
PCT/JP2006/311749
Other languages
French (fr)
Japanese (ja)
Inventor
Shuzo Nakagawa
Original Assignee
Techno Trading & Consultant Co., Ltd.
Nakagawa, Yoshihiro
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Techno Trading & Consultant Co., Ltd., Nakagawa, Yoshihiro filed Critical Techno Trading & Consultant Co., Ltd.
Priority to JP2007523388A priority Critical patent/JP5150254B2/en
Publication of WO2007004389A1 publication Critical patent/WO2007004389A1/en

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    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L3/00Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/34Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
    • A23L3/3454Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
    • A23L3/3463Organic compounds; Microorganisms; Enzymes
    • A23L3/3535Organic compounds containing sulfur
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/40Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
    • A01N47/46Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=C=S groups

Definitions

  • the present invention relates to an antibacterial film containing a volatile drug.
  • Volatile oily antibacterial substances such as isothiocyanate esters typified by isothiocyanate are known as substances that prevent and inhibit the growth of molds in foods.
  • Patent Document 1 proposes a fungicides using the isothiocyanate esters.
  • This anti-mold sheet has a structure in which isothiocyanate, which is a volatile chemical, and a predetermined resin are kneaded and the kneaded product is sandwiched with a gas permeation restricting layer.
  • Patent Document 1 JP 2003-171208
  • the kneading resin can be kneaded with isothiocyanate, can be reduced in viscosity, and can be kneaded at a relatively low temperature, resulting in low chemical loss.
  • rosin, rosin esters, or modified substances thereof are used.
  • IPCS International Chemical Safety Program
  • rosin is known to decompose on heating to produce irritating fumes and to cause asthma by repeated or long-term inhalation of such fumes.
  • IPCS International Chemical Safety Program
  • the present invention (1) is an antibacterial film obtained by blending isothiocyanates with a shellac-based adhesive and sanding the blend with a film.
  • the present invention (2) is an isothiocyanate ester isothiocyanate ester and a cyclodextrin inclusion compound of the isothiocyanate ester, and one of the films is a gas permeable film.
  • the gas permeable film force is gradually released immediately after use, so that a high concentration of isothiocyanate is used from the initial stage of use.
  • Acidic esters can be secured and external moisture is gradually absorbed through the water vapor permeable film, and the cyclodextrin inclusion compound of the isothiocyanate reacts with the moisture to remove the isothiocyanate.
  • long-term sustainability of isothiocyanate ester release can be ensured (two-stage sustained release).
  • the antibacterial film according to the best mode is a kneaded material layer 1 in which an isothiocyanate ester is blended with a shellac-based adhesive in a gas permeable film 2 and a water vapor permeable film 3. It has a structure with a sound.
  • the kneaded material layer 1 contains “isothiocyanate esters” as an immediate active ingredient.
  • isothiocyanate refers to isothiocyanate and its derivatives. For example, methyl isothiocyanate, ethyl isothiocyanate, n-propyl isothiocyanate, isopropyl isothiocyanate, n-isothiocyanate. Examples include chill, isobutyl isothiocyanate, isoamyl isothiocyanate, aryl isothiocyanate, isothiocyanate phenol, and benzyl isothiocyanate.
  • the esters may be chemically synthesized or derived from natural products, but are preferably derived from natural products from the viewpoint of biological safety.
  • a natural product-derived material it is preferable to use the above-mentioned substance derived from a natural shark rust or a power pear extract.
  • extraction refers to a steam distillation method or the like.
  • the kneaded material layer 1 contains “cyclodextrin inclusion compound of isothiocyanate” as a sustained-release active ingredient.
  • cyclodextrin is a cyclic oligosaccharide obtained by allowing an enzyme (cyclodextrin glucanotransferase) to act on starch.
  • ⁇ -cyclodextrin, ⁇ -cyclodextrin, ⁇ -cycle Rhodextrin can be mentioned, and ⁇ -cyclodextrin is preferred.
  • cyclodextrin inclusion compound of isothiocyanate esters refers to those in which isothiocyanate esters are encapsulated inside the inside of the donut-shaped ring of cyclodextrins (in the cavity). This inclusion compound is available from Shisui Minato Seika Co., Ltd. under the trade name Dexy Pearl®-100. In addition to the isothiocyanate esters, other substances such as isothiocyanate esters generally have odors as required, and foods and their odors!
  • fragrance or deodorant such as cinnamate, vanillin, gel acetate, pepper oil, ethyl acetate, etc. May be contained.
  • the kneaded material layer 1 uses a shellac-based adhesive as a base resin.
  • a shellac-based adhesive is a natural product obtained by refining the scab-like material secreted by the scale scale insect, called Laccifer lacca Kerr.
  • seed rack, refined shellac, and decolorized shellac that are raw materials for shellac.
  • white shellac There is white shellac.
  • the shellac-based adhesive is available under the trade name “Unique Paper Varnish FZA-5714-1”, for example.
  • the kneaded material layer 1 may contain various additives as necessary.
  • release accelerators for improving the release control performance of isothiocyanate esters for example, oil such as coconut oil and corn oil, cellulose fiber, cellulose powder) Cellulose, etc., inorganic substances such as titanium oxide, calcium silicate, etc.
  • anti-oxidation agents for example, BHT, vitamin C, etc.
  • adhesion aids for example, rubber adhesives, acrylic adhesives, etc.
  • Isothiocyanate esters and cyclodextrin of isothiocyanate ester The kneading ratio of isothiocyanate esters in the kneaded mixture of the clathrate compound and the shellac base adhesive is from 0.1 to 100 parts by weight with respect to 100 parts by weight of the kneaded product. 30.0 parts by weight is preferred, and 1.0-20. 0 parts by weight is more preferred.
  • the gas permeable film 2 is not particularly limited as long as it is permeable to volatilized isothiocyanate esters.
  • the water vapor permeable film 3 is not particularly limited as long as it is water vapor permeable, but is preferably one having a water vapor permeability (JIS Z 0208) force of 40 gZm 2 ′ 24h, for example, (1) PET film with a thickness of 9-16 ⁇ , (2) Polyurethane film with a thickness of 1-20 ⁇ , (3) Chlorinated polypropylene film with a thickness of 1-10 ⁇ m, (4) Thickness of 1-10 ⁇ m Examples thereof include a butyl chloride film, (5) a butyl chloride copolymer film having a thickness of 1 to 10 ⁇ , and (6) an ethylene acetate acetate copolymer film having a thickness of 1 to ⁇ .
  • JIS Z 0208 water vapor permeability
  • antibacterial is a concept that includes not only antibacterial in a narrow sense but also antifungal.
  • the film can be used, for example, on a food or in a form for coating or packaging food. Thereby, it is possible to achieve antibacterial, antifungal, insectproof and freshness maintenance of the food.
  • the amount of the isothiocyanate used above is not particularly limited, but is preferably 30 to 6000 mg with respect to the volatile drug-containing adhesive sheet lm 2 .
  • the antibacterial sheets (7 ⁇ 20 cm) of Production Examples 1 and 2 were coated on two commercially available cuttings and allowed to stand, and the occurrence of mold over time was observed.
  • a sample coated with the same size PP film was also tested.
  • force cracks occurred on the cutting bar 4 days after the start of the test.
  • the sheet produced in Production Example 1 showed no mold even after 30 days, and the sheet produced in Production Example 2 was strong, with no mold observed for more than 60 days.
  • the sheets of Production Example 1 and Production Example 2 have a fungicidal effect of 30 days or more, and also have high antibacterial activity in both culture tests of Escherichia coli and Staphylococcus aureus. And was found to be bactericidal.
  • FIG. 1 is a sectional view of a sheet according to the best mode.

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • Dentistry (AREA)
  • Nutrition Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Food Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Microbiology (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
  • Laminated Bodies (AREA)

Abstract

[PROBLEMS] To discover a resin which shows a good compatibility with an isothiocyanate ester when kneaded with the ester, produces no air bubble remaining therein when sandwiched between films, and is excellent in biological safety, and to provide a novel anti-bacterial sheet comprising a combination of an isothiocyanate ester and the resin. [MEANS FOR SOLVING PROBLEMS] An anti-bacterial film produced by blending an isothiocyanate ester with a shellac-type adhesive and sandwiching the resulting blend between films.

Description

明 細 書  Specification
抗菌フィルム  Antibacterial film
技術分野  Technical field
[0001] 本発明は、揮発性薬剤を含有する抗菌フィルムに関する。  [0001] The present invention relates to an antibacterial film containing a volatile drug.
背景技術  Background art
[0002] イソチォシアン酸ァリルに代表されるイソチォシアン酸エステル類等の揮発性油状 抗菌物質は、食品でのカビの発生ゃ菌の増殖等を防止'抑制する物質として既知で ある。ここで、特許文献 1には、このイソチォシアン酸エステル類を使用した防カビシ ートが提案されている。この防カビシートは、揮散性薬剤であるイソチォシアン酸ァリ ルと所定の榭脂とを混練し、当該混練物をガス透過規制層でサンドした構成を採つ ている。  [0002] Volatile oily antibacterial substances such as isothiocyanate esters typified by isothiocyanate are known as substances that prevent and inhibit the growth of molds in foods. Here, Patent Document 1 proposes a fungicides using the isothiocyanate esters. This anti-mold sheet has a structure in which isothiocyanate, which is a volatile chemical, and a predetermined resin are kneaded and the kneaded product is sandwiched with a gas permeation restricting layer.
特許文献 1 :特開 2003— 171208  Patent Document 1: JP 2003-171208
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0003] ここで、当該混練用榭脂としては、イソチォシアン酸ァリルと混練可能であること、粘 度を低下させることが可能であること、比較的低温で混練できるために薬剤ロスが少 ないこと、コーティングし易いこと等の理由で、ロジン、ロジンエステル又はこれらの変 性物が使用されている。しかしながら、これらの混練用榭脂を使用した場合には、得 られた製品に気泡が入り易ぐ得られた製品の外観が悪くなるという問題があった。更 には、国際化学物質安全性計画 (IPCS)によると、ロジンは、加熱すると分解し刺激 性フュームを生じ、当該フューム等の反復又は長期の吸入により喘息を起こすことが 知られている。そこで、イソチォシアン酸エステル類と混練した際に相性がよぐサン ドした際に気泡が残存せず、かつ、生体安全性に優れた榭脂を見出すと共に、イソ チォシアン酸エステル類と当該榭脂を組み合わせた新規な抗菌シートを提供するこ とを目的とする。 [0003] Here, the kneading resin can be kneaded with isothiocyanate, can be reduced in viscosity, and can be kneaded at a relatively low temperature, resulting in low chemical loss. For reasons such as easy coating, rosin, rosin esters, or modified substances thereof are used. However, when these kneading resins are used, there is a problem that the appearance of the obtained product is deteriorated because air bubbles easily enter the obtained product. In addition, according to the International Chemical Safety Program (IPCS), rosin is known to decompose on heating to produce irritating fumes and to cause asthma by repeated or long-term inhalation of such fumes. Thus, when a sand that is compatible with the isothiocyanate ester is found to be compatible with the foam, no bubbles remain and the biosafety of the fat is found. The purpose is to provide a new antibacterial sheet combined.
課題を解決するための手段  Means for solving the problem
[0004] 本発明者は鋭意研究の結果、榭脂としてシェラックベースの接着剤を採用すること により、上記の課題を達成できることを見出し、以下の発明(1)及び (2)を完成させた ものである。 [0004] As a result of diligent research, the present inventor has adopted a shellac-based adhesive as a resin. Thus, the inventors have found that the above-mentioned problems can be achieved, and have completed the following inventions (1) and (2).
[0005] 本発明(1)は、イソチォシアン酸エステル類をシェラックベースの接着剤とブレンド し、当該ブレンド物をフィルムでサンドして得られる抗菌フィルムである。  [0005] The present invention (1) is an antibacterial film obtained by blending isothiocyanates with a shellac-based adhesive and sanding the blend with a film.
[0006] 本発明(2)は、イソチォシアン酸エステル類力 イソチォシアン酸エステル類及び 前記イソチォシアン酸エステル類のサイクロデキストリン包接ィ匕合物であると共に、前 記フィルムの一方がガス透過性フィルムであり他方が水蒸気透過性フィルムである、 前記発明(1)の抗菌フィルムである。  [0006] The present invention (2) is an isothiocyanate ester isothiocyanate ester and a cyclodextrin inclusion compound of the isothiocyanate ester, and one of the films is a gas permeable film. The antibacterial film of the invention (1), wherein the other is a water vapor permeable film.
発明の効果  The invention's effect
[0007] 本発明(1)によれば、イソチォシアン酸エステル類と混練した際に相性がよぐサン ドした際に気泡が残存せず、かつ、長期間継続的に使用しても疾病 (例えば喘息)の 原因物質を放出せず生体安全性に優れて!/ヽると!ヽぅ効果を奏する。  [0007] According to the present invention (1), no bubbles remain when sanded well when kneaded with isothiocyanates, and even if used continuously for a long period of time (for example, It does not release the causative agent of asthma) and has excellent biological safety!
[0008] 本発明(2)によれば、揮発性の高 、イソチォシアン酸エステル類が一方のフィルム であるガス透過性フィルム力 使用直後から徐放されるので、使用の初期段階から高 濃度のイソチォシアン酸エステル類を担保できると共に、水蒸気透過性フィルムを介 して外部の湿気を徐々に吸収し、イソチォシアン酸エステル類のサイクロデキストリン 包接ィ匕合物が当該水分と反応してイソチォシアン酸エステル類を放出する結果、イソ チォシアン酸エステル類放出の長期持続性も担保できる(二段階徐放性)という効果 を奏する。  [0008] According to the present invention (2), since the highly volatile and isothiocyanate esters are one film, the gas permeable film force is gradually released immediately after use, so that a high concentration of isothiocyanate is used from the initial stage of use. Acidic esters can be secured and external moisture is gradually absorbed through the water vapor permeable film, and the cyclodextrin inclusion compound of the isothiocyanate reacts with the moisture to remove the isothiocyanate. As a result of release, long-term sustainability of isothiocyanate ester release can be ensured (two-stage sustained release).
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0009] 以下、本発明に係る最良形態について説明する。まず、本最良形態に係る抗菌フ イルムは、図 1に示すように、ガス透過性フィルム 2と水蒸気透過性フィルム 3に、イソ チォシアン酸エステル類をシェラックベースの接着剤にブレンドした混練物層 1をサ ンドした構造を採っている。 Hereinafter, the best mode according to the present invention will be described. First, as shown in FIG. 1, the antibacterial film according to the best mode is a kneaded material layer 1 in which an isothiocyanate ester is blended with a shellac-based adhesive in a gas permeable film 2 and a water vapor permeable film 3. It has a structure with a sound.
[0010] ここで、混練物層 1中には、即時性有効成分として「イソチォシアン酸エステル類」を 含有する。ここで、 「イソチォシアン酸エステル類」とは、イソチォシアン酸エステル及 びその誘導体を指し、例えば、イソチォシアン酸メチル、イソチォシアン酸ェチル、ィ ソチオシアン酸 n—プロピル、イソチォシアン酸イソプロピル、イソチォシアン酸 n—ブ チル、イソチォシアン酸イソブチル、イソチォシアン酸イソァミル、イソチォシアン酸ァ リル、イソチォシアン酸フエ-ル、イソチォシアン酸ベンジルを挙げることができる。尚 、前記エステル類は、化学合成でも天然物由来でもよいが、生体安全性の観点から 天然物由来が好適である。天然物由来としては、天然ヮサビ又は力ラシ抽出物由来 の前記物質を用いることが好適である。ここで、「抽出」とは、水蒸気蒸留法などを指 す。 Here, the kneaded material layer 1 contains “isothiocyanate esters” as an immediate active ingredient. Here, “isothiocyanate” refers to isothiocyanate and its derivatives. For example, methyl isothiocyanate, ethyl isothiocyanate, n-propyl isothiocyanate, isopropyl isothiocyanate, n-isothiocyanate. Examples include chill, isobutyl isothiocyanate, isoamyl isothiocyanate, aryl isothiocyanate, isothiocyanate phenol, and benzyl isothiocyanate. The esters may be chemically synthesized or derived from natural products, but are preferably derived from natural products from the viewpoint of biological safety. As a natural product-derived material, it is preferable to use the above-mentioned substance derived from a natural shark rust or a power pear extract. Here, “extraction” refers to a steam distillation method or the like.
[0011] 更に、混練物層 1中には、徐放性有効成分として「イソチォシアン酸エステルのサイ クロデキストリン包接ィ匕合物」を含有する。ここで、「サイクロデキストリン」とは、澱粉に 酵素 (サイクロデキストリングルカノトランスフヱラーゼ)を作用させて得られる環状オリ ゴ糖であり、例えば、 α—サイクロデキストリン、 β—サイクロデキストリン、 γ—サイク ロデキストリンを挙げることができ、 β—サイクロデキストリンが好適である。また、「イソ チォシアン酸エステル類のサイクロデキストリン包接ィ匕合物」とは、サイクロデキストリ ンのドーナツ構造の輪の内側(空洞内)にイソチォシアン酸エステル類を包み込んだ ものを指す。この包接ィ匕合物は、塩水港精糖株式会社からデキシーパール Κ— 100 という商品名で入手可能である。尚、包接される物質は、イソチォシアン酸エステル 類以外にも、必要に応じて、他の物質、例えば、イソチォシアン酸エステル類には総 じて匂 、があり、食品とこれらの匂!、の相性が合わな 、場合に芳香を有する物質によ り上記匂いを変えたり消したりするために、芳香物質又は消臭物質、例えばケィ皮酸 、バニリン、酢酸ゲラ -ル、ペッパーオイル、酢酸ェチル等を含有していてもよい。  Furthermore, the kneaded material layer 1 contains “cyclodextrin inclusion compound of isothiocyanate” as a sustained-release active ingredient. Here, “cyclodextrin” is a cyclic oligosaccharide obtained by allowing an enzyme (cyclodextrin glucanotransferase) to act on starch. For example, α-cyclodextrin, β-cyclodextrin, γ-cycle Rhodextrin can be mentioned, and β-cyclodextrin is preferred. The “cyclodextrin inclusion compound of isothiocyanate esters” refers to those in which isothiocyanate esters are encapsulated inside the inside of the donut-shaped ring of cyclodextrins (in the cavity). This inclusion compound is available from Shisui Minato Seika Co., Ltd. under the trade name Dexy Pearl®-100. In addition to the isothiocyanate esters, other substances such as isothiocyanate esters generally have odors as required, and foods and their odors! In order to change or extinguish the above-mentioned odor by substances having a fragrance if they are not compatible, fragrance or deodorant such as cinnamate, vanillin, gel acetate, pepper oil, ethyl acetate, etc. May be contained.
[0012] 次に、混練物層 1は、シェラックベースの接着剤を基材榭脂とする。ここで、 「シエラ ック」とは、 Laccifer lacca Kerrと称されるラックカイガラムシが分泌する榭脂状物 質を精製した天然物であり、例えば、セラック原料であるシードラック、精製セラック、 脱色セラック、白色セラックがある。尚、当該シヱラックベースの接着剤は、例えば、「 ユニークペーパーワニス FZA— 5714— 1」という商品名で荒川塗料工業株式会社 力 入手可能である。 Next, the kneaded material layer 1 uses a shellac-based adhesive as a base resin. Here, “Sierrac” is a natural product obtained by refining the scab-like material secreted by the scale scale insect, called Laccifer lacca Kerr. For example, seed rack, refined shellac, and decolorized shellac that are raw materials for shellac. There is white shellac. Note that the shellac-based adhesive is available under the trade name “Unique Paper Varnish FZA-5714-1”, for example.
[0013] 更に、混練物層 1は、上記成分以外に、必要に応じて適宜各種添加剤を加えても よい。例えば、イソチォシアン酸エステル類の放出制御性能を向上させるための放出 促進剤(例えば、ヤシ油、コーン油等のオイル、セルロース繊維、セルロースパウダー 等のセルロース類、酸化チタン、ケィ酸カルシウム等の無機物等)、イソチォシアン酸 エステル類の安定性を向上させるための酸ィ匕防止剤(例えば、 BHT、ビタミン C等)、 接着強度を向上させるための既知の接着補助剤 (例えば、ゴム系接着剤、アクリル系 接着剤等)を挙げることができる。 [0013] Furthermore, in addition to the above components, the kneaded material layer 1 may contain various additives as necessary. For example, release accelerators for improving the release control performance of isothiocyanate esters (for example, oil such as coconut oil and corn oil, cellulose fiber, cellulose powder) Cellulose, etc., inorganic substances such as titanium oxide, calcium silicate, etc.), anti-oxidation agents (for example, BHT, vitamin C, etc.) to improve the stability of isothiocyanate esters, to improve adhesive strength And known adhesion aids (for example, rubber adhesives, acrylic adhesives, etc.).
[0014] イソチォシアン酸エステル類及びイソチォシアン酸エステルのサイクロデキストリン 包接化合物とシェラックベース接着剤との混練物中におけるイソチォシアン酸エステ ル類の混練割合は、混練物 100重量部に対して 0. 1〜30. 0重量部が好適であり、 1. 0-20. 0重量部がより好適である。  [0014] Isothiocyanate esters and cyclodextrin of isothiocyanate ester The kneading ratio of isothiocyanate esters in the kneaded mixture of the clathrate compound and the shellac base adhesive is from 0.1 to 100 parts by weight with respect to 100 parts by weight of the kneaded product. 30.0 parts by weight is preferred, and 1.0-20. 0 parts by weight is more preferred.
[0015] 次に、ガス透過性フィルム 2は、揮発したイソチォシアン酸エステル類に対して透過 性を有するフィルムである限り特に限定されず、例えば、延伸または無延伸ポリプロ ピレン、ポリエチレン (例えば直鎖状低密度ポリエチレン、低密度ポリエチレン等)、ポ リエチレンテレフタレート、ポリメチルペンテン、生分解性フィルム {例えば、ポリ乳酸フ イルム (植物系(例えば、トウモロコシゃ澱粉)及び石油系 }等を挙げることができる。 尚、これらのフィルムは単独で使用してもよぐあるいは 2種以上を貼り合わせたもの であってもよい。また、ガス透過性フィルム 2の厚さは、好適には 10〜: ίΟΟ /ζ πι、より 好適には 30〜70 μ mである。  [0015] Next, the gas permeable film 2 is not particularly limited as long as it is permeable to volatilized isothiocyanate esters. For example, stretched or unstretched polypropylene, polyethylene (for example, linear) Low-density polyethylene, low-density polyethylene, etc.), polyethylene terephthalate, polymethylpentene, biodegradable films {for example, polylactic acid films (plant-based (for example, corn starch) and petroleum-based)} and the like. These films may be used alone or in combination of two or more, and the thickness of the gas permeable film 2 is preferably 10 to: ίΟΟ / ζ. πι, more preferably 30 to 70 μm.
[0016] 次に、水蒸気透過性フィルム 3は、水蒸気透過性である限り特に限定されないが、 水蒸気透過率 (JIS Z 0208)力 〜 40gZm2 ' 24hのものが好適であり、例えば、 (1)厚さ 9〜16 πιの PETフィルム、 (2)厚さ 1〜20 πιのポリウレタンフィルム、 (3) 厚さ 1〜10 μ mの塩素化ポリプロピレンフィルム、 (4)厚さ 1〜10 μ mの塩化ビュルフ イルム、 (5)厚さ 1〜10 πιの塩化ビュル系共重合体フィルム、 (6)厚さ 1〜20 πι のエチレン.酢酸ビュル共重合体フィルムを挙げることができる。 Next, the water vapor permeable film 3 is not particularly limited as long as it is water vapor permeable, but is preferably one having a water vapor permeability (JIS Z 0208) force of 40 gZm 2 ′ 24h, for example, (1) PET film with a thickness of 9-16 πι, (2) Polyurethane film with a thickness of 1-20 πι, (3) Chlorinated polypropylene film with a thickness of 1-10 μm, (4) Thickness of 1-10 μm Examples thereof include a butyl chloride film, (5) a butyl chloride copolymer film having a thickness of 1 to 10 πι, and (6) an ethylene acetate acetate copolymer film having a thickness of 1 to πι.
[0017] 次に、本最良形態に係る抗菌用フィルムの用途について説明する。ここで、「抗菌」 とは、狭義の抗菌のみならず、抗カビも包含する概念である。本フィルムは、例えば 食品上に載せたり、食品を被覆又は包装する形態で使用できる。これにより、上記食 品の抗菌'防カビ、防虫、鮮度保持を達成することができる。尚、上記に使用されるィ ソチオシアン酸エステル類の量は、特に限定されないが、揮散性薬剤含有粘着シー ト状物 lm2に対して 30〜6000mgが好適である。 実施例 Next, the use of the antibacterial film according to the best mode will be described. Here, “antibacterial” is a concept that includes not only antibacterial in a narrow sense but also antifungal. The film can be used, for example, on a food or in a form for coating or packaging food. Thereby, it is possible to achieve antibacterial, antifungal, insectproof and freshness maintenance of the food. The amount of the isothiocyanate used above is not particularly limited, but is preferably 30 to 6000 mg with respect to the volatile drug-containing adhesive sheet lm 2 . Example
[0018] 以下、実施例を参照しながら本発明を具体的に説明する。尚、本発明の技術的範 囲は、以下の実施例により何ら限定されるものではない。  Hereinafter, the present invention will be specifically described with reference to examples. The technical scope of the present invention is not limited in any way by the following examples.
[0019] 製诰例 1 [0019] Example 1
イソチォシアン酸ァリル 10重量部とシェラックベース接着剤(ユニークペーパーヮ- ス FZA— 5714— 1 (商標)、荒川塗料工業株式会社製) 90重量部とを混練し、当該 混練物をガス透過性フィルム (OTP35M (商標) 大塚テクノ株式会社製:酸素透過 量 9000cc/m2 ' 24h、 50 m)でサンド(塗工量 5g/m2)した後、 80〜120。Cで 30秒 加熱し、本例に係るフィルムを得た。 10 parts by weight of isothiocyanate allyl and 90 parts by weight of shellac base adhesive (unique paper base FZA-5714-1 (trademark), manufactured by Arakawa Paint Industry Co., Ltd.) are mixed with the gas-permeable film ( OTP35M (trademark) manufactured by Otsuka Techno Co., Ltd .: Oxygen permeation amount 9000cc / m 2 '24h, 50 m) sand (coating amount 5 g / m 2 ), then 80-120 The film according to this example was obtained by heating at C for 30 seconds.
[0020] 製诰例 2 [0020] Ironmaking example 2
イソチォシアン酸ァリル 10重量部、イソチォシアン酸ァリルを包接したサイクロデキ ストリン (塩水港精糖株式会社製、デキシーパール K 100) 10重量部及びシェラッ クベース接着剤(ユニークペーパーワニス FZA— 5714— 1 (商標)、荒川塗料工業 株式会社製) 80重量部とを混練し、当該混練物をガス透過性フィルム (OTP35M ( 商標) 大塚テクノ株式会社製:酸素透過量 9000cc/m2' 24h、 35 m)と水蒸気透 過性フィルム (OTP35H (商標) 大塚テクノ株式会社製:酸素透過量 13000cc/m2 · 24h、水蒸気透過量 32g/m2' 24h、 35 m)でサンドした後、 80〜120。Cで 30秒カロ 熱し、本例に係るフィルムを得た。 10 parts by weight of isothiocyanate allyl, 10 parts by weight of cyclodextrin clathrated with isothiocyanate allyl (Shimizu Minato Sugar Co., Ltd., Dixie Pearl K 100) and shellac base adhesive (unique paper varnish FZA-5714-1 (trademark), Arakawa Paint Industry Co., Ltd.) 80 parts by weight, and kneaded the gas-permeable film (OTP35M (trademark) Otsuka Techno Co., Ltd .: oxygen transmission rate 9000cc / m 2 '24h, 35 m) and water vapor transmission 80 to 120 after sanding with a temporary film (OTP35H (trademark) manufactured by Otsuka Techno Co., Ltd .: oxygen transmission rate 13000cc / m 2 · 24h, water vapor transmission rate 32g / m 2 '24h, 35m). The film according to this example was obtained by heating at C for 30 seconds.
[0021] 試験例 1 [0021] Test Example 1
上記製造例 1及び 2の抗菌シート (7 X 20cm)を市販の切り餅 2個上に被覆して放 置し、経時によるカビの発生状況を観察した。また、比較例として同サイズの PPフィ ルムを被覆したものも試験した。その結果、比較例は、試験開始 4日後に切り餅に力 ビが発生した。これに対し、製造例 1のシートは、 30日後においてもカビの発生は見 られず、製造例 2のシートに関しては、 60日以上もカビの発生が確認されな力つた。  The antibacterial sheets (7 × 20 cm) of Production Examples 1 and 2 were coated on two commercially available cuttings and allowed to stand, and the occurrence of mold over time was observed. As a comparative example, a sample coated with the same size PP film was also tested. As a result, in the comparative example, force cracks occurred on the cutting bar 4 days after the start of the test. In contrast, the sheet produced in Production Example 1 showed no mold even after 30 days, and the sheet produced in Production Example 2 was strong, with no mold observed for more than 60 days.
[0022] 試験例 2 [0022] Test Example 2
上記製造例 1及び 2の抗菌シートの抗菌効果を評価するために、特開平 11 332 534号公報に記載の方法に準じ、大腸菌(Escherichia coli IFO 3972)及び黄色ブド ゥ球菌 (Staphylococcus aureus subsp. aureus IFP 12732)の; ¾r SA',狭を? Tつ 7こ。尚、 試験に際しては、シャーレの全面を前記抗菌シートで被覆した。結果を表 1に示す。 In order to evaluate the antibacterial effect of the antibacterial sheets of Production Examples 1 and 2, according to the method described in JP-A-11 332 534, Escherichia coli IFO 3972 and Staphylococcus aureus subsp. Aureus IFP 12732); ¾r SA ', narrow? still, In the test, the entire petri dish was covered with the antibacterial sheet. The results are shown in Table 1.
[0023] [表 1] [0023] [Table 1]
Figure imgf000007_0001
Figure imgf000007_0001
[0024] 以上の結果より、製造例 1及び製造例 2のシートは、 30日以上の防カビ効果を奏す ることに加え、大腸菌及び黄色ブドウ球菌のいずれの培養試験においても、高い抗 菌性及び殺菌性を示すことが判明した。 [0024] From the above results, the sheets of Production Example 1 and Production Example 2 have a fungicidal effect of 30 days or more, and also have high antibacterial activity in both culture tests of Escherichia coli and Staphylococcus aureus. And was found to be bactericidal.
図面の簡単な説明  Brief Description of Drawings
[0025] [図 1]図 1は、本最良形態に係るシートの断面図である。 FIG. 1 is a sectional view of a sheet according to the best mode.

Claims

請求の範囲 The scope of the claims
[1] イソチォシアン酸エステル類をシェラックベースの接着剤とブレンドし、当該ブレンド 物をフィルムでサンドして得られる抗菌フィルム。  [1] An antibacterial film obtained by blending isothiocyanates with a shellac-based adhesive and sanding the blend with a film.
[2] イソチォシアン酸エステル類力 イソチォシアン酸エステル類及び前記イソチオシ アン酸エステル類のサイクロデキストリン包接ィ匕合物であると共に、前記フィルムの一 方がガス透過性フィルムであり他方が水蒸気透過性フィルムである、請求項 1記載の 抗菌フィルム。  [2] Strength of isothiocyanate ester A cyclodextrin inclusion compound of isothiocyanate ester and the isothiocyanate ester, and one of the films is a gas permeable film and the other is a water vapor permeable film. The antibacterial film according to claim 1, wherein
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EP2575452B1 (en) * 2010-05-23 2018-12-19 Takasago International Corporation Antimicrobial compositions
CN112425711A (en) * 2020-11-23 2021-03-02 东北林业大学 Acorn shell extract coating preservative and preparation method thereof
CN115590016A (en) * 2022-10-26 2023-01-13 中南大学湘雅三医院(Cn) Tumor sample storage device

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KR102374205B1 (en) * 2020-11-02 2022-03-16 주식회사 브니엘월드 Antibacterial Vinyl Wrap

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WO1995017819A1 (en) * 1993-12-28 1995-07-06 Rengo Co., Ltd. Controlled-release ait preparation, process for producing the same, and use thereof
JP2003171208A (en) * 2001-11-30 2003-06-17 Rengo Co Ltd Volatile chemical-containing pressure-sensitive adhesive sheetlike material

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EP2575452B1 (en) * 2010-05-23 2018-12-19 Takasago International Corporation Antimicrobial compositions
CN112425711A (en) * 2020-11-23 2021-03-02 东北林业大学 Acorn shell extract coating preservative and preparation method thereof
CN115590016A (en) * 2022-10-26 2023-01-13 中南大学湘雅三医院(Cn) Tumor sample storage device

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