JP3780589B2 - Antibacterial and antifungal composition - Google Patents

Description

【００１０】
（上式において、Ｘ，Ｙ，Ｚはハロゲンであり、これらは互いに同一であっても異なっていても良く、Ｒは有機基である。）
【００１１】
上式におけるＸ，Ｙ，ＺはＦ，Ｃｌ，Ｂｒ又はＩであり、又好ましいＲは構造中にイミド基を持つ有機基である。
上記(ロ) の好ましい具体例として以下の化合物がある。
即ち、Ｎ−（フルオロジクロロメチルチオ）フタルイミド、Ｎ，Ｎ−ジメチル−Ｎ’−（ジクロロフルオロメチルチオ）−Ｎ’−フェニルスルファミド、Ｎ，Ｎ−ジメチル−Ｎ’−（ジクロロフルオロメチルチオ）−Ｎ’−トリスルファミド、Ｎ−（トリクロルメチルチオ）フタルイミド、テトラクロルエチルチオテトラヒドロフタルイミド、Ｎ−トリクロルメチルチオ−４−シクロヘキセン−１，２−ジカルボキシイミド等である。
【００１２】
上記(ハ) の好ましい具体例として以下の化合物がある（尚、括弧《》内は慣用名である）。
即ち、α−［２−（４−クロロフェニル）エチル］−α−（１，１−ジメチルエチル）−１Ｈ−１，２，４−トリアゾール−１−イル−エタノール《デブコナゾール》、１−（４−クロロフェノキシ）３，３−ジメチル−１−（１Ｈ−１，２，４−トリアゾ−１−イル−２−ブタノン類《トリアジメフォン》、β−（４−クロロフェノキシ）−α−（１，１−ジメチル−エチル）−１Ｈ−１，２，４−トリアゾール−１−エタノール《トリアジメノール》、《ヘキサコナゾール》等のトリアゾール系化合物、２−ベンズイミダゾールカルバミン酸メチル、メチルベンズイミダゾリルカーバメート（ＢＣＭ）、メチル１−（ブチルカルバモイル）−２−ベンズイミダゾールカーバメイト（ベノミル）、２−（２’−フリール）−１Ｈ−ベンズイミダゾールおよび２−（４’−チアゾリル）ベンズイミダゾール（ＴＢＺ）等のベンズイミダゾール系化合物、１−［オルト−クロロ−β−［（パラ−クロロベンジル）オキシ］フェネチル］−イミダゾール１硝酸塩等のイミダゾール系化合物、１，２−ベンズイソチアゾリン−３−オン、２−（４−チオシアノメチルチオ）ベンズチアゾール等のチアゾール系化合物、インダゾール系化合物、ピラゾール系化合物、イソチアゾール系化合物等である。
【００１３】
尚、本発明における防黴性有機化合物は、防黴性に加え抗菌性を併せ持つものであっても良く、又１種類であっても良く、２種類以上を併用してもよい。
【００１４】
○層状珪酸塩
層状珪酸塩は、結晶層単位が互いに積み重なって層状構造をなしている珪酸塩であれば、特に制限されることなく使用でき、天然物と合成物のいずれでも良い。
好ましい層状珪酸塩として、粘土鉱物があり、その具体例として、以下のものがある。
即ち、モンモリロナイト、バイデライト、ヘクトライト、サポナイト等のスメクタイト族、バームキュライト族、イライト、白雲母、金雲母、黒雲母等の雲母族、マーガライト、クリントナイト等の脆雲母族、スドーアイト等の緑泥石族、カオリナイト、ハロイサイト等のカオリン類、アンチゴライト等の蛇紋石族等である。
その他の好ましい層状珪酸塩として以下のものがある。
即ち、マガディアイト、ケニヤアイト、カネマイト、マカタイト、アイラーアイト等の層状ナトリウム珪酸塩、トバモライト等の層状カルシウム珪酸塩、及び水酸イオン等の陰イオンをフッ素イオンで置換せしめた合成雲母等がある。
【００１５】
本発明における層状珪酸塩の粒径、含水量、陽イオン交換容量、色等は特に制限されないが、プラスチックやゴム或いは繊維等への練り込み加工に使用する場合、平均粒径１０μｍ以下の粉末が好ましく、より好ましくは平均粒径０．１〜７μｍの粉末であり、更に粒度分布が狭く、均一な粒径であることがより好ましい。
また、防黴性層状珪酸塩とした場合に充分な防黴効果を発揮させるために、陽イオン交換容量が０．１ｍｅｑ／ｇ以上であることが好ましい。
これらの層状珪酸塩は１種類のみを用いてもよいが、徐放性のコントロールをするために２種類以上を併用することもできる。
【００１６】
上記層状珪酸塩は、含まれるイオン交換可能な金属イオンを一部または全て他の金属イオンと置換して用いても良い。
交換する金属イオンは、イオン交換可能な金属イオンであれば特に制限はないが、リチウム、カルシウム、ナトリウム等が好ましい。
【００１７】
本発明における防黴性層状珪酸塩の層間に担持させた防黴性有機化合物の好ましい担持量の下限は、本発明における防黴性層状珪酸塩１００重量部（以下、単に部と略す）当たり０．１部であり、より好ましくは１部であり、特に好ましくは５部である。この担持量が少なすぎると防黴効果が低下する。尚、担持量の上限は層状珪酸塩と防黴性有機化合物の種類によって自ずから定り、不必要に多量に担持させた防黴性層状珪酸塩は、プラスチック等に練り込み加工する場合に、変色を起こしたり、徐放性のコントロールが難しくなる恐れがあるので、予備試験によって担持量の好適な上限を設定すると良い。
【００１８】
また、層状珪酸塩への防黴性有機化合物の担持方法は、特に制限はなく、基本的には防黴性有機化合物と層状珪酸塩を接触させれば良く、防黴性有機化合物が固相、液相、気相のいずれの状態であっても導入できる。
例えば、防黴性有機化合物が液相である場合の担持では、防黴性有機化合物を層状珪酸塩と混合攪拌し、その後乾燥、粉砕を行うか、或いは防黴性有機化合物を溶解性の高い溶媒に溶解した溶液と層状珪酸塩を混合撹拌し、その後ろ過、洗浄を行い、更に乾燥、粉砕することにより、防黴性有機化合物を層状珪酸塩に担持させた防黴性層状珪酸塩を得ることができる。尚、洗浄を行わず、そのまま乾燥、粉砕を行ってもよい。
【００１９】
上記の防黴性組成物の調製条件は特に制限はなく、使用する防黴性有機化合物及び層状珪酸塩の種類、防黴性有機化合物の担持量により適宜変化させることができる。具体的には、例えば、溶媒のｐＨは０．１〜１３、撹拌時間は０．５〜７２時間、撹拌温度は常温から例えば４０℃〜６０℃程度、撹拌数は１０〜１０００回／分であればよい。
【００２０】
○無機系抗菌剤
本発明における無機系抗菌剤は、銀及び銅等の抗菌性を有する金属イオンとして知られている抗菌性金属イオンを担持させた無機化合物であれば特に制限はなく、抗菌性金属イオンを担持させる無機化合物としては、例えば以下のものがある。
即ち、活性炭、活性アルミナ、シリカゲル等の無機系吸着剤、ゼオライト、ハイドロキシアパタイト、リン酸ジルコニウム、リン酸チタン、チタン酸カリウム、含水酸化ビスマス、含水酸化ジルコニウム、ハイドロタルサイト類化合物等の無機イオン交換体がある。
これらの無機化合物に抗菌性金属イオンを担持させる方法には特に制限はなく、今までに知られた担持方法はいずれも採用でき、例えば物理吸着又は化学吸着により担持させる方法、イオン交換反応により、担持させる方法、結合材により担持させる方法、抗菌性金属化合物を無機化合物に打ち込むことにより担持させる方法、蒸着、溶解析出反応、スパッタ等の薄膜形成法により無機化合物の表面に抗菌性金属化合物の薄層を形成させることにより担持させる方法がある。
【００２１】
上記の無機化合物の中で、無機イオン交換体は抗菌性金属イオンを強固に担持できることから好ましく、特に下記一般式［３］で示される四価金属リン酸塩系イオン交換体は好ましい化合物であり、特に好ましい抗菌剤は下記一般式［４］で示される化合物である
Ａ_ｂ Ｍ ^２ （ＰＯ_４）_３・ｎＨ_２Ｏ ［３］
（Ａはアルカリ金属イオン、アルカリ土類金属イオン、アンモニウムイオン又は水素イオンから選ばれる少なくとも１種のイオンであり、Ｍ^２は４価金属であり、ｎは０≦ｎ≦６を満たす数であり、ｂはｍｂ＝１を満たす正数である。但し、ｍはＡの価数である。）
Ｍ^１ _ａＡ_ｂ Ｍ ^２ （ＰＯ_４）_３・ｎＨ_２Ｏ ［４］
（Ｍ^１は銀、銅、亜鉛、錫、水銀、鉛、鉄、コバルト、ニッケル、マンガン、砒素、アンチモン、ビスマス、バリウム、カドミウム又はクロムから選ばれる少なくとも１種の金属イオンであり、Ａはアルカリ金属イオン、アルカリ土類金属イオン、アンモニウムイオン又は水素イオンから選ばれる少なくとも１種のイオンであり、Ｍ^２は４価金属であり、ｎは０≦ｎ≦６を満たす数であり、ａ及びｂはｌａ＋ｍｂ＝１を満たす正数である。但し、ｌはＭ^１の価数であり、ｍはＡの価数である。）
【００２２】
上記一般式［４］で示される化合物は、アモルファス又は空間群Ｒ3cに属する結晶性化合物であり、各構成イオンが３次元網目状構造を作る化合物を表す。
上記リン酸塩系抗菌剤は、日光に暴露したときの変色が少ないことから、３次元網目状構造を有する結晶性化合物が好ましい。
上記一般式［４］におけるＭ¹ は、いずれも抗菌性を示す金属として知られたものであり、これらの中で銀は、安全性の他、防黴、抗菌性及び防藻性を高めることができる金属として特に有効である。
【００２３】
上記一般式［４］におけるＡは、アルカリ金属イオン、アルカリ土類金属イオン、アンモニウムイオン又は水素イオンから選ばれる少なくとも１種のイオンであり、好ましい具体例には、リチウム、ナトリウム及びカリウム等のアルカリ金属イオン、マグネシウム又はカルシウム等のアルカリ土類金属イオン又は水素イオンがあり、これらの中では、化合物の安定性及び安価に入手できる点から、カリウム、リチウム、ナトリウム、アンモニウムイオン及び水素イオンが好ましいイオンである。
【００２４】
上記一般式［４］におけるＭ² は、４価金属であり、好ましい具体例には、ジルコニウム、チタン又は錫があり、化合物の安全性を考慮すると、ジルコニウム及びチタンは、特に好ましい４価金属である。
【００２５】
上記一般式［４］のリン酸塩系抗菌剤の具体例として、以下のものがある。
Ａｇ_0.005 Ｌｉ_0.995 Ｚｒ₂ （ＰＯ₄ ）₃
Ａｇ_0.01（ＮＨ₄ ）_0.99Ｚｒ₂ （ＰＯ₄ ）₃
Ａｇ_0.05Ｎａ_0.95Ｚｒ₂ （ＰＯ₄ ）₃
Ａｇ_0.2 Ｋ_0.8 Ｔｉ₂ （ＰＯ₄ ）₃
Ａｇ_0.1 Ｈ_0.9 Ｚｒ₂ （ＰＯ₄ ）₃
Ａｇ_0.5 Ｎａ_0.25Ｈ_0.25Ｚｒ₂ （ＰＯ₄ ）₃
Ａｇ_0.9 Ｎａ_0.1 Ｚｒ₂ （ＰＯ₄ ）₃
及び上記化合物１モルあたりの銀イオンの電荷量と同じ電荷量になるようにしながら、上記各式におけるＡｇをＺｎ、Ｍｎ、Ｎｉ、Ｐｂ、Ｈｇ、Ｓｎ又はＣｕと置換した化合物等がある。
【００２６】
上記リン酸塩系抗菌剤を合成する方法には、焼成法、湿式法及び水熱法等があり、何れも公知の方法である。
【００２７】
本発明の組成物において、抗菌性を発揮させるには、一般式［４］におけるａの値は大きい方がよいが、ａの値が０. ００１以上であれば、十分に抗菌性を発揮させることができる。しかし、ａの値が０. ００１未満であると、抗菌性を長時間発揮させることが困難となる恐れがあるので、ａの値を０. ０１以上の値とすることが好ましい。更に、樹脂の成形性や製品強度を維持し、かつ十分な抗菌性を長時間発揮させるためにはａの値を０. ０３以上とし、一般式［４］で示される化合物の樹脂に対する添加量を少なくすることが好ましい。又、経済性を考慮すると、ａの値は０. ７以下が適当である。
【００２８】
上記リン酸塩系抗菌剤は熱及び光の暴露に対して安定であり、５００℃、場合によっては８００℃〜１１００℃での加熱後であっても構造及び組成が全く変化せず、紫外線の照射によっても何等変色を起こさない。
又、上記リン酸塩系抗菌剤は、液体状態にある水と接触したり、酸性溶液中でも骨格構造の変化がみられない。従って、各種成形加工物を得る際の加工及び保存、さらには従来の抗菌剤のように、使用時において、加熱温度あるいは遮光条件等の制約を受けることがない。
【００２９】
本発明における無機系抗菌剤と下記に示す特定の金属酸化物とを併用することにより、本発明の抗菌効果を更に高めることができる。
【００３０】
○金属酸化物
上記金属酸化物は酸化亜鉛及び二酸化チタンから選ばれる少なくとも１種の化合物である。
【００３１】
酸化亜鉛は、天然物又は合成物の何れでもよく、性状、製造方法において特に制限はない。一般に亜鉛華として顔料に用いられている酸化亜鉛の他、インキ、充填剤、紫外線吸収剤、セラミックス原料、化粧品、歯科原料、媒熔剤、感光体、医薬品、触媒、電子材料、蛍光体、電池として用いられているもの等を使用できる。
【００３２】
二酸化チタンは、天然物又は合成物の何れでもよく、非晶質又は結晶質の何れであってもよく、性状、製造方法において特に制限はない。二酸化チタンは結晶構造によりアナタース、ルチル及びブルッカイトに分類されるが、本発明において、何れの結晶構造のものを用いてもよい。工業的に容易に入手できることから、アナタース及びルチルは好ましいものである。一般に顔料として用いられている二酸化チタンの他、インキ、化粧品、医薬品、釉薬、歯科材料、有機チタン原料、セラミックス原料、研磨剤、補強剤、触媒、電子材料として用いられているもの等を使用できる。
【００３３】
金属酸化物の粒子径、粒子の形状において特に制限はない。樹脂への分散性を考慮すると、好ましい平均粒子径は１０μｍ以下であり、好ましい粒子の形状は立方体状、直方体状、球状、針状である。
更に、上記金属酸化物は分散性向上、表面活性低減のため、表面処理を施したものを使用することができる。表面処理方法は湿式又は乾式の何れであってもよい。表面処理剤についての限定は無く、一般に用いられるアルミニウム、亜鉛、シリカ等の可溶性塩類を用いることができる。
【００３４】
本発明における無機系抗菌剤と上記金属酸化物を併用する場合、金属酸化物の好ましい配合割合は、無機系抗菌剤と金属酸化物の合計１００部を基準として、金属酸化物が５〜９０部である。金属酸化物の配合割合が５部より少ないと、金属酸化物と無機系抗菌剤の併用による抗菌効果の向上が困難となる恐れがあり、金属酸化物が９０部より多いと、無機系抗菌剤による抗菌効果を発揮させることが困難となる恐れがある。
また、十分な抗菌効果を発揮させるためには、無機系抗菌剤と金属酸化物からなる混合物における抗菌性金属イオンの含有率を０．５重量％以上とすることが好ましく、１重量％以上とすることがより好ましい。
【００３５】
○防黴性層状珪酸塩と無機系抗菌剤の配合割合
本発明の組成物における防黴性層状珪酸塩と無機系抗菌剤の好ましい配合割合は、両者の合計ｌ００部当たり、無機系抗菌剤が１〜９０部であり、より好ましくはｌ０〜８０部であり、特に好ましくは３０〜７０部である。無機系抗菌剤の割合が１部未満では十分な抗菌効果が得られず、また９０部を超えると十分な防黴効果が得られない恐れがある。
尚、無機系抗菌剤と金属酸化物を併用する場合は、両者の合計量を上記無機系抗菌剤の重量とする。
防黴性層状珪酸塩及び無機系抗菌剤の配合方法は、双方を均一に混合できる方法であれば特に制限はない。
【００３６】
○用途
本発明の抗菌防黴性組成物は、各種材料に配合して優れた抗菌防黴効果を付与する抗菌防黴剤として有用である。
配合することができる材料として、例えばシリコーン、アクリル等のゴム；塩化ビニル、ポリオレフィン、ポリウレタン、ＡＢＳ、ポリスチレン、酢酸ビニル、ポリカーボネート等のプラスチック等がある。
本発明の組成物は、材料に配合して成形したり、成形体の表面に被覆したりすることにより、成形体に抗菌防黴性を賦与することでき、成形体の形状は、公知の成形法により繊維、フィルム、シート、板或いはブロック等の種々の形状とすることができる。
【００３７】
また、本発明の抗菌防黴性組成物は、水又は有機溶剤等の液状媒体に懸濁させたものを、スプレーコーティング、コーターコーティング、ディッピング、刷毛塗り、ロールコーティング等の通常の塗布手段によって、各種金属やプラスチックス、セラミックス等の表面上に塗布し、皮膜を形成することもでき、そのようにして各種材質の物品における細菌及び黴の発育を阻止することができる。
本発明の組成物を各種材料に配合する好ましい割合は、抗菌防黴性を賦与しようとする材料１００部当たり、０．１〜３０部であり、より好ましくは０．５〜１０部である。
【００３８】
本発明の組成物を配合した材料又は成形体の具体的な用途として、タオル、カーペット、カーテン、衣類等の繊維製品；皮革；冷蔵庫、洗濯機、食器乾燥器、掃除機、空調機、テレビ、電話等の電化製品；壁紙、タイル、煉瓦、コンクリート、ネジ、目地等の建築材料；洗面器、歯ブラシ、ほうき、ホース、スリッパ、ごみ箱、たわし等の日曜雑貨品；まな板、三角コーナー、包丁等の台所用品；トイレタリー用品；各種コーティング材、塗料及び接着剤等がある。
以下、本発明を実施例により詳しく説明する。
【００３９】
【実施例】
（参考例１）
〔Ｃａ型層状珪酸塩の調製〕
０．１mol/l のＣａＣｌ₂ 水溶液１．０ｌに、層状珪酸塩であるＮａ型フッ素置換合成ウンモ１００．０ｇを加え、６０℃で４時間撹拌（３００ｒｐｍ）を行った。得られた懸濁液をイオン交換水で濾液の電導度が１００μＳ/cm 以下となるまで洗浄し、ついで１００℃で乾燥、粉砕してＣａ型層状珪酸塩を得た。
【００４０】
（参考例２）
〔防黴性層状珪酸塩Ａの調製〕
防黴性有機化合物としてアゾール誘導体化合物であるα−［２−（４−クロロフェニル）エチル］−α−（１，１−ジメチル−１Ｈ−１，２，４−トリアゾール−１−イル−エタノール７．５ｇと、参考例１で得たＣａ型層状珪酸塩を４２．５ｇ加え、乳鉢で十分に撹拌後、１２０℃でそのまま加熱した。得られた複合体前駆体を純水で洗浄し、１００℃にて真空乾燥を行い熟成を行った。乾燥後、粉砕を行って白色の防黴性層状珪酸塩Ａを得た。
【００４１】
（参考例３）
〔防黴性層状珪酸塩Ｂの調製〕
アセトン／水７０％溶液５００mlに、防黴性有機化合物として、分子内に複素６員環構造を持ち、環内に１つ以上の窒素原子を含む有機化合物である２，３，５，６−テトラクロロ−４−（メチルスルホニル）ピリジンを５．０ｇ加え、完全に溶解させた。そこへ参考例１で得たＣａ型層状珪酸塩を４５．０ｇ加え、室温で１時間撹拌後、電気炉でそのまま乾燥し、粉砕を行って白色の防黴性層状珪酸塩Ｂを得た。
【００４２】
（参考例４）
〔防黴性層状珪酸塩Ｃの調製〕
アセトン／水７０％溶液５００mlに、防黴性有機化合物として、ハロアルキルチオ系有機化合物であるＮ−（フルオロジクロロメチルチオ）フタルイミドを５．０ｇ加え、完全に溶解させた。そこへ参考例１で得たＣａ型層状珪酸塩を４５．０ｇ加え、室温で１時間撹拌後、電気炉でそのまま乾燥し、粉砕を行って白色の防黴性層状珪酸塩Ｃを得た。
【００４３】
（実施例１）
〔抗菌防黴性組成物Ａの調製〕
参考例２で得た防黴性層状珪酸塩Ａと下式［５］で表される無機系抗菌剤Ｘを等重量比で小型ヘンシェルミキサーを用いて均一に混合し、抗菌防黴性組成物Ａを得た。
Ａｇ_0.53Ｎａ_0.17Ｈ_0.30Ｚｒ₂ （ＰＯ₄ ）₃ ［５］
【００４４】
（実施例２）
〔抗菌防黴性組成物Ｂの調製〕
防黴性層状珪酸塩Ａに代えて参考例３で得た防黴性層状珪酸塩Ｂを用いた以外実施例１と同様にして抗菌防黴性組成物Ｂを得た。
【００４５】
（実施例３）
〔抗菌防黴性組成物Ｃの調製〕
防黴性層状珪酸塩Ａに代えて参考例４で得た防黴性層状珪酸塩Ｃを用いた以外実施例１と同様にして抗菌防黴性組成物Ｃを得た。
【００４６】
（実施例４）
〔抗菌防黴性組成物Ｄの調製〕
上式［５］で表される無機系抗菌剤Ｘと酸化亜鉛を、前者が９に対して後者を１の重量比で均一に混合したものを、参考例２で得た防黴性層状珪酸塩Ａの重量に対して０．７倍の比で均一に混合し、抗菌防黴性組成物Ｄを得た。
【００４７】
（比較例１）
実施例１において、防黴性層状珪酸塩Ａに代えて参考例２で得た防黴性層状珪酸塩Ａのみを用いた場合を比較例１とする。
【００４８】
（比較例２）
実施例１において、防黴性層状珪酸塩Ａに代えて参考例３で得た防黴性層状珪酸塩Ｂのみを用いた場合を比較例２とする。
【００４９】
（比較例３）
実施例１において、防黴性層状珪酸塩Ａに代えて参考例３で得た防黴性層状珪酸塩Ｃのみを用いた場合を比較例３とする。
【００５０】
○防黴性の評価１〔最小発育阻止濃度（ＭＩＣ）の測定〕
実施例１〜４及び比較例１〜３で調製した抗菌防黴性組成物を８ｍｌのポテトデキストロース培地中に４００、２００、１００、５０ｐｐｍの割合で混入させ、その上に黴の胞子を塗布し、１週間後の黴の発育具合で判断した。黴には黒麹黴（Aspergills niger）及び黒黴（Cladosporium cladospolies ）の２種類を用いた。黒麹黴を用いた場合のＭＩＣの測定結果を表１に示し、黒黴を用いた場合のＭＩＣの測定結果を表２に示す。又、各表において、参考データとして、抗菌防黴性組成物に代えて無機系抗菌剤Ｘを用いた場合の評価結果も合わせて示した。尚、各表における記号の意味は以下の通りである。
○：黴の発育が阻止されている。 ×：黴の発育が見られる。
【００５１】
【表１】

【００５２】
【表２】

【００５３】
（使用例１〜４）
実施例１〜４で調製した抗菌防黴性組成物を下記表３の組成物１４７．５ｇにそれぞれ２．５ｇ添加し、加熱ロールにて１５０℃で均一に５分間混練り後、プレス（１７０℃、１００Ｋｇ／ｃｍ² ）により厚さ２ｍｍ、縦１２ｃｍ、横１０ｃｍの板状に成形し、さらに３ｃｍ四方の大きさに切り取り、試験片を作製した。
尚、使用例番号と各使用例で用いた抗菌防黴性組成物の種類との対応は、以下の通りである。

【００５４】
【表３】

【００５５】
*1: ＴＳ１１００（東亞合成株式会社製）
*2: 東邦理化工業株式会社製
*3: ３００Ｋ（ダイセル化学工業社株式会社製）
*4: アデカスタブ３７（旭電化工業株式会社製商品名）
*5: アデカスタブ１０２（旭電化工業株式会社製商品名）
【００５６】
（比較使用例１〜３）
抗菌防黴性組成物に代えて、比較例１〜３で調製した防黴性層状珪酸塩を用いた以外は使用例１と同様にして試験片を作製した。
尚、比較使用例番号と各比較使用例で用いた防黴性層状珪酸塩の種類との対応は、以下の通りである。

【００５７】
（比較使用例４〜６）
抗菌防黴性組成物に代えて、下記（イ）、（ロ）又は（ハ）の防黴性有機化合物を、上記表３の組成物１４９．７５ｇに各々０．２５ｇ添加した以外は使用例１と同様にして試験片を作製した。
（イ）α−［２−（４−クロロフェニル）エチル］−α−（１，１−ジメチル−１Ｈ−１，２，４−トリアゾール−１−イル−エタノール
（ロ）２，３，５，６−テトラクロロ−４−（メチルスルホニル）ピリジン
（ハ）Ｎ−（フルオロジクロロメチルチオ）フタルイミド
尚、比較使用例番号と各比較使用例で用いた防黴性有機化合物の種類との対応は、以下の通りである。

【００５８】
（比較使用例７）
抗菌防黴性組成物に代えて、上式［５］で表される無機系抗菌剤Ｘを用いた以外は使用例１と同様にして試験片を作製した。
【００５９】
○防黴性の評価２〔ラップ法による胞子数の測定〕
使用例１〜４、比較使用例１〜７で作製した試験片上に麦芽エキス（０．０５％）含有胞子懸濁液（胞子数濃度： 4.5×10⁴/ml）を１００μｌ滴下し、２．５ｃｍ四方のラップにより密着させ、２５℃、湿度９０％で４８時間保持し、前後の胞子数の変化を測定した。評価用黴として黒麹黴（Aspergills niger）を用いた。
上記のようにして得られた防黴性試験の結果を下記表４に示す。
【００６０】
○防黴性の評価３〔ハロー法による防黴性の評価〕
使用例１〜４、比較使用例１〜７で作製した試験片を５０℃の温水中に７日間静置し、１日後及び７日後に防黴性の測定を行い、防黴効果の経時変化を評価した。防黴性の評価方法は、試験片をポテトデキストロース寒天培地に置き、１４日間培養後の阻止帯形成幅を測定することにより防黴性を評価した。尚、評価用黴として黒麹黴（Aspergills niger）を用いた。
上記のようにして得られた防黴性試験の結果を下記表４に示す。
【００６１】
・抗菌性試験
使用例１〜４、比較使用例１〜７で作製した試験片の抗菌力を以下の方法により評価した。
被検菌には大腸菌を用い、菌数が１０⁵ 前後となるように希釈液を調製した。次いで試験片（３ｃｍ四方）に１００μｌの希釈液を滴下し１．５ｃｍ四方のラップにより密着させ、３７℃で保存した。保存開始から０時間（初発菌数： 2.6×10⁵/ml）および６時間保存した後に、菌数測定用培地（ＳＣＤＬＰ液体培地）で試験片上の生残菌を洗い出し、この洗液を試験液とした。この試験液について、菌数測定用培地を用いる混釈平板培養法（３７℃２日間）により生菌数を測定して、１ｍｌ当たりの生菌数に換算した。尚、対象菌数は 8.3×10⁴/mlであり、ブランク菌数は 4.1×10⁴/mlであった。
上記のようにして得られた抗菌生試験の結果を下記表４に示す。
【００６２】
【表４】

【００６３】
注）表中の記号は以下のことを意味する。
〔胞子数の欄〕−：４８時間後の洗い出し時に菌糸の成長が認められ、胞子数の測定が不可能であった。
〔ハロー法の欄〕○：発育阻止帯の形成あり。×：発育阻止帯の形成なし。
〔総合評価の欄〕Ａ：抗菌性と防黴性が共に優れている。Ｂ：抗菌力と防黴性の少なくとも一方がやや劣っている。Ｃ：抗菌力と防黴性の少なくとも一方が劣っている。
【００６４】
表４からわかるように、本発明の防黴性層状珪酸塩は、抗菌性と防黴性が共に優れ、防黴剤を有する有機化合物を直接配合した場合に比べて、長時間洗浄を行っても防黴性が失われることはなく、防黴効果の持続性に優れている。又、特に真菌類に属する胞子の発芽を阻止する防黴能力に優れている。
【００６５】
【発明の効果】
本発明の抗菌防黴性組成物は、抗菌性と防黴性が共に優れ、特に真菌類に対する防黴性能に優れたものである。
この特性によって本発明の抗菌防黴性組成物は、各種ゴム、プラスチック等の材料及びそれらからなるフィルム、シート等の成形品、並びに各種繊維、紙、皮革、塗料、接着剤、断熱材、コーキング材等に適用する抗菌防黴剤として有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an antibacterial / antifungal composition containing an antifungal layered silicate and an inorganic antibacterial agent, and is excellent in water resistance, chemical resistance, heat resistance, antifungal durability and antibacterial properties. In particular, the present invention relates to an antibacterial and antifungal composition excellent in antifungal performance that inhibits germination of spores.
The composition of the present invention is an antibacterial and antifungal agent that can impart antibacterial and antifungal properties to a material or a molded body by blending with a material such as rubber or plastic and molding or coating the surface of the molded body. Useful as an agent.
[0002]
[Prior art]
Conventionally, various antibacterial / antifungal agents have been developed for imparting antibacterial / antifungal properties to desired materials, and organic and inorganic antibacterial / antifungal agents are known.
As an organic antibacterial and antifungal agent, quaternary ammonium salt compounds such as benzalkonium chloride, sulfur-containing benzimidazole compounds such as 2,4-thiazolylbenzimidazole, bisthiocyanate compounds such as methylenebisthiocyanate, Antifungal agents such as quinolinol compounds such as 8-quinolinol, alcohol compounds such as ethanol, aldehyde compounds such as formalin, phenol compounds such as cresol, and carboxylic acid compounds such as sorbic acid are known.
On the other hand, an inorganic antibacterial / antifungal agent is known in which metal ions exhibiting antibacterial properties such as silver, copper, and zinc are supported on activated carbon, apatite, zeolite, tetravalent metal phosphate, and the like.
[0003]
However, conventional antibacterial and antifungal agents have their merits and demerits in each of organic and inorganic systems, and have problems to be improved.
In other words, since organic antibacterial and antifungal agents generally have poor heat resistance, when used for kneading into plastics or fibers, they may cause problems such as discoloration and foaming, and volatilization and decomposition may occur during processing.黴 The effect was not able to be demonstrated. In addition, organic materials are inferior in chemical resistance and have a relatively high solubility in various solvents, so that elution occurs during use, and the antifungal effect is reduced, and there is a concern about adverse effects on the human body. There is a problem that the possible applications are limited.
In addition, although the inorganic antibacterial / antifungal agent is excellent in heat resistance and chemical resistance, it has a problem that it is inferior in the antifungal effect against fungi compared with the antibacterial effect against bacteria.
As a technique for solving the above-mentioned problems, an antibacterial antifungal silicate obtained by substituting at least a part of ion-exchangeable metal ions of a layered silicate with an antibacterial antifungal organic coordination compound is known (Japanese Patent Application Laid-Open No. Hei 11 (1998)). 4-292410).
[0004]
[Problems to be solved by the invention]
However, organic antibacterial and antifungal agents tend to be inferior to the antibacterial effect against bacteria compared to the fungicidal effect against fungi, contrary to inorganic ones.
Furthermore, an antibacterial and antifungal intercalation compound is known in which a transition metal such as silver and an organic substance are introduced as a complex salt between layers of a layered compound in order to enhance the antibacterial effect against bacteria (Japanese Patent Laid-Open No. 1-221304). ), The fungicidal effect on fungi is not sufficient, and there are many cases where the complex salt is colored depending on the combination of the transition metal and the organic substance, and the use is limited.
An object of the present invention is to provide an antibacterial / antifungal composition having both excellent antibacterial and antifungal properties, and particularly excellent antifungal properties against fungi.
[0005]
[Means for Solving the Problems]
Therefore, as a result of intensive studies to solve the above-mentioned problems, the present inventors have made an antibacterial layered silicate supported by a layered silicate and an inorganic antibacterial agent coexist. It has been found that the above problems can be solved, and the present invention has been completed.
That is, the present invention is an antibacterial and antifungal composition comprising an antifungal layered silicate in which an antifungal organic compound is supported between layered silicate layers and an inorganic antibacterial agent.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described in detail below.
○ Antifungal organic compounds
The antifungal organic compound in the present invention is not particularly limited, but those that are soluble in a polar organic solvent or those that are soluble in an acid or alkali are preferred.
Preferred antifungal organic compounds include (a) a compound having a hetero 6-membered ring structure in the molecule and containing one or more nitrogen atoms in the ring, (b) a haloalkylthio compound or (c) an azole derivative compound, and There are quaternary ammonium compounds such as benzalkonium chloride, and the compounds (a), (b) and (c) are particularly preferred.
[0007]
Preferred specific examples of the above (a) include the following compounds.
That is, pyridine compounds such as 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine and 2-pyridinethiol-1-oxide zinc, pyridazine compounds, pyrimidine compounds, triazine compounds, pyrazine compounds Compounds, quinoline compounds, quinazoline compounds, phenanthrodin compounds, phenanthroline compounds, phenazine compounds, and the like.
[0008]
A preferable compound of the above (b) is a compound represented by the following general formula [2].
[0009]
[Chemical 1]

[0010]
(In the above formula, X, Y, and Z are halogens, which may be the same or different from each other, and R is an organic group.)
[0011]
X, Y and Z in the above formula are F, Cl, Br or I, and preferred R is an organic group having an imide group in the structure.
Preferable specific examples of the above (b) include the following compounds.
That is, N- (fluorodichloromethylthio) phthalimide, N, N-dimethyl-N ′-(dichlorofluoromethylthio) -N′-phenylsulfamide, N, N-dimethyl-N ′-(dichlorofluoromethylthio) -N '-Trisulfamide, N- (trichloromethylthio) phthalimide, tetrachloroethylthiotetrahydrophthalimide, N-trichloromethylthio-4-cyclohexene-1,2-dicarboximide and the like.
[0012]
Preferred examples of the above (c) include the following compounds (in parentheses << >> are common names).
That is, α- [2- (4-chlorophenyl) ethyl] -α- (1,1-dimethylethyl) -1H-1,2,4-triazol-1-yl-ethanol << debuconazole >>, 1- (4- Chlorophenoxy) 3,3-dimethyl-1- (1H-1,2,4-triazo-1-yl-2-butanone << triazimephone >>, β- (4-chlorophenoxy) -α- (1, 1-dimethyl-ethyl) -1H-1,2,4-triazole-1-ethanol Triazole compounds such as “triazimenol” and “hexaconazole”, methyl 2-benzimidazolecarbamate, methylbenzimidazolyl carbamate ( BCM), methyl 1- (butylcarbamoyl) -2-benzimidazole carbamate (benomyl), 2- (2′-freel) -1H-benzimi Benzimidazole compounds such as sol and 2- (4′-thiazolyl) benzimidazole (TBZ), imidazole compounds such as 1- [ortho-chloro-β-[(para-chlorobenzyl) oxy] phenethyl] -imidazole mononitrate Compounds, thiazole compounds such as 1,2-benzisothiazolin-3-one, 2- (4-thiocyanomethylthio) benzthiazole, indazole compounds, pyrazole compounds, isothiazole compounds, and the like.
[0013]
In addition, the antifungal organic compound in the present invention may have antibacterial properties in addition to antifungal properties, or may be one type, or two or more types may be used in combination.
[0014]
○ Layered silicate
The layered silicate can be used without particular limitation as long as it is a silicate having crystal layer units stacked on each other to form a layered structure, and may be either a natural product or a synthetic product.
Preferable layered silicates include clay minerals, and specific examples thereof include the following.
That is, smectites such as montmorillonite, beidellite, hectorite, and saponite, balm curites, illite, muscovite, phlogopite, biotite, mica, such as margarite, clintonite, etc., green mud such as sudite Stone groups, kaolins such as kaolinite and halloysite, and serpentine groups such as antigolite.
Other preferred layered silicates include the following.
That is, there are layered sodium silicates such as magadiite, kenyanite, kanemite, macatite, and eyerite, layered calcium silicates such as tobermorite, and synthetic mica in which anions such as hydroxide ions are substituted with fluorine ions.
[0015]
The particle size, water content, cation exchange capacity, color and the like of the layered silicate in the present invention are not particularly limited, but when used for kneading into plastic, rubber or fiber, a powder having an average particle size of 10 μm or less is used. More preferably, it is a powder having an average particle size of 0.1 to 7 μm, and it is more preferable that the particle size distribution is narrow and the particle size is uniform.
Further, in order to exhibit a sufficient antifungal effect when the antifungal layered silicate is used, it is preferable that the cation exchange capacity is 0.1 meq / g or more.
These layered silicates may be used alone or in combination of two or more in order to control sustained release.
[0016]
The layered silicate may be used by replacing some or all of the ion exchangeable metal ions with other metal ions.
The metal ion to be exchanged is not particularly limited as long as it is an ion-exchangeable metal ion, but lithium, calcium, sodium and the like are preferable.
[0017]
The lower limit of the preferred loading amount of the antifungal organic compound supported between the layers of the antifungal layered silicate in the present invention is 0 per 100 parts by weight (hereinafter simply referred to as “parts”) of the antifungal layered silicate in the present invention. .1 part, more preferably 1 part, and particularly preferably 5 parts. If the amount is too small, the antifungal effect is lowered. The upper limit of the loading amount is naturally determined by the type of the layered silicate and the antifungal organic compound, and the antifungal layered silicate loaded in an unnecessarily large amount is discolored when kneaded into a plastic or the like. It is preferable to set a suitable upper limit of the carrying amount by a preliminary test.
[0018]
Further, the method for supporting the antifungal organic compound on the layered silicate is not particularly limited. Basically, the antifungal organic compound may be brought into contact with the layered silicate, and the antifungal organic compound is in a solid phase. It can be introduced in any state of liquid phase and gas phase.
For example, in the case where the antifungal organic compound is in a liquid phase, the antifungal organic compound is mixed and stirred with the layered silicate, and then dried and pulverized, or the antifungal organic compound is highly soluble. The solution dissolved in the solvent and the layered silicate are mixed and stirred, then filtered and washed, and further dried and pulverized to obtain an antifungal layered silicate having the layered silicate supported on the layered silicate. be able to. In addition, you may dry and grind | pulverize as it is, without wash | cleaning.
[0019]
The conditions for preparing the above antifungal composition are not particularly limited, and can be appropriately changed depending on the type of the antifungal organic compound and the layered silicate used and the amount of the antifungal organic compound supported. Specifically, for example, the pH of the solvent is 0.1 to 13, the stirring time is 0.5 to 72 hours, the stirring temperature is from room temperature to, for example, about 40 ° C. to 60 ° C., and the number of stirring is 10 to 1000 times / minute. I just need it.
[0020]
○ Inorganic antibacterial agents
The inorganic antibacterial agent in the present invention is not particularly limited as long as it is an inorganic compound carrying antibacterial metal ions known as metal ions having antibacterial properties such as silver and copper, and carries antibacterial metal ions. Examples of inorganic compounds include the following.
That is, inorganic ion exchange such as activated carbon, activated alumina, silica gel and other inorganic adsorbents, zeolite, hydroxyapatite, zirconium phosphate, titanium phosphate, potassium titanate, hydrous bismuth, hydrous zirconium, hydrotalcite compounds There is a body.
There are no particular limitations on the method of supporting the antibacterial metal ions on these inorganic compounds, and any of the known supporting methods can be adopted, for example, a method of supporting by physical adsorption or chemical adsorption, by ion exchange reaction, A method of supporting, a method of supporting by a binder, a method of supporting an antibacterial metal compound by driving it into an inorganic compound, a thin film of an antibacterial metal compound on the surface of an inorganic compound by a thin film forming method such as vapor deposition, dissolution precipitation reaction, sputtering There is a method of supporting by forming a layer.
[0021]
  Among the above inorganic compounds, inorganic ion exchangers are preferable because they can firmly carry antibacterial metal ions, and in particular, tetravalent metal phosphate ion exchangers represented by the following general formula [3] are preferable compounds. A particularly preferred antibacterial agent is a compound represented by the following general formula [4]
    A_b M ² (PO₄)₃・ NH₂O [3]
(A is at least one ion selected from alkali metal ions, alkaline earth metal ions, ammonium ions or hydrogen ions;²Is a tetravalent metal, n is a number satisfying 0 ≦ n ≦ 6, and b is a positive number satisfying mb = 1. Where m is the valence of A. )
    M¹ _aA_b M ² (PO₄)₃・ NH₂O [4]
(M¹Is at least one metal ion selected from silver, copper, zinc, tin, mercury, lead, iron, cobalt, nickel, manganese, arsenic, antimony, bismuth, barium, cadmium or chromium, A is an alkali metal ion, At least one ion selected from alkaline earth metal ions, ammonium ions or hydrogen ions;²Is a tetravalent metal, n is a number satisfying 0 ≦ n ≦ 6, and a and b are positive numbers satisfying la + mb = 1. Where l is M¹And m is the valence of A. )
[0022]
The compound represented by the general formula [4] is an amorphous or crystalline compound belonging to the space group R3c, and represents a compound in which each constituent ion forms a three-dimensional network structure.
The phosphate-based antibacterial agent is preferably a crystalline compound having a three-dimensional network structure because it is less discolored when exposed to sunlight.
M in the general formula [4]¹Are known as metals exhibiting antibacterial properties, among which silver is particularly effective as a metal that can enhance antifungal properties, antibacterial properties, and algal control properties in addition to safety.
[0023]
A in the general formula [4] is at least one ion selected from alkali metal ions, alkaline earth metal ions, ammonium ions, or hydrogen ions. Preferred specific examples include alkalis such as lithium, sodium, and potassium. There are metal ions, alkaline earth metal ions such as magnesium or calcium, or hydrogen ions. Among these, potassium, lithium, sodium, ammonium ions, and hydrogen ions are preferred ions because of the stability of the compound and availability at low cost. It is.
[0024]
M in the general formula [4]²Is a tetravalent metal, and preferred examples include zirconium, titanium or tin. In view of the safety of the compound, zirconium and titanium are particularly preferred tetravalent metals.
[0025]
Specific examples of the phosphate antibacterial agent of the general formula [4] include the following.
Ag_0.005Li_0.995Zr₂(PO_Four)_Three
Ag_0.01(NH_Four)_0.99Zr₂(PO_Four)_Three
Ag_0.05Na_0.95Zr₂(PO_Four)_Three
Ag_0.2K_0.8Ti₂(PO_Four)_Three
Ag_0.1H_0.9Zr₂(PO_Four)_Three
Ag_0.5Na_0.25H_0.25Zr₂(PO_Four)_Three
Ag_0.9Na_0.1Zr₂(PO_Four)_Three
In addition, there are compounds in which Ag in each of the above formulas is substituted with Zn, Mn, Ni, Pb, Hg, Sn, or Cu while maintaining the same charge amount as that of silver ions per mole of the compound.
[0026]
Methods for synthesizing the phosphate antibacterial agent include a firing method, a wet method and a hydrothermal method, all of which are known methods.
[0027]
In the composition of the present invention, in order to exhibit antibacterial properties, it is preferable that the value of a in the general formula [4] is large, but if the value of a is 0.001 or more, sufficient antibacterial properties are exhibited. be able to. However, if the value of a is less than 0.001, it may be difficult to exhibit antibacterial properties for a long time. Therefore, the value of a is preferably set to a value of 0.01 or more. Furthermore, in order to maintain the moldability and product strength of the resin and to exhibit sufficient antibacterial properties for a long time, the value of a is set to 0.03 or more, and the amount of the compound represented by the general formula [4] added to the resin Is preferably reduced. In consideration of economy, the value of a is suitably 0.7 or less.
[0028]
The phosphate antibacterial agent is stable to exposure to heat and light, and the structure and composition do not change at all even after heating at 500 ° C., and in some cases 800 ° C. to 1100 ° C. No discoloration caused by irradiation.
In addition, the phosphate antibacterial agent does not come into contact with water in a liquid state or change in the skeleton structure even in an acidic solution. Therefore, processing and storage when obtaining various molded products, and further, there are no restrictions such as heating temperature or light shielding conditions during use unlike conventional antibacterial agents.
[0029]
By using together the inorganic antibacterial agent in the present invention and the specific metal oxide shown below, the antibacterial effect of the present invention can be further enhanced.
[0030]
○ Metal oxide
The metal oxide is at least one compound selected from zinc oxide and titanium dioxide.
[0031]
Zinc oxide may be either a natural product or a synthetic product, and there is no particular limitation on the properties and production method. In addition to zinc oxide, which is generally used for pigments as zinc white, inks, fillers, UV absorbers, ceramic raw materials, cosmetics, dental raw materials, solvents, photoreceptors, pharmaceuticals, catalysts, electronic materials, phosphors, batteries What is used as can be used.
[0032]
Titanium dioxide may be either a natural product or a synthetic product, and may be either amorphous or crystalline, and there is no particular limitation on the properties and production method. Titanium dioxide is classified into anatase, rutile and brookite depending on the crystal structure, but any crystal structure may be used in the present invention. Anatase and rutile are preferred because they are easily available industrially. In addition to titanium dioxide, which is generally used as a pigment, inks, cosmetics, pharmaceuticals, glazes, dental materials, organic titanium materials, ceramic materials, abrasives, reinforcing agents, catalysts, materials used as electronic materials, etc. can be used. .
[0033]
There are no particular restrictions on the particle diameter and particle shape of the metal oxide. Considering the dispersibility in the resin, the preferable average particle diameter is 10 μm or less, and the preferable particle shape is a cubic shape, a rectangular parallelepiped shape, a spherical shape, or a needle shape.
Further, the above metal oxide may be subjected to surface treatment for improving dispersibility and reducing surface activity. The surface treatment method may be either wet or dry. There is no limitation on the surface treatment agent, and generally used soluble salts such as aluminum, zinc, and silica can be used.
[0034]
When the inorganic antibacterial agent and the above metal oxide are used in combination in the present invention, the preferred blending ratio of the metal oxide is 5 to 90 parts of the metal oxide based on a total of 100 parts of the inorganic antibacterial agent and the metal oxide. It is. When the blending ratio of the metal oxide is less than 5 parts, it may be difficult to improve the antibacterial effect due to the combined use of the metal oxide and the inorganic antibacterial agent. When the metal oxide content exceeds 90 parts, the inorganic antibacterial agent is present. It may be difficult to exert the antibacterial effect.
In order to exert a sufficient antibacterial effect, the content of antibacterial metal ions in the mixture composed of the inorganic antibacterial agent and the metal oxide is preferably 0.5% by weight or more, and 1% by weight or more. More preferably.
[0035]
○ Mixing ratio of antifungal layered silicate and inorganic antibacterial agent
The preferable blending ratio of the antifungal layered silicate and the inorganic antibacterial agent in the composition of the present invention is 1 to 90 parts of the inorganic antibacterial agent, more preferably 10 to 80 parts per 100 parts in total. Yes, particularly preferably 30 to 70 parts. If the proportion of the inorganic antibacterial agent is less than 1 part, a sufficient antibacterial effect cannot be obtained, and if it exceeds 90 parts, a sufficient antifungal effect may not be obtained.
In addition, when using together an inorganic antibacterial agent and a metal oxide, let the total amount of both be the weight of the said inorganic antibacterial agent.
The blending method of the antifungal layered silicate and the inorganic antibacterial agent is not particularly limited as long as both can be mixed uniformly.
[0036]
○ Application
The antibacterial / antifungal composition of the present invention is useful as an antibacterial / antifungal agent that is blended with various materials and imparts an excellent antibacterial / antifungal effect.
Examples of materials that can be blended include rubbers such as silicone and acrylic; plastics such as vinyl chloride, polyolefin, polyurethane, ABS, polystyrene, vinyl acetate, and polycarbonate.
The composition of the present invention can be provided with antibacterial and antifungal properties by molding it by blending it with the material or coating the surface of the molded body. Various shapes such as a fiber, a film, a sheet, a plate or a block can be obtained by the method.
[0037]
In addition, the antibacterial and antifungal composition of the present invention is a suspension in a liquid medium such as water or an organic solvent, by a normal application means such as spray coating, coater coating, dipping, brush coating, roll coating, It can also be applied on the surface of various metals, plastics, ceramics, etc. to form a film, and in this way, the growth of bacteria and sputum in articles of various materials can be prevented.
The preferable ratio which mix | blends the composition of this invention with various materials is 0.1-30 parts per 100 parts of materials which are going to provide antibacterial and antifungal property, More preferably, it is 0.5-10 parts.
[0038]
Specific applications of the material or molded body in which the composition of the present invention is blended include textiles such as towels, carpets, curtains and clothes; leather; refrigerators, washing machines, dish dryers, vacuum cleaners, air conditioners, televisions, Electric appliances such as telephones; Wallpapers, tiles, bricks, concrete, screws, joints and other building materials; Kitchenware; toiletries; various coating materials, paints and adhesives.
Hereinafter, the present invention will be described in detail with reference to examples.
[0039]
【Example】
(Reference Example 1)
[Preparation of Ca-type layered silicate]
0.1 mol / l CaCl₂100.0 g of Na-type fluorine-substituted synthetic ummo, which is a layered silicate, was added to 1.0 l of an aqueous solution, and stirred (300 rpm) at 60 ° C. for 4 hours. The obtained suspension was washed with ion exchange water until the conductivity of the filtrate was 100 μS / cm 2 or less, then dried and pulverized at 100 ° C. to obtain a Ca-type layered silicate.
[0040]
(Reference Example 2)
[Preparation of antifungal layered silicate A]
6. α- [2- (4-Chlorophenyl) ethyl] -α- (1,1-dimethyl-1H-1,2,4-triazol-1-yl-ethanol, which is an azole derivative compound as an antifungal organic compound 5 g and 42.5 g of the Ca-type layered silicate obtained in Reference Example 1 were added, and after sufficiently stirring in a mortar, the mixture was heated as it was at 120 ° C. The obtained composite precursor was washed with pure water and 100 ° C. After drying, the mixture was ripened and pulverized to obtain a white antifungal layered silicate A.
[0041]
(Reference Example 3)
[Preparation of antifungal layered silicate B]
2,3,5,6-, which is an organic compound having a hetero 6-membered ring structure in the molecule and containing one or more nitrogen atoms in the molecule as an antifungal organic compound in 500 ml of an acetone / water 70% solution 5.0 g of tetrachloro-4- (methylsulfonyl) pyridine was added and completely dissolved. Thereto, 45.0 g of the Ca-type layered silicate obtained in Reference Example 1 was added, stirred at room temperature for 1 hour, dried in an electric furnace as it was, and pulverized to obtain a white antifungal layered silicate B.
[0042]
(Reference Example 4)
[Preparation of antifungal layered silicate C]
To 500 ml of 70% acetone / water solution, 5.0 g of N- (fluorodichloromethylthio) phthalimide, which is a haloalkylthio organic compound, was added as an antifungal organic compound and completely dissolved. Thereto, 45.0 g of the Ca-type layered silicate obtained in Reference Example 1 was added, stirred at room temperature for 1 hour, then dried as it was in an electric furnace, and pulverized to obtain white antifungal layered silicate C.
[0043]
(Example 1)
[Preparation of antibacterial and antifungal composition A]
The antibacterial and antifungal composition is obtained by uniformly mixing the antifungal layered silicate A obtained in Reference Example 2 and the inorganic antibacterial agent X represented by the following formula [5] at an equal weight ratio using a small Henschel mixer. A was obtained.
Ag_0.53Na_0.17H_0.30Zr₂(PO_Four)_Three  [5]
[0044]
(Example 2)
[Preparation of antibacterial and antifungal composition B]
An antibacterial and antifungal composition B was obtained in the same manner as in Example 1 except that the antifungal layered silicate B obtained in Reference Example 3 was used in place of the antifungal layered silicate A.
[0045]
(Example 3)
[Preparation of antibacterial and antifungal composition C]
An antibacterial and antifungal composition C was obtained in the same manner as in Example 1 except that the antifungal layered silicate C obtained in Reference Example 4 was used in place of the antifungal layered silicate A.
[0046]
(Example 4)
[Preparation of antibacterial and antifungal composition D]
The antibacterial layered silicic acid obtained in Reference Example 2 obtained by uniformly mixing the inorganic antibacterial agent X and zinc oxide represented by the above formula [5] with the former being 9 and the latter being uniformly mixed at a weight ratio of 1 The mixture was uniformly mixed at a ratio of 0.7 times the weight of the salt A to obtain an antibacterial and antifungal composition D.
[0047]
(Comparative Example 1)
In Example 1, the case where only the antifungal layered silicate A obtained in Reference Example 2 was used in place of the antifungal layered silicate A is referred to as Comparative Example 1.
[0048]
(Comparative Example 2)
In Example 1, the case where only the antifungal layered silicate B obtained in Reference Example 3 was used in place of the antifungal layered silicate A was referred to as Comparative Example 2.
[0049]
(Comparative Example 3)
In Example 1, the case where only the antifungal layered silicate C obtained in Reference Example 3 was used in place of the antifungal layered silicate A is referred to as Comparative Example 3.
[0050]
○ Evaluation of antifungal property 1 [Measurement of minimum inhibitory concentration (MIC)]
  The antibacterial and antifungal compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 3 were placed in 8 ml of potato dextrose medium.400, 200, 100, 50The mixture was mixed at a ratio of ppm, and spore spores were applied thereon, and the growth of the cocoons after one week was judged. Two types of moths were used: Aspergills niger and Cladosporium cladospolies. Table 1 shows the MIC measurement results when using black panther, and Table 2 shows the MIC measurement results when using black panther. Moreover, in each table | surface, it replaced with the antibacterial and antifungal composition, and also showed the evaluation result at the time of using the inorganic type antibacterial agent X as reference data. In addition, the meaning of the symbol in each table | surface is as follows.
    ○: Growth of moths is blocked. X: Growth of cocoon is seen.
[0051]
[Table 1]

[0052]
[Table 2]

[0053]
(Usage examples 1-4)
2.5 g of each of the antibacterial and antifungal compositions prepared in Examples 1 to 4 was added to 147.5 g of the composition shown in Table 3 below, kneaded uniformly at 150 ° C. for 5 minutes with a heating roll, and press (170 ℃, 100Kg / cm²) To form a plate having a thickness of 2 mm, a length of 12 cm, and a width of 10 cm, and further cut into a size of 3 cm square to prepare a test piece.
The correspondence between the usage example number and the type of the antibacterial and antifungal composition used in each usage example is as follows.

[0054]
[Table 3]

[0055]
* 1: TS1100 (manufactured by Toagosei Co., Ltd.)
* 2: Toho Rika Kogyo Co., Ltd.
* 3: 300K (manufactured by Daicel Chemical Industries, Ltd.)
* 4: ADK STAB 37 (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.)
* 5: ADK STAB 102 (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.)
[0056]
(Comparative use examples 1 to 3)
A test piece was prepared in the same manner as in Use Example 1 except that the antifungal layered silicate prepared in Comparative Examples 1 to 3 was used instead of the antibacterial and antifungal composition.
In addition, the correspondence between the comparative use example number and the type of the antifungal layered silicate used in each comparative use example is as follows.

[0057]
(Comparative Use Examples 4-6)
Instead of the antibacterial and antifungal composition, the following (A), (B) or (C) the antifungal organic compound was used except that 0.25 g was added to 149.75 g of the composition shown in Table 3 above. A test piece was prepared in the same manner as in Example 1.
(A) α- [2- (4-Chlorophenyl) ethyl] -α- (1,1-dimethyl-1H-1,2,4-triazol-1-yl-ethanol
(B) 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine
(C) N- (fluorodichloromethylthio) phthalimide
The correspondence between the comparative use example number and the type of the antifungal organic compound used in each comparative use example is as follows.

[0058]
(Comparative use example 7)
A test piece was prepared in the same manner as in Use Example 1 except that the inorganic antibacterial agent X represented by the above formula [5] was used instead of the antibacterial and antifungal composition.
[0059]
○ Evaluation of antifungal property 2 [Measurement of the number of spores by the lapping method]
Malt extract (0.05%)-containing spore suspension (spore number concentration: 4.5 × 10 5) on the test pieces prepared in Use Examples 1 to 4 and Comparative Use Examples 1 to 7^Four100 ml of / ml) was dropped, and it was brought into close contact with a 2.5 cm square wrap, kept at 25 ° C. and 90% humidity for 48 hours, and the change in the number of spores before and after was measured. A black candy (Aspergills niger) was used as an evaluation candy.
The results of the antifungal test obtained as described above are shown in Table 4 below.
[0060]
○ Evaluation of antifungal property 3 [Evaluation of antifungal property by halo method]
The test pieces prepared in Use Examples 1 to 4 and Comparative Use Examples 1 to 7 were allowed to stand in 50 ° C. warm water for 7 days, and the antifungal properties were measured after 1 and 7 days. Evaluated. The antifungal evaluation method evaluated the antifungal property by placing a test piece on a potato dextrose agar medium, and measuring the width of formation of the inhibition band after 14 days of culture. In addition, black moth (Aspergills niger) was used as an evaluation candy.
The results of the antifungal test obtained as described above are shown in Table 4 below.
[0061]
・ Antimicrobial test
The antibacterial activity of the test pieces prepared in Use Examples 1 to 4 and Comparative Use Examples 1 to 7 was evaluated by the following method.
E. coli is used as the test bacterium, and the number of bacteria is 10^FiveDilution liquid was prepared so that it might become before and after. Next, 100 μl of the diluted solution was dropped onto the test piece (3 cm square), and the specimen was brought into close contact with a 1.5 cm square wrap and stored at 37 ° C. 0 hours from the start of storage (number of initial bacteria: 2.6 × 10^Five/ ml) and 6 hours of storage, the surviving bacteria on the test piece were washed out with a medium for measuring the number of bacteria (SCDLP liquid medium), and this washing solution was used as a test solution. With respect to this test solution, the number of viable bacteria was measured by a pour plate culture method (37 ° C., 2 days) using a medium for measuring the number of bacteria, and converted to the number of viable bacteria per ml. The target number of bacteria is 8.3 x 10^Four/ ml, blank bacteria count is 4.1 × 10^Four/ ml.
The results of the antibacterial biotest obtained as described above are shown in Table 4 below.
[0062]
[Table 4]

[0063]
Note) Symbols in the table mean the following.
[Spore count column]-: Mycelium growth was observed at the time of washing out after 48 hours, and measurement of the spore count was impossible.
[Hello method column] ○: A stunt zone is formed. X: No growth inhibitory zone formed.
[Comprehensive evaluation column] A: Both antibacterial and antifungal properties are excellent. B: At least one of antibacterial activity and antifungal property is slightly inferior. C: At least one of antibacterial activity and antifungal property is inferior.
[0064]
As can be seen from Table 4, the antifungal layered silicate of the present invention is excellent in both antibacterial and antifungal properties, and is washed for a long time as compared with the case where an organic compound having an antifungal agent is directly blended. However, the antifungal property is not lost and the durability of the antifungal effect is excellent. In addition, it has an excellent antifungal ability that prevents germination of spores belonging to fungi.
[0065]
【The invention's effect】
The antibacterial and antifungal composition of the present invention is excellent in both antibacterial and antifungal properties, and particularly excellent in antifungal performance against fungi.
Due to this characteristic, the antibacterial and antifungal composition of the present invention is made of various rubbers, plastics, and the like, and molded articles such as films and sheets made of them, and various fibers, paper, leather, paints, adhesives, heat insulating materials, caulking It is useful as an antibacterial and antifungal agent applied to materials and the like.

Claims (2)

An antifungal organic compound which is an organic compound having one or more nitrogen atoms in the ring, a haloalkylthio organic compound, or an azole derivative compound is supported between layers of the layered silicate. An antibacterial and antifungal composition comprising an antifungal layered silicate and an inorganic antibacterial agent represented by the following general formula [4] .
_{^{M 1 a A b M 2 (}} PO 4) 3 · nH 2 O [4]
(M ¹ is at least one metal ion selected silver, copper, zinc, tin, mercury, lead, iron, cobalt, nickel, manganese, arsenic, antimony, bismuth, barium, cadmium or chromium, A is an alkali It is at least one ion selected from metal ions, alkaline earth metal ions, ammonium ions, or hydrogen ions, M ² is a tetravalent metal, n is a number that satisfies 0 ≦ n ≦ 6, and a and b Is a positive number satisfying la + mb = 1, where l is the valence of M ¹ and m is the valence of A.) The antibacterial and antifungal composition according to claim 1, further comprising at least one metal oxide selected from zinc oxide and titanium dioxide.