JP3824120B2 - Photopolymerizable monomer composition having antibacterial properties, and solvent-free ultraviolet and electron beam curable resin compositions having antibacterial properties - Google Patents
Photopolymerizable monomer composition having antibacterial properties, and solvent-free ultraviolet and electron beam curable resin compositions having antibacterial properties Download PDFInfo
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Description
【０００１】
【発明の属する技術分野】
本発明は，銀系無機抗菌剤の微粒子を分散した，重合硬化後にすべて樹脂となり環境に悪影響を与える有機溶剤を一切生じない抗菌性を有する光重合性モノマー組成物，および該光重合性モノマー組成物を添加した，抗菌性を有する無溶剤タイプの紫外線および電子線硬化樹脂組成物に関するもので，フローリング，階段，手摺，机，紙器，包装材，タッチパネル，金属容器，電話器、複写機、パソコン、ファクシミリ、医療機器、病院用掃除機などに塗装または印刷，コーティングすることにより，それらに抗菌・防カビ性を付与できるものである。
【０００２】
【従来の技術】
従来、銀イオンが抗菌・防カビ性を有していることは知られており、銀イオンを各種の無機物質に担持した銀系無機抗菌剤について種々の発明がなされている。例えば、特公昭６３−５４０１３号公報には、比表面積の大きいゼオライトにイオン交換により銀イオンを担持させた殺菌性ゼオライト組成物が、特開昭６２−２１００９８号公報には、酸化銀を添加溶融した抗菌性ガラスが、特開平１−２２１３０４号公報には、モンモリロナイト等の無機層状化合物の層間にアンミン銀を担持させた抗菌剤が、特開平２−９６５０８号公報には、難溶性リン酸塩や縮合リン塩酸に銀イオンを担持させた抗菌剤が、特開平３−８３９０６号公報には、リン酸ジルコニウムにイオン交換により銀イオンを担持させた抗菌剤が、特開平３−２１８７６５号公報には、ハイドロキシアパタイトに銀イオンを吸着保持させた後焼成して得た抗菌剤が、更に、特開平３−２７５６２７号公報には、マグネシウムアルミノケイ酸塩に銀イオンを担持させた抗菌剤が開示されている。
【０００３】
一般的に銀系無機抗菌剤は粉末であり，塗料やインクなどにそのまま混ぜると攪拌機で分散しても，二次凝集を起こすため使用できなかった。このような問題点を解決するものとして，特開平６−２４７８１７号公報には、有機溶剤の中で銀系無機抗菌剤を湿式粉砕することにより，溶剤系の塗料やインキなどにそのまま添加しても二次凝集が生じないという特徴を有する，平均粒子径が０．３μm以下の銀系無機抗菌剤微粒子の懸濁液が開示されている。
【０００４】
【発明が解決しようとする課題】
しかし，有機溶剤は，地球温暖化やシックハウスなどの問題があり，これら有機溶剤を一切含まず，現場でそのまま塗料等に添加でき，または多品種少量生産の塗料あるいはインキ，コーティング材などにも対応できる使い勝手の極めて良い無溶剤タイプの銀系無機抗菌剤微粒子の懸濁液，または銀系無機抗菌剤微粒子を含んだ無溶剤タイプの紫外線または電子線硬化樹脂の塗料あるいはインキ，コーティング材が望まれていた。
【０００５】
【課題を解決するための手段】
上記の問題を達成するために、無溶剤タイプの紫外線または電子線硬化樹脂に添加して使用するための抗菌性を有する光重合性モノマー組成物であって、光重合性モノマーに銀系無機抗菌剤の粉末を加えたのち、湿式粉砕機を用いて粉砕することにより、平均粒子径が０．５μmを超え１．５μm以下の範囲にある銀系無機抗菌剤の微粒子を光重合性モノマーに分散したことを特徴とする、抗菌性を有する光重合性モノマー組成物，および無溶剤タイプ紫外線または電子線硬化樹脂に該抗菌性を有する光重合性モノマー組成物を添加して，０．０５〜３０重量％の銀系無機抗菌剤微粒子を含ませたことを特徴とする，抗菌性を有する無溶剤タイプの紫外線および電子線硬化樹脂組成物を提供する。
【０００６】
本発明に用いる銀系無機抗菌剤は、銀イオンを各種の無機物質に担持した銀系無機抗菌剤、例えば、抗菌・防カビ性リン酸塩（特願平２−４１８２７７号、特願平３−３１５６１８号）、前述の殺菌性ゼオライト組成物、抗菌性ガラス、モンモリロナイト等の無機層状化合物の層間にアンミン銀を担持させた抗菌剤難溶性リン酸塩や縮合リン酸塩に銀イオンを担持させた抗菌剤、リン酸ジルコニウムにイオン交換により銀イオンを担持させた抗菌剤、ハイドロキシアパタイトに銀イオンを吸着保持させた後焼成して得た抗菌剤、及びマグネシウムアルミノケイ酸塩に銀イオンを担持させた抗菌剤などを，制限なく利用できるが，これらに限られるものではない。
【０００７】
本発明に用いる光重合性モノマーとしては、２−エチルヘキシルアクリレート，２−ヒドロキシエチルアクリレート，２−ヒドロキシプロピルアクリレート，２−ヒドロキシエチルアクリロイルホスフェート，１，３−ブタンジオールジアクリレート，１，４−ブタンジオールジアクリレート，１，６−ヘキサンジオールジアクリレート，ジエチレングリコールジアクリレート，トリプロピレングリコールジアクリレート，ネオベンチルグリコールジアクリレート，ポリエチレングリコール４００ジアクリレート，ヒドロキシビバリン酸エステルネオベンチルグリコールジアクリレート，トリメチロールプロパントリアクリレート，ペンタエリスリトールトリアクリレート，ジペンタエリスリトールヘキサアクリレートなどの少なくとも１種を使用できるが，これらに限られるものではない。
【０００８】
また，これら光重合性モノマーとプレポリマーであるオリゴマーとを混ぜて使用してもよい。これら光重合性モノマーは、銀系無機抗菌剤を溶解することがなく，銀イオンもほとんど光重合性モノマーに移行することがないので、懸濁液が光で変色するなどの問題がないので好都合である。なお，これら光重合性モノマーが長期の保存などで変質しないように，公知の重合防止剤を添加してもよい。
【０００９】
本発明に関わる平均粒子径が０．５μmを超え１．５μm以下の範囲にある銀系無機抗菌剤の微粒子を光重合性モノマーに分散する方法は，銀系無機抗菌剤および光重合性モノマーを，公知の媒体ミル、遊星ミル、振動ボ−ルミル、ボ−ルミルなどの湿式粉砕機にかけることにより得られる。このとき粉砕を促進させ，分散性を改善するためなどに公知の分散剤や，チタネート系，アルミニウム系およびシラン系カップリング剤などを制限なく用いてもよい。
【００１０】
このとき銀系無機抗菌剤の平均粒子径は、分散性および保存安定性に優れた懸濁液を得るために０．５μmを超え１．５μm以下の範囲とすることが好ましく，０．６〜１．０μmとすることがより好ましい。平均粒子径が０．５μm以下とするには大きな粉砕エネルギーを必要とし，光重合性モノマーを変質させることから好ましくない。また，平均粒子径が１．５μmを超えると抗菌剤が沈降固化し易くなり，安定した懸濁液が得られないので好ましくない。
【００１１】
本発明に係わる無溶剤タイプの紫外線または電子線硬化樹脂は，木材塗装，紙・フィルムの印刷，金属印刷，プラスチック容器の印刷，プラスチックのハードコートおよびメタライジング加工などに用いられる，ラジカル重合型，ラジカル付加重合型およびカチオン重合型などの無溶剤タイプの紫外線または電子線硬化樹脂を制限なく使用できる。
【００１２】
本発明に係わる抗菌性を有する無溶剤タイプの紫外線および電子線硬化樹脂組成物は，前述の光重合性モノマー組成物を添加して，上述の無溶剤タイプの紫外線または電子線硬化樹脂に０．０５〜３０重量％の銀系無機抗菌剤微粒子を含ませ，より好ましくは０．２〜３重量％とする。０．０５重量％未満では，紫外線または電子線を照射して硬化させた塗膜の抗菌性が不十分であり，３０重量％を超えると塗膜の物性に著しい悪影響を及ぼすので好ましくない。
【００１３】
【作用】
本発明は上記のような構成を採用することにより、銀系無機抗菌剤の微粒子を含むにも拘わらず分散性および保存安定性に優れた光重合性モノマー組成物を可能とし，該光重合性モノマー組成物を添加した抗菌性を有する無溶剤タイプ紫外線および電子線硬化樹脂組成物は，フローリング，階段，手摺，机，紙器，包装材，タッチパネル，金属容器，電話器、複写機、パソコン、ファクシミリ、医療機器、病院用掃除機などに塗装または印刷，コーティングすることにより，重合硬化後にすべて樹脂となり環境に悪影響を与える有機溶剤を一切生じないで，それらに抗菌・防カビ性を付与できる。
【００１４】
【発明の実施の形態】
１．銀系無機抗菌剤の調製
［参考実施例１］ 抗菌・防カビ性リン酸塩の調製
２５％リン酸水溶液７５０mlを５０℃に加熱し、撹拌しながら酸化亜鉛（ＺｎＯ）１９４．７ｇを加えて反応させ、更に水酸化カルシウム（Ｃａ（ＯＨ）２）３５．４ｇを加えて反応させる。反応スラリ−を温室に冷却した後、２lボ−ルミルに移し、６時間連和してから硝酸銀（ＡｇＮＯ３）２５．２ｇを添加し、更に４時間連和を続けた。得られた反応スラリ−を水洗し、濾過した後、２５０℃で乾燥し、粉砕して粉末（以下「粉末１」という）とした。粉末１に担持された銀イオンの含有量は、３．０重量％、平均粒径は２．７μmであった。
【００１５】
［参考実施例２］ ゼオライトを担持体とした抗菌剤の調製
１／２０Ｍ硝酸銀水溶液１，５００mlにナトリウムタイプのＡ型ゼオライト（東ソ−製トヨビルダ−）の乾燥物２５０ｇを加え、温室にて３時間撹拌してから濾過し、水洗して過剰の銀イオンを除去した。これを１１０℃で乾燥し、粉砕して粉末（以下「粉末２」という）とした。粉末２に担持された銀イオンの含有量は３．１重量％、平均粒径は３．１μmであった。
【００１６】
［参考実施例３］リン酸ジルコニウムを担持体とした抗菌剤の調整
１／２０Ｍ硝酸銀水溶液１，５００mlにリン酸ジルコニウム（ＩＸＥ−１００；東亜合成化学製）の乾燥物２５０ｇを加え、温室にて３時間撹拌してから濾過し、水洗して過剰な銀イオンを除去した。これを１１０℃で乾燥し、粉砕して粉末（以下「粉末３」という）とした。粉末３に担持された銀イオンの含有量は３．０重量％、平均粒径は０．７２μmであった。
【００１７】
２．光重合モノマー組成物の調製
［実施例１］
トリプロピレングリコールジアクリレート３ｋｇに参考実施例１で得た「粉末１」３ｋｇを加え、ホモジナイザ−で１０分間分散混合してから、媒体ミル（容量１リットルのパ−ルミルＰＭＩＲＬ−Ｖ型、アシザワ製）を用いて湿式粉砕した。２mm径のアルミナ製の粉砕ビ−ズ（新東Ｖセラックス製）１，１５０ｇを用い、５００ml／minの処理スピ−ドで５パス行って光重合モノマー組成物（以下「モノマー組成物１」という）を得た。モノマー組成物１に含まれる銀系無機抗菌剤微粒子の平均粒子径は０．６７μmであった。また，得られたモノマー組成物１をブリキ缶に入れ、１ヶ月間放置したが、沈降固化は全く見られなかった。
【００１８】
［実施例２］
２−ヒドロキシエチルアクリレート３kｇにチタネ−ト系カップリング剤（味の素（株）製、品名：プレンアクトＫＲＴＴＳ）３０ｇと参考実施例２で得た「粉末２」３ｋｇを加え、ホモジナイザ−で１０分間分散混合してから、媒体ミル（容量１リットルのパ−ルミルＰＭＩＲＬ−Ｖ型、アシザワ製）を用いて湿式粉砕した。２mm径のアルミナ製の粉砕ビ−ズ（新東Ｖセラックス製）１，１５０ｇを用い、１パス５００ml／minの処理スピ−ドで５パス行って光重合モノマー組成物（以下「モノマー組成物２」という）を得た。モノマー組成物２に含まれる銀系無機抗菌剤微粒子の平均粒子径は０．８３μmであった。また、得られたモノマー組成物２をブリキ缶に入れ、１ヶ月間放置したが、沈降固化は全く見られなかった。
【００１９】
［実施例３］
ペンタエリスリトールトリアクリレート３ｋｇにアルミニウム系カップリング剤（味の素（株）製，品名：プレンアクトＡＬ−Ｍ）３０ｇと参考実施例３で得た「粉末３」３ｋｇを加え、ホモジナイザ−で１０分間分散混合してから、媒体ミル（１Ｌパ−ルミルＰＭＩＲＬ−Ｖ型、アシザワ製）を用いて湿式粉砕した。２mm径のアルミナ製の粉砕ビ−ズ（新東Ｖセラックス製）１，１５０ｇを用い、１パス５００ml／minの処理スピ−ドで５パス行って光重合モノマー組成物（以下「モノマー組成物３」という）を得た。モノマー組成物３に含まれる銀系無機抗菌剤微粒子の平均粒子径は０．６８μmであった。また、得られたモノマー組成物３をブリキ缶に入れ、１ヶ月間放置したが、沈降固化は全く見られなかった。
【００２０】
［実施例４］ 紫外線硬化塗料の調製
抗菌剤濃度が１重量％となるようにモノマー組成物１，２および３をそれぞれ無溶剤タイプウレタンアクリレート紫外線硬化塗料に添加し攪拌機で混合して，抗菌性を有する無溶剤タイプ紫外線および電子線硬化樹脂組成物（以下「樹脂組成物１」，「樹脂組成物２」および「樹脂組成物３」という）を得た。また、得られた樹脂組成物をそれぞれブリキ缶に入れ、２ヶ月間放置したが、異常は全く見られなかった。
【００２１】
[実施例５] 試験片の作製
上で得られた樹脂組成物１，２，および３をそれぞれロールコーターでポリエステル樹脂シート（厚さ１００μｍ）に塗布してから，紫外線を照射して塗料を硬化させ，試験片（以下それぞれ「試験片１」，「試験片２」および「試験片３」という）を得た。また，同様にして抗菌剤が入っていない塗料で試験片（以下「試験片０」という）を得た。
【００２２】
３．抗菌性およびカビ抵抗性試験
［実施例６］ 抗菌性試験
実施例５で得られた「試験片１」，「試験片２」，「試験片３」および「試験片０」について抗菌性試験を行った。ここでは試験片（５０×５０mm）２枚を塗装面を外側にして接着剤で貼り合わせたものを試験片とした。該試験片が丁度入るようにポリエチレンフィルムをヒ−トシ−ルして袋を作った。この袋に試験片を入れて、大腸菌（ＩＦＯ３９７２）および黄色ブドウ球菌（ＩＦＯ１２７３２）を用い加圧密着法により抗菌性試験を行った。これらの試験片を入れたポリエチレン袋の中に菌液を０．１ml滴下した後、テストピ−スの両面に菌液が隈なく行き渡るようにした後、フィルム内部の空気を排出し密閉した。その後、重しで加圧してふ卵器に入れ、２４時間後にリン酸緩衝液（１０ml）で袋中の生残菌を洗い出し、この洗い出し液１mlについて、ＳＣＤＬＰ寒天培地を用い混釈平板培養法により生残菌数を測定した。その結果（表１）から、本発明による光重合モノマ−組成物を添加した紫外線硬化塗料を用いた試験片は、顕著な抗菌性が認められた。
【００２３】
【表１】
[実施例７] カビ抵抗性試験
実施例５で得られた「試験片１」，「試験片２」，「試験片３」および「試験片０」についてカビ抵抗性試験を行った。あらかじめ滅菌しておいた寒天をシャ−レに入れ固化させた。その寒天の上に試験片をそれぞれのシャーレに置いた。また，０．００５％スルホコハク酸ジオクチルナトリウム水溶液１０mlに別途培養したアスペルギルス・ニガ−（ＩＦＯ４４１４）を５白金耳取り、遠心分離により胞子を分離し，その胞子を生理食塩水１０mlに入れた菌液をそれぞれのシャ−レの試験片の上に墳霧し、２５℃、１４日間ふ卵器で培養した。その結果（表２）から、本発明による光重合モノマー組成物を添加した紫外線硬化塗料を用いた試験片は、顕著なカビ抵抗性が認められた。
【００２５】
【表２】
【発明の効果】
以上の説明から明らかなように、本発明に係わる抗菌性を有する光重合性モノマー組成物にあっては，分散性および保存安定性に優れ，取扱いも容易で，無溶剤タイプの紫外線および電子線硬化樹脂にそのまま添加することにより簡単に得られる，抗菌性を有する無溶剤タイプの紫外線および電子線硬化樹脂組成物は，分散性に優れ、長期保存しても沈降・固化することがなく，フローリング，階段，手摺，机，紙器，包装材，タッチパネル，金属容器，電話器、複写機、パソコン、ファクシミリ、医療機器、病院用掃除機などに塗装または印刷，コーティングすることにより，重合硬化後にすべて樹脂となり環境に悪影響を与える有機溶剤を一切生じないで，それらに顕著な抗菌・防カビ性を付与できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a photopolymerizable monomer composition having antibacterial properties in which fine particles of a silver-based inorganic antibacterial agent are dispersed, which becomes a resin after polymerization and curing and does not produce any organic solvent that adversely affects the environment, and the photopolymerizable monomer composition things were added, it relates ultraviolet and electron beam curable resin composition of the non-solvent type having antimicrobial, flooring, stairs, handrails, desk, paper containers, packaging material, a touch panel, a metal container, telephones, copying machines, computer By coating, printing, or coating on facsimiles, medical equipment, hospital vacuum cleaners, etc., they can be given antibacterial and antifungal properties.
[0002]
[Prior art]
Conventionally, it is known that silver ions have antibacterial and antifungal properties, and various inventions have been made on silver-based inorganic antibacterial agents in which silver ions are supported on various inorganic substances. For example, Japanese Patent Publication No. 63-54013 discloses a bactericidal zeolite composition in which silver ions are supported on a zeolite having a large specific surface area by ion exchange, and Japanese Patent Application Laid-Open No. 62-210098 discloses addition and melting of silver oxide. JP-A-1-221304 discloses an antibacterial agent in which ammine silver is supported between layers of an inorganic layered compound such as montmorillonite, and JP-A-2-96508 discloses a sparingly soluble phosphate. An antibacterial agent in which silver ions are supported on condensed phosphoric hydrochloric acid is disclosed in JP-A-3-83906, and an antibacterial agent in which silver ions are supported on zirconium phosphate by ion exchange is disclosed in JP-A-3-218765. An antibacterial agent obtained by adsorbing and holding silver ions on hydroxyapatite and then baking is further disclosed in JP-A-3-275627 as magnesium aluminum. Antibacterial agents obtained by supporting silver ion into the silicate is disclosed.
[0003]
In general, silver-based inorganic antibacterial agents are powders, and when mixed in paints and inks as they are, they can not be used because they cause secondary aggregation even when dispersed with a stirrer. In order to solve such problems, Japanese Patent Application Laid-Open No. 6-247817 discloses that a silver-based inorganic antibacterial agent is wet pulverized in an organic solvent and added as it is to a solvent-based paint or ink. Also disclosed is a suspension of silver-based inorganic antibacterial fine particles having an average particle size of 0.3 μm or less, which is characterized in that secondary aggregation does not occur.
[0004]
[Problems to be solved by the invention]
However, organic solvents have problems such as global warming and sick house. These organic solvents are not included at all and can be added to paints as they are on site, or they can be used for paints, inks, coating materials, etc. produced in small quantities. Suspension of solvent-free silver-based inorganic antibacterial fine particles that are extremely easy to use, or solvent-free ultraviolet or electron beam curable resin paints, inks, or coating materials containing silver-based inorganic antibacterial fine particles are desired. It was.
[0005]
[Means for Solving the Problems]
In order to achieve the above problems, a photopolymerizable monomer composition having antibacterial properties for use in addition to a solvent-free ultraviolet or electron beam curable resin, wherein the silver-based inorganic antibacterial agent is used as the photopolymerizable monomer. After adding the powder of the agent, the fine particles of the silver-based inorganic antibacterial agent having an average particle diameter exceeding 0.5 μm and 1.5 μm or less are dispersed in the photopolymerizable monomer by pulverization using a wet pulverizer The photopolymerizable monomer composition having antibacterial properties, and the photopolymerizable monomer composition having antibacterial properties added to a solventless ultraviolet or electron beam curable resin, Provided is a solvent-free ultraviolet and electron beam curable resin composition having antibacterial properties, characterized by containing fine particles of silver-based inorganic antibacterial agent by weight%.
[0006]
The silver-based inorganic antibacterial agent used in the present invention is a silver-based inorganic antibacterial agent in which silver ions are supported on various inorganic substances, for example, an antibacterial / antifungal phosphate (Japanese Patent Application No. 2-418277, Japanese Patent Application No. 3). No. 315618), antibacterial poorly soluble phosphates or condensed phosphates in which an ammine silver is supported between layers of an inorganic layered compound such as the aforementioned bactericidal zeolite composition, antibacterial glass, montmorillonite, etc. Antibacterial agent, silver phosphate supported on zirconium phosphate by ion exchange, antibacterial agent obtained by adsorbing and holding silver ion on hydroxyapatite and baking, and magnesium aluminosilicate supporting silver ion Antibacterial agents can be used without limitation, but are not limited to these.
[0007]
Examples of the photopolymerizable monomer used in the present invention include 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethylacryloyl phosphate, 1,3-butanediol diacrylate, 1,4-butanediol. Diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, tripropylene glycol diacrylate, neobendyl glycol diacrylate, polyethylene glycol 400 diacrylate, hydroxybivalate ester neoventyl glycol diacrylate, trimethylolpropane At least one of triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, etc. Can be used, not limited thereto.
[0008]
Further, these photopolymerizable monomers and prepolymer oligomers may be mixed and used. These photopolymerizable monomers do not dissolve the silver-based inorganic antibacterial agent, and silver ions hardly transfer to the photopolymerizable monomer, so there is no problem such as the suspension being discolored by light. It is. In addition, you may add a well-known polymerization inhibitor so that these photopolymerizable monomers may not change by long-term storage etc.
[0009]
A method of dispersing the fine particles of the silver based inorganic antibacterial agent having an average particle diameter according to the present invention is to 0.5μm in the following ranges exceed 1.5μm photopolymerizable monomer, a silver based inorganic antibacterial agent and a photopolymerizable monomer Is obtained by subjecting to a wet mill such as a known media mill, planetary mill, vibrating ball mill, ball mill or the like. At this time, in order to promote pulverization and improve dispersibility, known dispersants, titanate-based, aluminum-based and silane-based coupling agents may be used without limitation.
[0010]
The average particle diameter in this case silver based inorganic antibacterial agent is preferably to exceed 1.5μm following range 0.5μm to obtain a good suspension dispersibility and storage stability, 0.6 It is more preferable to set it to -1.0 micrometer. A large pulverization energy is required to make the average particle size 0.5 μm or less, which is not preferable because the photopolymerizable monomer is altered. The average particle diameter of 1.5μm is exceeded and antimicrobial agent tends to settle solidified undesirable because not obtained a stable suspension.
[0011]
Solvent-free ultraviolet or electron beam curable resins for use in the present invention, wood coatings, printing paper and film, metal printing, plastic containers, used for hard coat and metallizing processing plastics, radical polymerization type, the solvent-free ultraviolet or electron beam curable resins such as a radical addition polymerization and cationic polymerization type can be used without limitation.
[0012]
Ultraviolet and electron beam curable resin composition of the non-solvent type having antimicrobial according to the present invention, by adding the aforementioned photopolymerizable monomer composition, the solvent-free ultraviolet or electron beam curable resins described above zero. It contains 0.5 to 30% by weight of silver-based inorganic antibacterial agent fine particles, more preferably 0.2 to 3% by weight. It is less than 0.05 wt%, is insufficient antimicrobial coating film was cured by irradiation with ultraviolet light or an electron beam, since 30 wt% Significant adverse effect on the physical properties of the ultra-El and coating is not preferred.
[0013]
[Action]
By adopting the configuration as described above, the present invention enables a photopolymerizable monomer composition excellent in dispersibility and storage stability despite containing fine particles of a silver-based inorganic antibacterial agent. Antibacterial solvent-free UV and electron beam curable resin composition with added monomer composition is flooring, staircase, handrail, desk, paper container, packaging material, touch panel, metal container, telephone, copier, personal computer, facsimile By painting, printing, or coating on medical equipment, hospital vacuum cleaners, etc., it becomes an all-resin after polymerization and curing, and no organic solvent that adversely affects the environment is generated, and it can be given antibacterial and antifungal properties.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
1. Preparation of silver-based inorganic antibacterial agent [Reference Example 1] Preparation of antibacterial / antifungal phosphate 750 ml of 25% aqueous phosphoric acid solution was heated to 50 ° C., and 194.7 g of zinc oxide (ZnO) was added while stirring. Further, 35.4 g of calcium hydroxide (Ca (OH) 2 ) is added and reacted. After cooling the reaction slurry to the greenhouse, it was transferred to a 2 liter ball mill, mixed for 6 hours, then added with 25.2 g of silver nitrate (AgNO 3 ), and continued for another 4 hours. The obtained reaction slurry was washed with water, filtered, dried at 250 ° C., and pulverized to obtain a powder (hereinafter referred to as “powder 1”). The content of silver ions supported on the powder 1 was 3.0% by weight, and the average particle size was 2.7 μm.
[0015]
[Reference Example 2] Preparation of antibacterial agent using zeolite as support body To 1,500 ml of 1/20 M silver nitrate aqueous solution, 250 g of a dried product of sodium type A zeolite (Toyo Builder manufactured by Tosoh Corporation) was added, and 3 g in a greenhouse. After stirring for a period of time, the mixture was filtered and washed with water to remove excess silver ions. This was dried at 110 ° C. and pulverized to obtain a powder (hereinafter referred to as “powder 2”). The content of silver ions supported on the powder 2 was 3.1% by weight, and the average particle size was 3.1 μm.
[0016]
[Reference Example 3] Preparation of antibacterial agent using zirconium phosphate as a support body To 1,500 ml of 1/20 M silver nitrate aqueous solution, 250 g of a dried product of zirconium phosphate (IXE-100; manufactured by Toagosei Co., Ltd.) was added. After stirring for 3 hours, the mixture was filtered and washed with water to remove excess silver ions. This was dried at 110 ° C. and pulverized to obtain a powder (hereinafter referred to as “powder 3”). The content of silver ions supported on the powder 3 was 3.0% by weight, and the average particle size was 0.72 μm.
[0017]
2. Preparation of photopolymerizable monomer composition [Example 1]
3 kg of “Powder 1” obtained in Reference Example 1 was added to 3 kg of tripropylene glycol diacrylate, dispersed and mixed with a homogenizer for 10 minutes, and then a media mill (Pal mill PMIRL-V type with a capacity of 1 liter, manufactured by Ashizawa) ). Using 1,150 g of pulverized beads made of alumina having a diameter of 2 mm (manufactured by Shinto V Serax), a photopolymerization monomer composition (hereinafter referred to as “monomer composition 1”) was performed for 5 passes at a treatment speed of 500 ml / min. ) The average particle diameter of the silver-based inorganic antibacterial fine particles contained in the monomer composition 1 was 0.67 μm. Further, the obtained monomer composition 1 was put in a tin can and allowed to stand for 1 month, but no precipitation solidification was observed.
[0018]
[Example 2]
Add 30g of titanate coupling agent (Ajinomoto Co., Ltd., product name: Preneact KRTTS) and 3kg of "Powder 2" obtained in Reference Example 2 to 3kg of 2-hydroxyethyl acrylate, and disperse and mix for 10 minutes with a homogenizer. Then, wet pulverization was performed using a medium mill (Pal Mill PMIRL-V type having a capacity of 1 liter, manufactured by Ashizawa). A photopolymerization monomer composition (hereinafter referred to as “monomer composition 2”) was prepared by using 1,150 g of a 2 mm diameter crushed bead made of alumina (manufactured by Shinto V Serax) at a treatment speed of 1 pass of 500 ml / min for 5 passes. "). The average particle diameter of the silver-based inorganic antibacterial fine particles contained in the monomer composition 2 was 0.83 μm. Further, the obtained monomer composition 2 was put in a tin can and allowed to stand for 1 month, but no precipitation solidification was observed.
[0019]
[Example 3]
To 3 kg of pentaerythritol triacrylate, 30 g of an aluminum coupling agent (manufactured by Ajinomoto Co., Inc., product name: Preneact AL-M) and 3 kg of “Powder 3” obtained in Reference Example 3 are added, and dispersed and mixed for 10 minutes with a homogenizer. Then, it was wet pulverized using a media mill (1 L Pal Mill PMIRL-V type, manufactured by Ashizawa). A photopolymerization monomer composition (hereinafter referred to as “monomer composition 3”) was obtained by using 1,150 g of a 2 mm diameter crushed bead made of alumina (manufactured by Shinto V Serax) at a treatment speed of 1 pass of 500 ml / min for 5 passes. "). The average particle diameter of the silver-based inorganic antibacterial fine particles contained in the monomer composition 3 was 0.68 μm. Further, the obtained monomer composition 3 was put in a tin can and allowed to stand for 1 month, but no precipitation solidification was observed.
[0020]
[Example 4] Preparation of UV-curable paint Monomer compositions 1, 2 and 3 were added to a solvent-free urethane acrylate UV-curable paint so that the antibacterial agent concentration would be 1% by weight and mixed with a stirrer to obtain antibacterial properties. Solvent-free ultraviolet and electron beam curable resin compositions (hereinafter referred to as “resin composition 1”, “resin composition 2” and “resin composition 3”) were obtained. Further, each of the obtained resin compositions was put in a tin can and allowed to stand for 2 months, but no abnormality was observed.
[0021]
[Example 5] Resin compositions 1, 2, and 3 obtained in the preparation of test pieces were each applied to a polyester resin sheet (thickness: 100 μm) with a roll coater, and then cured by irradiating with ultraviolet rays. Thus, test specimens (hereinafter referred to as “test specimen 1”, “test specimen 2”, and “test specimen 3”) were obtained. Similarly, a test piece (hereinafter referred to as “test piece 0”) was obtained with a paint containing no antibacterial agent.
[0022]
3. Antibacterial and fungal resistance test [Example 6] Antibacterial test was conducted on "Test piece 1", "Test piece 2", "Test piece 3" and "Test piece 0" obtained in Antibacterial test example 5. went. Here, a test piece was prepared by bonding two test pieces (50 × 50 mm) together with an adhesive with the coating surface facing outward. A polyethylene film was heat-sealed so that the test piece just entered and a bag was made. A test piece was put in this bag, and an antibacterial test was conducted by a pressure contact method using Escherichia coli (IFO3972) and Staphylococcus aureus (IFO12732). After 0.1 ml of the bacterial solution was dropped into a polyethylene bag containing these test pieces, the bacterial solution was allowed to spread over both sides of the test piece, and then the air inside the film was discharged and sealed. After that, pressurize with a weight and put into an incubator. After 24 hours, wash out the surviving bacteria in the bag with phosphate buffer solution (10 ml), and use 1 ml of this washing solution by pour plate culture method using SCDLP agar medium. The number of surviving bacteria was measured. From the result (Table 1), the test piece using the ultraviolet curable coating material to which the photopolymerized monomer composition according to the present invention was added showed remarkable antibacterial properties.
[0023]
[Table 1]
[Example 7] Mold resistance test The "test specimen 1", "test specimen 2", "test specimen 3" and "test specimen 0" obtained in Example 5 were subjected to a mold resistance test. Agar previously sterilized was placed in a dish and solidified. A test piece was placed on each petri dish on the agar. In addition, 5 platinum Aspergillus niger (IFO4414) separately cultured in 10 ml of 0.005% dioctyl sodium sulfosuccinate aqueous solution was collected, and the spore was separated by centrifugation, and the spore was placed in 10 ml of physiological saline. It sprayed on the test piece of each dish, and it culture | cultivated with the incubator at 25 degreeC for 14 days. From the results (Table 2), the test piece using the ultraviolet curable paint to which the photopolymerizable monomer composition according to the present invention was added showed remarkable mold resistance.
[0025]
[Table 2]
【The invention's effect】
As apparent from the above description, in the photopolymerizable monomer composition with antimicrobial properties in accordance with the present invention, excellent dispersibility and storage stability, handling is easy, the solvent-free ultraviolet or electron beam obtained simply by directly added to the curable resin, UV and electron beam curing resin composition of the non-solvent type having antibacterial activity, excellent dispersibility, without having to settle and solidified even if long-term storage, flooring , Stairs, handrails, desks, paper containers, packaging materials, touch panels, metal containers, telephones, photocopiers, personal computers, facsimiles, medical equipment, hospital vacuum cleaners, etc. It does not produce any organic solvents that adversely affect the environment, and can impart remarkable antibacterial and antifungal properties to them.
Claims (2)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07402099A JP3824120B2 (en) | 1999-03-18 | 1999-03-18 | Photopolymerizable monomer composition having antibacterial properties, and solvent-free ultraviolet and electron beam curable resin compositions having antibacterial properties |
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|---|---|---|---|
| JP07402099A JP3824120B2 (en) | 1999-03-18 | 1999-03-18 | Photopolymerizable monomer composition having antibacterial properties, and solvent-free ultraviolet and electron beam curable resin compositions having antibacterial properties |
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| JP3824120B2 true JP3824120B2 (en) | 2006-09-20 |
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| DE102005050186A1 (en) * | 2005-10-18 | 2007-04-19 | Dreve Otoplastik Gmbh | Low viscosity, radiation-hardenable composition for antimicrobial medical products, especially adaptive ear pieces, is based on e.g. (meth)acrylates, glass or silver antimicrobials and photoinitiators |
| KR101312882B1 (en) * | 2007-12-07 | 2013-09-30 | (주)엘지하우시스 | Kitchen furniture having superior stain resistance |
| US20100135949A1 (en) * | 2008-12-01 | 2010-06-03 | Becton, Dickinson And Company | Antimicrobial compositions |
| JP2010173115A (en) * | 2009-01-27 | 2010-08-12 | Panasonic Electric Works Co Ltd | Woody plate |
| JP2011057855A (en) * | 2009-09-10 | 2011-03-24 | Univ Of Tokushima | Active energy ray-curable composition, coating agent and resin film |
| JP5935133B2 (en) * | 2012-03-29 | 2016-06-15 | フジコピアン株式会社 | Hard coat film |
| US9352119B2 (en) | 2012-05-15 | 2016-05-31 | Becton, Dickinson And Company | Blood control IV catheter with antimicrobial properties |
| US9579486B2 (en) | 2012-08-22 | 2017-02-28 | Becton, Dickinson And Company | Blood control IV catheter with antimicrobial properties |
| US9695323B2 (en) * | 2013-02-13 | 2017-07-04 | Becton, Dickinson And Company | UV curable solventless antimicrobial compositions |
| US9750928B2 (en) | 2013-02-13 | 2017-09-05 | Becton, Dickinson And Company | Blood control IV catheter with stationary septum activator |
| US10376686B2 (en) | 2014-04-23 | 2019-08-13 | Becton, Dickinson And Company | Antimicrobial caps for medical connectors |
| US9789279B2 (en) | 2014-04-23 | 2017-10-17 | Becton, Dickinson And Company | Antimicrobial obturator for use with vascular access devices |
| US9675793B2 (en) | 2014-04-23 | 2017-06-13 | Becton, Dickinson And Company | Catheter tubing with extraluminal antimicrobial coating |
| US10232088B2 (en) | 2014-07-08 | 2019-03-19 | Becton, Dickinson And Company | Antimicrobial coating forming kink resistant feature on a vascular access device |
| US10493244B2 (en) | 2015-10-28 | 2019-12-03 | Becton, Dickinson And Company | Extension tubing strain relief |
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1999
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