JP4339456B2 - Antibacterial paint and antibacterial product using the same - Google Patents

Description

【００７３】
８）塗膜の外観
前記実施例１〜１８および比較例１〜６で得られた試験片を用いて塗膜の状態を目視観察し、下記の基準で評価した。
良好；平滑かつ均一な外観に優れる良好な塗膜を形成している。
不良；平滑性に劣る、または不均一で外観に劣る塗膜を形成している。
【００７４】
９）塗膜の剥離
前記実施例１〜１８および比較例１〜６で得られた試験片を用いて塗膜の剥離状態を目視観察し、下記の基準で評価した。
なし；基材からの塗膜剥離は認められない。
あり；基材からの塗膜剥離が認められる。
【００７５】
１０）試験菌名
大腸菌；Ｅｓｃｈｅｒｉｃｈｉａ ｃｏｌｉ（ＩＦＯ３９７２）
黄色ブドウ球菌； Ｓｔａｐｈｙｌｏｃｏｃｃｕｓ ａｕｒｅｕｓ （ＩＦＯ１２７３２）
【００７６】
表１から明らかなように、本発明の実施例１〜１８で得られた試験片は比較例１〜６で得られた試験片と比較して、塗膜の外観および耐剥離性に有意差がなく優れた外観を示すことがわかる。さらに、ＰＣシート、 ＰＰシート、ＰＥシート、ＰＥＴシート、ＰＡシート、およびＡＬ箔の基材の違いによる塗膜の外観および耐剥離性に有意差がなく優れた外観を示すことがわかる。
また、本発明の実施例１〜１８で得られた試験片は比較例１〜６で得られた試験片と比較して、未洗浄試験片、洗浄試験片共に大腸菌および黄色ブドウ球菌に対する抗菌効果が優れていることがわかる。さらに、ＰＣシート、 ＰＰシート、ＰＥシート、ＰＥＴシート、ＰＡシート、およびＡＬ箔の基材の違いによる抗菌効果に有意差がないことがわかる。
【００７７】
実施例１９
ビニルピロリドンとビニルアセテートのコポリマー（組成比１：１）を２０重量部、ＩＰＡを１８０重量部、ε−ポリリジン２５重量％水溶液を２０重量部およびソルビタン系界面活性剤「ツイーン４０」を５重量部の割合で混合して得られた均一溶液を２０℃に２４時間保存して熟成させ、塗料を作製し、該塗料をＰＰシート上に塗布・製膜して試験片２５を作製し、所定の試験に供した。
【００７８】
実施例２０
ε−ポリリジン２５重量％水溶液を２０重量部の割合に代えてε−ポリリジン１０重量％水溶液を５０重量部の割合に代えた以外は実施例１９に準拠して試験片２６を作製し、所定の試験に供した。
【００７９】
比較例７
ε−ポリリジン水溶液を添加しなかった以外は実施例１９に準拠して試験片２７を作製し、所定の試験に供した。
【００８０】
１１）シートの外観観察試験２
前記の実施例１９〜２０および比較例７で得られた試験片の外観について目視で観察したところ、いずれの試料も優れた外観および耐剥離性を示した。
【００８１】
１２）抗菌性試験３、４
前記の実施例１９〜２０および比較例７で得られた試験片について抗菌性試験１および抗菌性試験２で述べた抗菌性試験方法と同様の方法で抗菌性試験を実施したしたところ、実施例１９〜２０で得られた試験片は比較例７で得られた試験片と比較して優れた抗菌効果を示した。
【００８２】
実施例２１
ＰＶＰのとＰＶＡＣの混合物（組成比１：１）を２０重量部、エチルアルコールを１５０重量部、メチルエチルケトンを５０重量部、ε−ポリリジン２５重量％水溶液を２０重量部の割合で混合して得られた均一溶液を２０℃に２４時間保存して熟成させ、塗料を作製し、該塗料をＰＰシート上に塗布・製膜して試験片２８を作製し、所定の試験に供した。
【００８３】
比較例８
ε−ポリリジン水溶液を添加しなかった以外は実施例２１に準拠して試験片２９を作製し、所定の試験に供した。
【００８４】
１３）シートの外観観察試験３
前記の実施例２１および比較例８で得られた試験片の外観について目視で観察したところ、いずれの試料も優れた外観および耐剥離性を示した。
【００８５】
１４）抗菌性試験５、６
前記の実施例２１および比較例８で得られた試験片について抗菌性試験１および抗菌性試験２で述べた抗菌性試験方法と同様の方法で抗菌性試験を実施したしたところ、実施例２１で得られた試験片は比較例８で得られた試験片と比較して優れた抗菌効果を示した。
【００８６】
実施例２２
ビニルピロリドンとビニルアセテートのコポリマー（組成比８：２）を２０重量部、ＩＰＡを１８０重量部、ε−ポリリジン２５重量％水溶液を２０重量部の割合で混合して得られた均一溶液を２０℃に２４時間保存して熟成させ、塗料を作製し、該塗料をＰＰシート上に塗布・製膜して試験片３０を作製し、所定の試験に供した。
【００８７】
比較例９
ε−ポリリジン水溶液を添加しなかった以外は実施例３７に準拠して試験片３１を作製し、所定の試験に供した。
【００８８】
１５）シートの外観観察試験４
前記の実施例２２および比較例９で得られた試験片の外観について目視で観察したところ、いずれの試料も優れた外観および耐剥離性を示した。
【００８９】
１６）抗菌性試験７、８
前記の実施例２２および比較例９で得られた試験片について抗菌性試験１および抗菌性試験２で述べた抗菌性試験方法と同様の方法で抗菌性試験を実施したしたところ、実施例２２で得られた試験片は比較例９で得られた試験片と比較して優れた抗菌効果を示した。
【００９０】
実施例２３
ε−ポリリジン２５重量％水溶液２０重量部を粉末状ε−ポリリジン（純度９７％）５重量部の割合に代えた以外は実施例４に準拠して試験片３２を作製し、所定の試験に供した。
【００９１】
１７）シートの外観観察試験５
前記の実施例２３および比較例２で得られた試験片の外観について目視で観察したところ、いずれの試料も優れた外観および耐剥離性を示した。
【００９２】
１８）抗菌性試験９、１０
前記の実施例２３および比較例２で得られた試験片について抗菌性試験１および抗菌性試験２で述べた抗菌性試験方法と同様の方法で抗菌性試験を実施したしたところ、実施例２３で得られた試験片は比較例２で得られた試験片と比較して優れた抗菌効果を示した。
【００９３】
実施例２４
ε−ポリリジン２５重量％水溶液２０重量部をε−ポリリジン担持シリカゲル１０重量部（ε−ポリリジン含有率１０重量％）に変更した以外は実施例１に準拠して試験片３３を作製し、所定の試験に供した。
【００９４】
１９）シートの外観観察試験６
前記の実施例２４および比較例２で得られた試験片の外観について目視で観察したところ、いずれの試料も優れた外観および耐剥離性を示した。
【００９５】
２０）抗菌性試験１１、１２
前記の実施例２４および比較例２で得られた試験片について抗菌性試験１および抗菌性試験２で述べた抗菌性試験方法と同様の方法で抗菌性試験を実施したしたところ、実施例２４で得られた試験片は比較例２で得られた試験片と比較して優れた抗菌効果を示した。
【００９６】
実施例２５
ε−ポリリジン２５重量％水溶液２０重量部をε−ポリリジン−グリシン混合物２０重量部（ε−ポリリジン含有率５重量％）に変更した以外は実施例１に準拠して試験片３４を作製し、所定の試験に供した。
【００９７】
２１）シートの外観観察試験７
前記の実施例２５および比較例２で得られた試験片の外観について目視で観察したところ、いずれの試料も優れた外観および耐剥離性を示した。
【００９８】
２２）抗菌性試験１３、１４
前記の実施例２５および比較例２で得られた試験片について抗菌性試験１および抗菌性試験２で述べた抗菌性試験方法と同様の方法で抗菌性試験を実施したしたところ、実施例２５で得られた試験片は比較例２で得られた試験片と比較して優れた抗菌効果を示した。。
【００９９】
実施例２６
ビニルピロリドンとビニルアセテートのコポリマー（組成比１：１）を２０重量部、ＩＰＡを１８０重量部、ε−ポリリジン２５重量％水溶液を２０重量部および１０重量％シリカゾルを含むエチルアルコール溶液を１０重量部の割合で混合して得られた均一溶液を２０℃に２４時間保存して熟成させ、塗料を作製し、該塗料をＰＰシート上に塗布・製膜して試験片３５を作製し、所定の試験に供した。
【０１００】
比較例１０
ε−ポリリジン水溶液を添加しなかった以外は実施例２６に準拠して試験片３６を作製し、所定の試験に供した。
【０１０１】
２３）シートの外観観察試験８
前記の実施例２６および比較例１０で得られた試験片の外観について目視で観察したところ、いずれの試料も優れた外観および耐剥離性を示した。
【０１０２】
２４）抗菌性試験１５、１６
前記の実施例２６および比較例１０で得られた試験片について抗菌性試験１および抗菌性試験２で述べた抗菌性試験方法と同様の方法で抗菌性試験を実施したしたところ、実施例２６で得られた試験片は比較例１０で得られた試験片と比較して優れた抗菌効果を示した。
【０１０３】
実施例２７
ＰＶＰとＰＶＡＣの混合物（組成比１：１）を２０重量部、ＩＰＡを１８０重量部、ε−ポリリジン２５重量％水溶液を１重量部およびヨードを０．００２重量部の割合に混合して得られた均一溶液を２０℃に２４時間保存して熟成させて、塗料を作製し、該塗料をＰＰシート上に塗布・製膜して試験片３７を作製し、所定の試験に供した。
【０１０４】
比較例１１
ヨードを添加しなかった以外は実施例２７に準拠して試験片３８を作製し、所定の試験に供した。
【０１０５】
比較例１２
ε−ポリリジン水溶液を添加しなかった以外は実施例２７に準拠して試験片３９を作製し、所定の試験に供した。
【０１０６】
２５）シートの外観観察試験９
前記の実施例２７および比較例１１〜１２で得られた試験片の外観について目視で観察したところ、いずれの試料も優れた外観および耐剥離性を示した。
【０１０７】
２６）抗菌性試験１７、１８
前記の実施例２７および比較例１１〜１２で得られた試験片について抗菌性試験１および抗菌性試験２で述べた抗菌性試験方法と同様の方法で抗菌性試験を実施したしたところ、実施例２７で得られた試験片は比較例１１〜１２で得られた試験片と比較して優れた抗菌効果を示した。
【０１０８】
実施例２８
ε−ポリリジン２５重量％水溶液を５重量部、シラン変成ポリメタクリル酸エステル（チッソ（株）サイラコートＳＣＴ−８１０１）の２０重量％ＩＰＡ−酢酸エチル混合溶液を９５重量部、シュガーエステルを１重量部の割合に混合して得られた均一溶液を２０℃に２４時間保存して熟成させて、塗料を作製し、該塗料を予めヘキサメチレンジイソシアネートの１重量％キシレン溶液で処理した５０ｍｍ×５０ｍｍ×１ｍｍのＰＣシート上に塗布・製膜して試験片４０を作製し、所定の試験に供した。
【０１０９】
比較例１３
ε−ポリリジン水溶液を添加しなかった以外は実施例２８に準拠して試験片４１を作製し、所定の試験に供した。
【０１１０】
実施例２８
基材をＰＣシートからＰＰシートに代えた以外は実施例２８に準拠して試験片４２を作製し、所定の試験に供した。
【０１１１】
比較例１４
基材をＰＣシートからＰＰシートに代えた以外は比較例１３に準拠して試験片４３を作製し、所定の試験に供した。
【０１１２】
実施例２９
基材をＰＣシートからＰＥシートに代えた以外は実施例２８に準拠して試験片４４を作製し、所定の試験に供した。
【０１１３】
比較例１５
基材をＰＣシートからＰＥシートに代えた以外は比較例１３に準拠して試験片４５を作製し、所定の試験に供した。
【０１１４】
実施例３０
基材をＰＣシートからＰＥＴシートに代えた以外は実施例２８に準拠して試験片４６を作製し、所定の試験に供した。
【０１１５】
比較例１６
基材をＰＣシートからＰＥＴシートに代えた以外は比較例１３に準拠して試験片４７を作製し、所定の試験に供した。
【０１１６】
実施例３１
基材をＰＣシートからＰＡシートに代えた以外は実施例２８に準拠して試験片４８を作製し、所定の試験に供した。
【０１１７】
比較例１７
基材をＰＣシートからＰＡシートに代えた以外は比較例１３に準拠して試験片４９を作製し、所定の試験に供した。
【０１１８】
実施例３２
基材をＰＣシートからＡＬ箔に代えた以外は実施例２８に準拠して試験片５０を作製し、所定の試験に供した。
【０１１９】
比較例１８
基材をＰＣシートからＡＬ箔に代えた以外は比較例１３に準拠して試験片５１を作製し、所定の試験に供した。
【０１２０】
２７）シートの外観観察試験１０
前記の実施例２８〜３３および比較例１３〜１８で得られた試験片の外観について目視で観察した。その結果を後述の表２に示した。
【０１２１】
２８）抗菌性試験１９、２０
前記の実施例２８〜３３および比較例１３〜１８で得られた試験片について抗菌性試験１および抗菌性試験２で述べた抗菌性試験方法と同様の方法で抗菌性試験を実施した。その結果を後述の表２に示した。
【０１２２】
【表２】

【０１２３】
２９）塗膜の外観
前記実施例２８〜３３および比較例１３〜１８で得られた試験片を用いて塗膜の状態を目視観察し、下記の基準で評価した。
良好；平滑かつ均一な外観に優れる良好な塗膜を形成している。
不良；平滑性に劣る、または不均一で外観に劣る塗膜を形成している。
３０）塗膜の剥離
前記実施例２８〜３３および比較例１３〜１８で得られた試験片を用いて塗膜の剥離状態を目視観察し、下記の基準で評価した。
なし；基材からの塗膜剥離は認められない。
あり；基材からの塗膜剥離が認められる。
【０１２４】
３１）試験菌名
大腸菌；Ｅｓｃｈｅｒｉｃｈｉａ ｃｏｌｉ（ＩＦＯ３９７２）
黄色ブドウ球菌； Ｓｔａｐｈｙｌｏｃｏｃｃｕｓ ａｕｒｅｕｓ （ＩＦＯ１２７３２）
【０１２５】
表２から明らかなように、本発明の実施例２８〜３３で得られた試験片は比較例１３〜１８で得られた試験片と比較して、塗膜の外観および耐剥離性に有意差がなく優れた外観を示すことがわかる。さらに、ＰＣシート、 ＰＰシート、ＰＥシート、ＰＥＴシート、ＰＡシート、およびＡＬ箔の基材の違いによる塗膜の外観および耐剥離性に有意差がなく優れた外観を示すことがわかる。
また、本発明の実施例２８〜３３で得られた試験片は比較例１３〜１８で得られた試験片と比較して、未洗浄試験片、洗浄試験片共に大腸菌および黄色ブドウ球菌に対する抗菌効果が優れていることがわかる。さらに、ＰＣシート、 ＰＰシート、ＰＥシート、ＰＥＴシート、ＰＡシート、およびＡＬ箔の基材の違いによる抗菌効果に有意差がないことがわかる。
【０１２６】
実施例３４
ε−ポリリジン２５重量％水溶液５重量部をシラン変成ポリメタクリル酸エステル（チッソ（株）サイラコートＳＣＴ−１１０１）の２０重量％ｎ−ブチルアルコール溶液９５重量部、アナタース型酸化チタン１０重量部、シュガーエステル１重量部を混合して得られた均一溶液を２０℃に２４時間保存して熟成させ、これを塗料として予めヘキサメチレンジイソシアネートの１％キシレン溶液で処理した５０ｍｍ×５０ｍｍ×１ｍｍのＰＰシート上に塗布・製膜して試験片５２を作製し、所定の試験に供した。
【０１２７】
比較例１９
ε−ポリリジン水溶液を添加しなかった以外は実施例３４に準拠して試験片５３を作製した。
【０１２８】
３２）シートの外観観察試験１１
前記の実施例３４および比較例１９で得られた試験片の外観について目視で観察したところ、いずれの試料も優れた外観および耐剥離性を示した。
【０１２９】
３３）抗菌性試験２１、２２
前記の実施例３４および比較例１９で得られた試験片について抗菌性試験１および抗菌性試験２で述べた抗菌性試験方法と同様の方法で抗菌性試験を実施したしたところ、実施例３４で得られた試験片は比較例１９で得られた試験片と比較して優れた抗菌効果を示した。
【０１３０】
実施例３５
ε−ポリリジン２５重量％水溶液５重量部、重合度約２５０−水酸基量約２０モル％のブチラール樹脂２０重量部、エチレングリコールブチルエーテル５重量部を混合して得られた均一溶液を２０℃に２４時間保存して熟成させ、これを塗料として５０ｍｍ ×５０ｍｍ ×１ｍｍのＰＣシート上に塗布・製膜して試験片５４を作製し、所定の試験に供した。
【０１３１】
実施例３６
ε−ポリリジン２５重量％水溶液を２．５重量部に代えた以外は実施例３５に準拠して試験片５５を作製した。
【０１３２】
実施例３７
ε−ポリリジン２５重量％水溶液を１重量部に代えた以外は実施例３５に準拠して試験片５６を作製し、所定の試験に供した。
【０１３３】
比較例２０
ε−ポリリジン水溶液を添加しなかった以外は実施例３５に準拠して試験片５７を作製し、所定の試験に供した。
【０１３４】
実施例３８
基材をＰＣシートからＰＰシートに代えた以外は実施例３５に準拠して試験片５８を作製し、所定の試験に供した。
【０１３５】
実施例３９
基材をＰＣシートからＰＰシートに代えた以外は実施例３５に準拠して試験片５９を作製し、所定の試験に供した。
【０１３６】
実施例４０
基材をＰＣシートからＰＰシートに代えた以外は実施例３５に準拠して試験片６０を作製し、所定の試験に供した。
【０１３７】
比較例２１
基材をＰＣシートからＰＰシートに代えた以外は比較例２０に準拠して試験片６１を作製し、所定の試験に供した。
【０１３８】
実施例４１
基材をＰＣシートからＰＥシートに代えた以外は実施例３５に準拠して試験片６２を作製し、所定の試験に供した。
【０１３９】
実施例４２
基材をＰＣシートからＰＥシートに代えた以外は実施例３５に準拠して試験片６３を作製し、所定の試験に供した。
【０１４０】
実施例４３
基材をＰＣシートからＰＥシートに代えた以外は実施例３５に準拠して試験片６４を作製し、所定の試験に供した。
【０１４１】
比較例２２
基材をＰＣシートからＰＥシートに代えた以外は比較例２０に準拠して試験片６５を作製し、所定の試験に供した。
【０１４２】
実施例４４
基材をＰＣシートからＰＥＴシートに代えた以外は実施例３５に準拠して試験片６６を作製し、所定の試験に供した。
【０１４３】
実施例４５
基材をＰＣシートからＰＥＴシートに代えた以外は実施例３５に準拠して試験片６７を作製し、所定の試験に供した。
【０１４４】
実施例４６
基材をＰＣシートからＰＥＴシートに代えた以外は実施例３５に準拠して試験片６８を作製し、所定の試験に供した。
【０１４５】
比較例２３
基材をＰＣシートからＰＥＴシートに代えた以外は比較例２０に準拠して試験片６９を作製し、所定の試験に供した。
【０１４６】
実施例４７
基材をＰＣシートからＰＡシートに代えた以外は実施例３５に準拠して試験片７０を作製し、所定の試験に供した。
【０１４７】
実施例４８
基材をＰＣシートからＰＡシートに代えた以外は実施例３５に準拠して試験片７１を作製し、所定の試験に供した。
【０１４８】
実施例４９
基材をＰＣシートからＰＡシートに代えた以外は実施例３５に準拠して試験片７２を作製し、所定の試験に供した。
【０１４９】
比較例２４
基材をＰＣシートからＰＡシートに代えた以外は比較例２０に準拠して試験片７３を作製し、所定の試験に供した。
【０１５０】
実施例５０
基材をＰＣシートからシリカ被膜を有するＡＬ箔に代えた以外は実施例３５に準拠して試験片７４を作製し、所定の試験に供した。
【０１５１】
実施例５１
基材をＰＣシートからＡＬ箔に代えた以外は実施例３５に準拠して試験片７５を作製し、所定の試験に供した。
【０１５２】
実施例５２
基材をＰＣシートからＡＬ箔に代えた以外は実施例３５に準拠して試験片７６を作製し、所定の試験に供した。
【０１５３】
比較例２５
基材をＰＣシートからＡＬ箔に代えた以外は比較例２０に準拠して試験片７７を作製し、所定の試験に供した。
【０１５４】
３４）シートの外観観察試験１２
前記の実施例３５〜５２および比較例２０〜２５で得られた試験片の外観について目視で観察した。その結果を後述の表３に示した。
【０１５５】
３５）抗菌性試験２３、２４
前記の実施例３５〜５２および比較例２０〜２５で得られた試験片について抗菌性試験１および抗菌性試験２で述べた抗菌性試験方法と同様の方法で抗菌性試験を実施した。その結果を後述の表３に示した。
【０１５６】
【表３】

【０１５７】
３６）塗膜の外観
前記実施例３５〜５２および比較例２０〜２５で得られた試験片を用いて塗膜の状態を目視観察し、下記の基準で評価した。
良好；平滑かつ均一な外観に優れる良好な塗膜を形成している。
不良；平滑性に劣る、または不均一で外観に劣る塗膜を形成している。
【０１５８】
３７）塗膜の剥離
前記実施例３５〜５２および比較例２０〜２５で得られた試験片を用いて塗膜の剥離状態を目視観察し、下記の基準で評価した。
なし；基材からの塗膜剥離は認められない。
あり；基材からの塗膜剥離が認められる。
【０１５９】
３８）試験菌名
大腸菌；Ｅｓｃｈｅｒｉｃｈｉａ ｃｏｌｉ（ＩＦＯ３９７２）
黄色ブドウ球菌； Ｓｔａｐｈｙｌｏｃｏｃｃｕｓ ａｕｒｅｕｓ （ＩＦＯ１２７３２）
【０１６０】
表３から明らかなように、本発明の実施例３５〜５２で得られた試験片は比較例２０〜２５で得られた試験片と比較して、塗膜の外観および耐剥離性に有意差がなく優れた外観を示すことがわかる。さらに、ＰＣシート、 ＰＰシート、ＰＥシート、ＰＥＴシート、ＰＡシート、およびＡＬ箔の基材の違いによる塗膜の外観および耐剥離性に有意差がなく優れた外観を示すことがわかる。
また、本発明の実施例３５〜５２で得られたε−ポリリジンを含む塗料を塗布・製膜した試験片は比較例２０〜２５で得られた試験片と比較して、未洗浄試験片、洗浄試験片共に大腸菌および黄色ブドウ球菌に対する抗菌効果が優れていることがわかる。さらに、ＰＣシート、 ＰＰシート、ＰＥシート、ＰＥＴシート、ＰＡシート、およびＡＬ箔の基材の違いによる抗菌効果に有意差がないことがわかる。
【０１６１】
実施例５３
ε−ポリリジン２５重量％水溶液５重量部、重合度約２００−水酸基量約２３％のホルマール樹脂２０重量部、エチレングリコールブチルエーテル５重量部を混合して得られた均一溶液を２０℃に２４時間保存して熟成させ、これを塗料として５０ｍｍ ×５０ｍｍ ×１ｍｍのＰＰシート上に塗布・製膜して試験片７８を作製し、所定の試験に供した。
【０１６２】
実施例５４
ε−ポリリジン２５重量％水溶液を２．５重量部に代えた以外は実施例５３に準拠して試験片７９を作製し、所定の試験に供した。
【０１６３】
実施例５５
ε−ポリリジン２５重量％水溶液を１重量部に代えた以外は実施例５３に準拠して試験片８０を作製し、所定の試験に供した。
【０１６４】
比較例２６
ε−ポリリジン水溶液を添加しなかった以外は実施例５３に準拠して試験片８１を作製し、所定の試験に供した。
【０１６５】
３９）シートの外観観察試験１３
前記の実施例５３〜５５および比較例２６で得られた試験片の外観について目視で観察したところ、いずれの試料も優れた外観および耐剥離性を示した。
【０１６６】
４０）抗菌性試験２５、２６
前記の実施例５３〜５５および比較例２６で得られた試験片について抗菌性試験１および抗菌性試験２で述べた抗菌性試験方法と同様の方法で抗菌性試験を実施したしたところ、実施例５３〜５５で得られた試験片は比較例２６で得られた試験片と比較して優れた抗菌効果を示した。
【０１６７】
実施例５６
ε−ポリリジン２５重量％水溶液５重量部、重合度約２５０−水酸基量約２０モル％のブチラール樹脂２０重量部、エチレングリコールブチルエーテル５重量部およびシリコーン第４級アンモニウム塩（３−トリメトキシシリルプロピルジメチルアンモニウムクロライド）の３５重量％水溶液０．５重量部を混合して得られた均一溶液を２０℃に２４時間保存して熟成させ、これを塗料として５０ｍｍ×５０ｍｍ×１ｍｍのＰＰシート上に塗布・製膜して試験片８２を作製し、所定の試験に供した。
【０１６８】
比較例２７
ε−ポリリジン水溶液を添加しなかった以外は実施例５６に準拠して試験片８３を作製し、所定の試験に供した。
【０１６９】
４１）シートの外観観察試験１４
前記の実施例５６および比較例２７で得られた試験片の外観について目視で観察したところ、いずれの試料も優れた外観および耐剥離性を示した。
【０１７０】
４２）抗菌性試験２７、２８
前記の実施例５６および比較例２７で得られた試験片について抗菌性試験１および抗菌性試験２で述べた抗菌性試験方法と同様の方法で抗菌性試験を実施したしたところ、実施例５６で得られた試験片は比較例２７で得られた試験片と比較して優れた抗菌効果を示した。。
【０１７１】
実施例５７
ＰＶＰとＰＶＡＣの混合物（組成比１：１）１０重量部、重合度約５００−水酸基量約１０モル％のブチラール樹脂１０重量部、エチルアルコール５０重量部、酢酸エチレングリコールエチルエーテル５重量部およびε−ポリリジン２５重量％水溶液５重量部を混合して得られた均一溶液を２０℃に２４時間保存して熟成させ、これを塗料としてＰＰシート上に塗布・製膜して試験片８４を作製し、所定の試験に供した。
【０１７２】
比較例２８
ε−ポリリジン水溶液を添加しなかった以外は実施例５７に準拠して試験片８５を作製し、所定の試験に供した。
【０１７３】
４３）シートの外観観察試験１５
前記の実施例５７および比較例２８で得られた試験片の外観について目視で観察したところ、いずれの試料も優れた外観および耐剥離性を示した。
【０１７４】
４４）抗菌性試験２７、２８
前記の実施例５７および比較例２８で得られた試験片について抗菌性試験１および抗菌性試験２で述べた抗菌性試験方法と同様の方法で抗菌性試験を実施したしたところ、実施例５７で得られた試験片は比較例２８で得られた試験片と比較して優れた抗菌効果を示した。
【０１７５】
実施例５８
ビニルピロリドンとビニルアセテートのコポリマー（組成比１：１）１０重量部、重合度約５００−水酸基量約１０モル％のブチラール樹脂１０重量部、シラン変成ポリメタクリル酸エステル（チッソ（株）サイラコートＳＣＴ−８１０１）の２０重量％ＩＰＡ−酢酸エチル混合溶液５０重量部およびε−ポリリジン２５重量％水溶液５重量部を混合して得られた均一溶液を２０℃に２４時間保存して熟成させ、これを塗料としてＰＰシート上に塗布・製膜して試験片８６を作製し、所定の試験に供した。
【０１７６】
比較例２９
ε−ポリリジン水溶液を添加しなかった以外は実施例５８に準拠して試験片８７を作製し、所定の試験に供した。
【０１７７】
４５）シートの外観観察試験１６
前記の実施例５８および比較例２９で得られた試験片の外観について目視で観察したところ、いずれの試料も優れた外観および耐剥離性を示した。
【０１７８】
４６）抗菌性試験３１、３２
前記の実施例５８および比較例２９で得られた試験片について抗菌性試験１および抗菌性試験２で述べた抗菌性試験方法と同様の方法で抗菌性試験を実施したしたところ、実施例５８で得られた試験片は比較例２９で得られた試験片と比較して優れた抗菌効果を示した。
【０１７９】
実施例５９
重合度約２５０−水酸基量約２０モル％のブチラール樹脂２０重量部、ＩＰＡ７５重量部、ブチルセルソルブ５重量部およびε−ポリリジン２５重量％水溶液５重量部を混合して得られた均一溶液を２０℃に２４時間保存して熟成させ、これを塗料としてＰＰシート上に塗布・製膜して試験片８８を作製し、所定の試験に供した。
【０１８０】
比較例３０
ε−ポリリジン水溶液を添加しなかった以外は実施例５９に準拠して試験片８９を作製し、所定の試験に供した。
【０１８１】
４７）シートの外観観察試験１７
前記の実施例５９および比較例３０で得られた試験片の外観について目視で観察したところ、いずれの試料も優れた外観および耐剥離性を示した。
【０１８２】
４８）抗菌性試験３３、３４
前記の実施例５９および比較例３０で得られた試験片について抗菌性試験１および抗菌性試験２で述べた抗菌性試験方法と同様の方法で抗菌性試験を実施したしたところ、実施例５９で得られた試験片は比較例３０で得られた試験片と比較して優れた抗菌効果を示した。
【０１８３】
実施例６０
重合度約２５０−水酸基量約２０モル％のブチラール樹脂２０重量部、ＩＰＡ７５重量部、ブチルセルソルブ５重量部を混合して得られた均一溶液をＡ液とする。Ａ液にさらにε−ポリリジン２５重量％水溶液５重量部を混合して得られた均一溶液をＢ液とする。
エチレン酢酸ビニルコポリマーの１５μｍ厚みフィルムの片面にＡ液を塗布・製膜して約１５μｍの被膜を形成し、さらに別の片面にＢ液を塗布・製膜して約１５μｍの被膜を形成させ試験片９０を作製し、所定の試験に供した。
【０１８４】
比較例３１
エチレン酢酸ビニルコポリマーの１５μｍ厚みフィルムになにも塗布しないものを用意し試験片９１を作製し、所定の試験に供した。
【０１８５】
４９）酸素透過性試験
前記の実施例６０および比較例３１の酸素透過量についてＪＩＳ Ｋ７１２６に従って酸素透過量の測定を行った。その結果を後述の表４に示した。
【０１８６】
【表４】

以 上
【０１８７】
１）試験方法：ＪＩＳ Ｋ７１２６
【０１８８】
表４から明らかなように、本発明の実施例６０で得られた試験片は比較例３１で得られた塗料を塗布・製膜していない試験片と比較して、酸素透過性が低いことがわかる。
【０１８９】
【発明の効果】
本発明の抗菌性塗料、および該塗料を用いて得られる塗布膜を有する抗菌製品は人体に対する毒性が極めて低く、優れた抗菌性を有し、かつその抗菌性を金属製品、ガラス製品、陶磁器およびセラミック製品、プラスチック製品、木製品、繊維製品、紙製品等様々な製品に対して容易に付与可能であり、環境中の微生物増殖抑制、食品の腐敗防止の分野で幅広く好適に利用できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an antibacterial paint and an antibacterial product having a coating film of the paint.
More specifically, ε-polylysine, ε-polylysine salt, ε-polylysine complex, ε-polylysine adduct (hereinafter collectively referred to as εPLs) is used as an antibacterial agent, polyvinylpyrrolidone homopolymer or copolymer, acetalized resin or At least one component of a modified polymethacrylate (hereinafter collectively referred to as a vehicle) is a vehicle, and a lower alcohol and its ester, glycol and its monoether, its monoether ester, and at least one lower ketone. An antibacterial paint having a compatible solvent (hereinafter collectively referred to as a solvent), a paint further containing iodine or a quaternary ammonium salt in the paint, and an antibacterial having a coating film obtained using the paint Regarding products.
[0002]
[Prior art]
According to the 1997 White Paper on Health and Welfare, modernization of the living environment and the internationalization of various raw materials related to diversification are said to increase the chance of infection on a global scale. In this context, there is a growing trend toward a hygienic and comfortable living environment, and there is a demand for products that have been antibacterial processed not only in welfare facilities, medical / medical facilities and public facilities, but also in general clothing, food and living spaces. Yes.
[0003]
For example, inorganic antibacterial agents obtained by ion-exchange of metal ions having antibacterial properties such as silver ions and copper ions with inorganic solid particles having ion exchange ability such as zeolite compounds and zirconium compounds have already been made into plastic molded products. Kneaded products are available on the market, and it has also been proposed to make paints using urethane-based vehicles (Saburo Kubota, et al., Antibacterial and Fungus, 26, [6], 301-307 (1998)).
However, such inorganic antibacterial agents have problems such as inactivation in an environment where chlorine, sulfur, and the like coexist, an allergic symptom-inducing action, and coloration of a molded product due to discoloration of a metal compound.
[0004]
In addition, antibacterial agents obtained by organic chemical synthesis, for example, organic antibacterial agents typified by imidazole compounds, etc., exhibit a strong antibacterial effect in a very small amount, but have low safety for the human body, including food packaging It is difficult to use for life related purposes.
[0005]
In contrast, organic antibacterial agents that are separated and extracted from natural products such as ε-polylysine obtained by culturing microorganisms belonging to the genus Streptomyces, hinokitiol extracted from cypress and hiba, mustard High safety has been confirmed for natural antibacterial substances (hereinafter referred to as natural antibacterial agents) such as allyl isocyanate extracted from wasabi, and they are also used for food preservation. In recent years, research using natural antibacterial agents has been actively conducted for the purpose of obtaining safer antibacterial processed products, and proposals and practical applications for products kneaded into plastics, textile products, and paper products Has been. However, for example, with hinokitiol and allyl isothiocyanate, the former is decomposed by light and loses its antibacterial effect, and the latter has a weak point that is difficult to generalize due to a unique odor. Poor affinity with.
[0006]
On the other hand, ε-polylysine is an oligopeptide of human essential amino acid L-lysine obtained from Streptomyces microorganisms and is a food preservative recorded in the existing additive list of the Ministry of Health and Welfare. Its versatility is expected from the object-oriented trend.
[0007]
Iodine, a natural inorganic antibacterial agent, is limited in its use due to its colorability, but it can be used practically if it is added in a minute amount. It is a substance that does not impair the effect.
[0008]
The present applicant previously disclosed in JP 10-237320 A, an antibacterial resin composition in which εPLs are kneaded into plastic, urushi, boil oil, oily varnish, oily enamel, and the like, which are active substances equivalent to plastic Antibacterial paints mixed with paints and antibacterial resin molded articles obtained using these compositions were proposed.
[0009]
However, since εPLs are extremely hydrophilic and are usually present as aqueous solutions, the water content is 15% by weight or less for stable use in plastics, urushi, boil oil, oil varnish, oil enamel, etc. Concentration / drying treatment must be applied to the product, and the production cost and versatility are limited.
[0010]
[Problems to be solved by the invention]
The inventors of the present invention have intensively studied to solve the above-mentioned problems of the prior art. As a result, at least one of polyvinyl pyrrolidone, polyvinyl pyrrolidone copolymer, acetalized resin or modified polymethacrylic acid ester as a vehicle is used as a vehicle, and a lower alcohol and its ester, glycol and its monoether and its monoether as compatible solvents. By using at least one of the above esters and lower ketones as its component, not only εPLs having a water content of 15% by weight or less as antibacterial agents, but also uniform and highly stable coatings can be obtained even when εPLs aqueous solutions are used. In addition, the coating film after drying and curing has a smooth and beautiful finish, and it has been found that a paint having high antibacterial effect and excellent durability can be obtained. Furthermore, iodine and quaternary ammonium salts are used as antibacterial aids. In combination, the antibacterial effect of the paint is further improved. The inventors have found that the amount of εPLs used can be reduced, and have completed the present invention based on these findings.
[0011]
As is clear from the above description, the object of the present invention is to have extremely low toxicity to the human body, have excellent antibacterial properties, and have antibacterial properties for metal products, glass products, ceramics and ceramic products, plastic products, wooden products. It is an object of the present invention to provide an antibacterial paint that can be easily applied to various products such as textile products and paper products, and can be widely used in the fields of inhibiting the growth of microorganisms in the environment and preventing food spoilage.
[0012]
[Means for Solving the Problems]
The present invention is configured as follows.
(1) An antibacterial paint containing an antibacterial agent, a vehicle and a compatible solvent, wherein the antibacterial paint contains ε-polylysine, ε-polylysine salt or an adduct thereof as an antibacterial agent.
[0013]
(2) The antibacterial paint as described in the above item (1), further comprising iodine and / or a quaternary ammonium salt.
[0014]
(3) The content of ε-polylysine, ε-polylysine salt or an adduct thereof is 0.001% to 50% by weight with respect to the antibacterial paint, and any one of the first and second items Antibacterial paint according to item.
[0015]
(4) The iodine content is 0.0001% to 1.0% by weight with respect to the antibacterial paint, and the quaternary ammonium salt content is 0.0001% by weight with respect to the antibacterial paint. The antibacterial coating material according to the above item 2, which is 10% by weight or more.
[0016]
(5) The antibacterial property according to any one of Items 1 to 4, wherein the vehicle is one or more vehicles selected from polyvinyl pyrrolidone, a copolymer of polyvinyl pyrrolidone, an acetalized resin, and a modified polymethacrylic acid ester. paint.
[0017]
(6) The compatible solvent according to any one of items 1 to 5, wherein the compatible solvent is one or more solvents selected from lower alcohols having 1 to 8 carbon atoms and derivatives thereof, glycol and derivatives thereof. Antibacterial paint.
[0018]
(7) The content of the vehicle is 0.5% to 95% by weight of polyvinylpyrrolidone, 0.5% to 95% by weight of the copolymer of polyvinylpyrrolidone, and 0.5% by weight of the acetalized resin with respect to the antibacterial paint. The antibacterial paint according to any one of Items 1 to 6, which is a content selected from -95% by weight and modified polymethacrylic acid ester (0.1% by weight to 50% by weight).
[0019]
(8) The antibacterial paint according to any one of claims 1 to 7, wherein the content of the compatible solvent is 0.5% by weight to 95% by weight with respect to the antibacterial paint.
[0020]
(9) An antibacterial product comprising the coating film of the antibacterial paint according to any one of items 1 to 8.
[0021]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
The ε-polylysine used in the present invention is, for example, culturing Streptomyces alpras subspices lysinopolymeras belonging to the genus Streptomyces, which is an ε-polylysine producing bacterium described in Patent No. 1245361, in a medium, It is obtained by separating and collecting ε-polylysine from the obtained culture. The ε-polylysine is a substance recorded in the existing additive list of the Ministry of Health and Welfare and is used for food preservatives and the like.
[0022]
In the present invention, ε-polylysine can be used in a free form, but it can also be used in the form of an ε-polylysine salt, an ε-polylysine complex, and an ε-polylysine adduct. There is no substantial difference in the antibacterial effect of ε-polylysine, whether in free form, in salt, complex or adduct form.
[0023]
As ε-polylysine salts, salts of ε-polylysine with inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, lactic acid, propionic acid, fumaric acid, malic acid, citric acid, maleic acid, adipic acid, gluconic acid Salts with organic acids such as caproic acid, lauric acid, stearic acid and other medium and long chain saturated fatty acids, oleic acid, linoleic acid, arachidonic acid and other medium chain and long chain unsaturated fatty acids And the like.
[0024]
The ε-polylysine complex is a complex compound of ε-polylysine, the ε-polylysine adduct is an adduct of ε-polylysine with, for example, aluminum halide, ε-polylysine is silica gel, natural and synthetic zeolite, diatomaceous earth. Silicate compounds such as talc, clay, hydrotalcite, calcium carbonate, phosphate compounds, and supports supported on inorganic substances such as titanium oxide, ε-polylysine such as cellulose compounds, plastics, activated carbon, sugars, etc. For example, a supported material supported on an organic material. Further, the adduct in the present invention includes not only the case where ε-polylysine is physically, chemically and electrically bound to the carrier, but also the case where ε-polylysine is simply attached to the carrier.
[0025]
The water content of εPLs used in the present invention is not particularly limited, but when ε-polylysine is used, an aqueous solution having an ε-polylysine concentration of 20 to 25% by weight is preferable.
[0026]
The vehicle used in the present invention contains at least one of vinyl pyrrolidone homopolymer or copolymer, acetalized resin or modified polymethacrylic acid ester as a component.
[0027]
As the copolymer of vinyl pyrrolidone, a random copolymer of vinyl pyrrolidone and vinyl acetate is known. Vinylpyrrolidone : Any vinyl acetate ratio can be used, but a composition having a composition of 1: 9 to 8: 2 is preferable because the uniformity of the water-containing composition can be obtained.
[0028]
Acetalized resin is a polymer obtained by acetalizing polyvinyl alcohol with butyraldehyde or formaldehyde. By properly selecting the molecular weight and the amount of hydroxyl groups in the molecule, compatibility with εPLs and uniformity of coatings are achieved. Although it can be adjusted, those having a degree of polymerization of about 100 to 800 and a hydroxyl group amount of about 20 ± 10 mol% are preferred.
[0029]
Polymethacrylate is also a general-purpose polymer, and a commercially available product can be used, but an alkoxysilyl group (—O—R—Si (OR ′)) is present in the ester moiety. _Four The modified polymethacrylic acid ester having) is suitable for operation in a water-containing paint.
[0030]
In addition, hydrophilic polymers such as polyvinyl alcohol and carboxymethyl cellulose can be added to the vehicles used in the present invention according to the purpose.
[0031]
Examples of the compatible solvent used in the present invention include lower alcohols and esters thereof, glycols and monoethers thereof, esters of monoethers, lower ketones, and mixtures of one or more thereof. The lower alcohol is an aliphatic alcohol having 1 to 8 carbon atoms, more preferably an aliphatic alcohol having 1 to 4 carbon atoms, and the ester of the lower alcohol is an ester of the lower alcohol and acetic acid.
[0032]
Glycols and their monoethers and their monoether esters are the methyl ethers or butyl ethers of glycols and their acetates, commonly known as cellosolve.
[0033]
The lower ketone is a ketone having 3 to 6 carbon atoms such as acetone, methyl ethyl ketone, or methyl isobutyl ketone.
[0034]
In the paint of the present invention, surfactants, curing accelerators and stabilizers, additives, and the like can be used as additives. As the surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant can be used. In particular, a quaternary salt type surfactant containing silicon has an affinity for ε-polylysine. .
[0035]
As the curing accelerator, diisocyanates and the like can be used, but hexamethylene diisocyanate and isophorone diisocyanate having low toxicity are preferable when the paint is used for food-related applications.
[0036]
A colloidal inorganic oxide can be used as the stabilizer, but colloidal silica is preferable because it has a viscosity adjusting action.
[0037]
In addition to these, various pigments and dyes widely used in paints may be added as needed, and glycerin fatty acid esters and sucrose esters as long as they do not deteriorate the paint performance. Antibacterial effects and synergistic effects of surfactants such as acetic acid, lactic acid, succinic acid, tartaric acid, fumaric acid, gluconic acid, adipic acid, amino acids such as glycine and alanine, and other εPLs Various substances that promote the antibacterial effect of substances exhibiting effects and εPLs may be added.
[0038]
The coating material of the present invention is widely used for coating, such as spraying, dipping, spin coating, gravure printing, etc. on the surface of metal products, glass products, ceramics and ceramic products, plastic products, wood products, textile products, paper products, etc. Can adhere and form an antibacterial film. After the coating, it can be cured by air drying at room temperature or by heating for several minutes to several hours in a temperature range of 60 to 120 ° C. depending on the properties of the raw materials. Moreover, it may be overcoated as necessary, and further curing by ultraviolet irradiation is possible.
[0039]
In addition, a film obtained by treating one side with an acetalized resin and coating the other side with a paint of the present invention containing εPLs exhibits barrier properties against oxygen as well as antibacterial properties and is useful as a food packaging material. The film used for the substrate is ethylene / vinyl acetate copolymer, stretched polyethylene, stretched polypropylene, stretched polyester, stretched polyamide, aluminum foil, silicon oxide (SiO 2 ₂ ) A film for food packaging such as an attached aluminum foil can be used, but is not particularly limited as long as it is a base material used for food packaging.
[0040]
【Example】
Hereinafter, the present invention will be described in detail using test examples and examples. In addition, an Example does not limit this invention at all.
[0041]
Example 1
20 parts by weight of a mixture (composition ratio 1: 1) of polyvinylpyrrolidone (hereinafter abbreviated as PVP) and polyvinyl acetate (hereinafter abbreviated as PVAC), isopropyl alcohol (hereinafter abbreviated as IPA). )) And a uniform solution obtained by mixing 20 parts by weight of an ε-polylysine 25% by weight aqueous solution at 24 ° C. for 24 hours, and aged to prepare a coating. The paint was applied and formed on a 50 mm × 50 mm × 1 mm polycarbonate sheet (hereinafter abbreviated as “PC sheet”) to produce a test piece 1 and subjected to a predetermined test.
[0042]
Example 2
A test piece 2 was prepared in accordance with Example 1 except that the 25 wt% aqueous solution of ε-polylysine was changed to a ratio of 10 parts by weight, and a predetermined test was performed.
[0043]
Example 3
A test piece 3 was prepared in accordance with Example 1 except that the 25 weight% aqueous solution of ε-polylysine was changed to 5 parts by weight, and a predetermined test was performed.
[0044]
Comparative Example 1
A test piece 4 was prepared according to Example 1 except that the ε-polylysine aqueous solution was not added, and a predetermined test was performed.
[0045]
Example 4
A test piece 5 was prepared in accordance with Example 1 except that the substrate was changed from a PC sheet to a polypropylene sheet (hereinafter abbreviated as PP sheet), and a predetermined test was performed.
[0046]
Example 5
A test piece 6 was prepared according to Example 2 except that the base material was changed from the PC sheet to the PP sheet, and a predetermined test was performed.
[0047]
Example 6
A test piece 7 was prepared according to Example 3 except that the substrate was changed from the PC sheet to the PP sheet, and a predetermined test was performed.
[0048]
Comparative Example 2
A test piece 8 was prepared according to Comparative Example 1 except that the substrate was changed from the PC sheet to the PP sheet, and a predetermined test was performed.
[0049]
Example 7
A test piece 9 was prepared according to Example 1 except that the substrate was changed from a PC sheet to a polyethylene sheet (hereinafter abbreviated as PE sheet), and a predetermined test was performed.
[0050]
Example 8
A test piece 10 was prepared according to Example 2 except that the substrate was changed from a PC sheet to a PE sheet, and a predetermined test was performed.
[0051]
Example 9
A test piece 11 was prepared according to Example 3 except that the substrate was changed from a PC sheet to a PE sheet, and a predetermined test was performed.
[0052]
Comparative Example 3
A test piece 12 was prepared in accordance with Comparative Example 1 except that the substrate was changed from a PC sheet to a PE sheet, and a predetermined test was performed.
[0053]
Example 10
A test piece 13 was prepared in accordance with Example 1 except that the substrate was changed from a PC sheet to a polyethylene terephthalate sheet (hereinafter abbreviated as PET sheet), and a predetermined test was performed.
[0054]
Example 11
A test piece 14 was prepared according to Example 2 except that the substrate was changed from a PC sheet to a PET sheet, and a predetermined test was performed.
[0055]
Example 12
A test piece 15 was prepared according to Example 3 except that the substrate was changed from a PC sheet to a PET sheet, and a predetermined test was performed.
[0056]
Comparative Example 4
A test piece 16 was prepared according to Comparative Example 1 except that the substrate was changed from a PC sheet to a PET sheet, and a predetermined test was performed.
[0057]
Example 13
A test piece 17 was prepared in accordance with Example 1 except that the base material was changed from a PC sheet to a nylon sheet (hereinafter abbreviated as PA sheet), and a predetermined test was performed.
[0058]
Example 14
A test piece 18 was prepared in accordance with Example 2 except that the substrate was changed from a PC sheet to a PA sheet, and a predetermined test was performed.
[0059]
Example 15
A test piece 19 was prepared according to Example 3 except that the substrate was changed from a PC sheet to a PA sheet, and a predetermined test was performed.
[0060]
Comparative Example 5
A test piece 20 was prepared according to Comparative Example 1 except that the substrate was changed from a PC sheet to a PA sheet, and a predetermined test was performed.
[0061]
Example 16
A test piece 21 was prepared in accordance with Example 1 except that the base material was changed from a PC sheet to an aluminum foil having a silica coating (hereinafter abbreviated as AL foil), and a predetermined test was performed.
[0062]
Example 17
A test piece 22 was prepared in accordance with Example 2 except that the substrate was changed from a PC sheet to an AL foil, and a predetermined test was performed.
[0063]
Example 18
A test piece 23 was prepared according to Example 3 except that the base material was changed from the PC sheet to the AL foil, and a predetermined test was performed.
[0064]
Comparative Example 6
A test piece 24 was prepared in accordance with Comparative Example 1 except that the substrate was changed from a PC sheet to an AL foil, and a predetermined test was performed.
[0065]
1) Sheet appearance observation test 1
The appearance of each test piece obtained in Examples 1 to 18 and Comparative Examples 1 to 6 was visually observed. The results are shown in Table 1 below.
[0066]
2) Antibacterial test 1
About the test piece which wash | cleaned each test piece obtained in the said Examples 1-18 and Comparative Examples 1-6 on the conditions for a flow rate of 2 liter / min using tap water for 0-30 minutes, the following antibacterial property An antibacterial test was carried out by the test method.
[0067]
3) Antibacterial test method (film adhesion method)
The antibacterial property test was conducted according to the “film adhesion method”, which is a synthetic resin antibacterial test method defined in “Antibacterial Evaluation Method for Silver and Other Inorganic Antibacterial Agents (1995)”.
[0068]
4) Preparation of test bacterial solution
Ordinary bouillon medium is diluted 500-fold with sterilized purified water, pH is adjusted to 7.0 ± 0.2, E. coli (Escherichia coli, IFO 3972) is transformed into viable bacteria in the medium with a sterile pipette. Number is 3.0 × 10 ^Five It adjusted so that it might become a density | concentration of piece / milliliter.
[0069]
5) Test piece adjustment
The test piece for the antibacterial test was lightly wiped 2-3 times with pharmacopoeia gauze soaked with ethanol and dried at room temperature.
[0070]
6) Antibacterial test
Each test piece is put into a sterilized petri dish, and 0.5 ml of the inoculum solution is inoculated on the test surface, and a sterilized polyethylene-coated film is placed on the test surface and covered, and then the temperature is 35 ± 1 ° C. Incubation was performed for 24 hours under conditions of relative humidity of 90% or more. After completion of the culture, the bacteria adhering to each test piece and clothing film were thoroughly washed out in a sterile petri dish using SCDLP medium (10 ml), and the number of viable bacteria in 1 ml of the washed liquid was determined by the standard agar medium method. It was measured. After completion of the test, the difference in increase / decrease value was calculated by the following formula, and the result is shown in Table 1 described later.
Increase / decrease value difference = log (B / A)-log (C / A)
Antibacterial unprocessed sample
[A]: Viable count immediately after inoculation
[B]: Number of viable cells after fixed-time culture operation
Antibacterial processed sample
[C]: Number of viable cells after fixed-time culture operation
[0071]
7) Antibacterial test 2
Test specimens obtained in Examples 1 to 18 and Comparative Examples 1 to 6 were treated as Staphylococcus aureus (IFO12732) in the same manner as the antibacterial test method described in Antibacterial Test 1. The antibacterial test was carried out. The results are shown in Table 1 below.
[0072]
[Table 1]

[0073]
8) Appearance of coating film
Using the test pieces obtained in Examples 1 to 18 and Comparative Examples 1 to 6, the state of the coating film was visually observed and evaluated according to the following criteria.
Good: A good coating film excellent in smooth and uniform appearance is formed.
Poor: A coating film with poor smoothness or non-uniform appearance and poor appearance is formed.
[0074]
9) Peeling of coating film
Using the test pieces obtained in Examples 1 to 18 and Comparative Examples 1 to 6, the peeled state of the coating film was visually observed and evaluated according to the following criteria.
None; no film peeling from the substrate.
Yes; peeling of the coating from the substrate is observed.
[0075]
10) Test bacteria name
Escherichia coli (IFO 3972)
Staphylococcus aureus (IFO12732)
[0076]
As is clear from Table 1, the test pieces obtained in Examples 1 to 18 of the present invention were significantly different from the test pieces obtained in Comparative Examples 1 to 6 in the appearance and peel resistance of the coating film. It can be seen that there is no appearance and an excellent appearance. Furthermore, it can be seen that there is no significant difference in the appearance and peeling resistance of the coating film due to the difference in the base materials of PC sheet, PP sheet, PE sheet, PET sheet, PA sheet, and AL foil, and an excellent appearance is shown.
In addition, the test pieces obtained in Examples 1 to 18 of the present invention have antibacterial effects against Escherichia coli and Staphylococcus aureus in both the unwashed test pieces and the washed test pieces as compared with the test pieces obtained in Comparative Examples 1 to 6. It is understood that is superior. Furthermore, it can be seen that there is no significant difference in the antibacterial effect due to the difference in the base materials of PC sheet, PP sheet, PE sheet, PET sheet, PA sheet, and AL foil.
[0077]
Example 19
20 parts by weight of a copolymer of vinylpyrrolidone and vinyl acetate (composition ratio 1: 1), 180 parts by weight of IPA, 20 parts by weight of 25% by weight ε-polylysine aqueous solution, and 5 parts by weight of a sorbitan surfactant “Tween 40” A homogeneous solution obtained by mixing at a ratio of 20% is stored at 20 ° C. for 24 hours to be aged, and a coating material is prepared. The coating material is applied and formed on a PP sheet to prepare a test piece 25. It used for the test.
[0078]
Example 20
A test piece 26 was prepared in accordance with Example 19 except that the ε-polylysine 25 wt% aqueous solution was replaced with 20 parts by weight and the ε-polylysine 10 wt% aqueous solution was replaced with 50 parts by weight. It used for the test.
[0079]
Comparative Example 7
A test piece 27 was prepared according to Example 19 except that the ε-polylysine aqueous solution was not added, and was subjected to a predetermined test.
[0080]
11) Sheet appearance observation test 2
When the appearances of the test pieces obtained in Examples 19 to 20 and Comparative Example 7 were visually observed, all the samples showed excellent appearance and peel resistance.
[0081]
12) Antibacterial test 3, 4
The test pieces obtained in Examples 19 to 20 and Comparative Example 7 were subjected to an antibacterial test in the same manner as the antibacterial test described in the antibacterial test 1 and the antibacterial test 2. The test pieces obtained in 19 to 20 showed an excellent antibacterial effect as compared with the test piece obtained in Comparative Example 7.
[0082]
Example 21
It is obtained by mixing 20 parts by weight of a mixture of PVP and PVAC (composition ratio 1: 1), 150 parts by weight of ethyl alcohol, 50 parts by weight of methyl ethyl ketone, and 20 parts by weight of 25% by weight ε-polylysine aqueous solution. The uniform solution was stored at 20 ° C. for 24 hours for aging to prepare a coating material. The coating material was applied onto a PP sheet to form a test piece 28, which was subjected to a predetermined test.
[0083]
Comparative Example 8
A test piece 29 was prepared according to Example 21 except that the ε-polylysine aqueous solution was not added, and was subjected to a predetermined test.
[0084]
13) Sheet appearance observation test 3
When the appearances of the test pieces obtained in Example 21 and Comparative Example 8 were visually observed, all of the samples showed excellent appearance and peel resistance.
[0085]
14) Antibacterial test 5, 6
The test pieces obtained in Example 21 and Comparative Example 8 were subjected to an antibacterial test in the same manner as the antibacterial test described in antibacterial test 1 and antibacterial test 2. The obtained test piece showed an excellent antibacterial effect as compared with the test piece obtained in Comparative Example 8.
[0086]
Example 22
A homogeneous solution obtained by mixing 20 parts by weight of a copolymer of vinylpyrrolidone and vinyl acetate (composition ratio 8: 2), 180 parts by weight of IPA, and 20 parts by weight of an aqueous solution of 25% by weight of ε-polylysine is 20 ° C. And aged for 24 hours to prepare a coating material. The coating material was applied and formed on a PP sheet to prepare a test piece 30, which was subjected to a predetermined test.
[0087]
Comparative Example 9
A test piece 31 was prepared according to Example 37 except that the ε-polylysine aqueous solution was not added, and was subjected to a predetermined test.
[0088]
15) Sheet appearance observation test 4
When the appearances of the test pieces obtained in Example 22 and Comparative Example 9 were visually observed, all of the samples showed excellent appearance and peel resistance.
[0089]
16) Antibacterial test 7, 8
When the antibacterial test was performed on the test pieces obtained in Example 22 and Comparative Example 9 in the same manner as the antibacterial test described in Antibacterial Test 1 and Antibacterial Test 2, The obtained test piece showed an excellent antibacterial effect as compared with the test piece obtained in Comparative Example 9.
[0090]
Example 23
A test piece 32 was prepared in accordance with Example 4 except that 20 parts by weight of an aqueous solution of 25% by weight of ε-polylysine was replaced with 5 parts by weight of powdered ε-polylysine (purity 97%) and used for a predetermined test. did.
[0091]
17) Sheet appearance observation test 5
When the appearances of the test pieces obtained in Example 23 and Comparative Example 2 were visually observed, all of the samples showed excellent appearance and peel resistance.
[0092]
18) Antibacterial test 9, 10
The test pieces obtained in Example 23 and Comparative Example 2 were subjected to an antibacterial test in the same manner as the antibacterial test described in Antibacterial Test 1 and Antibacterial Test 2. The obtained test piece showed an excellent antibacterial effect as compared with the test piece obtained in Comparative Example 2.
[0093]
Example 24
A test piece 33 was prepared according to Example 1 except that 20 parts by weight of an ε-polylysine 25% by weight aqueous solution was changed to 10 parts by weight of ε-polylysine-supported silica gel (ε-polylysine content 10% by weight). It used for the test.
[0094]
19) Sheet appearance observation test 6
When the appearances of the test pieces obtained in Example 24 and Comparative Example 2 were visually observed, all of the samples showed excellent appearance and peel resistance.
[0095]
20) Antibacterial test 11, 12
The test pieces obtained in Example 24 and Comparative Example 2 were subjected to an antibacterial test in the same manner as the antibacterial test described in Antibacterial Test 1 and Antibacterial Test 2. The obtained test piece showed an excellent antibacterial effect as compared with the test piece obtained in Comparative Example 2.
[0096]
Example 25
A test piece 34 was prepared according to Example 1 except that 20 parts by weight of an ε-polylysine 25% by weight aqueous solution was changed to 20 parts by weight of an ε-polylysine-glycine mixture (ε-polylysine content 5% by weight). The test was conducted.
[0097]
21) Sheet appearance observation test 7
When the appearances of the test pieces obtained in Example 25 and Comparative Example 2 were visually observed, all of the samples showed excellent appearance and peel resistance.
[0098]
22) Antibacterial test 13, 14
When the antibacterial test was performed on the test pieces obtained in Example 25 and Comparative Example 2 in the same manner as the antibacterial test described in Antibacterial Test 1 and Antibacterial Test 2, The obtained test piece showed an excellent antibacterial effect as compared with the test piece obtained in Comparative Example 2. .
[0099]
Example 26
20 parts by weight of a copolymer of vinylpyrrolidone and vinyl acetate (composition ratio 1: 1), 180 parts by weight of IPA, 20 parts by weight of 25% by weight ε-polylysine aqueous solution and 10 parts by weight of an ethyl alcohol solution containing 10% by weight silica sol A uniform solution obtained by mixing at a ratio of 20% is stored at 20 ° C. for 24 hours to be aged to prepare a paint, and the paint is applied to a PP sheet to form a test piece 35. It used for the test.
[0100]
Comparative Example 10
A test piece 36 was prepared according to Example 26 except that the ε-polylysine aqueous solution was not added, and was subjected to a predetermined test.
[0101]
23) Sheet appearance observation test 8
When the appearances of the test pieces obtained in Example 26 and Comparative Example 10 were visually observed, all of the samples showed excellent appearance and peel resistance.
[0102]
24) Antibacterial test 15, 16
The test pieces obtained in Example 26 and Comparative Example 10 were subjected to an antibacterial test in the same manner as the antibacterial test described in the antibacterial test 1 and the antibacterial test 2. The obtained test piece showed an excellent antibacterial effect as compared with the test piece obtained in Comparative Example 10.
[0103]
Example 27
It is obtained by mixing 20 parts by weight of a mixture of PVP and PVAC (composition ratio 1: 1), 180 parts by weight of IPA, 1 part by weight of 25 wt% aqueous solution of ε-polylysine and 0.002 parts by weight of iodine. The uniform solution was stored at 20 ° C. for 24 hours and aged to prepare a coating material. The coating material was applied and formed on a PP sheet to prepare a test piece 37, which was subjected to a predetermined test.
[0104]
Comparative Example 11
A test piece 38 was produced according to Example 27 except that no iodine was added, and was subjected to a predetermined test.
[0105]
Comparative Example 12
A test piece 39 was prepared according to Example 27 except that the ε-polylysine aqueous solution was not added, and was subjected to a predetermined test.
[0106]
25) Sheet appearance observation test 9
When the appearances of the test pieces obtained in Example 27 and Comparative Examples 11 to 12 were visually observed, all the samples showed excellent appearance and peel resistance.
[0107]
26) Antibacterial test 17, 18
When the antibacterial test was carried out by the same method as the antibacterial test described in the antibacterial test 1 and the antibacterial test 2 for the test pieces obtained in Example 27 and Comparative Examples 11-12, the example The test piece obtained in 27 showed an excellent antibacterial effect as compared with the test pieces obtained in Comparative Examples 11-12.
[0108]
Example 28
5 parts by weight of an ε-polylysine 25% by weight aqueous solution, 95 parts by weight of a 20% by weight IPA-ethyl acetate mixed solution of silane-modified polymethacrylic acid ester (Tisso Co., Ltd. Silacoat SCT-8101), and 1 part by weight of sugar ester The uniform solution obtained by mixing in a proportion was stored at 20 ° C. for 24 hours and aged to prepare a paint, and the paint was treated with a 1% by weight xylene solution of hexamethylene diisocyanate in a size of 50 mm × 50 mm × 1 mm. A test piece 40 was prepared by coating and forming a film on a PC sheet and subjected to a predetermined test.
[0109]
Comparative Example 13
A test piece 41 was prepared according to Example 28 except that the ε-polylysine aqueous solution was not added, and was subjected to a predetermined test.
[0110]
Example 28
A test piece 42 was prepared in accordance with Example 28 except that the substrate was changed from a PC sheet to a PP sheet, and subjected to a predetermined test.
[0111]
Comparative Example 14
A test piece 43 was prepared in accordance with Comparative Example 13 except that the base material was changed from the PC sheet to the PP sheet, and subjected to a predetermined test.
[0112]
Example 29
A test piece 44 was prepared according to Example 28 except that the substrate was changed from a PC sheet to a PE sheet, and subjected to a predetermined test.
[0113]
Comparative Example 15
A test piece 45 was prepared in accordance with Comparative Example 13 except that the substrate was changed from a PC sheet to a PE sheet, and subjected to a predetermined test.
[0114]
Example 30
A test piece 46 was prepared according to Example 28 except that the substrate was changed from a PC sheet to a PET sheet, and subjected to a predetermined test.
[0115]
Comparative Example 16
A test piece 47 was prepared in accordance with Comparative Example 13 except that the substrate was changed from a PC sheet to a PET sheet, and subjected to a predetermined test.
[0116]
Example 31
A test piece 48 was prepared according to Example 28 except that the substrate was changed from a PC sheet to a PA sheet, and subjected to a predetermined test.
[0117]
Comparative Example 17
A test piece 49 was prepared according to Comparative Example 13 except that the substrate was changed from a PC sheet to a PA sheet, and subjected to a predetermined test.
[0118]
Example 32
A test piece 50 was prepared according to Example 28 except that the base material was changed from the PC sheet to the AL foil, and subjected to a predetermined test.
[0119]
Comparative Example 18
A test piece 51 was prepared according to Comparative Example 13 except that the base material was changed from the PC sheet to the AL foil, and subjected to a predetermined test.
[0120]
27) Sheet appearance observation test 10
The appearance of the test pieces obtained in Examples 28 to 33 and Comparative Examples 13 to 18 was visually observed. The results are shown in Table 2 below.
[0121]
28) Antibacterial test 19, 20
The test pieces obtained in Examples 28 to 33 and Comparative Examples 13 to 18 were subjected to an antibacterial test in the same manner as the antibacterial test method described in the antibacterial test 1 and the antibacterial test 2. The results are shown in Table 2 below.
[0122]
[Table 2]

[0123]
29) Appearance of coating film
Using the test pieces obtained in Examples 28 to 33 and Comparative Examples 13 to 18, the state of the coating film was visually observed and evaluated according to the following criteria.
Good: A good coating film excellent in smooth and uniform appearance is formed.
Poor: A coating film with poor smoothness or non-uniform appearance and poor appearance is formed.
30) Peeling of coating film
Using the test pieces obtained in Examples 28 to 33 and Comparative Examples 13 to 18, the peeled state of the coating film was visually observed and evaluated according to the following criteria.
None; no film peeling from the substrate.
Yes; peeling of the coating from the substrate is observed.
[0124]
31) Test bacteria name
Escherichia coli (IFO 3972)
Staphylococcus aureus (IFO12732)
[0125]
As is apparent from Table 2, the test pieces obtained in Examples 28 to 33 of the present invention were significantly different in the appearance and peel resistance of the coating film as compared with the test pieces obtained in Comparative Examples 13 to 18. It can be seen that there is no appearance and an excellent appearance. Furthermore, it can be seen that there is no significant difference in the appearance and peeling resistance of the coating film due to the difference in the base materials of PC sheet, PP sheet, PE sheet, PET sheet, PA sheet, and AL foil, and an excellent appearance is shown.
In addition, the test pieces obtained in Examples 28 to 33 of the present invention were more antibacterial against Escherichia coli and Staphylococcus aureus than both the test pieces obtained in Comparative Examples 13 to 18 and unwashed test pieces. It is understood that is superior. Furthermore, it can be seen that there is no significant difference in the antibacterial effect due to the difference in the base materials of PC sheet, PP sheet, PE sheet, PET sheet, PA sheet, and AL foil.
[0126]
Example 34
5 parts by weight of an ε-polylysine 25% by weight aqueous solution, 95 parts by weight of a 20% by weight n-butyl alcohol solution of silane-modified polymethacrylic acid ester (Chisso Corp. Silacoat SCT-1101), 10 parts by weight of anatase-type titanium oxide, sugar ester The homogeneous solution obtained by mixing 1 part by weight was stored at 20 ° C. for 24 hours and aged, and this was applied as a paint on a 50 mm × 50 mm × 1 mm PP sheet previously treated with 1% xylene solution of hexamethylene diisocyanate. A test piece 52 was produced by coating and film formation and subjected to a predetermined test.
[0127]
Comparative Example 19
A test piece 53 was prepared according to Example 34 except that the ε-polylysine aqueous solution was not added.
[0128]
32) Sheet appearance observation test 11
When the appearances of the test pieces obtained in Example 34 and Comparative Example 19 were visually observed, all of the samples showed excellent appearance and peel resistance.
[0129]
33) Antibacterial test 21, 22
When the test pieces obtained in Example 34 and Comparative Example 19 were subjected to an antibacterial test in the same manner as the antibacterial test described in Antibacterial Test 1 and Antibacterial Test 2, in Example 34, The obtained test piece showed an excellent antibacterial effect as compared with the test piece obtained in Comparative Example 19.
[0130]
Example 35
A homogeneous solution obtained by mixing 5 parts by weight of an ε-polylysine 25% by weight aqueous solution, 20 parts by weight of a butyral resin having a polymerization degree of about 250-hydroxyl group amount of about 20 mol%, and 5 parts by weight of ethylene glycol butyl ether at 20 ° C. for 24 hours. The sample was stored and aged, and applied as a paint onto a 50 mm × 50 mm × 1 mm PC sheet to form a test piece 54, which was subjected to a predetermined test.
[0131]
Example 36
A test piece 55 was prepared in accordance with Example 35 except that the 25 weight% aqueous solution of ε-polylysine was replaced with 2.5 parts by weight.
[0132]
Example 37
A test piece 56 was prepared according to Example 35 except that the 25 wt% aqueous solution of ε-polylysine was replaced with 1 part by weight, and subjected to a predetermined test.
[0133]
Comparative Example 20
A test piece 57 was prepared according to Example 35 except that the ε-polylysine aqueous solution was not added, and was subjected to a predetermined test.
[0134]
Example 38
A test piece 58 was produced according to Example 35 except that the substrate was changed from a PC sheet to a PP sheet, and was subjected to a predetermined test.
[0135]
Example 39
A test piece 59 was prepared according to Example 35 except that the base material was changed from the PC sheet to the PP sheet, and subjected to a predetermined test.
[0136]
Example 40
A test piece 60 was prepared according to Example 35 except that the substrate was changed from a PC sheet to a PP sheet, and was subjected to a predetermined test.
[0137]
Comparative Example 21
A test piece 61 was prepared in accordance with Comparative Example 20 except that the base material was changed from the PC sheet to the PP sheet, and subjected to a predetermined test.
[0138]
Example 41
A test piece 62 was prepared according to Example 35 except that the substrate was changed from a PC sheet to a PE sheet, and subjected to a predetermined test.
[0139]
Example 42
A test piece 63 was prepared in accordance with Example 35 except that the substrate was changed from a PC sheet to a PE sheet, and subjected to a predetermined test.
[0140]
Example 43
A test piece 64 was prepared according to Example 35 except that the substrate was changed from a PC sheet to a PE sheet, and subjected to a predetermined test.
[0141]
Comparative Example 22
A test piece 65 was prepared in accordance with Comparative Example 20 except that the substrate was changed from a PC sheet to a PE sheet, and subjected to a predetermined test.
[0142]
Example 44
A test piece 66 was prepared in accordance with Example 35 except that the substrate was changed from a PC sheet to a PET sheet, and subjected to a predetermined test.
[0143]
Example 45
A test piece 67 was produced according to Example 35 except that the substrate was changed from a PC sheet to a PET sheet, and subjected to a predetermined test.
[0144]
Example 46
A test piece 68 was prepared according to Example 35 except that the substrate was changed from a PC sheet to a PET sheet, and was subjected to a predetermined test.
[0145]
Comparative Example 23
A test piece 69 was produced according to Comparative Example 20 except that the substrate was changed from a PC sheet to a PET sheet, and subjected to a predetermined test.
[0146]
Example 47
A test piece 70 was prepared according to Example 35 except that the substrate was changed from a PC sheet to a PA sheet, and subjected to a predetermined test.
[0147]
Example 48
A test piece 71 was prepared according to Example 35 except that the substrate was changed from a PC sheet to a PA sheet, and subjected to a predetermined test.
[0148]
Example 49
A test piece 72 was prepared according to Example 35 except that the substrate was changed from a PC sheet to a PA sheet, and subjected to a predetermined test.
[0149]
Comparative Example 24
A test piece 73 was prepared in accordance with Comparative Example 20 except that the substrate was changed from a PC sheet to a PA sheet, and subjected to a predetermined test.
[0150]
Example 50
A test piece 74 was prepared according to Example 35 except that the substrate was changed from a PC sheet to an AL foil having a silica coating, and subjected to a predetermined test.
[0151]
Example 51
A test piece 75 was prepared according to Example 35 except that the base material was changed from the PC sheet to the AL foil, and subjected to a predetermined test.
[0152]
Example 52
A test piece 76 was prepared in accordance with Example 35 except that the substrate was changed from a PC sheet to an AL foil, and subjected to a predetermined test.
[0153]
Comparative Example 25
A test piece 77 was prepared in accordance with Comparative Example 20 except that the base material was changed from the PC sheet to the AL foil, and subjected to a predetermined test.
[0154]
34) Sheet appearance observation test 12
The appearance of the test pieces obtained in Examples 35 to 52 and Comparative Examples 20 to 25 was visually observed. The results are shown in Table 3 below.
[0155]
35) Antibacterial test 23, 24
The test pieces obtained in Examples 35 to 52 and Comparative Examples 20 to 25 were subjected to an antibacterial test in the same manner as the antibacterial test methods described in the antibacterial test 1 and the antibacterial test 2. The results are shown in Table 3 below.
[0156]
[Table 3]

[0157]
36) Appearance of coating film
Using the test pieces obtained in Examples 35 to 52 and Comparative Examples 20 to 25, the state of the coating film was visually observed and evaluated according to the following criteria.
Good: A good coating film excellent in smooth and uniform appearance is formed.
Poor: A coating film with poor smoothness or non-uniform appearance and poor appearance is formed.
[0158]
37) Peeling of coating film
Using the test pieces obtained in Examples 35 to 52 and Comparative Examples 20 to 25, the peeled state of the coating film was visually observed and evaluated according to the following criteria.
None; no film peeling from the substrate.
Yes; peeling of the coating from the substrate is observed.
[0159]
38) Test bacteria name
Escherichia coli (IFO 3972)
Staphylococcus aureus (IFO12732)
[0160]
As is apparent from Table 3, the test pieces obtained in Examples 35 to 52 of the present invention are significantly different from the test pieces obtained in Comparative Examples 20 to 25 in the appearance and peel resistance of the coating film. It can be seen that there is no appearance and an excellent appearance. Furthermore, it can be seen that there is no significant difference in the appearance and peeling resistance of the coating film due to the difference in the base materials of PC sheet, PP sheet, PE sheet, PET sheet, PA sheet, and AL foil, and an excellent appearance is shown.
Moreover, the test piece which apply | coated and formed the coating film containing the epsilon-polylysine obtained in Examples 35-52 of this invention compared with the test piece obtained in Comparative Examples 20-25, an unwashed test piece, It can be seen that both the cleaning test pieces have excellent antibacterial effects against Escherichia coli and Staphylococcus aureus. Furthermore, it can be seen that there is no significant difference in the antibacterial effect due to the difference in the base materials of PC sheet, PP sheet, PE sheet, PET sheet, PA sheet, and AL foil.
[0161]
Example 53
A homogeneous solution obtained by mixing 5 parts by weight of an ε-polylysine 25% by weight aqueous solution, 20 parts by weight of a formal resin having a degree of polymerization of about 200-hydroxyl amount of about 23%, and 5 parts by weight of ethylene glycol butyl ether is stored at 20 ° C. for 24 hours. Then, it was aged and applied as a paint onto a 50 mm × 50 mm × 1 mm PP sheet to form a test piece 78, which was subjected to a predetermined test.
[0162]
Example 54
A test piece 79 was prepared in accordance with Example 53 except that the 25 wt% aqueous solution of ε-polylysine was changed to 2.5 parts by weight and subjected to a predetermined test.
[0163]
Example 55
A test piece 80 was prepared in accordance with Example 53 except that the 25 wt% aqueous solution of ε-polylysine was replaced with 1 part by weight, and subjected to a predetermined test.
[0164]
Comparative Example 26
A test piece 81 was prepared according to Example 53 except that the ε-polylysine aqueous solution was not added, and was subjected to a predetermined test.
[0165]
39) Sheet appearance observation test 13
When the appearances of the test pieces obtained in Examples 53 to 55 and Comparative Example 26 were visually observed, all the samples showed excellent appearance and peel resistance.
[0166]
40) Antibacterial test 25, 26
The test pieces obtained in Examples 53 to 55 and Comparative Example 26 were subjected to an antibacterial test in the same manner as the antibacterial test described in antibacterial test 1 and antibacterial test 2. The test pieces obtained in 53 to 55 showed an excellent antibacterial effect as compared with the test piece obtained in Comparative Example 26.
[0167]
Example 56
5 parts by weight of an ε-polylysine 25% by weight aqueous solution, 20 parts by weight of a butyral resin having a polymerization degree of about 250 and a hydroxyl group amount of about 20 mol%, 5 parts by weight of ethylene glycol butyl ether and a silicone quaternary ammonium salt (3-trimethoxysilylpropyldimethyl) A homogeneous solution obtained by mixing 0.5 parts by weight of a 35% by weight aqueous solution of ammonium chloride) was stored at 20 ° C. for 24 hours and aged, and this was applied as a paint on a PP sheet of 50 mm × 50 mm × 1 mm. A test piece 82 was produced by film formation and subjected to a predetermined test.
[0168]
Comparative Example 27
A test piece 83 was prepared according to Example 56 except that the ε-polylysine aqueous solution was not added, and was subjected to a predetermined test.
[0169]
41) Sheet appearance observation test 14
When the appearances of the test pieces obtained in Example 56 and Comparative Example 27 were visually observed, all of the samples showed excellent appearance and peel resistance.
[0170]
42) Antibacterial test 27, 28
The test pieces obtained in Example 56 and Comparative Example 27 were subjected to an antibacterial test in the same manner as the antibacterial test described in antibacterial test 1 and antibacterial test 2. The obtained test piece showed an excellent antibacterial effect as compared with the test piece obtained in Comparative Example 27. .
[0171]
Example 57
10 parts by weight of a mixture of PVP and PVAC (composition ratio 1: 1), 10 parts by weight of butyral resin having a degree of polymerization of about 500-hydroxyl amount of about 10 mol%, 50 parts by weight of ethyl alcohol, 5 parts by weight of ethylene glycol ethyl ether and ε -A homogeneous solution obtained by mixing 5 parts by weight of a polylysine 25% by weight aqueous solution was stored at 20 ° C for 24 hours and aged, and this was applied as a paint on a PP sheet to form a test piece 84. And subjected to a predetermined test.
[0172]
Comparative Example 28
A test piece 85 was prepared according to Example 57 except that the ε-polylysine aqueous solution was not added, and was subjected to a predetermined test.
[0173]
43) Sheet appearance observation test 15
When the appearances of the test pieces obtained in Example 57 and Comparative Example 28 were visually observed, all of the samples showed excellent appearance and peel resistance.
[0174]
44) Antibacterial test 27, 28
The test pieces obtained in Example 57 and Comparative Example 28 were subjected to an antibacterial test in the same manner as the antibacterial test described in antibacterial test 1 and antibacterial test 2. The obtained test piece showed an excellent antibacterial effect as compared with the test piece obtained in Comparative Example 28.
[0175]
Example 58
10 parts by weight of a copolymer of vinylpyrrolidone and vinyl acetate (composition ratio 1: 1), 10 parts by weight of a butyral resin having a degree of polymerization of about 500-hydroxyl amount of about 10 mol%, a silane-modified polymethacrylic acid ester (Tisso Corp. Silacoat SCT-) 8101), a homogeneous solution obtained by mixing 50 parts by weight of a 20% by weight IPA-ethyl acetate mixed solution and 5 parts by weight of an ε-polylysine 25% by weight aqueous solution, stored at 20 ° C. for 24 hours, and aged. A test piece 86 was prepared by coating and forming a film on a PP sheet and subjected to a predetermined test.
[0176]
Comparative Example 29
A test piece 87 was prepared in accordance with Example 58 except that the ε-polylysine aqueous solution was not added, and subjected to a predetermined test.
[0177]
45) Sheet appearance observation test 16
When the appearances of the test pieces obtained in Example 58 and Comparative Example 29 were visually observed, all of the samples showed excellent appearance and peel resistance.
[0178]
46) Antibacterial test 31, 32
The test pieces obtained in Example 58 and Comparative Example 29 were subjected to an antibacterial test in the same manner as the antibacterial test described in antibacterial test 1 and antibacterial test 2. The obtained test piece showed an excellent antibacterial effect as compared with the test piece obtained in Comparative Example 29.
[0179]
Example 59
A homogeneous solution obtained by mixing 20 parts by weight of a butyral resin having a degree of polymerization of about 250-hydroxyl group amount of about 20 mol%, 75 parts by weight of IPA, 5 parts by weight of butyl cellosolve, and 5 parts by weight of an aqueous solution of 25% by weight of ε-polylysine. The specimen was aged by storing at 24 ° C. for 24 hours, and this was applied as a paint on a PP sheet to form a test piece 88, which was subjected to a predetermined test.
[0180]
Comparative Example 30
A test piece 89 was prepared according to Example 59 except that the ε-polylysine aqueous solution was not added, and was subjected to a predetermined test.
[0181]
47) Sheet appearance observation test 17
When the appearances of the test pieces obtained in Example 59 and Comparative Example 30 were visually observed, all of the samples showed excellent appearance and peel resistance.
[0182]
48) Antibacterial test 33, 34
The test pieces obtained in Example 59 and Comparative Example 30 were subjected to an antibacterial test in the same manner as the antibacterial test described in antibacterial test 1 and antibacterial test 2. The obtained test piece showed an excellent antibacterial effect as compared with the test piece obtained in Comparative Example 30.
[0183]
Example 60
A uniform solution obtained by mixing 20 parts by weight of a butyral resin having a polymerization degree of about 250-hydroxyl group amount of about 20 mol%, 75 parts by weight of IPA, and 5 parts by weight of butyl cellosolve is designated as A liquid. The B solution is a homogeneous solution obtained by further mixing 5 parts by weight of a 25 wt% aqueous solution of ε-polylysine with the A liquid.
Apply and form A solution on one side of a 15 μm thick film of ethylene vinyl acetate copolymer to form a coating of about 15 μm, and apply and form B solution on another side to form a coating of about 15 μm. A piece 90 was made and subjected to a predetermined test.
[0184]
Comparative Example 31
A test piece 91 was prepared by applying an ethylene vinyl acetate copolymer film having a thickness of 15 μm that was not applied at all, and was subjected to a predetermined test.
[0185]
49) Oxygen permeability test
The oxygen permeation amount of Example 60 and Comparative Example 31 was measured according to JIS K7126. The results are shown in Table 4 below.
[0186]
[Table 4]

more than
[0187]
1) Test method: JIS K7126
[0188]
As is clear from Table 4, the test piece obtained in Example 60 of the present invention has a lower oxygen permeability than the test piece obtained by applying the paint obtained in Comparative Example 31 without coating or film formation. I understand.
[0189]
【The invention's effect】
The antibacterial paint of the present invention and the antibacterial product having the coating film obtained by using the paint have extremely low toxicity to the human body, have excellent antibacterial properties, and have antibacterial properties of metal products, glass products, ceramics and It can be easily applied to various products such as ceramic products, plastic products, wood products, textile products, paper products, etc., and can be suitably used in a wide range of fields such as suppression of microbial growth in the environment and prevention of food spoilage.

Claims (7)

Antibacterial agent, polyvinylpyrrolidone, random copolymer of vinylpyrrolidone and vinyl acetate, at least one of acetal resin or modified polymethacrylic acid ester, lower alcohol having 1 to 8 carbon atoms and ester thereof, glycol and monoether thereof and An antibacterial paint containing at least one of an ester of monoether or a ketone having 3 to 6 carbon atoms, and containing ε-polylysine or ε-polylysine salt as an antibacterial agent . The antibacterial paint according to claim 1, further comprising iodine and / or a quaternary ammonium salt. The antibacterial paint according to any one of claims 1 and 2, wherein the content of ε -polylysine or ε-polylysine salt is 0.001 wt% to 50 wt% with respect to the antibacterial paint. The iodine content is 0.0001% to 1.0% by weight with respect to the antibacterial paint, and the quaternary ammonium salt content is 0.0001% to 10% with respect to the antibacterial paint. The antibacterial paint according to claim 2, which is%. The content of at least one of polyvinylpyrrolidone, a random copolymer of vinylpyrrolidone and vinyl acetate, an acetal resin or a modified polymethacrylic acid ester thereof is 0.5 to 95% by weight of polyvinylpyrrolidone with respect to the antibacterial paint. Polyvinylpyrrolidone copolymer in an amount selected from 0.5% to 95% by weight, acetalized resin from 0.5% to 95% by weight, and modified polymethacrylic acid ester from 0.1% to 50% by weight. The antibacterial paint according to any one of claims 1 to 4 . The content of at least one of lower alcohols having 1 to 8 carbon atoms and esters thereof, glycols and monoethers thereof and esters of monoethers, or ketones having 3 to 6 carbon atoms is 0.5% with respect to the antibacterial paint. The antibacterial paint according to any one of claims 1 to 5 , wherein the antibacterial paint has a weight% to 95% by weight. An antibacterial product having the coating film of the antibacterial paint according to any one of claims 1 to 6 .