JP2019059907A - 殺菌作用を備えた表面を有する合成高分子膜、光硬化性樹脂組成物、合成高分子膜の製造方法、および合成高分子膜の表面を用いた殺菌方法 - Google Patents
殺菌作用を備えた表面を有する合成高分子膜、光硬化性樹脂組成物、合成高分子膜の製造方法、および合成高分子膜の表面を用いた殺菌方法 Download PDFInfo
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- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
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- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
- B29C33/3842—Manufacturing moulds, e.g. shaping the mould surface by machining
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/42—Moulds or cores; Details thereof or accessories therefor characterised by the shape of the moulding surface, e.g. ribs or grooves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/34—Component parts, details or accessories; Auxiliary operations
- B29C41/38—Moulds, cores or other substrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
- B29C2035/0827—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using UV radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2007/00—Flat articles, e.g. films or sheets
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Physics & Mathematics (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Thermal Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Shaping Of Tube Ends By Bending Or Straightening (AREA)
- Polymerisation Methods In General (AREA)
- Apparatus For Disinfection Or Sterilisation (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
nm超500nm未満の範囲内にある。ここで、凸部34Apの「2次元的な大きさ」とは、表面の法線方向から見たときの凸部34Apの面積円相当径を指す。例えば、凸部34Apが円錐形の場合、凸部34Apの2次元的な大きさは、円錐の底面の直径に相当する。また、凸部34Apの典型的な隣接間距離Dintは20nm超1000nm以下であ
る。図1(a)に例示するように、凸部34Apが密に配列されており、隣接する凸部34Ap間に間隙が存在しない(例えば、円錐の底面が部分的に重なる)場合には、凸部34Apの2次元的な大きさDpは隣接間距離Dintと等しい。凸部34Apの典型的な高さDhは、50nm以上500nm未満である。後述するように、凸部34Apの高さDhが150nm以下であっても殺菌作用を発現する。合成高分子膜34Aの厚さtsに特に制限はなく、凸部34Apの高さDhより大きければよい。
組成の異なる紫外線硬化性樹脂を用いて、図1(a)に示したフィルム50Aと同様の構造を有する試料フィルムを作製した。使用した原材料を表1に示す。
あった。いずれも無溶剤で合成高分子膜を作製した。
2:溶けやすい 1mL以上 10mL未満
3:やや溶けやすい 10mL以上 30mL未満
4:やや溶けにくい 30mL以上 100mL未満
5:溶けにくい 100mL以上 1000mL未満
6:極めて溶けにくい 1000mL以上 10000mL未満
7:ほとんど溶けない 10000mL以上
試料フィルム上に飛散した菌液(水)に対する殺菌性を評価した。菌液を付与した試料フィルムを室温・大気中に放置した際の殺菌性を評価した。ここでは、黄色ブドウ球菌に対する殺菌性を評価した。具体的な評価方法は以下の通りである。各試料フィルムについて、N=3で実験を行った。
(1)初期菌数が1E+06CFU/mLとなるように、黄色ブドウ球菌を含む菌液を1/500NB培地を用いて調製した。
(2)各試料フィルム(5cm角)の上に、上記菌液10μLを滴下した。
(3)室温(約25℃)、大気中に、15分間、放置した後、SCDLP培地を試料フィルムにかけ流し、菌を洗い出した(洗い出し液)。
(4)洗い出し液を適宜PBSで希釈を行い、標準寒天培地等で培養し、菌数をカウントした。
生菌率(%)=各試料フィルムの菌数(N=3の合計)/PETフィルムの菌数(N=3の合計)×100
転写性を評価するために、ガラス基板(約5cm×約5cm)上にアルミニウム膜(厚さ:約1μm)を形成し、このアルミニウム膜に陽極酸化とエッチングとを交互に繰り返すことによって、上記同様のポーラスアルミナ層(Dpは約200nm、Dintは約200nm、Dhは約150nm)を形成した。得られたポーラスアルミナ層の表面に酸素プラズマ洗浄(100W、25秒)を施し、水に対する接触角を125°〜130°に調整した。これは、紫外線硬化性樹脂に対する型の表面の離型性を低下させるためである。
◎: 初期から10回目まで変わらず軽く剥離できる。
〇: 初期は軽いが、徐々に重くなる傾向がある。
△: 初期から重いが、型の表面に合成高分子膜(紫外線硬化樹脂)が残存する等の不具合の発生なし。
×: 10回の転写中に、型の表面に合成高分子膜が残存する不具合が発生。
脱イオン水を0.01mol/L−塩酸および0.011mol/L−水酸化ナトリウムにてpH=7.0±0.1に調整した。すなわち、このようにして、中性の水を用意した。
電極:株式会社堀場製作所製、pH電極、型番:0040−10D(半導体センサ)
サンプリングシート:株式会社堀場製作所製、サンプリングシートB、型番:Y011A
各試料フィルムから水に抽出される酸をGC−MS(ガスクロマトグラフ質量分析計)を用いて以下のようにして同定した。
熱分解装置:FRONTIER LAB 社製 EGA/PY−3030D
条件: 400℃/30sec
GC−MS装置: Agilent Technologies 社製 7890A(GC) 5975C(MS)
カラム: FRONTIER LAB 製 UA5HT−30M−0.1F
条件:オーブン 40℃⇒320℃(20℃/min)
カラム流量 1mL/min
スプリット比 100:1
ペンタン酸、ヘキサン酸、ヘプタン酸、オクタン酸などの脂肪酸類
安息香酸、2,4,6−トリメチル安息香酸、サリチル酸などの芳香族カルボン酸類
コハク酸、フマル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、o−フタル酸等の2塩基酸類などが挙げられる。
34Ap、34Bp 凸部
42A、42B ベースフィルム
50A、50B フィルム
100、100A、100B モスアイ用型
Claims (14)
- 複数の凸部または凹部を有する表面を備える合成高分子膜であって、
架橋構造を有し、前記架橋構造は、ウレタン構造を構成する窒素元素を含まず、
前記合成高分子膜は、有機カルボン酸を含み、前記有機カルボン酸1gを溶解するために必要な水の量が10mL以上10000mL未満であり、
前記合成高分子膜の前記表面に200μLの水を滴下後、5分後の水溶液のpHが5以下であり、前記水溶液の面積円相当径が20mm以上である、合成高分子膜。 - 前記合成高分子膜の法線方向から見たとき、前記複数の凸部または凹部の2次元的な大きさは20nm超1μm以下の範囲内にある、請求項1に記載の合成高分子膜。
- 前記合成高分子膜の法線方向から見たとき、前記複数の凸部または凹部の2次元的な大きさは500nm未満である、請求項2に記載の合成高分子膜。
- 前記合成高分子膜の法線方向から見たとき、前記複数の凸部または凹部の2次元的な大きさは500nm以上である、請求項2に記載の合成高分子膜。
- 前記合成高分子膜は、前記有機カルボン酸よりも強い酸をさらに含む、請求項1から4のいずれかに記載の合成高分子膜。
- 前記有機カルボン酸は、2,4,6−トリメチル安息香酸、スベリン酸またはセバシン酸である、請求項1から5のいずれかに記載の合成高分子膜。
- 前記合成高分子膜は、光硬化性樹脂から形成されており、前記有機カルボン酸は、前記光硬化性樹脂に含まれていた光重合開始剤の光分解によって生成されたものである、請求項1から6のいずれかに記載の合成高分子膜。
- 前記光重合開始剤は、ビス(2,4,6−トリメチルベンゾイル)−フェニルホスフィンオキシドを含む、請求項7に記載の合成高分子膜。
- 前記光重合開始剤は、ジフェニル(2,4,6−トリメトキシベンゾイル)ホスフィンオキシドをさらに含む、請求項8に記載の合成高分子膜。
- 前記架橋構造はエチレンオキサイド単位を含む、請求項1から9のいずれかに記載の合成高分子膜。
- 請求項1から10のいずれかに記載の合成高分子膜の前記表面に、水を含む液体を接触させることによって、前記液体を殺菌する方法。
- 表面に殺菌作用を有する合成高分子膜の製造に用いられる光硬化性樹脂組成物であって、
光硬化性樹脂と、
有機カルボン酸または、前記有機カルボン酸を発生する光酸発生剤と
を含み、
前記有機カルボン酸1gを溶解するために必要な水の量が10mL以上10000mL未満である、光硬化性樹脂組成物。 - 前記光硬化性樹脂は、ラジカル重合性である、請求項12に記載の光硬化性樹脂組成物。
- 表面に殺菌作用を有する合成高分子膜を製造する方法であって、
請求項12または13に記載の光硬化性樹脂組成物に水を混合した後に、光照射を行う工程を含む、合成高分子膜の製造方法。
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JP2021147385A (ja) * | 2020-03-13 | 2021-09-27 | 株式会社リコー | 樹脂構造体、抗病原体活性付加物、樹脂構造体の製造方法、抗病原体活性付加物の製造方法、樹脂構造体の製造装置、及び抗病原体活性付加物の製造装置 |
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JP2016153510A (ja) * | 2014-11-20 | 2016-08-25 | シャープ株式会社 | 殺菌作用を備えた表面を有する合成高分子膜 |
JP2016104545A (ja) * | 2014-12-01 | 2016-06-09 | 大日本印刷株式会社 | 抗菌性物品 |
WO2016175170A1 (ja) * | 2015-04-30 | 2016-11-03 | シャープ株式会社 | 殺菌作用を備えた表面を有する合成高分子膜 |
JP2016210164A (ja) * | 2015-05-01 | 2016-12-15 | 大日本印刷株式会社 | カビ繁殖抑制部材、及び農業用カビ繁殖抑制物品 |
WO2017014086A1 (ja) * | 2015-07-17 | 2017-01-26 | シャープ株式会社 | 殺菌作用を備えた表面を有する合成高分子膜およびそれを備えるフィルム |
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JP7060065B2 (ja) | 2020-03-13 | 2022-04-26 | 株式会社リコー | 樹脂構造体、抗病原体活性付加物、樹脂構造体の製造方法、抗病原体活性付加物の製造方法、樹脂構造体の製造装置、及び抗病原体活性付加物の製造装置 |
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