JP6944781B2 - 抗菌コーティング剤、抗菌性積層体、抗菌性積層体の製造方法、および抗菌性積層体を用いたフィルムまたはシート、包装容器、包装袋、蓋材 - Google Patents
抗菌コーティング剤、抗菌性積層体、抗菌性積層体の製造方法、および抗菌性積層体を用いたフィルムまたはシート、包装容器、包装袋、蓋材 Download PDFInfo
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- JP6944781B2 JP6944781B2 JP2017001494A JP2017001494A JP6944781B2 JP 6944781 B2 JP6944781 B2 JP 6944781B2 JP 2017001494 A JP2017001494 A JP 2017001494A JP 2017001494 A JP2017001494 A JP 2017001494A JP 6944781 B2 JP6944781 B2 JP 6944781B2
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- 239000004576 sand Substances 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 235000012046 side dish Nutrition 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- IDYFACFOJYNFAX-UHFFFAOYSA-J tetrafluoroantimony Chemical compound F[Sb](F)(F)F IDYFACFOJYNFAX-UHFFFAOYSA-J 0.000 description 1
- FAUOSXUSCVJWAY-UHFFFAOYSA-N tetrakis(hydroxymethyl)phosphanium Chemical compound OC[P+](CO)(CO)CO FAUOSXUSCVJWAY-UHFFFAOYSA-N 0.000 description 1
- IOIHFHNPXJFODN-UHFFFAOYSA-M tetrakis(hydroxymethyl)phosphanium;hydroxide Chemical compound [OH-].OC[P+](CO)(CO)CO IOIHFHNPXJFODN-UHFFFAOYSA-M 0.000 description 1
- QCYSBUVYPCMNHT-UHFFFAOYSA-N tetrakis(hydroxymethyl)phosphanium;nitrate Chemical compound [O-][N+]([O-])=O.OC[P+](CO)(CO)CO QCYSBUVYPCMNHT-UHFFFAOYSA-N 0.000 description 1
- ZTBDCHNXDHUMCJ-UHFFFAOYSA-K tetrakis(hydroxymethyl)phosphanium;phosphate Chemical compound [O-]P([O-])([O-])=O.OC[P+](CO)(CO)CO.OC[P+](CO)(CO)CO.OC[P+](CO)(CO)CO ZTBDCHNXDHUMCJ-UHFFFAOYSA-K 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000000427 thin-film deposition Methods 0.000 description 1
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical class SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- NRRLNAOLZWXZRP-UHFFFAOYSA-N triethyl(octyl)stannane Chemical compound CCCCCCCC[Sn](CC)(CC)CC NRRLNAOLZWXZRP-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- XZVPFLCTEMAYFI-UHFFFAOYSA-M trimethylstannyl acetate Chemical compound CC(=O)O[Sn](C)(C)C XZVPFLCTEMAYFI-UHFFFAOYSA-M 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 229960000834 vinyl ether Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- JRPGMCRJPQJYPE-UHFFFAOYSA-N zinc;carbanide Chemical group [CH3-].[CH3-].[Zn+2] JRPGMCRJPQJYPE-UHFFFAOYSA-N 0.000 description 1
- IPSRAFUHLHIWAR-UHFFFAOYSA-N zinc;ethane Chemical group [Zn+2].[CH2-]C.[CH2-]C IPSRAFUHLHIWAR-UHFFFAOYSA-N 0.000 description 1
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Description
(1)厚さが5〜300μmの基材と、該基材の一方に抗菌コーティング剤からなる膜厚が0.01〜10μmとなるように設けられたコーティング層と、を備え、前記コーティング層と相対する反対面が抗菌機能を備える抗菌性積層体に用いる抗菌コーティング剤であって、
前記抗菌コーティング剤は、熱可塑性樹脂(A)と、有機抗菌剤(B)と、溶媒(C)とを含み、
前記熱可塑性樹脂(A)が、ロジン類、ロジン変性フェノール樹脂、硝化綿、セルロースアセチルプロピオネート、セルロースアセチルブチレート、塩化ビニリデン、ポリアミド樹脂、塩化ビニル−酢酸ビニル共重合体、ポリエステル樹脂、ブチラール樹脂、塩素化ポリプロピレン樹脂、塩素化エチレンビニルアセテート樹脂、エチレンビニルアセテート樹脂、アクリル樹脂、ウレタン樹脂、エチレン−ビニルアルコール樹脂、スチレンマレイン酸樹脂、アルキッド樹脂から選ばれる少なくとも1つであり、
前記有機抗菌剤(B)は、前記抗菌コーティング剤中に3〜30質量%含有しており、
かつ、有機ヨード系抗菌剤(b1)、ピリジン系抗菌剤(b2)、ハロアルキルチオ系抗菌剤(b3)、チアゾール系抗菌剤(b4)、ベンゾイミダゾール系抗菌剤(b5)、イソフタロニトリル系抗菌剤(b6)、フェノール系抗菌剤(b7)、トリアジン系抗菌剤(b8)、臭素系抗菌剤(b9)、第4級アンモニウム塩系抗菌剤(b10)、有機金属系抗菌剤(b11)またはそれらの混合物から選ばれる少なくとも1つであることを特徴とする抗菌コーティング剤、
(2)前記(1)に記載の抗菌コーティング剤において、
前記有機ヨード系抗菌剤(b1)が、ヨードスルホニルベンゼン化合物、ヨウ化不飽和脂肪族化合物から選ばれる少なくとも1つを含むことを特徴とする抗菌コーティング剤、
(3)前記(1)または(2)に記載の抗菌コーティング剤において、
前記ピリジン系抗菌剤(b2)が、ピリジンチオール−1−オキシド化合物、ハロゲン化されたピリジン誘導体から選ばれる少なくとも1つを含むことを特徴とする抗菌コーティング剤、
(4)前記(1)〜(3)のいずれかに記載の抗菌コーティング剤において、
前記ハロアルキルチオ系抗菌剤(b3)が、ハロアルキルチオスルファミド化合物、ハロアルキルチオスルフィミド化合物、ハロアルキルチオフタルイミド化合物、ハロアルキルチオテトラヒドロフタルイミド化合物から選ばれる少なくとも1つを含むことを特徴とする抗菌コーティング剤、
(5)前記(1)〜(4)のいずれかに記載の抗菌コーティング剤において、
前記チアゾール系抗菌剤(b4)が、イソチアゾリン−3−オン化合物、ベンゾチアゾール化合物から選ばれる少なくとも1つを含むことを特徴とする抗菌コーティング剤、
(6)前記(1)〜(5)のいずれかに記載の抗菌コーティング剤において、
前記ベンゾイミダゾール系抗菌剤(b5)が、ベンゾイミダゾールカルバミン酸化合物、イオウ原子含有ベンゾイミダゾール化合物、ベンゾイミダゾールの環式化合物誘導体から選ばれる少なくとも1つを含むことを特徴とする抗菌コーティング剤、
(7)厚さが5〜300μmの基材と、該基材の一方に抗菌コーティング剤からなる膜厚が0.01〜10μmとなるように設けられたコーティング層と、を備える抗菌性積層体であって、
前記抗菌コーティング剤が(1)〜(6)のいずれかに記載の抗菌コーティング剤であり、かつ前記コーティング層と相対する反対面が抗菌機能を備えることを特徴とする抗菌性積層体、
(8)厚さが5〜300μmの基材と、該基材の一方に抗菌コーティング剤からなる膜厚が0.01〜10μmとなるように設けられたコーティング層と、前記コーティング層と相対する反対面にヒートシール層と、を備える抗菌性積層体であって、
前記抗菌コーティング剤が(1)〜(6)のいずれかに記載の抗菌コーティング剤であり、かつ前記ヒートシール層が抗菌機能を備えることを特徴とする抗菌性積層体、
(9)厚さが5〜300μmの基材の一方に、抗菌コーティング剤からなる膜厚が0.01〜10μmとなるように設けられたコーティング層を形成する印刷工程からなる抗菌性積層体の製造方法であって、
前記印刷工程が、シルクスクリーン印刷方式、グラビア印刷方式、オフセット印刷方式、フレキソ印刷方式、ローラーコーター方式、刷毛塗り方式、スプレー方式、ナイフジェットコーター方式であり、
前記抗菌コーティング剤が(1)〜(6)のいずれかに記載の抗菌コーティング剤であり、かつ前記コーティング層と相対する反対面が抗菌機能を備えることを特徴とする抗菌性積層体の製造方法、
(10)厚さが5〜300μmの基材の一方に、抗菌コーティング剤からなる膜厚が0.01〜10μmとなるように設けられたコーティング層を形成する印刷工程と、
前記コーティング層と相対する反対面にヒートシール層を付与する形成工程と、
からなる抗菌性積層体の製造方法であって、
前記印刷工程が、シルクスクリーン印刷方式、グラビア印刷方式、オフセット印刷方式、フレキソ印刷方式、ローラーコーター方式、刷毛塗り方式、スプレー方式、ナイフジェットコーター方式であり、
前記抗菌コーティング剤が(1)〜(6)のいずれかに記載の抗菌コーティング剤であることを特徴とする抗菌性積層体の製造方法、
(11)前記グラビア印刷方式が多色グラビア印刷機による印刷方式であることを特徴とする(9)または(10)に記載の抗菌性積層体の製造方法、
(12)前記(7)に記載の抗菌性積層体を用いて形成されたことを特徴とするフィルム、
(13)前記(7)に記載の抗菌性積層体を用いて形成されたことを特徴とするシート、
(14)前記(7)に記載の抗菌性積層体を用いて形成されたことを特徴とする包装容器、
(15)前記(8)に記載の抗菌性積層体を用いて形成されたことを特徴とする包装袋、
(16)前記(8)に記載の抗菌性積層体を用いて形成されたことを特徴とする蓋材、
に関するものである。
硬化性樹脂の場合、コーティング剤中に固形分で10〜90質量%であることが好ましく、15〜70質量%であることがより好ましい。
コーティング剤1(実施例1)
ポリアミド−ニトロセルロース樹脂系溶液(1:1、固形分30%)50部に、有機抗菌剤(2−ピリジンチオール−1−オキシドナトリウム)を10部添加し、撹拌しながら、酢酸エチル10部、トルエン20部、イソプロピルアルコール10部を添加して、コーティング剤1を作製した。同様に、表1〜6の配合に従い、コーティング剤1と同様に、コーティング剤2〜39を作製した。ただし、コーティング剤37は、抗菌剤が溶剤に分散しなかったため、コーティング剤として使用することは困難であった。
NEWMAC VESTA白インキ(東京インキ(株)製)80部に、有機抗菌剤(2−ピリジンチオール−1−オキシドナトリウム)を5部添加し、撹拌しながら、酢酸エチル5部、トルエン5部、イソプロピルアルコール5部を添加して、コーティング剤40を作製した。
ポリアミド−ニトロセルロース樹脂系溶液(1:1、固形分30%)50部に、無機系抗菌剤(銀系抗菌剤、ノバロンAG300、東亞合成(株)製)を5部添加し、撹拌しながら、酢酸エチル10部、トルエン20部、イソプロピルアルコール15部を添加して、コーティング剤41を作製した。
積層体について、JIS Z 2801:2012に準拠して、以下のようにして実施した。
40mm×40mmに切断した試験片の表面に、大腸菌(Escherichia coli)および黄色ブドウ球菌(Staphylococcus aureus)をそれぞれ含む菌液を滴下し、その上から30mm×30mm×0.09mmのポリエチレンフィルムを密着させ、温度35℃、湿度90%の条件下で24時間培養した。培養後、ポリエチレンフィルムおよび試験片に付着している菌体をSCDLP培地10ml(V)で洗い出した。洗い出した液を1ml取り、リン酸緩衝生理食塩水9mlの入った試験管に加え、混合し、さらに、この試験管から1mlを取り、別の試験管に入ったリン酸緩衝生理食塩水9mlに入れて、混合して、10倍希釈液を作製し、洗い出し液と10倍希釈液それぞれ1ml(1倍希釈:D)をシャーレ2枚に分注した。シャーレ1枚あたり、46〜48℃に保温した標準寒天培地15〜20mlを加え、よく混合し、温度35℃、湿度90%の条件下で40〜48時間培養した後、大腸菌および黄色ブドウ球菌の生菌数をそれぞれカウントした。評価の基準は、無加工のポリエチレンフィルム試験片を用いた。試験はそれぞれ3回行った。表7〜表10に大腸菌の結果、表11〜表14に黄色ブドウ球菌の結果を示した。
N=(C×D×V)/A
N:生菌数(試験片1cm2あたり)
C:集落数(採用した2枚のシャーレの集落数平均値)
D:希釈倍数(採用したシャーレに分注した希釈液の希釈倍率)
V:洗い出しに用いたSCDLP培地の液量(ml)
A:被覆フィルムの表面積(cm2)
ただし、Cが<1の場合はCを1として生菌数を算出した。例えば、V=10ml、A=9cm2、D=1の場合、N<1.1と表示した。
抗菌活性値(R)は以下の方法により算出した。
R=log(B/A)−log(C/A)=log(B/C)
A:無加工試験片の接種直後の生菌数の平均値(個)
B:無加工試験片の24時間後の生菌数の平均値(個)
C:抗菌加工試験片の24時間後の生菌数の平均値(個)
ただし、生菌数(N)が<1.1の場合、1.1で計算した。小数点以下2けた目は切り捨て、小数点以下1けたで表示した。
抗菌活性値(R)が2以上のとき、抗菌効果があると判断でき、○:2以上(抗菌効果がある)、△:2未満、1以上(弱い抗菌効果)、×:1未満(抗菌効果がない)の3段階で評価した。
積層体1のLLDPE面(実施例125)、積層体2のCPP面(実施例126)、積層体50のCPP面(実施例127)が内面になるように、ヒートシールして開口部を有する袋状にし、開口部からカステラ(カステラカット(レギュラー)、(株)文明堂総本店製)を入れた後、開口部をヒートシールにより閉じた。これを25℃の恒温室に静置し、1週間後に、開封し、カステラの外観を目視にて観察し、かびの発生を確認した。なお、コーティング剤を塗布していないCPP基材に同カステラを入れ、同様に袋状にし、同時比較した(比較例17)。
○:かびの発生が確認できない、×:かびの発生が確認できる、の2段階で評価した。表15に抗菌効果試験結果を示した。
積層体6(実施例128)および46(比較例18)を20cm×20cmの大きさにカットし、PE面が内面になるように、ハンバーガー(商品名:ハンバーガー、山崎製パン(株)製)を包んだ。これを25℃の恒温室に静置し、1週間後に、包みを取り、ハンバーガーの外観を目視にて観察し、かびの発生を確認した。
○:かびの発生が確認できない、×:かびの発生が確認できる、の2段階で評価した。表15に抗菌効果試験結果を示した。
積層体1について、抗菌効果が確認されたLLDPE面について、フーリエ変換赤外分光光度計(Frontier FT−IR、株式会社パーキン・エルマー・ジャパン製)を用い、ATR法により、赤外吸収スペクトルを測定し、つづいて、同積層体1のLLDPE面をクロロホルムにて、拭き取り、同様に赤外吸収スペクトルを測定した。未処理のLLDPE面およびクロロホルム処理のLLDPE面ともに、2−ピリジンチオール−1−オキシドナトリウムは検出されなかった。
また、グラビア印刷方式にて塗工できることから、食品包装用途に限らず、食品保存用途、農業用途、土木用途、漁業用途、自動車内外装用途、船舶用途、日用品用途、建材内外装用途、住設機器用途、医療・医療機器用途、医薬用途、家電品用途、家具類用途、文具類・事務用品用途、販売促進用途、商業用途、電機電子産業用途および産業資材用途などの各種抗菌性フィルム、シール、ラベル、シートなどさらにそれを利用した包装容器に広く適用できる。
2 基材
3 コーティング層
4 ヒートシール性を有する基材(ヒートシール層)
5 ヒートシール性を有さない基材
6 ヒートシール層
7 インキ層
8 抗菌機能を有する面
Claims (16)
- 厚さが5〜300μmの基材と、該基材の一方に抗菌コーティング剤からなる膜厚が0.01〜10μmとなるように設けられたコーティング層と、を備え、前記コーティング層と相対する反対面が抗菌機能を備える抗菌性積層体に用いる抗菌コーティング剤であって、
前記抗菌コーティング剤は、熱可塑性樹脂(A)と、有機抗菌剤(B)と、溶媒(C)とを含み、
前記熱可塑性樹脂(A)が、ロジン類、ロジン変性フェノール樹脂、硝化綿、セルロースアセチルプロピオネート、セルロースアセチルブチレート、塩化ビニリデン、ポリアミド樹脂、塩化ビニル−酢酸ビニル共重合体、ポリエステル樹脂、ブチラール樹脂、塩素化ポリプロピレン樹脂、塩素化エチレンビニルアセテート樹脂、エチレンビニルアセテート樹脂、アクリル樹脂、ウレタン樹脂、エチレン−ビニルアルコール樹脂、スチレンマレイン酸樹脂、アルキッド樹脂から選ばれる少なくとも1つであり、
前記有機抗菌剤(B)は、前記抗菌コーティング剤中に3〜30質量%含有しており、
かつ、有機ヨード系抗菌剤(b1)、ピリジン系抗菌剤(b2)、ハロアルキルチオ系抗菌剤(b3)、チアゾール系抗菌剤(b4)、ベンゾイミダゾール系抗菌剤(b5)、イソフタロニトリル系抗菌剤(b6)、フェノール系抗菌剤(b7)、トリアジン系抗菌剤(b8)、臭素系抗菌剤(b9)、第4級アンモニウム塩系抗菌剤(b10)、有機金属系抗菌剤(b11)またはそれらの混合物から選ばれる少なくとも1つであることを特徴とする抗菌コーティング剤。 - 前記請求項1に記載の抗菌コーティング剤において、
前記有機ヨード系抗菌剤(b1)が、ヨードスルホニルベンゼン化合物、ヨウ化不飽和脂肪族化合物から選ばれる少なくとも1つを含むことを特徴とする抗菌コーティング剤。 - 前記請求項1または2に記載の抗菌コーティング剤において、
前記ピリジン系抗菌剤(b2)が、ピリジンチオール−1−オキシド化合物、ハロゲン化されたピリジン誘導体から選ばれる少なくとも1つを含むことを特徴とする抗菌コーティング剤。 - 前記請求項1〜3のいずれかに記載の抗菌コーティング剤において、
前記ハロアルキルチオ系抗菌剤(b3)が、ハロアルキルチオスルファミド化合物、ハロアルキルチオスルフィミド化合物、ハロアルキルチオフタルイミド化合物、ハロアルキルチオテトラヒドロフタルイミド化合物から選ばれる少なくとも1つを含むことを特徴とする抗菌コーティング剤。 - 前記請求項1〜4のいずれかに記載の抗菌コーティング剤において、
前記チアゾール系抗菌剤(b4)が、イソチアゾリン−3−オン化合物、ベンゾチアゾール化合物から選ばれる少なくとも1つを含むことを特徴とする抗菌コーティング剤。 - 前記請求項1〜5のいずれかに記載の抗菌コーティング剤において、
前記ベンゾイミダゾール系抗菌剤(b5)が、ベンゾイミダゾールカルバミン酸化合物、イオウ原子含有ベンゾイミダゾール化合物、ベンゾイミダゾールの環式化合物誘導体から選ばれる少なくとも1つを含むことを特徴とする抗菌コーティング剤。 - 厚さが5〜300μmの基材と、該基材の一方に抗菌コーティング剤からなる膜厚が0.01〜10μmとなるように設けられたコーティング層と、を備える抗菌性積層体であって、
前記抗菌コーティング剤が請求項1〜6のいずれかに記載の抗菌コーティング剤であり、かつ前記コーティング層と相対する反対面が抗菌機能を備えることを特徴とする抗菌性積層体。 - 厚さが5〜300μmの基材と、該基材の一方に抗菌コーティング剤からなる膜厚が0.01〜10μmとなるように設けられたコーティング層と、前記コーティング層と相対する反対面にヒートシール層と、を備える抗菌性積層体であって、
前記抗菌コーティング剤が請求項1〜6のいずれかに記載の抗菌コーティング剤であり、かつ前記ヒートシール層が抗菌機能を備えることを特徴とする抗菌性積層体。 - 厚さが5〜300μmの基材の一方に、抗菌コーティング剤からなる膜厚が0.01〜10μmとなるように設けられたコーティング層を形成する印刷工程からなる抗菌性積層体の製造方法であって、
前記印刷工程が、シルクスクリーン印刷方式、グラビア印刷方式、オフセット印刷方式、フレキソ印刷方式、ローラーコーター方式、刷毛塗り方式、スプレー方式、ナイフジェットコーター方式であり、
前記抗菌コーティング剤が請求項1〜6のいずれかに記載の抗菌コーティング剤であり、かつ前記コーティング層と相対する反対面が抗菌機能を備えることを特徴とする抗菌性積層体の製造方法。 - 厚さが5〜300μmの基材の一方に、抗菌コーティング剤からなる膜厚が0.01〜10μmとなるように設けられたコーティング層を形成する印刷工程と、
前記コーティング層と相対する反対面にヒートシール層を付与する形成工程と、
からなる抗菌性積層体の製造方法であって、
前記印刷工程が、シルクスクリーン印刷方式、グラビア印刷方式、オフセット印刷方式、フレキソ印刷方式、ローラーコーター方式、刷毛塗り方式、スプレー方式、ナイフジェットコーター方式であり、
前記抗菌コーティング剤が請求項1〜6のいずれかに記載の抗菌コーティング剤であることを特徴とする抗菌性積層体の製造方法。 - 前記グラビア印刷方式が多色グラビア印刷機による印刷方式であることを特徴とする請求項9または10に記載の抗菌性積層体の製造方法。
- 前記請求項7に記載の抗菌性積層体を用いて形成されたことを特徴とするフィルム。
- 前記請求項7に記載の抗菌性積層体を用いて形成されたことを特徴とするシート。
- 前記請求項7に記載の抗菌性積層体を用いて形成されたことを特徴とする包装容器。
- 前記請求項8に記載の抗菌性積層体を用いて形成されたことを特徴とする包装袋。
- 前記請求項8に記載の抗菌性積層体を用いて形成されたことを特徴とする蓋材。
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