JP7461727B2 - Antibacterial base film, antibacterial food containers and antibacterial food sheets - Google Patents
Antibacterial base film, antibacterial food containers and antibacterial food sheets Download PDFInfo
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- 230000000844 anti-bacterial effect Effects 0.000 title claims description 205
- 235000013305 food Nutrition 0.000 title claims description 32
- 229920005989 resin Polymers 0.000 claims description 67
- 239000011347 resin Substances 0.000 claims description 67
- 229910052709 silver Inorganic materials 0.000 claims description 46
- 239000004332 silver Substances 0.000 claims description 46
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 44
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 39
- -1 polybutylene terephthalate Polymers 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 23
- 239000002270 dispersing agent Substances 0.000 claims description 19
- 239000010419 fine particle Substances 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 19
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- 239000002923 metal particle Substances 0.000 claims description 18
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- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 claims description 10
- 235000019204 saccharin Nutrition 0.000 claims description 10
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 229920005992 thermoplastic resin Polymers 0.000 claims description 8
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 4
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 4
- FTLYMKDSHNWQKD-UHFFFAOYSA-N (2,4,5-trichlorophenyl)boronic acid Chemical compound OB(O)C1=CC(Cl)=C(Cl)C=C1Cl FTLYMKDSHNWQKD-UHFFFAOYSA-N 0.000 claims description 3
- HEKURBKACCBNEJ-UHFFFAOYSA-M potassium;1,1-dioxo-1,2-benzothiazol-2-id-3-one Chemical compound [K+].C1=CC=C2C(=O)[N-]S(=O)(=O)C2=C1 HEKURBKACCBNEJ-UHFFFAOYSA-M 0.000 claims description 3
- 229940085605 saccharin sodium Drugs 0.000 claims description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 33
- 238000010828 elution Methods 0.000 description 12
- 239000011859 microparticle Substances 0.000 description 11
- 238000001125 extrusion Methods 0.000 description 10
- 235000012046 side dish Nutrition 0.000 description 9
- 229920003002 synthetic resin Polymers 0.000 description 9
- 239000000057 synthetic resin Substances 0.000 description 9
- 239000004743 Polypropylene Substances 0.000 description 8
- 238000002845 discoloration Methods 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 229920001155 polypropylene Polymers 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 229920005672 polyolefin resin Polymers 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000010411 cooking Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 230000000149 penetrating effect Effects 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- ORYURPRSXLUCSS-UHFFFAOYSA-M silver;octadecanoate Chemical compound [Ag+].CCCCCCCCCCCCCCCCCC([O-])=O ORYURPRSXLUCSS-UHFFFAOYSA-M 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
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- 238000007865 diluting Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000009820 dry lamination Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
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- 239000010408 film Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
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- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
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Description
本発明は、紙等の基材層の上に銀等の抗菌性金属微粒子を分散させて含む抗菌性樹脂層を形成して成る抗菌性原反、並びに、これを用いて製作される抗菌性食品用容器及び抗菌性食品用シートに関する。 The present invention relates to an antibacterial base fabric that is made by forming an antibacterial resin layer containing dispersed antibacterial metal particles such as silver on a base layer such as paper, and to antibacterial food containers and antibacterial food sheets that are manufactured using the same.
特許文献１に、電子レンジやオーブン等での加熱調理が可能な耐熱性紙容器が記載されている。この従来の耐熱性紙容器は、耐熱紙に特定の特性を有するポリブチレンテレフタレート（ＰＢＴ）を積層して製作した原反を用いて製造したものである。詳しくは、末端カルボキシル基含有量を６０ミリ当量／ｋｇ未満に規定したＰＢＴを用いる点、及び、耐熱紙に積層した後のＰＢＴの結晶化度を１０～３０％の範囲とした点を特色としている。このような特性を有するＰＢＴを耐熱紙に積層して成る原反で製作した紙容器は、電子レンジやオーブン等で高温調理しても容器形状の崩れや変形、外観の変化をもたらさない耐熱性を示すとの利点を有する。 Patent Document 1 describes a heat-resistant paper container that can be used for cooking in a microwave oven, oven, etc. This conventional heat-resistant paper container is manufactured using a base roll made by laminating polybutylene terephthalate (PBT) with specific properties onto heat-resistant paper. More specifically, it is characterized by the use of PBT with a terminal carboxyl group content specified to be less than 60 milliequivalents/kg, and the crystallinity of the PBT after lamination onto the heat-resistant paper being in the range of 10-30%. A paper container manufactured from a base roll made by laminating PBT with such properties onto heat-resistant paper has the advantage of exhibiting heat resistance that does not cause the container to collapse or deform or change in appearance even when cooked at high temperatures in a microwave oven, oven, etc.
ところで一般に弁当箱におかずを収容するための容器として薄い紙基材と合成樹脂とを積層した積層体をプレス成形することで得られる襞付きのおかずケースが知られており、このようなおかずケースに抗菌性を付与したいという要望がある。この場合、食品が接する面である合成樹脂層に抗菌性を付与することが考えられ、合成樹脂製品に抗菌性を付与する技術として、特許文献２に、銀化合物を含有する抗菌性マスターバッチについて記載されている。この抗菌性マスターバッチは、ベースとなるオレフィン樹脂と、抗菌性を示す脂肪酸銀と、脂肪酸銀を分散させるため分散剤から成るものであって、詳しくは、オレフィン樹脂の塩素含有量を１ｐｐｍ以下、分散剤の酸解離定数（ｐＫａ）を４．０以下、脂肪酸銀の含有量を０．１～２重量％、及び、脂肪酸銀と分散剤との重量比を１：０．５～１：１０に設定したところを特徴としている。具体的には、オレフィン樹脂としてメタロセン系触媒ポリプロピレンが用いられ、分散剤としてサッカリンが用いられる。そして、この抗菌性マスターバッチを用いることにより、抗菌性を有する樹脂成形体を製造することができるとされている。すなわち、抗菌性マスターバッチを熱可塑性樹脂に配合し、従来公知の溶融成形法を用いて、最終成形品の用途に応じた形状、例えば、粒状、ペレット状、繊維状、フィルム、シート、容器等とすることにより、目的の抗菌性樹脂製品を得ることができる。ここで、抗菌性マスターバッチの熱可塑性樹脂への配合量は、抗菌性マスターバッチを合成樹脂にて１０倍～４０倍に希釈して混合するのが望ましいとされている。又、抗菌性マスターバッチを配合する熱可塑性樹脂としては、抗菌性マスターバッチに用いたのと同種のオレフィン樹脂、特にポリプロピレンを使用するのが好適であるとされている。 By the way, a pleated side dish case obtained by press-molding a laminate of a thin paper base material and a synthetic resin is generally known as a container for storing side dishes in a lunch box, and there is a demand for imparting antibacterial properties to such a side dish case. In this case, it is considered to impart antibacterial properties to the synthetic resin layer, which is the surface that comes into contact with food, and Patent Document 2 describes an antibacterial master batch containing a silver compound as a technology for imparting antibacterial properties to synthetic resin products. This antibacterial master batch is composed of an olefin resin as a base, a fatty acid silver exhibiting antibacterial properties, and a dispersant for dispersing the fatty acid silver. In detail, it is characterized in that the chlorine content of the olefin resin is set to 1 ppm or less, the acid dissociation constant (pKa) of the dispersant is set to 4.0 or less, the fatty acid silver content is set to 0.1 to 2 wt%, and the weight ratio of the fatty acid silver to the dispersant is set to 1:0.5 to 1:10. Specifically, a metallocene-catalyzed polypropylene is used as the olefin resin, and saccharin is used as the dispersant. It is said that by using this antibacterial master batch, a resin molded product having antibacterial properties can be manufactured. That is, the antibacterial masterbatch is blended with a thermoplastic resin, and then, using a conventionally known melt molding method, the desired antibacterial resin product can be obtained by forming the resin into a shape appropriate for the intended use of the final molded product, such as granules, pellets, fibers, films, sheets, containers, etc. Here, it is considered desirable to mix the antibacterial masterbatch into the thermoplastic resin by diluting the antibacterial masterbatch 10 to 40 times with a synthetic resin. It is also considered preferable to use the same type of olefin resin, particularly polypropylene, as the thermoplastic resin to be blended with the antibacterial masterbatch.
前述のおかずケースは、喫食時に電子レンジで食品を加熱したり、揚げたてや焼きたての高温状態の食品を載せたりして用いられるので、食品に接する合成樹脂に耐熱性が要求され、前述したようなＰＢＴが合成樹脂として用いられている。そして、おかずケースの表面に耐熱性樹脂をラミネートした耐熱性容器に抗菌性を付与しようとする場合、特許文献２に記載の抗菌性マスターバッチの技術を利用することが考えられる。しかし特許文献２では、抗菌性マスターバッチを配合する合成樹脂が融点の低いポリプロピレンであるため、耐熱性を有する容器を得ることができない。 The above-mentioned side dish cases are used to heat food in a microwave oven when eaten, or to hold hot fried or baked food, so the synthetic resin that comes into contact with the food must be heat resistant, and the above-mentioned PBT is used as the synthetic resin. If one wishes to impart antibacterial properties to a heat-resistant container in which the surface of a side dish case is laminated with a heat-resistant resin, one possibility is to use the antibacterial masterbatch technology described in Patent Document 2. However, in Patent Document 2, the synthetic resin with which the antibacterial masterbatch is mixed is polypropylene, which has a low melting point, so a heat-resistant container cannot be obtained.
そこで、特許文献１に記載の耐熱性紙容器のＰＢＴ層に、特許文献２の抗菌性マスターバッチを配合することが考えられる。しかし当業者の技術常識では、特許文献１に記載の耐熱性紙容器に特許文献２に記載の抗菌技術を組み合わせても、十分な抗菌性能を得るのは難しいであろうと考えられる。何故ならば、特許文献１で使用されるＰＢＴはポリエステル樹脂であるのに対し、特許文献２の抗菌性マスターバッチが配合されるポリプロピレンはガラス転移温度が低い（約０℃）オレフィン樹脂であり、両者は構造や物性の点で大きく異なる性質を有している。そのため、特許文献１のＰＢＴに特許文献２の抗菌性マスターバッチを配合したときに、合成樹脂の種類が異なるので相溶性が悪く抗菌性金属微粒子を均一に分散できず所望の抗菌性を得ることができない。又、特許文献２に記載されるように、抗菌性マスターバッチのベースとなる樹脂としてポリプロピレンとしては、塩素成分の含有量が低いポリプロピレンを用いなければならない。何故ならば、塩素成分と抗菌性銀粒子から溶出した銀イオンとが反応して塩化銀を生成し、この塩化銀が光により変色することで、このマスターバッチを配合して得られた容器等の変色が生じてしまうからである。又、変色を抑えるために特許文献２のような塩素成分が低いポリプロピレンをマスターバッチとして用いることは、使用できる樹脂の種類を狭め、コストアップにもつながるため難しい。 Therefore, it is considered to blend the antibacterial master batch of Patent Document 2 into the PBT layer of the heat-resistant paper container described in Patent Document 1. However, according to the technical common sense of a person skilled in the art, it is thought that it would be difficult to obtain sufficient antibacterial performance even if the heat-resistant paper container described in Patent Document 1 is combined with the antibacterial technology described in Patent Document 2. This is because the PBT used in Patent Document 1 is a polyester resin, while the polypropylene blended with the antibacterial master batch of Patent Document 2 is an olefin resin with a low glass transition temperature (about 0°C), and the two have significantly different properties in terms of structure and physical properties. Therefore, when the antibacterial master batch of Patent Document 2 is blended with the PBT of Patent Document 1, the types of synthetic resins are different, so the compatibility is poor and the antibacterial metal particles cannot be uniformly dispersed, and the desired antibacterial properties cannot be obtained. In addition, as described in Patent Document 2, polypropylene with a low content of chlorine components must be used as the polypropylene resin that serves as the base resin for the antibacterial master batch. This is because the chlorine components react with the silver ions eluted from the antibacterial silver particles to generate silver chloride, and this silver chloride discolors when exposed to light, causing discoloration of the container obtained by blending this master batch. Furthermore, using polypropylene with a low chlorine content as a masterbatch to prevent discoloration, as described in Patent Document 2, is difficult because it narrows the types of resins that can be used and leads to increased costs.
又、抗菌性マスターバッチのベースとなる樹脂としてポリプロピレンに代えてＰＢＴを用いることが考えられるが、その場合に、このマスターバッチをＰＢＴに配合して抗菌性樹脂とし、これを紙上に押出ラミネートすることにより抗菌性原反が得られるが、この抗菌性原反が黄色に変化（黄変）するような着色を生じることがあった。この原因について本発明者らが鋭意検討したところ、抗菌性マスターバッチに含まれる抗菌性銀微粒子の分散剤が影響していることを突き止めた。 It is also possible to use PBT instead of polypropylene as the base resin for the antibacterial masterbatch. In this case, the masterbatch is mixed with PBT to produce an antibacterial resin, which is then extrusion laminated onto paper to obtain antibacterial base fabric. However, this antibacterial base fabric may become discolored, turning yellow (yellowing). The inventors have conducted extensive research into the cause of this and have discovered that the dispersant for the antibacterial silver particles contained in the antibacterial masterbatch is the cause.
そこで本発明は、抗菌性能を確実に発揮すると共に、抗菌性樹脂層の着色（変色）が抑制された抗菌性原反、並びに、これを用いて製作される抗菌性食品用容器及び抗菌性食品用シートを提供することを目的とする。 The present invention aims to provide an antibacterial base fabric that reliably exerts antibacterial performance while suppressing coloration (discoloration) of the antibacterial resin layer, as well as an antibacterial food container and an antibacterial food sheet manufactured using the same.
上記目的を達成するため、請求項１記載の発明は、耐熱性を有する基材層の少なくとも一方表面に抗菌性樹脂から成る抗菌性樹脂層が形成された抗菌性原反であって、抗菌性樹脂は、粒径が３００ｎｍ以下の抗菌性金属微粒子と分散剤としてサッカリン、サッカリンナトリウム及びサッカリンカリウムのうちの少なくとも一種を含むイミノ基を有するアミド化合物とを含むポリブチレンテレフタレート又はポリエチレンテレフタレートである熱可塑性樹脂から成り、抗菌性金属微粒子の抗菌性樹脂に対する配合比率が０．００７５～０．０２重量％の範囲であり、分散剤の抗菌性樹脂に対する配合比率が０．００７５～０．０２重量％の範囲であり、抗菌性樹脂層の厚みが１～１００μｍの範囲である、抗菌性原反である。 In order to achieve the above object, the invention described in claim 1 is an antibacterial base fabric in which an antibacterial resin layer made of an antibacterial resin is formed on at least one surface of a heat-resistant base layer, the antibacterial resin being made of a thermoplastic resin which is polybutylene terephthalate or polyethylene terephthalate containing antibacterial metal microparticles having a particle size of 300 nm or less and an amide compound having an imino group which contains at least one of saccharin, saccharin sodium and saccharin potassium as a dispersant, the blending ratio of the antibacterial metal microparticles to the antibacterial resin being in the range of 0.0075 to 0.02 weight %, the blending ratio of the dispersant to the antibacterial resin being in the range of 0.0075 to 0.02 weight %, and the thickness of the antibacterial resin layer being in the range of 1 to 100 μm.
このように構成すると、抗菌性樹脂層は、粒径が３００ｎｍ以下の抗菌性金属微粒子を０．００７５～０．０２重量％の範囲で含むから、透明性を損なわずに、抗菌性を得るのに必要な金属溶出量を確保できる。抗菌性金属微粒子の含有量が０．００７５重量％未満では、必要な抗菌性能を得るのが困難である。含有量が０．０２重量％を超えても抗菌性能は増大するが、０．０２重量％で必要十分な抗菌性能が得られるため、これ以上の抗菌性金属微粒子を配合したとしてもコストアップとなってしまう。更に、配合量が過度に多くなると抗菌性樹脂中の抗菌性金属微粒子の分散性も悪くなるので好ましくない。抗菌性金属微粒子は耐熱性に優れるので、抗菌性能を保持するのが容易である。 When configured in this way, the antibacterial resin layer contains antibacterial metal particles with a particle size of 300 nm or less in the range of 0.0075 to 0.02 weight %, so that the amount of metal elution required to obtain antibacterial properties can be secured without impairing transparency. If the content of antibacterial metal particles is less than 0.0075 weight %, it is difficult to obtain the required antibacterial performance. If the content exceeds 0.02 weight %, the antibacterial performance increases, but since sufficient antibacterial performance is obtained with 0.02 weight %, even if more antibacterial metal particles are blended, the cost will increase. Furthermore, if the blending amount is excessively large, the dispersibility of the antibacterial metal particles in the antibacterial resin will also deteriorate, which is not preferable. Since the antibacterial metal particles have excellent heat resistance, it is easy to maintain antibacterial performance.
又、本発明では、抗菌性原反を構成する抗菌性樹脂中に抗菌性金属微粒子の分散を目的して含まれる分散剤の含有量を０．００７５～０．０２重量％の範囲とした。本発明者らが変色原因を検討したところ、次のようなことを突き止めた。一般に、ＰＢＴの融点は結晶化度にもよるが２２３℃かそれ以上の温度であるため、ＰＢＴを押出法によりラミネートする場合は溶融温度を融点より高い２７０℃～３００℃の条件として行う必要があるところ、分散剤として用いられるサッカリン、サッカリンナトリウム、サッカリンカリウム等のイミノ基を有するアミド化合物の融点が２３０℃付近でありＰＢＴの押出時の溶融温度条件よりも低いため、高温条件下で分散剤が分解等の変質を起こすことがあり、それにより変色していることがわかった。そして、分散剤の抗菌性金属微粒子に対する配合比率及び抗菌性樹脂に対する配合比率を所定の範囲内とすれば、抗菌性金属微粒子を抗菌性樹脂中に確実に分散させることができると共に、抗菌性樹脂層が着色されるのを抑制できることがわかった。分散剤の含有量が０．００７５重量％未満では、抗菌性金属粒子の分散が確実ではなくなる。含有量が０．０２重量％を超えると、加熱溶融により抗菌性樹脂層が着色するおそれがある。抗菌性樹脂層の厚みを１～１００μｍの範囲としたから、基材層に水分が浸み込むのを阻止する防水層として機能する。抗菌性樹脂層の厚みが１μｍ未満では、防水層の機能を発揮できないおそれがある。厚みが１００μｍを超えると、コスト高を招く。又、抗菌性原反の成形性が低下する。 In addition, in the present invention, the content of the dispersant contained in the antibacterial resin constituting the antibacterial base fabric for the purpose of dispersing the antibacterial metal particles is set to a range of 0.0075 to 0.02% by weight. The inventors have investigated the cause of discoloration and have found the following. Generally, the melting point of PBT is 223°C or higher, depending on the degree of crystallization, so when laminating PBT by extrusion, the melting temperature must be set at 270°C to 300°C, which is higher than the melting point. However, the melting point of amide compounds having imino groups, such as saccharin, saccharin sodium, and saccharin potassium, used as dispersants, is around 230°C, which is lower than the melting temperature condition during extrusion of PBT, so that the dispersant may decompose or otherwise change in quality under high temperature conditions, which causes discoloration. It has been found that if the compounding ratio of the dispersant to the antibacterial metal particles and the compounding ratio to the antibacterial resin are set within a predetermined range, the antibacterial metal particles can be reliably dispersed in the antibacterial resin and the antibacterial resin layer can be prevented from being colored. If the dispersant content is less than 0.0075% by weight, the antibacterial metal particles will not be dispersed reliably. If the content exceeds 0.02% by weight, the antibacterial resin layer may become discolored by heating and melting. The thickness of the antibacterial resin layer is set to a range of 1 to 100 μm, so it functions as a waterproof layer that prevents moisture from penetrating into the base layer. If the antibacterial resin layer is less than 1 μm in thickness, it may not function as a waterproof layer. If the thickness exceeds 100 μm, it will lead to high costs. In addition, the moldability of the antibacterial base fabric will decrease.
請求項２記載の発明は、請求項１記載の発明の構成において、熱可塑性樹脂はポリブチレンテレフタレートであるものである。 The invention described in claim 2 is the same as the invention described in claim 1, in which the thermoplastic resin is polybutylene terephthalate.
このように構成すると、抗菌性樹脂をポリブチレンテレフタレートとしたので、耐熱性、成形性に優れたものとすることができる。 By configuring it in this way, the antibacterial resin is polybutylene terephthalate, which makes it possible to achieve excellent heat resistance and moldability.
請求項３記載の発明は、請求項１又は請求項２記載の発明の構成において、抗菌性金属微粒子は銀微粒子であるものである。 The invention described in claim 3 is the same as the invention described in claim 1 or claim 2, in which the antibacterial metal microparticles are silver microparticles.
このように構成すると、銀微粒子は安定性、安全性に優れ、人体に毒性を与えるおそれがない。 When configured in this way, the silver microparticles are highly stable and safe, and there is no risk of them being toxic to the human body.
請求項４記載の発明は、請求項１～請求項３のいずれかに記載の発明の構成において、基材層は紙から成るものである。 The invention described in claim 4 is the structure of any one of the inventions described in claims 1 to 3 , wherein the base layer is made of paper.
このように構成すると、紙は、プレス成形が容易であり、製品に保形性を容易に与えることができ、且つ安価である。 When constructed in this way, the paper is easy to press mold, can easily give shape retention to products, and is inexpensive.
請求項５記載の発明は、請求項１～請求項４のいずれかに記載の抗菌性原反を用いて製作した抗菌性食品用容器である。 The invention described in claim 5 is an antibacterial food container produced using the antibacterial base film described in any one of claims 1 to 4 .
このように構成すると、耐熱性に優れる抗菌性食品用容器の製造コストを抑えられる。 This configuration reduces the manufacturing costs of heat-resistant antibacterial food containers.
請求項６記載の発明は、請求項１～請求項４のいずれかに記載の抗菌性原反を用いて製作した抗菌性食品用シートである。 The invention described in claim 6 is an antibacterial food sheet produced using the antibacterial base material described in any one of claims 1 to 4 .
このように構成すると、耐熱性に優れる抗菌性食品用シートの製造コストを抑えられる。 This configuration reduces the manufacturing costs of the heat-resistant antibacterial food sheet.
以上説明したように、請求項１記載の発明は、少量の抗菌性金属微粒子で確実に抗菌性能を発揮する製品を、低コストで提供することができる。抗菌性樹脂層の透明性が維持されるので、基材層に図柄等を印刷したときに、その意匠性が損なわれない。又、抗菌性樹脂層の変色を抑制できる。 As explained above, the invention described in claim 1 can provide a product that reliably exhibits antibacterial performance with a small amount of antibacterial metal microparticles at low cost. Because the transparency of the antibacterial resin layer is maintained, the design is not impaired when a pattern or the like is printed on the base layer. In addition, discoloration of the antibacterial resin layer can be suppressed.
請求項２記載の発明は、請求項１記載の発明の効果に加えて、高温調理が可能な食品収容用容器の製造に適した抗菌性原反を提供できる。 The invention described in claim 2 provides the effects of the invention described in claim 1, as well as an antibacterial base material suitable for manufacturing food storage containers that can be used for high-temperature cooking.
請求項３記載の発明は、請求項１又は請求項２記載の発明の効果に加えて、食品収容用として安全な製品を提供することができる。 The invention described in claim 3 provides the effects of the invention described in claim 1 or claim 2, as well as a product that is safe for storing food.
請求項４記載の発明は、請求項１～請求項３のいずれかに記載の発明の効果に加えて、成形性、保形性が良好な抗菌性原反を、安価に提供できる。 The invention described in claim 4 has the effects of the invention described in any one of claims 1 to 3 , and further has the advantage of being able to provide an antibacterial base sheet having good moldability and shape retention at low cost.
請求項５記載の発明は、高温環境でも使用可能な抗菌性食品用容器を安価に提供できる。 The invention as recited in claim 5 can provide an antibacterial food container that can be used in a high-temperature environment at low cost.
請求項６記載の発明は、高温環境でも使用可能な抗菌性食品用シートを安価に提供できる。 The sixth aspect of the present invention makes it possible to provide an inexpensive antibacterial food sheet that can be used in high-temperature environments.
本発明に係る抗菌性原反は、基材層と、基材層の少なくとも一方表面に形成された抗菌性樹脂層とを有する。基材層としては例えば紙が用いられる。紙を用いる場合、その種類や坪量は問わないが、おかずケースのような容器を製造する場合、坪量としては２０ｇ／ｍ２～１００ｇ／ｍ２が好ましく、２０ｇ／ｍ２～８０ｇ／ｍ２がより好ましい。抗菌性樹脂層はポリブチレンテレフタレート（以下、ＰＢＴ）から成り、これに粒径が３００ｎｍ以下の抗菌性金属微粒子を分散させて含む。 The antibacterial raw sheet according to the present invention has a base layer and an antibacterial resin layer formed on at least one surface of the base layer. For example, paper is used as the base layer. When paper is used, the type and basis weight are not important, but when manufacturing a container such as a side dish case, the basis weight is preferably 20 g/m 2 to 100 g/m 2 , and more preferably 20 g/m 2 to 80 g/m 2. The antibacterial resin layer is made of polybutylene terephthalate (hereinafter, PBT), and contains antibacterial metal fine particles having a particle size of 300 nm or less dispersed therein.
尚、本発明における抗菌性金属微粒子とは、金属単体で構成される微粒子のみならず金属と他の化合物とが結合した微粒子であって抗菌性を備えたもの、例えば脂肪酸金属塩のような金属を含む抗菌性を備えた無機微粒子も含むものであり、本明細書では便宜上、総称して抗菌性微粒子と呼ぶ。又、抗菌性金属微粒子の粒径は、透過電子顕微鏡（Transmission Electron Microscope：ＴＥＭ）による観察にて得られた拡大画像において、抗菌性金属微粒子の各々の粒径を計測することで確認でき、個々の微粒子が３００ｎｍ以下であればよい。抗菌性金属微粒子は同じ含有量であっても粒径が小さくなれば抗菌性金属微粒子の比表面積が増大し、より少ない含有量で抗菌性を発揮しやすくなる。従って、抗菌性微粒子の粒径は１００ｎｍ以下であることが好ましく、更には５０ｎｍ以下であることがより好ましい。尚、抗菌性微粒子の粒径の下限値は特に限定されないが、１ｎｍ以上であればよく、５ｎｍ以上であることが好ましい。１ｎｍ未満となるとマスターバッチ作製時においてもＰＢＴ中での分散性が極めて悪くなる。抗菌性金属微粒子は銀微粒子であり、ＰＢＴに対する配合量は０．００７５～０．０２重量％の範囲に調整される。尚、抗菌性金属微粒子の溶出量は１０μｇ／ｍ２以上となるように設定することが好ましい。 In addition, the antibacterial metal fine particles in the present invention include not only fine particles composed of a single metal but also fine particles in which a metal is bonded with another compound and has antibacterial properties, for example, inorganic fine particles containing a metal such as a fatty acid metal salt and have antibacterial properties, and for convenience, they are collectively referred to as antibacterial fine particles in this specification. In addition, the particle size of the antibacterial metal fine particles can be confirmed by measuring the particle size of each of the antibacterial metal fine particles in an enlarged image obtained by observation with a transmission electron microscope (TEM), and each fine particle may be 300 nm or less. Even if the content of the antibacterial metal fine particles is the same, if the particle size is smaller, the specific surface area of the antibacterial metal fine particles increases, and it becomes easier to exhibit antibacterial properties with a smaller content. Therefore, the particle size of the antibacterial fine particles is preferably 100 nm or less, and more preferably 50 nm or less. In addition, the lower limit of the particle size of the antibacterial fine particles is not particularly limited, but it is sufficient that it is 1 nm or more, and preferably 5 nm or more. If it is less than 1 nm, the dispersibility in PBT becomes extremely poor even when the master batch is prepared. The antibacterial metal particles are silver particles, and the amount of silver mixed with PBT is adjusted to the range of 0.0075 to 0.02% by weight. The amount of the antibacterial metal particles that dissolves is preferably set to 10 μg/ m2 or more.
本例の抗菌性原反を製造するには、抗菌性樹脂層を構成するＰＢＴに直接銀粒子を添加して分散させてもよいが、抗菌性樹脂層中に銀粒子を効率よく分散させるためには銀粒子を高濃度で配合したＰＢＴベースのマスターバッチを予め準備した上で、このマスターバッチを別途ＰＢＴに配合することが好ましい。マスターバッチを準備する場合、始めに銀微粒子を分散させて含ませたＰＢＴを準備する。例えば、ＰＢＴに対し、銀成分としてステアリン酸銀及び分散剤としてイミノ基を有するアミド化合物であるサッカリン等を配合したものを加熱混合し、押出成形機を用いて押出成形した後、冷却処理、ペレタイズ処理等を経た粒状のマスターバッチを用いることができる。但し、抗菌性金属微粒子を含むＰＢＴをベースとしたマスターバッチであればその製造方法は特に問わない。本例の抗菌性原反を得るにあたっては、マスターバッチ中の銀成分及び分散剤をそれぞれ０．５重量％に調整したものを用いた。尚、必要に応じマスターバッチには、充填剤、可塑剤、レベリング剤、増粘剤、減粘剤、安定剤、酸化防止剤、紫外線吸収剤等の補助成分を添加することができる。 To manufacture the antibacterial base cloth of this example, silver particles may be added directly to the PBT constituting the antibacterial resin layer and dispersed therein, but in order to efficiently disperse the silver particles in the antibacterial resin layer, it is preferable to prepare a PBT-based master batch containing silver particles at a high concentration in advance and then separately mix this master batch with the PBT. When preparing the master batch, first prepare PBT containing dispersed silver particles. For example, PBT containing silver stearate as the silver component and saccharin, an amide compound having an imino group, as a dispersant is heated and mixed, extruded using an extruder, and then cooled and pelletized to obtain a granular master batch. However, as long as the master batch is based on PBT and contains antibacterial metal particles, the manufacturing method is not particularly important. In obtaining the antibacterial base cloth of this example, a master batch containing silver components and dispersants adjusted to 0.5% by weight was used. If necessary, auxiliary ingredients such as fillers, plasticizers, leveling agents, thickeners, viscosity reducers, stabilizers, antioxidants, and UV absorbers can be added to the master batch.
このようにして得られたマスターバッチをＰＢＴに対し１.５～４．０重量％の範囲で配合し、これを溶融混合して、抗菌性樹脂を得る。この抗菌性樹脂は、銀微粒子が均一に分散した状態で含まれ、抗菌性樹脂中の銀微粒子の含有量は０．００７５～０．０２重量％の範囲である。又、分散剤（サッカリン等）の含有量は０．００７５～０．０２重量％である。そして、この抗菌性樹脂を、紙の少なくとも一方の表面にＴダイによる押出ラミネーションにより、１～１００μｍの範囲で設定した厚みに積層してＰＢＴから成る抗菌性樹脂層を形成することにより、目的の抗菌性原反が製造される。前述の押出ラミネーション法以外にも、ドライラミネーション法等、公知の方法を使用できる。押出ラミネーション法の場合、ＰＢＴを主体とする抗菌性樹脂の押出温度は通常２７０～３００℃に設定される。 The master batch thus obtained is blended with PBT in a range of 1.5 to 4.0% by weight, and this is melt-mixed to obtain an antibacterial resin. This antibacterial resin contains silver particles uniformly dispersed therein, and the content of silver particles in the antibacterial resin is in the range of 0.0075 to 0.02% by weight. The content of the dispersant (saccharin, etc.) is 0.0075 to 0.02% by weight. This antibacterial resin is then laminated to a thickness set in the range of 1 to 100 μm on at least one surface of the paper by extrusion lamination using a T-die to form an antibacterial resin layer made of PBT, thereby producing the desired antibacterial raw sheet. In addition to the above-mentioned extrusion lamination method, known methods such as dry lamination can also be used. In the case of extrusion lamination, the extrusion temperature of the antibacterial resin mainly made of PBT is usually set to 270 to 300°C.
製造された抗菌性原反は、これを用いておかずケースのような食品収容用途の容器を製造した場合において抗菌性樹脂層側を食品と接する面としたとき、抗菌性樹脂層が食品から生じる水分の防水層として機能し、基材層に水分が浸み込むのを阻止する。基材層に紙を用いるので、比較的安価に製造できると共に、抗菌性原反をプレス成形して製品を製造すること、及び、製品に保形性を与えることが容易にできる。抗菌性樹脂層の主成分をＰＢＴとするから、耐熱性、成形性に優れる容器を提供できる。抗菌性金属微粒子を銀微粒子としたので、安定性、安全性に優れる。銀微粒子の粒径を３００ｎｍ以下としたので、０．００７５～０．０２重量％という少ない配合量で、抗菌性能を発揮させるのに必要な１０μｇ／ｍ２以上の銀溶出量を得ることが可能である。銀微粒子が０．００７５重量％未満では必要な抗菌性能を得るのが困難であり、０．０２重量％を超えても抗菌性能は増大しない。これにより、抗菌性樹脂層の透明性を損なわずに抗菌性を発揮させることができると共に、製造コストを抑えることができる。ＰＢＴ及び銀微粒子はいずれも耐熱性に優れるので、加熱時等の高温下での使用が可能であり、且つ抗菌性を失わないという利点を有する。又、抗菌性樹脂層の透明性が維持されると共に変色が抑えられるので、基材層に図柄等を印刷したときに、その意匠性を損なうことがない。 When the antibacterial raw roll thus produced is used to produce a container for storing food such as a side dish case, and the antibacterial resin layer is the surface that contacts the food, the antibacterial resin layer functions as a waterproof layer against moisture generated from the food, preventing the moisture from penetrating into the base layer. Since paper is used for the base layer, it can be produced relatively inexpensively, and it is easy to produce a product by press-molding the antibacterial raw roll and to give the product shape retention. Since the main component of the antibacterial resin layer is PBT, a container with excellent heat resistance and moldability can be provided. Since the antibacterial metal fine particles are silver fine particles, it is excellent in stability and safety. Since the particle size of the silver fine particles is 300 nm or less, it is possible to obtain a silver elution amount of 10 μg/m 2 or more required to exhibit antibacterial performance with a small blending amount of 0.0075 to 0.02 wt %. If the silver fine particles are less than 0.0075 wt %, it is difficult to obtain the required antibacterial performance, and even if they exceed 0.02 wt %, the antibacterial performance does not increase. This allows the antibacterial resin layer to exhibit antibacterial properties without impairing its transparency, and also reduces manufacturing costs. Both PBT and silver particles have excellent heat resistance, so they can be used at high temperatures, such as when heated, and have the advantage of not losing their antibacterial properties. In addition, the transparency of the antibacterial resin layer is maintained and discoloration is suppressed, so that when a pattern or the like is printed on the base layer, the design is not impaired.
更に、本例では、分散剤であるサッカリン等の含有量を０．００７５～０．０２重量％の範囲に設定したので、抗菌性金属微粒子を抗菌性樹脂中に確実に分散させることができると共に、抗菌性樹脂層が着色するのを抑制できる。分散剤の含有量が０．００７５重量％未満では、抗菌性金属粒子の分散が確実ではなくなる。含有量が０．０２重量％を超えると、加熱溶融時の変色で抗菌性樹脂層を着色するおそれがある。抗菌性樹脂層の厚みを１～１００μｍの範囲、好ましくは５～３０μｍの範囲としたから、基材層に水分が浸み込むのを阻止する防水層として確実に機能させることができる。抗菌性樹脂層の厚みが１μｍ未満では、防水層の機能を発揮できないおそれがある。厚みが１００μｍを超えると、コスト高を招くおそれがある。又、抗菌性原反の成形性が低下するおそれがある。 In addition, in this example, the content of the dispersant, saccharin, etc., is set in the range of 0.0075 to 0.02 weight percent, so that the antibacterial metal particles can be reliably dispersed in the antibacterial resin, and the antibacterial resin layer can be prevented from becoming discolored. If the content of the dispersant is less than 0.0075 weight percent, the antibacterial metal particles are not reliably dispersed. If the content exceeds 0.02 weight percent, the antibacterial resin layer may be discolored due to discoloration during heating and melting. Since the thickness of the antibacterial resin layer is set in the range of 1 to 100 μm, preferably in the range of 5 to 30 μm, it can reliably function as a waterproof layer that prevents moisture from penetrating the base layer. If the thickness of the antibacterial resin layer is less than 1 μm, the function of the waterproof layer may not be exhibited. If the thickness exceeds 100 μm, the cost may increase. In addition, the moldability of the antibacterial raw roll may be reduced.
本例の抗菌性原反は、以上のような利点を有することにより、成形性、保形性、耐熱性が良好である。そして、これを用いて製造した容器は、食品の加熱調理等、酸や油等の存在下での高温環境の使用が可能であり、加熱しても抗菌性能が失われないので食品収容用として安全であり、且つ安価である。 The antibacterial base fabric of this example has the above advantages, and therefore has good moldability, shape retention, and heat resistance. Furthermore, containers manufactured using this fabric can be used in high-temperature environments in the presence of acids, oils, etc., such as when cooking food, and since the antibacterial properties are not lost even when heated, they are safe for use in food storage, and are inexpensive.
尚、本発明に係る抗菌性原反を用いることにより、高温環境でも使用可能な抗菌性食品用容器を安価に提供することができる。ここで抗菌性食品用容器とは、弁当箱内におかずを区分けして収納するためのおかずケースのようなカップ状の容器、液体を収納する紙コップ、食品を収納する紙カップや紙トレー、紙皿等を含む。 By using the antibacterial base material according to the present invention, it is possible to provide antibacterial food containers that can be used in high-temperature environments at low cost. Here, antibacterial food containers include cup-shaped containers such as side dish cases for storing side dishes separately in a lunch box, paper cups for storing liquids, paper cups and paper trays for storing food, paper plates, etc.
又、本発明に係る抗菌性原反を用いることにより、高温環境でも使用可能な抗菌性食品用シートを安価に提供することができる。ここで、抗菌性食品用シートとは、食品を載置するため或いは食品を覆うために使用されるシート状の製品である。 In addition, by using the antibacterial base material of the present invention, it is possible to provide an antibacterial food sheet that can be used in high-temperature environments at low cost. Here, an antibacterial food sheet is a sheet-like product used for placing food on or covering food.
尚、本発明に係る抗菌性原反において、熱可塑性樹脂は、ＰＢＴ以外に、ポリエチレンテレフタレート（ＰＥＴ）等を使用することができる。 In addition, in the antibacterial base fabric of the present invention, the thermoplastic resin that can be used is polyethylene terephthalate (PET) in addition to PBT.
又、抗菌性金属微粒子としては、銀以外に、金、銅等の抗菌性を有するものを使用することができる。 In addition to silver, antibacterial metal particles such as gold and copper can also be used.
更に、基材層の素材は、紙の外に、合成樹脂、金属、セラミック、織布又は不織布、及び、これらの複合材を使用することができ、特に耐熱性を備えるものが好ましい。 In addition to paper, the base layer can be made of synthetic resin, metal, ceramic, woven or nonwoven fabric, or a composite of these materials, with heat-resistant materials being particularly preferred.
更に、抗菌性樹脂層は、基材層の一方表面に形成するだけでなく、表裏両面に形成することもできる。 In addition, the antibacterial resin layer can be formed not only on one surface of the base material layer, but also on both the front and back surfaces.
［第１の実施例］
ステアリン酸銀０．５重量％、サッカリン０．５重量％を配合したＰＢＴを加熱混合した後、造粒処理等を経て、ＰＢＴベースのマスターバッチを得た。マスターバッチにおける銀微粒子の粒径は５～１００ｎｍの範囲内であった。
[First embodiment]
PBT containing 0.5% by weight of silver stearate and 0.5% by weight of saccharin was heated and mixed, and then subjected to a granulation process, etc. to obtain a PBT-based master batch. The particle size of the silver particles in the master batch was within the range of 5 to 100 nm.
次に、上記のマスターバッチを０．５、１．０、２．５、３．０及び４．０重量％の比率で配合したＰＢＴを溶融混合して、５種類の抗菌性樹脂を得た。この抗菌性樹脂に含まれる銀微粒子の含有量は、それぞれ０．００２５、０．００５、０．０１２５、０．０１５及び０．０２重量％であった。又、サッカリンの含有量は、それぞれ銀微粒子の含有量と同量の含有量であった。 Next, the above master batch was melt-mixed with PBT in ratios of 0.5, 1.0, 2.5, 3.0, and 4.0% by weight to obtain five types of antibacterial resins. The silver microparticle contents in these antibacterial resins were 0.0025, 0.005, 0.0125, 0.015, and 0.02% by weight, respectively. The saccharin contents were the same as the silver microparticle contents in each case.
最後に、この抗菌性樹脂を、紙（坪量：３５ｇ／ｍ２）の一方の表面に押出法により積層して抗菌性樹脂層（厚み：１５μｍ）を形成し、５種類の抗菌性原反を製造した。このときの押出温度は２７０～３００℃で行った。 Finally, this antibacterial resin was laminated on one surface of paper (basis weight: 35 g/m 2 ) by extrusion to form an antibacterial resin layer (thickness: 15 μm) to produce five types of antibacterial raw sheets. The extrusion temperature was 270 to 300° C.
得られた各抗菌性原反からＪＩＳ Ｚ ２８０１に規定する抗菌性試験用の試験体を作製するために、５種の抗菌性原反それぞれについて右端付近、中央、左端付近の各領域から試験体を切り出した。そして、切り出した試験体について、ＪＩＳ Ｚ ２８０１に規定する試験方法に従い、抗菌性を測定した。結果を表１に示す。 To prepare specimens for antibacterial testing as specified in JIS Z 2801 from each of the obtained antibacterial raw rolls, specimens were cut out from the right end, center, and left end areas of each of the five types of antibacterial raw rolls. The antibacterial properties of the cut specimens were then measured according to the test method specified in JIS Z 2801. The results are shown in Table 1.
又、製造された各抗菌性原反の抗菌性樹脂層を観察したが、いずれも目立つ着色は観察されなかった。 The antibacterial resin layer of each antibacterial substrate was also observed, but no noticeable coloring was observed in any of them.
［第２の実施例］
第１の実施例と同様にして、抗菌性樹脂中のマスターバッチの配合量をそれぞれ０．５、１．０、２．０、２．５、３．０、４．０重量％となるように調整して、抗菌性樹脂中の銀微粒子の含有量が０．００２５、０．００５、０．０１、０．０１２５、０．０１５及び０．０２重量％、サッカリンの含有量がそれぞれ銀微粒子の含有量と同量の含有量である６種類の抗菌性樹脂を調整し、それらを用いて、紙（坪量：３５ｇ／ｍ２）の一方の表面に押出法により積層して抗菌性樹脂層（厚み：１５μｍ）を形成することにより作製した抗菌性原反の銀溶出量及び抗菌性を測定した。
[Second embodiment]
Similarly to the first embodiment, the blending amount of the master batch in the antibacterial resin was adjusted to 0.5, 1.0, 2.0, 2.5, 3.0 and 4.0% by weight, respectively, to prepare six types of antibacterial resins in which the contents of silver microparticles in the antibacterial resin were 0.0025, 0.005, 0.01, 0.0125, 0.015 and 0.02% by weight and the contents of saccharin were the same as the contents of silver microparticles. These were used to laminate on one surface of paper (basis weight: 35 g/ m2 ) by extrusion to form an antibacterial resin layer (thickness: 15 μm), and the amount of silver elution and antibacterial properties of the antibacterial raw sheet were measured.
銀微粒子の抗菌性能は水中に溶出する銀溶出量を測定することで抗菌性能の指標とすることができる。銀溶出量は、以下のようにして算出した。 The antibacterial activity of silver microparticles can be measured by measuring the amount of silver dissolved in water, which can be used as an indicator of antibacterial activity. The amount of silver dissolved was calculated as follows.
先ず、０．０５％Ｔｗｅｅｎ８０（登録商標）水溶液を常温下で３時間攪拌し、銀溶出用の溶出液を作製した。次に、抗菌性原反の試験体から５４００ｃｍ２を切り出して溶出用試料として準備し、当該試料を上記溶出液４５０ｍｌに含侵させて、５０℃で１６時間放置した。その後、銀が溶出した溶出液を孔径０．８０μＬのメンブレンフィルター（ＡＤＶＡＮＴＥＣ社製）にてろ過し、イットリウム濃度が１ｐｐｍになるようにYttrium ICP standard［Y(NO３)３ in HNO３ 2-3%、CertiPUR(登録商標)］（ＭＥＲＣＫ社製）をろ過後の溶出水に加えて測定液とした。測定液中の銀イオン量を、ＩＣＰ発光分光分析装置（ｉＣＡＰ６５００：ＴｈｅｒｍｏＦｉｓｈｅｒＳＣＩＥＮＴＩＦＩＣ社製）にて測定した測定液の銀イオン濃度（ｐｐｍ）から求め、溶出用試料１ｍ２あたりの銀溶出量を算出した。 First, 0.05% Tween 80 (registered trademark) aqueous solution was stirred at room temperature for 3 hours to prepare an elution solution for silver elution. Next, 5400 cm2 was cut out from the antibacterial raw cloth test piece to prepare an elution sample, and the sample was impregnated with 450 ml of the elution solution and left at 50 ° C for 16 hours. After that, the elution solution from which silver was eluted was filtered with a membrane filter (manufactured by ADVANTEC) with a pore size of 0.80 μL, and Yttrium ICP standard [Y(NO 3 ) 3 in HNO 3 2-3%, CertiPUR (registered trademark)] (manufactured by MERCK) was added to the elution water after filtration so that the yttrium concentration was 1 ppm to prepare a measurement solution. The amount of silver ions in the measurement solution was determined from the silver ion concentration (ppm) of the measurement solution measured using an ICP emission spectrometer (iCAP6500: manufactured by ThermoFisher SCIENTIFIC), and the amount of silver eluted per m2 of the elution sample was calculated.
抗菌性の測定方法は、ＪＩＳ Ｚ ２８０１に規定する試験方法に従った。 The antibacterial properties were measured according to the test method specified in JIS Z 2801.
結果を表２に示す。 The results are shown in Table 2.
又、製造された各抗菌性原反の抗菌性樹脂層を観察したが、いずれも目立つ着色は観察されなかった。 The antibacterial resin layer of each antibacterial substrate was also observed, but no noticeable coloring was observed in any of them.
Claims (6)
前記抗菌性樹脂は、粒径が３００ｎｍ以下の抗菌性金属微粒子と分散剤としてサッカリン、サッカリンナトリウム及びサッカリンカリウムのうちの少なくとも一種を含むイミノ基を有するアミド化合物とを含むポリブチレンテレフタレート又はポリエチレンテレフタレートである熱可塑性樹脂から成り、
前記抗菌性金属微粒子の前記抗菌性樹脂に対する配合比率が０．００７５～０．０２重量％の範囲であり、
前記分散剤の前記抗菌性樹脂に対する配合比率が０．００７５～０．０２重量％の範囲であり、
前記抗菌性樹脂層の厚みが１～１００μｍの範囲である、
抗菌性原反。 An antibacterial base fabric having an antibacterial resin layer made of an antibacterial resin formed on at least one surface of a heat-resistant base layer,
The antibacterial resin is made of a thermoplastic resin which is polybutylene terephthalate or polyethylene terephthalate containing antibacterial metal fine particles having a particle size of 300 nm or less and an amide compound having an imino group, which includes at least one of saccharin, saccharin sodium , and saccharin potassium as a dispersant;
The blending ratio of the antibacterial metal fine particles to the antibacterial resin is in the range of 0.0075 to 0.02% by weight,
The blending ratio of the dispersant to the antibacterial resin is in the range of 0.0075 to 0.02% by weight,
The thickness of the antibacterial resin layer is in the range of 1 to 100 μm.
Antibacterial base material.
An antibacterial food sheet formed from the antibacterial base material according to any one of claims 1 to 4 .
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000093296A (en) | 1998-09-18 | 2000-04-04 | Polyplastics Co | Heat-resistant paper container for heat cooking |
| JP2006026945A (en) | 2004-07-12 | 2006-02-02 | Seiji Kagawa | Polybutylene terephthalate film laminate and its use |
| JP2008308645A (en) | 2007-06-18 | 2008-12-25 | Sumitomo Electric Ind Ltd | Antibacterial coating material, antibacterial article formed by using the same, antibacterial film and antibacterial tape |
| JP2012036188A (en) | 2004-07-30 | 2012-02-23 | Acrymed Inc | Antimicrobial silver composition |
| JP2013241643A (en) | 2012-05-18 | 2013-12-05 | Toyo Seikan Group Holdings Ltd | Dispersion liquid containing silver ultrafine particle, and method of manufacturing the same |
| JP2014037361A (en) | 2012-08-14 | 2014-02-27 | Toyo Seikan Group Holdings Ltd | Antimicrobial master batch and molded article using the same |
| JP2018100234A (en) | 2016-12-20 | 2018-06-28 | 東罐マテリアル・テクノロジー株式会社 | Metal fine particle, metal fine particle-containing fluid dispersion, and production method thereof |
| JP2018100255A (en) | 2016-03-28 | 2018-06-28 | 東洋製罐グループホールディングス株式会社 | Dispersion liquid, method for producing the same, and copper compound particles |
-
2019
- 2019-09-30 JP JP2019179770A patent/JP7461727B2/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000093296A (en) | 1998-09-18 | 2000-04-04 | Polyplastics Co | Heat-resistant paper container for heat cooking |
| JP2006026945A (en) | 2004-07-12 | 2006-02-02 | Seiji Kagawa | Polybutylene terephthalate film laminate and its use |
| JP2012036188A (en) | 2004-07-30 | 2012-02-23 | Acrymed Inc | Antimicrobial silver composition |
| JP2008308645A (en) | 2007-06-18 | 2008-12-25 | Sumitomo Electric Ind Ltd | Antibacterial coating material, antibacterial article formed by using the same, antibacterial film and antibacterial tape |
| JP2013241643A (en) | 2012-05-18 | 2013-12-05 | Toyo Seikan Group Holdings Ltd | Dispersion liquid containing silver ultrafine particle, and method of manufacturing the same |
| JP2014037361A (en) | 2012-08-14 | 2014-02-27 | Toyo Seikan Group Holdings Ltd | Antimicrobial master batch and molded article using the same |
| JP2018100255A (en) | 2016-03-28 | 2018-06-28 | 東洋製罐グループホールディングス株式会社 | Dispersion liquid, method for producing the same, and copper compound particles |
| JP2018100234A (en) | 2016-12-20 | 2018-06-28 | 東罐マテリアル・テクノロジー株式会社 | Metal fine particle, metal fine particle-containing fluid dispersion, and production method thereof |
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| JP2021053961A (en) | 2021-04-08 |
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