JP2021053953A - Antibacterial raw fabric, and container for antibacterial food product and sheet for antibacterial food product - Google Patents
Antibacterial raw fabric, and container for antibacterial food product and sheet for antibacterial food product Download PDFInfo
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 216
- 235000013305 food Nutrition 0.000 title claims abstract description 42
- 239000004744 fabric Substances 0.000 title claims abstract description 23
- 239000010419 fine particle Substances 0.000 claims abstract description 62
- 229920005989 resin Polymers 0.000 claims abstract description 56
- 239000011347 resin Substances 0.000 claims abstract description 56
- 229910052709 silver Inorganic materials 0.000 claims abstract description 53
- 239000004332 silver Substances 0.000 claims abstract description 53
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052751 metal Inorganic materials 0.000 claims abstract description 41
- 239000002184 metal Substances 0.000 claims abstract description 41
- 239000002245 particle Substances 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 25
- 238000010828 elution Methods 0.000 claims abstract description 16
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 35
- 239000002994 raw material Substances 0.000 claims description 20
- -1 polybutylene terephthalate Polymers 0.000 claims description 18
- 238000010030 laminating Methods 0.000 abstract description 5
- 239000004594 Masterbatch (MB) Substances 0.000 description 31
- 239000000123 paper Substances 0.000 description 19
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 229920003002 synthetic resin Polymers 0.000 description 9
- 239000000057 synthetic resin Substances 0.000 description 9
- 235000012046 side dish Nutrition 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 7
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000002270 dispersing agent Substances 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
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 235000021186 dishes Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 2
- 229940081974 saccharin Drugs 0.000 description 2
- 235000019204 saccharin Nutrition 0.000 description 2
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 2
- 150000003839 salts Chemical class 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
- 239000002562 thickening agent Substances 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
- 150000007513 acids Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic 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
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000009820 dry lamination Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000945 filler 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
- 239000010931 gold Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 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
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Package Specialized In Special Use (AREA)
Abstract
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 comprises an antibacterial raw fabric formed by forming an antibacterial resin layer containing antibacterial metal fine particles such as silver dispersed on a base material layer such as paper, and an antibacterial material produced by using the antibacterial raw fabric. Regarding food containers and antibacterial food sheets.
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。このような紙容器は、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 cooked in a microwave oven, an oven, or the like. This conventional heat-resistant paper container is manufactured by using a raw fabric produced by laminating polybutylene terephthalate (PBT) having specific characteristics on heat-resistant paper. Such a paper container has an advantage that it exhibits heat resistance that does not cause the container shape to collapse, deform, or change in appearance even when cooked at a high temperature in a microwave oven or an oven.
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るが、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 side dish case with folds obtained by press-molding a laminate of a thin paper base material and a synthetic resin as a container for storing side dishes in a lunch box is generally known, and such a side dish case There is a desire to impart antibacterial properties to the plastic. In this case, it is conceivable to impart antibacterial properties to the synthetic resin layer, which is the surface in contact with food. However, as a technique for imparting antibacterial properties to synthetic resin products, Patent Document 2 describes an antibacterial masterbatch containing a silver compound. Is described. This antibacterial master batch is composed of a base olefin resin, fatty acid silver exhibiting antibacterial properties, and a dispersant for dispersing the fatty acid silver. Specifically, the chlorine content of the olefin resin is 1 ppm or less. The acid dissociation constant (pKa) of the dispersant is 4.0 or less, the content of silver fatty acid is 0.1 to 2% by weight, and the weight ratio of silver fatty acid and the dispersant is 1: 0.5 to 1:10. The feature is that it is set to. Specifically, metallocene-based catalyst polypropylene is used as the olefin resin, and saccharin is used as the dispersant. Then, it is said that a resin molded product having antibacterial properties can be produced by using this antibacterial masterbatch. That is, an antibacterial masterbatch is blended with a thermoplastic resin, and a conventionally known melt molding method is used to shape the final molded product according to the intended use, for example, granular, pelleted, fibrous, film, sheet, container, etc. Therefore, the desired antibacterial resin product can be obtained. Here, it is desirable that the amount of the antibacterial masterbatch blended into the thermoplastic resin is such that the antibacterial masterbatch is diluted 10 to 40 times with a synthetic resin and mixed. Further, as the thermoplastic resin to be blended with the antibacterial masterbatch, it is said that it is preferable to use the same type of olefin resin as that used for the antibacterial masterbatch, particularly polypropylene.
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、揚げたてや焼き立ての高温状態の食品を載せたりして用いられるので、食品と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。 Since the above-mentioned side dish case is used by heating food in a microwave oven at the time of eating or placing freshly fried or freshly baked food in a high temperature state, heat resistance is required for the synthetic resin in contact with the food, as described above. PBT is used as a synthetic resin. Then, when trying to impart antibacterial properties to a heat-resistant container in which a heat-resistant resin is laminated on the surface of the side dish case, it is conceivable to use the antibacterial masterbatch technique described in Patent Document 2. However, in Patent Document 2, since the synthetic resin containing the antibacterial masterbatch is polypropylene having a low melting point, it is not possible to obtain a container having heat resistance.
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。また、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の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、そ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 conceivable to add the antibacterial masterbatch of Patent Document 2 to the PBT layer of the heat-resistant paper container described in Patent Document 1. However, according to the common general technical knowledge of those skilled in the art, it is considered 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, whereas the polypropylene containing the antibacterial masterbatch of Patent Document 2 is an olefin resin having a low glass transition temperature (about 0 ° C.). Both have properties that are significantly different in terms of structure and physical properties. Therefore, when the antibacterial masterbatch of Patent Document 2 is blended with the PBT of Patent Document 1, the type of synthetic resin is different, so that the compatibility is poor and the antibacterial metal fine particles cannot be uniformly dispersed, and the desired antibacterial property can be obtained. I can't. Further, as described in Patent Document 2, polypropylene having a low chlorine component content must be used as the polypropylene as the base resin of the antibacterial masterbatch. The reason is that the chlorine component reacts with the silver ions eluted from the antibacterial silver particles to generate silver chloride, and the silver chloride is discolored by light, so that the container obtained by blending this master batch, etc. This is because discoloration occurs. Further, it is difficult to use polypropylene having a low chlorine component as a masterbatch as in Patent Document 2 in order to suppress discoloration because it narrows the types of resins that can be used and leads to cost increase.
そこで本発明は、容器等を製造するための原反として使用される、ＰＢＴを紙基材などの基材表面にラミネートしたものに抗菌性を付与した抗菌性原反、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。 Therefore, the present invention uses an antibacterial raw fabric, which is used as a raw fabric for manufacturing containers and the like, and which imparts antibacterial properties to a material obtained by laminating PBT on the surface of a substrate such as a paper substrate, and using this. It is an object of the present invention to provide a container for an antibacterial food product and a sheet for an antibacterial food product to be manufactured.
上記目的を達成するため、請求項１記載の発明は、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抗菌性原反であって、抗菌性樹脂層は、粒径が３００ｎｍ以下の抗菌性金属微粒子を分散させて含ませたポリブチレンテレフタレートから成り、抗菌性金属微粒子の溶出量が１０μｇ／ｍ２以上である、抗菌性原反である。 In order to achieve the above object, the invention according to claim 1 is an antibacterial raw fabric having a base material layer and an antibacterial resin layer formed on at least one surface of the base material layer, and is an antibacterial resin layer. Is an antibacterial raw fabric composed of polybutylene terephthalate in which antibacterial metal fine particles having a particle size of 300 nm or less are dispersed and contained, and the elution amount of the antibacterial metal fine particles is 10 μg / m 2 or more.
このように構成すると、抗菌性樹脂層に分散させて含ませた抗菌性金属微粒子が溶出して抗菌性を示す。従来の当業者の技術常識では、ポリブチレンテレフタレートから抗菌性金属微粒子は溶出しにくいと考えられていたが、この予測に反し、抗菌性金属微粒子であれば、ポリブチレンテレフタレートからでも所要の溶出量が得られるという新たな知見が得られた。この発明の抗菌性原反を用いて容器を製造すると、抗菌性樹脂層は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。抗菌性樹脂層の主成分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。抗菌性樹脂層に含ませる抗菌性金属微粒子の粒径が３００ｎｍ以下なので、少量で大きい溶出量を得られるから、製造コストを抑えることができる。抗菌性金属微粒子の溶出量が１０μｇ／ｍ２以上なので、食品用として必要な抗菌性能を発揮する。又、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。 With this configuration, the antibacterial metal fine particles dispersed and contained in the antibacterial resin layer are eluted to exhibit antibacterial properties. Conventional technical knowledge of those skilled in the art has considered that antibacterial metal fine particles are difficult to elute from polybutylene terephthalate, but contrary to this prediction, antibacterial metal fine particles require a required amount of elution even from polybutylene terephthalate. A new finding was obtained that When a container is manufactured using the antibacterial raw material of the present invention, the antibacterial resin layer functions as a waterproof layer and prevents moisture from infiltrating into the base material layer. Since the main component of the antibacterial resin layer is polybutylene terephthalate, it can be made excellent in heat resistance and moldability. Since the particle size of the antibacterial metal fine particles contained in the antibacterial resin layer is 300 nm or less, a large elution amount can be obtained with a small amount, so that the production cost can be suppressed. Since the elution amount of the antibacterial metal fine particles is 10 μg / m 2 or more, the antibacterial performance required for food is exhibited. Further, since the antibacterial metal fine particles have excellent heat resistance, it is easy to maintain the antibacterial performance.
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、抗菌性樹脂層は、抗菌性金属微粒子を０．００７５〜０．０２重量％の範囲で含むものである。 The invention according to claim 2 is the constitution of the invention according to claim 1, wherein the antibacterial resin layer contains antibacterial metal fine particles in the range of 0.0075 to 0.02% by weight.
このように構成すると、抗菌性を発揮するのに必要な抗菌性金属微粒子の溶出量を得られる。又、抗菌性樹脂層の透明性を損なわない。 With this configuration, the amount of elution of antibacterial metal fine particles required to exhibit antibacterial properties can be obtained. Moreover, the transparency of the antibacterial resin layer is not impaired.
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。 In the invention according to claim 3, the antibacterial metal fine particles are silver fine particles in the constitution of the invention according to claim 1 or 2.
このように構成すると、銀微粒子は安定性、安全性に優れるから、人体に毒性を与えるおそれがない。 With this structure, the silver fine particles are excellent in stability and safety, so that there is no risk of causing toxicity 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。 In the invention according to claim 4, in the constitution of the invention according to any one of claims 1 to 3, the base material layer is made of paper.
このように構成すると、抗菌性原反をプレス成形して製品を製造するのが容易であり、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。 With such a configuration, it is easy to press-mold the antibacterial raw material to manufacture a product, and it is possible to easily impart shape retention to the product and it 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 according to claim 5 is an antibacterial food container manufactured by using the antibacterial raw material according to 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。 With this configuration, the manufacturing cost of an antibacterial food container having excellent heat resistance can be suppressed.
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 according to claim 6 is an antibacterial food sheet produced by using the antibacterial raw material according to 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。 With this configuration, the manufacturing cost of an antibacterial food sheet having excellent heat resistance can be suppressed.
請求項１記載の発明は、食品の加熱調理等、酸や油等の存在下での高温環境での使用が可能であり、且つ抗菌性能を備える製品を低コストで提供できる。 The invention according to claim 1 can be used in a high temperature environment in the presence of an acid, oil, or the like, such as cooking food, and can provide a product having antibacterial performance at low cost.
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、抗菌性金属微粒子の含有量を０．００７５〜０．０２重量％の範囲とすることで、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しない。又、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。 The invention according to claim 2 reliably exhibits antibacterial performance by setting the content of the antibacterial metal fine particles in the range of 0.0075 to 0.02% by weight in addition to the effect of the invention according to claim 1. Products can be provided at low cost. If the content of the antibacterial metal fine particles is less than 0.0075% by weight, it is difficult to obtain the required antibacterial performance. The antibacterial performance does not increase even if the content exceeds 0.02% by weight. Further, since the transparency of the antibacterial resin layer is maintained, the design property is not impaired when a pattern or the like is printed on the base material layer.
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。
請求項４記載の発明は、請求項１から請求項３のいずれかに記載の発明の効果に加えて、成形性、保形性が良好な製品を、安価に提供できる。
The invention according to claim 3 can provide a safe product for food storage in addition to the effects of the invention according to claim 1 or 2.
The invention according to claim 4 can inexpensively provide a product having good moldability and shape retention in addition to the effects of the invention according to any one of claims 1 to 3.
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 according to claim 5 can inexpensively provide an antibacterial food container that can be used even in a high temperature environment.
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 invention according to claim 6 can inexpensively provide an antibacterial food sheet that can be used even in a high temperature environment.
本発明の第１の実施の形態による抗菌性原反は、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には、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 fabric according to the first embodiment of the present invention has a base material layer and an antibacterial resin layer formed on at least one surface of the base material layer. For example, paper is used as the base material layer. If paper is used, but no limitation on the type and basis weight, in the production of containers, such as dishes case is preferably from 20g / m 2 ~100g / m 2 as basis weight, 20 g / m 2 to 80 g / M 2 is more preferable. 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。また、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、さらには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、抗菌性樹脂層中における抗菌性金属微粒子の配合量は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される。 The antibacterial metal fine particles in the present invention are not only fine particles composed of a single metal but also fine particles in which a metal and another compound are bonded and have antibacterial properties, for example, a metal such as a fatty acid metal salt. Inorganic fine particles having antibacterial properties including the above are also included, and are collectively referred to as antibacterial fine particles in the present specification for convenience. 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 a magnified image obtained by observation with a transmission electron microscope (TEM). The fine particles of the above may be 300 nm or less. Even if the content of the antibacterial metal fine particles is the same, the smaller the particle size, the larger the specific surface area of the antibacterial metal fine particles, and the smaller the content, the easier it is to exhibit antibacterial properties. Therefore, the particle size of the antibacterial fine particles is preferably 100 nm or less, and more preferably 50 nm or less. The lower limit of the particle size of the antibacterial fine particles is not particularly limited, but may be 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 masterbatch is produced. The antibacterial metal fine particles are silver fine particles, and the blending amount of the antibacterial metal fine particles in the antibacterial resin layer is adjusted in the range of 0.0075 to 0.02% by weight. The elution amount of the antibacterial metal fine particles is set to be 10 μg / m 2 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、銀粒子として脂肪酸金属塩であるステアリン酸銀及び分散剤としてサッカリン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。本発明の第１の実施の形態による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を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。 In order to produce the antibacterial raw material of this example, silver particles may be directly added and dispersed in the PBT constituting the antibacterial resin layer, but in order to efficiently disperse the silver particles in the antibacterial resin layer. It is preferable to prepare a PBT-based master batch in which silver particles are blended in a high concentration in advance, and then separately blend this master batch into PBT. When preparing a masterbatch, first prepare a PBT in which silver fine particles are dispersed and contained. For example, PBT containing silver stearate, which is a fatty acid metal salt as silver particles, and saccharin as a dispersant, is heated and mixed, extruded using an extrusion molding machine, and then cooled, pelletized, and the like. Granular master batches can be used. However, the production method is not particularly limited as long as it is a masterbatch based on PBT containing antibacterial metal fine particles. In obtaining the antibacterial raw fabric according to the first embodiment of the present invention, the silver component in the masterbatch adjusted to 0.5% by weight was used. If necessary, auxiliary components such as a filler, a plasticizer, a leveling agent, a thickener, a thickener, a stabilizer, an antioxidant, and an ultraviolet absorber can be added to the masterbatch.
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。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積層して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。抗菌性樹脂層を積層する手段は、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など公知の方法を使用できる。 The masterbatch thus obtained is blended in the range of 1.5 to 4.0% by weight with respect to PBT, and this is melt-mixed to obtain an antibacterial resin. This antibacterial resin is contained in a state where silver fine particles are uniformly dispersed, and the content of silver fine particles in the antibacterial resin is in the range of 0.0075 to 0.02% by weight. Then, the target antibacterial raw fabric is produced by laminating this antibacterial resin on at least one surface of the paper by extrusion lamination with a T die to form an antibacterial resin layer. As a means for laminating the antibacterial resin layer, a known method such as a dry lamination method can be used in addition to the extrusion lamination method described above.
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、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。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、抗菌性食品用製品の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。 When a container for food storage such as a side dish is manufactured using this, the antibacterial resin layer is made from the food when the antibacterial resin layer side is the surface in contact with the food. It functions as a waterproof layer for the generated moisture and prevents the moisture from seeping into the base material layer. Since paper is used as the base material layer, it can be manufactured at a relatively low cost, and it is possible to easily manufacture a product by press-molding an antibacterial raw material and to impart shape retention to the product. Since the main component of the antibacterial resin layer is PBT, it is possible to provide a container having excellent heat resistance and moldability. 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 necessary for exerting antibacterial performance with a small blending amount of 0.0075 to 0.02% by weight. Is. As a result, the antibacterial property can be exhibited without impairing the transparency of the antibacterial resin layer, and the manufacturing cost of the antibacterial food product can be suppressed. Since both PBT and silver fine particles are excellent in heat resistance, they have the advantages that they can be used at high temperatures such as when heated and that antibacterial properties are not lost.
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。又、銀微粒子の含有量を０．００７５〜０．０２重量％の範囲とすることで、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。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％を超えると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、これ以上の銀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。さらに、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。又、この範囲内であれば、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、その意匠性を損なうことがない。抗菌性樹脂層の厚みは、好ましくは１〜１００μｍの範囲、より好ましくは５〜３０μｍの範囲とすればよい。この範囲内であれば、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。 The antibacterial raw fabric of this example has the above-mentioned advantages, and therefore has good moldability, shape retention, and heat resistance. The container manufactured using this can be used in a high temperature environment in the presence of acids, oils, etc., such as for cooking foods, and the antibacterial performance is not lost even when heated, so that it can be used for storing foods. It is safe and inexpensive. Further, by setting the content of the silver fine particles in the range of 0.0075 to 0.02% by weight, it is possible to provide a product that reliably exhibits antibacterial performance at low cost. If the amount of silver fine particles is less than 0.0075% by weight, it is difficult to obtain the required antibacterial performance, and if it exceeds 0.02% by weight, the antibacterial performance increases, but if it exceeds 0.02% by weight, the necessary and sufficient antibacterial performance is obtained. Therefore, even if more silver fine particles are blended, the cost will increase. Further, if the blending amount is excessively large, the dispersibility of the antibacterial metal fine particles in the antibacterial resin also deteriorates, which is not preferable. Further, within this range, the transparency of the antibacterial resin layer is maintained, so that the design property is not impaired when a pattern or the like is printed on the base material layer. The thickness of the antibacterial resin layer may be preferably in the range of 1 to 100 μm, more preferably in the range of 5 to 30 μm. Within this range, it can be reliably functioned as a waterproof layer that prevents moisture from seeping into the base material 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 material may decrease.
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 raw material according to the present invention, it is possible to provide an antibacterial food container that can be used even in a high temperature environment at low cost. Here, the antibacterial food container is a cup-shaped container such as a side dish case for separating and storing side dishes in a lunch box, a paper cup for storing liquid, a paper cup or paper tray for storing food, and paper. Including dishes and the like.
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。 Further, by using the antibacterial raw material according to the present invention, it is possible to provide an antibacterial food sheet that can be used even in a high temperature environment at low cost. Here, the antibacterial food sheet is a sheet-like product used for placing food or covering food.
尚、本発明の抗菌性食品容器及び抗菌性食品用シートは、抗菌性樹脂層を備えるが、抗菌性樹脂層を構成するＰＢＴの結晶化度が９％以上であることが好ましい。９％以上とすることにより、前述のように抗菌性樹脂層中に抗菌性金属微粒子の含有量が少量であったとしても良好な抗菌性能を示すようになる。ＰＢＴの結晶化度が９％未満の場合は、抗菌性能が低下するおそれがある。尚、ＰＢＴの結晶化度の上限は特に限定されないが２０％程度であればよい。 The antibacterial food container and the sheet for antibacterial food of the present invention include an antibacterial resin layer, and the crystallinity of PBT constituting the antibacterial resin layer is preferably 9% or more. When it is 9% or more, good antibacterial performance is exhibited even if the content of the antibacterial metal fine particles in the antibacterial resin layer is small as described above. If the crystallinity of PBT is less than 9%, the antibacterial performance may deteriorate. The upper limit of the crystallinity of PBT is not particularly limited, but may be about 20%.
尚、本発明に係る抗菌性原反において、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 the antibacterial raw fabric according to the present invention, as the antibacterial metal fine particles, those having antibacterial properties such as gold and copper can be used in addition to silver.
又、基材層の素材は、紙の他に、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。 Further, as the material of the base material layer, in addition to paper, synthetic resin, metal, ceramic, woven fabric or non-woven fabric, and composite materials thereof can be used, and those having heat resistance are particularly preferable.
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。 Further, 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％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 Example]
After heating and mixing PBT containing 0.5% by weight of silver stearate, a PBT-based masterbatch was obtained through granulation treatment and the like. The particle size of the silver fine particles in the masterbatch was in 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。 Next, PBT containing the above masterbatch in a ratio of 0.5, 1.0, 2.5, 3.0 and 4.0% by weight was melt-mixed to obtain five types of antibacterial resins. .. The contents of the silver fine particles contained in this antibacterial resin were 0.0025, 0.005, 0.0125, 0.015 and 0.02% by weight, respectively.
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。 This antibacterial resin was laminated on one surface of paper (basis weight: 35 g / m 2 ) by an extrusion method to form an antibacterial resin layer (thickness: 15 μm), and five types of antibacterial raw fabrics were produced. ..
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成するために、５種類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、切り出した下記試験体について、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。 In order to prepare a test piece for an antibacterial test specified in JIS Z 2801 from each of the obtained antibacterial raw materials, a test piece was prepared from each region near the right end, the center, and the left end for each of the five types of antibacterial raw materials. Was cut out. Then, the antibacterial properties of the following test pieces cut out were measured according to the test method specified in JIS Z 2801. The results are shown in Table 1.
［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％である６種類の抗菌性樹脂を調整し、それらを用いて作成した抗菌性原反の銀溶出量及び抗菌性を測定した。また、銀微粒子の含有量が０．０１２５、０．０１５、０．０２重量％のものについては、それぞれの含有量の抗菌性原反を用いて抗菌性食品容器を成形した。尚、これらの抗菌性食品容器としては、当該抗菌性食品容器を構成する抗菌性樹脂層のＰＢＴ結晶化度が異なるものを準備した。
[Second Example]
In the same manner as in the first embodiment, the blending amounts of the master batch in the antibacterial resin are 0.5, 1.0, 2.0, 2.5, 3.0 and 4.0% by weight, respectively. 6 types of antibacterial resins in which the content of silver fine particles in the antibacterial resin is 0.0025, 0.005, 0.01, 0.0125, 0.015 and 0.02% by weight are adjusted to The amount of silver elution and the antibacterial property of the antibacterial raw material prepared using them were measured. Further, for those having a silver fine particle content of 0.0125, 0.015, 0.02% by weight, an antibacterial food container was molded using the antibacterial raw material having each content. As these antibacterial food containers, those having different degrees of PBT crystallinity of the antibacterial resin layer constituting the antibacterial food container were prepared.
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 performance of silver fine particles can be used as an index of antibacterial performance by measuring the amount of silver eluted in water. The amount of silver eluted 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, a 0.05% Tween 80 (registered trademark) aqueous solution was stirred at room temperature for 3 hours to prepare an eluate for silver elution. Next, 5400 cm 2 was cut out from the test piece of the antibacterial raw material and prepared as a sample for elution, and the sample was impregnated with 450 ml of the above eluate and left at 50 ° C. for 16 hours. After that, the eluate from which silver was eluted was filtered through a membrane filter (manufactured by ADVANTEC) with a pore size of 0.80 μL, and the yttrium concentration was 1 ppm. Yttrium ICP standard [Y (NO 3 ) 3 in HNO 3 2-3 %, CertiPUR (registered trademark)] (manufactured by MERCK) was added to the eluate after filtration 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 by an ICP emission spectrophotometer (iCAP6500: manufactured by ThermoFiser SCIENTIFIC), and the amount of silver elution per 1 m 2 of the elution sample was calculated. ..
結晶化度は、抗菌性原反を用いて成形された抗菌性食品容器を測定用試験体として、広角Ｘ線回折測定装置を用いて透過法により相対結晶化度を算出することにより求めた。 The crystallinity was determined by calculating the relative crystallinity by a transmission method using a wide-angle X-ray diffraction measuring device using an antibacterial food container molded using an antibacterial raw material as a test body for measurement.
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 method for measuring the antibacterial property was in accordance with the test method specified in JIS Z 2801.
結果を表２に示す。 The results are shown in Table 2.
［比較例］
粒径０．５μｍの銀粒子１０重量％を配合したＰＢＴ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、造粒処理等を経て、ＰＢＴベースのマスターバッチを得る。
[Comparison example]
PBT containing 10% by weight of silver particles having a particle size of 0.5 μm is heated and mixed, extruded using an extrusion molding machine, and then cooled, granulated, and the like to obtain a PBT-based masterbatch.
次に、上記のマスターバッチを抗菌性樹脂層中に２．５、３．０、４．０及び５．０重量％の比率となるように配合したＰＢＴを溶融混合して、４種類の樹脂組成物を得た。この樹脂組成物に含まれる銀粒子の含有量は、それぞれ０．２５、０．３、０．４及び０．５重量％である。 Next, PBT in which the above masterbatch was blended in an antibacterial resin layer at a ratio of 2.5, 3.0, 4.0 and 5.0% by weight was melt-mixed and four kinds of resins were mixed. The composition was obtained. The contents of the silver particles contained in this resin composition are 0.25, 0.3, 0.4 and 0.5% by weight, respectively.
最後に、この樹脂組成物を、紙の一方の表面に押出成形法により積層して樹脂層を形成し、４種類の比較原反を製造する。 Finally, this resin composition is laminated on one surface of the paper by an extrusion molding method to form a resin layer, and four types of comparative raw fabrics are produced.
得られた各比較原反について、第１の実施例と同様にして、右端付近、中央、左端付近の抗菌性を、ＪＩＳ Ｚ ２８０１に規定する試験方法に従って測定した。結果を表３に示す。 For each of the obtained comparative raw fabrics, the antibacterial properties near the right end, the center, and the vicinity of the left end were measured according to the test method specified in JIS Z 2801 in the same manner as in the first example. The results are shown in Table 3.
Claims (6)
前記抗菌性樹脂層は、粒径が３００ｎｍ以下の抗菌性金属微粒子を分散させて含ませたポリブチレンテレフタレートから成り、
前記抗菌性金属微粒子の溶出量が１０μｇ／ｍ２以上である、抗菌性原反。 An antibacterial raw fabric having a base material layer and an antibacterial resin layer formed on at least one surface of the base material layer.
The antibacterial resin layer is made of polybutylene terephthalate in which antibacterial metal fine particles having a particle size of 300 nm or less are dispersed and contained.
An antibacterial raw fabric in which the elution amount of the antibacterial metal fine particles is 10 μg / m 2 or more.
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| 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 |
| JP2008143024A (en) * | 2006-12-11 | 2008-06-26 | Toray Ind Inc | Matted laminated polyester film and wall paper |
| WO2016047568A1 (en) * | 2014-09-22 | 2016-03-31 | 富士フイルム株式会社 | Antibacterial sheet, antibacterial coat, laminated body, and antibacterial fluid |
| WO2018116980A1 (en) * | 2016-12-20 | 2018-06-28 | 東洋製罐グループホールディングス株式会社 | Metal microparticles, and dispersion liquid containing metal microparticles and method for producing same |
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| 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 |
| JP2008143024A (en) * | 2006-12-11 | 2008-06-26 | Toray Ind Inc | Matted laminated polyester film and wall paper |
| WO2016047568A1 (en) * | 2014-09-22 | 2016-03-31 | 富士フイルム株式会社 | Antibacterial sheet, antibacterial coat, laminated body, and antibacterial fluid |
| WO2018116980A1 (en) * | 2016-12-20 | 2018-06-28 | 東洋製罐グループホールディングス株式会社 | Metal microparticles, and dispersion liquid containing metal microparticles and method for producing same |
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