JP6638955B2 - Water resistant and organic solvent resistant composition - Google Patents
Water resistant and organic solvent resistant composition Download PDFInfo
- Publication number
- JP6638955B2 JP6638955B2 JP2016571941A JP2016571941A JP6638955B2 JP 6638955 B2 JP6638955 B2 JP 6638955B2 JP 2016571941 A JP2016571941 A JP 2016571941A JP 2016571941 A JP2016571941 A JP 2016571941A JP 6638955 B2 JP6638955 B2 JP 6638955B2
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- Prior art keywords
- glutamic acid
- pga
- decalinium
- antibacterial
- poly
- Prior art date
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- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
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- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
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- 229910052719 titanium Inorganic materials 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/19—Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/04—Polyamides derived from alpha-amino carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
- C09D177/04—Polyamides derived from alpha-amino carboxylic acids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Description
本発明は、耐水性と耐有機溶媒性に優れる抗菌性組成物に関するものである。 The present invention relates to an antimicrobial composition having excellent water resistance and organic solvent resistance.
近年、我が国での高齢化社会や世界的人口増加が見込まれる中、健康で安全な生活を過すためには、食品・医療などのライフサイエンス分野において、衛生環境の改善が求められている。介護現場や医療現場など、食品を扱う現場では、度々、食中毒やウイルス感染症が発生、蔓延することがあり、年々、従事者の衛生に対する関心が高まりつつある。このような背景の下、食中毒や感染症などの原因となる病原性の微生物を予防的に抑制する目的で、抗菌材料の高機能化が強く要望されている。 In recent years, as Japan's aging society and the global population are expected to increase, in order to live a healthy and safe life, improvements in the hygiene environment are required in the life science fields such as food and medical care. Food poisoning and viral infectious diseases often occur and spread in food handling sites such as nursing care sites and medical sites, and the interest of workers in hygiene is increasing year by year. Against this background, there is a strong demand for highly functional antibacterial materials for the purpose of prophylactically suppressing pathogenic microorganisms that cause food poisoning and infectious diseases.
一般的に、食品加工や医療の現場での使用設備への抗菌性の付与は、設備表面へ抗菌剤を噴霧、塗布することで実施されている。しかしながら、一般的な抗菌剤は、湿気や水などの外部環境によって抗菌成分が除々に劣化したり流失するため、抗菌効果が安定的に持続しないものが多い。 In general, antibacterial properties are imparted to equipment used in food processing and medical sites by spraying and applying an antibacterial agent to the equipment surface. However, many of the general antibacterial agents do not stably maintain the antibacterial effect because the antibacterial component gradually deteriorates or flows away due to the external environment such as moisture or water.
抗菌材料に使用される抗菌剤は、無機系抗菌剤、有機系抗菌剤、天然系抗菌剤に大別される。無機系抗菌剤としては、銀、銅、亜鉛などの金属イオンが古くから知られている。特に銀イオンは、抗菌効果の持続性が高く耐熱性にも優れているので、プラスチック等に配合する際の成形加工に適している。しかし銀イオンは、真菌類に対する抑制効果が弱いことが欠点である。 Antibacterial agents used for antibacterial materials are roughly classified into inorganic antibacterial agents, organic antibacterial agents, and natural antibacterial agents. As an inorganic antibacterial agent, metal ions such as silver, copper, and zinc have been known for a long time. In particular, silver ions have high antimicrobial effect and high heat resistance, and are therefore suitable for molding when blended with plastics and the like. However, silver ions have a disadvantage in that they have a weak inhibitory effect on fungi.
有機系抗菌剤としては、含窒素系抗菌剤、含硫黄系抗菌剤、含リン系抗菌剤などの化学合成品が挙げられ、建材、農薬、水産などの産業用資材に使用される。その中でも第四級アンモニウム塩は、より安全性が高いため、医療や食品などの衛生分野を中心に使用されている。しかし、これらの抗菌剤は高い水溶性を有するために基材への接着性が悪く、表面塗装、配合、複合化が困難であり、無機系抗菌剤と比べて加工性が大きく劣るものである。即ち、基材へ有機系抗菌剤を配合しても、抗菌成分が水により溶出してしまい、抗菌性が持続しない。一方、キトサン、カテキン、ヒノキチオールといった天然系抗菌剤は高い安全性を有し、使用者に安心を与えるものであるが、化学合成品よりも製造コストが高く、耐熱性や加工性が悪い点でも依然として課題が残る。 Organic antibacterial agents include chemically synthesized products such as nitrogen-containing antibacterial agents, sulfur-containing antibacterial agents, and phosphorus-containing antibacterial agents, and are used as industrial materials such as building materials, agricultural chemicals, and fisheries. Among them, quaternary ammonium salts are used mainly in the field of hygiene such as medical care and food because of their higher safety. However, these antibacterial agents have high water solubility and therefore have poor adhesion to the substrate, and are difficult to apply, blend, and compound on the surface, and their workability is significantly inferior to inorganic antibacterial agents. . That is, even if an organic antibacterial agent is added to the substrate, the antibacterial component is eluted by water, and the antibacterial property is not maintained. On the other hand, natural antibacterial agents such as chitosan, catechin, and hinokitiol have high safety and provide users with peace of mind, but they also have higher manufacturing costs than chemically synthesized products and have poor heat resistance and processability. Challenges remain.
上記の問題を解決するため、基材へ第四級アンモニウム塩を固定化する技術が知られている。例えば特許文献１には、オクタデシルジメチル（３−トリエトキシシリルプロピル）アンモニウムクロライドを含む組成物が開示されている。当該発明は、ガラスやセルロースなど酸素官能基を含む基材に対し、オクタデシルジメチル（３−トリエトキシシリルプロピル）アンモニウムクロライドを固着させる技術である。即ち、分子中の３−トリエトキシシリル基が基材表面の酸素官能基と化学的に結合し、接着するものである。しかし、本化合物の対アニオンである塩化物イオンは、鉄を含有する基材に対して強い腐食性を示すため、防腐食性が課題となる。 In order to solve the above problem, a technique for immobilizing a quaternary ammonium salt on a substrate is known. For example, Patent Document 1 discloses a composition containing octadecyldimethyl (3-triethoxysilylpropyl) ammonium chloride. The present invention is a technique for fixing octadecyldimethyl (3-triethoxysilylpropyl) ammonium chloride to a substrate containing an oxygen functional group such as glass or cellulose. That is, the 3-triethoxysilyl group in the molecule is chemically bonded to the oxygen functional group on the surface of the substrate, and adheres. However, chloride ion, which is a counter anion of the present compound, exhibits strong corrosiveness to an iron-containing substrate, so that corrosion resistance is an issue.
かかる現状を鑑みると、抗菌材料としては、十分な抗菌性を有し、さらに、抗菌持続性が高く、人体への安全性、低環境負荷、簡便な加工性、低腐食性といった高機能化が望まれる。 In view of the current situation, antibacterial materials have sufficient antibacterial properties, have high antibacterial persistence, and have advanced functions such as safety to the human body, low environmental load, easy processing, and low corrosion. desired.
上記の問題を解決する抗菌剤として、特許文献２には、ポリ−γ−グルタミン酸イオンと第四級アンモニウムイオンから形成されるイオンコンプレックス（以下、「ＰＧＡＩＣ」と記載することもある）が記載されている。当該イオンコンプレックスは水に不溶性のポリマーであり、有機系抗菌剤と同等の抗菌性や安全性を有し、基材との接着性が高く、表面塗装、配合、複合化が可能であるため、加工性に優れるものである。また、腐食性を有するハロゲンを含まないため、低腐食性に優れた素材である。さらには、当該イオンコンプレックスは、それ自体、プラスチック、フィルム、繊維などへ成型可能な物性を有している。当該特許文献には、イオンコンプレックスから成形されたフィルムが、抗菌性をも有する材料としての有用性も有することが記載されている。 As an antibacterial agent that solves the above problem, Patent Document 2 describes an ion complex formed from poly-γ-glutamate ion and quaternary ammonium ion (hereinafter, may be described as “PGAIC”). ing. Since the ion complex is a water-insoluble polymer, it has the same antibacterial properties and safety as an organic antibacterial agent, has high adhesiveness to a substrate, and can be surface-coated, compounded, and compounded, It has excellent workability. Further, since it does not contain corrosive halogen, it is a material excellent in low corrosiveness. Furthermore, the ion complex itself has physical properties that can be molded into plastics, films, fibers, and the like. The patent document describes that a film formed from an ion complex also has utility as a material having antibacterial properties.
尚、ポリ−γ−グルタミン酸（以下、「ＰＧＡ」と記載することもある）は、微生物より産生されるバイオベースポリマーであり、グルタミン酸のα−アミノ基とγ−カルボキシ基がアミド結合で結ばれたポリアミノ酸である。ＰＧＡは納豆の糸引きの主成分として知られるようになったが、その魅力的な特性として、生分解性と接着性を兼ね備えている。さらには、化粧品に使用される天然保湿剤成分であり、皮膚への高い安全性を有している。 In addition, poly-γ-glutamic acid (hereinafter sometimes referred to as “PGA”) is a bio-based polymer produced by a microorganism, and an α-amino group and a γ-carboxy group of glutamic acid are connected by an amide bond. Polyamino acids. PGA has become known as the main component of natto stringing, but has attractive properties that combine biodegradability and adhesion. Furthermore, it is a natural humectant component used in cosmetics, and has high skin safety.
特許文献３に記載のＰＧＡとヘキサデシルピリジニウム（以下、「ＨＤＰ+」と記載することもある）から形成されるＰＧＡＩＣは、非共有結合であるイオン結合で形成されながらも、水不溶性である一方でアルコールに対する溶解性が高いため、ＰＧＡＩＣのアルコール溶液を基材へ噴霧または塗布することにより、基材表面上に抗菌性の高分子被膜を形成することが可能である。即ち、当該ＰＧＡＩＣを含有する高分子被膜は、基材との密着性と接着性が強く、さらに耐水性が高いため実用性を有している。一方、エタノールやイソプロピルアルコール等の低級アルコールは、食品加工現場での設備、医療現場での医療機器、医用器具、リネン、食器などの消毒剤や清拭剤として多用されている。これらの設備にて従来のＰＧＡＩＣを使用する場合、低級アルコールの影響によりＰＧＡＩＣが溶出して抗菌持続性が低下する可能性が懸念される。そのため、食品加工や医療の現場で使用される抗菌材料は、耐水性だけではなく、低級アルコール等の有機溶媒に対する耐久性をも備えねばならない。PGAIC formed from PGA and hexadecylpyridinium (hereinafter sometimes referred to as “HDP + ”) described in Patent Document 3, while being formed by a non-covalent ionic bond, is insoluble in water. Therefore, the antibacterial polymer film can be formed on the surface of the substrate by spraying or applying an alcohol solution of PGAIC to the substrate. That is, the polymer coating containing the PGAIC has high adhesiveness and adhesion to the substrate, and has high water resistance, and thus has practicality. On the other hand, lower alcohols such as ethanol and isopropyl alcohol are frequently used as disinfectants and cleaning agents for facilities at food processing sites, medical equipment at medical sites, medical instruments, linens, tableware, and the like. When conventional PGAIC is used in these facilities, there is a concern that PGAIC may elute due to the influence of lower alcohol and the antimicrobial persistence may be reduced. Therefore, antibacterial materials used in food processing and medical sites must have not only water resistance but also durability to organic solvents such as lower alcohols.
上述したように、衛生設備などへ使用する抗菌素材には、耐水性に加えて低級アルコール等に対する有機溶媒耐性を有し、抗菌性を長期間、安定的に保つための高性能化が強く望まれる。さらには、生分解性を備えた環境調和型の素材の創出も望まれる。 As described above, antibacterial materials used in sanitary facilities, etc., have organic solvent resistance to lower alcohols in addition to water resistance, and long-term antibacterial properties, and high performance to stably maintain antibacterial properties are strongly desired. It is. It is also desired to create a biodegradable environment-friendly material.
本発明者らは、上記課題を解決するために鋭意研究を重ねた結果、塩化デカリニウムと呼ばれる二頭型第四級アンモニウム塩とＰＧＡとで塩を形成することにより、水に対して不溶化するのみならず、おそらくはデカリニウムがＰＧＡ分子を架橋する作用も有することから、消毒などに用いられる低級アルコールなどの有機溶媒に対しても耐性を示すようになることを見出し、抗菌性新素材である「ＰＧＡデカリニウム」の開発に成功した。即ち、本発明に係るＰＧＡデカリニウムが耐水性のみならず低級アルコール等に対する耐有機溶媒性に優れ、さらには抗菌被膜基材などとして十分な抗菌作用を安定的に示すことを見出し、本発明を完成するに至った。 The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, by forming a salt with a two-headed quaternary ammonium salt called decalinium chloride and PGA, they are only insolubilized in water. In addition, since possibly decalinium also has a function of cross-linking PGA molecules, it has been found that it becomes resistant to organic solvents such as lower alcohols used for disinfection and the like, and a new antibacterial material, "PGA" Decalinium "was successfully developed. That is, the inventors have found that the PGA decalinium according to the present invention is excellent not only in water resistance but also in organic solvent resistance to lower alcohols and the like, and furthermore, shows a sufficient antibacterial action as an antibacterial coating substrate and the like, and completed the present invention. I came to.
以下、本発明を示す。 Hereinafter, the present invention will be described.
［１］ ポリ−γ−グルタミン酸とデカリニウムを含むことを特徴とする組成物。 [1] A composition comprising poly-γ-glutamic acid and decalinium.
［２］ ポリ−γ−グルタミン酸を構成するグルタミン酸のうちＬ−グルタミン酸の占める割合が９０％以上である上記［１］に記載の組成物。 [2] The composition according to the above [1], wherein the proportion of L-glutamic acid in glutamic acid constituting poly-γ-glutamic acid is 90% or more.
［３］ ポリ−γ−グルタミン酸を構成するグルタミン酸がＬ−グルタミン酸からなる上記［１］または［２］に記載の組成物。 [3] The composition according to the above [1] or [2], wherein the glutamic acid constituting poly-γ-glutamic acid is L-glutamic acid.
［４］ 水に不溶性である上記［１］〜［３］のいずれかに記載の組成物。 [4] The composition according to any one of the above [1] to [3], which is insoluble in water.
［５］ 有機溶媒に不溶性である上記［１］〜［４］のいずれかに記載の組成物。 [5] The composition according to any one of [1] to [4], which is insoluble in an organic solvent.
［６］ 少なくともポリ−γ−グルタミン酸を含有する溶液、および、少なくともデカリニウムを含有する溶液とを含むことを特徴とするコーティング剤。 [6] A coating agent comprising: a solution containing at least poly-γ-glutamic acid; and a solution containing at least decalinium.
［７］ ポリ−γ−グルタミン酸を含む溶液を基材に塗布する工程、および、デカリニウムを含む溶液を基材に塗布する工程を含むことを特徴とするコーティング方法。 [7] A coating method comprising a step of applying a solution containing poly-γ-glutamic acid to a substrate, and a step of applying a solution containing decalinium to the substrate.
［８］ ポリ−γ−グルタミン酸を含む溶液を基材に塗布した後、デカリニウムを含む溶液を基材に塗布する上記［７］に記載のコーティング方法。 [8] The coating method according to the above [7], wherein a solution containing poly-γ-glutamic acid is applied to a substrate, and then a solution containing decalinium is applied to the substrate.
［９］ ポリ−γ−グルタミン酸を構成するグルタミン酸のうちＬ−グルタミン酸の占める割合が９０％以上である上記［７］または［８］に記載のコーティング方法。 [9] The coating method according to the above [7] or [8], wherein the proportion of L-glutamic acid in the glutamic acid constituting poly-γ-glutamic acid is 90% or more.
［１０］ ポリ−γ−グルタミン酸を構成するグルタミン酸がＬ−グルタミン酸からなる上記［７］または［８］に記載のコーティング方法。 [10] The coating method according to the above [7] or [8], wherein glutamic acid constituting poly-γ-glutamic acid is L-glutamic acid.
本発明に係る組成物は、水に対して不溶であり耐水性を示すのみならず、消毒剤などとして用いられる低級アルコール等に対する耐有機溶媒性も高い。さらには基材に対しても適度な接着特性を有することから基材表面への被膜形成が可能である。また、本発明組成物は、デカリニウム由来の優れた抗菌性を示す。即ち、本発明によって、耐久性の高い抗菌性被膜を基材表面に形成可能であることから、食品加工や医療の現場などで使用される抗菌材料として優れた特性を有しており、広範囲の産業分野で利用可能な材料を提供することができる。 The composition according to the present invention is not only insoluble in water and exhibits water resistance, but also has high organic solvent resistance to lower alcohols and the like used as disinfectants and the like. Furthermore, since it has an appropriate adhesive property to the substrate, it is possible to form a film on the surface of the substrate. Further, the composition of the present invention exhibits excellent antibacterial properties derived from decalinium. That is, according to the present invention, since a highly durable antibacterial film can be formed on the surface of a substrate, it has excellent properties as an antibacterial material used in food processing and medical sites, and has a wide range of properties. Materials that can be used in the industrial field can be provided.
本発明に係る組成物は、ポリ−γ−グルタミン酸（ＰＧＡ）とデカリニウムとを含むことを特徴とする。 The composition according to the present invention is characterized by containing poly-γ-glutamic acid (PGA) and decalinium.
ポリ−γ−グルタミン酸（ＰＧＡ）とは、グルタミン酸のα−アミノ基とγ−カルボキシ基とがアミド結合したポリアミノ酸である。ＰＧＡの種類は、特に制限されない。例えば、Ｌ−グルタミン酸のみからなるもの、Ｄ−グルタミン酸のみからなるもの、両方を含むものがあるが、何れも用いることができる。但し、一方の割合がより多い方が立体規則性に優れ、強度なども高くなり、また、よく乾燥すれば融点（約１５０℃）をも示す様になる。この融点は、イオンコンプレックスとすることで、より明確となる。さらに、Ｌ−グルタミン酸からなるものの方が生分解性に優れるので、Ｌ−グルタミン酸の含有割合が９０％以上であるＰＧＡを用いることが好ましく、実質的にＬ−グルタミン酸のみからなるものがより好ましい。ここで「実質的にＬ−グルタミン酸のみからなるＰＧＡ」とは、ラセミ化を伴わない条件で加水分解した場合、Ｌ−グルタミン酸のみが検出され、Ｄ−グルタミン酸が検出されないＰＧＡをいう。 Poly-γ-glutamic acid (PGA) is a polyamino acid in which an α-amino group and a γ-carboxy group of glutamic acid are amide-bonded. The type of PGA is not particularly limited. For example, there are ones consisting only of L-glutamic acid, ones consisting only of D-glutamic acid, and those containing both, and any of them can be used. However, the higher the ratio, the better the stereoregularity, the higher the strength and the like, and if it is dried well, it will show a melting point (about 150 ° C.). This melting point becomes clearer by using an ion complex. Furthermore, since L-glutamic acid is more excellent in biodegradability, it is preferable to use PGA having an L-glutamic acid content of 90% or more, and it is more preferable to use PGA containing substantially only L-glutamic acid. Here, the term "PGA substantially consisting of only L-glutamic acid" refers to a PGA in which, when hydrolyzed under conditions without racemization, only L-glutamic acid is detected and D-glutamic acid is not detected.
使用するＰＧＡの分子サイズも特に制限されないが、平均分子質量で１０ｋＤ以上のものが好適である。一般的に、分子サイズが大きいほど強度などの性能が高くなる。一方、分子サイズが過剰に大きなＰＧＡは製造コストが大きく、また、製造が技術的に難しい場合もあるので、通常は１，０００ｋＤ以下とする。 The molecular size of PGA to be used is not particularly limited, but those having an average molecular mass of 10 kD or more are preferable. Generally, the larger the molecular size, the higher the performance such as strength. On the other hand, PGA having an excessively large molecular size requires a large production cost and may be technically difficult to produce. Therefore, the PGA is usually 1,000 kD or less.
ＰＧＡは、市販されているものがあればそれを用いてもよいし、別途製造してもよい。但し、通常の条件でグルタミン酸を重合するとポリ−α−グルタミン酸が得られるので、微生物を使って生合成させることが好ましい。ＰＧＡを生産する微生物としては、Ｂａｃｉｌｌｕｓ ｓｕｂｔｉｌｉｓ ｖａｒ． ｎａｔｔｏ（納豆菌）、Ｂａｃｉｌｌｕｓ ｓｕｂｔｉｌｉｓ ｓｕｂｓｐ． ｃｈｕｎｇｋｏｏｋｊａｎｇ（戦国醤菌）、Ｂａｃｉｌｌｕｓ ｍｅｇａｔｅｒｉｕｍ、Ｂａｃｉｌｌｕｓ ａｎｔｈｒａｃｉｓ、Ｂａｃｉｌｌｕｓ ｈａｌｏｄｕｒａｎｓ、Ｎａｔｒｉａｌｂａ ａｅｇｙｐｔｉａｃａ、Ｈｙｄｒａなどがある。分子サイズの大きいＰＧＡを製造できる微生物としては、枯草菌であるＢａｃｉｌｌｕｓ ｓｕｂｔｉｌｉｓや超好塩古細菌であるＮａｔｒｉａｌｂａ ａｅｇｙｐｔｉａｃａがある。この中でも、Ｌ−グルタミン酸のみからなるＰＧＡを生産する微生物であるＮａｔｒｉａｌｂａ ａｅｇｙｔｉａｃａによって生産されたＰＧＡを用いることが好ましい。 PGA may be used if it is commercially available, or may be manufactured separately. However, if glutamic acid is polymerized under ordinary conditions, poly-α-glutamic acid can be obtained, so that biosynthesis is preferably performed using a microorganism. Examples of microorganisms that produce PGA include Bacillus subtilis var. natto (natto), Bacillus subtilis subsp. chungookjang (Sengoku soy sauce), Bacillus megaterium, Bacillus anthracis, Bacillus halodurans, Natalba aegyptiaca, Hydra and the like. Microorganisms capable of producing PGA having a large molecular size include Bacillus subtilis, which is Bacillus subtilis, and Natrialba aegyptiaca, which is a super-halophilic archaeon. Among them, it is preferable to use PGA produced by Natrialba aegitiaca, which is a microorganism that produces PGA consisting only of L-glutamic acid.
本発明に係る組成物に含まれるデカリニウムは、下記化学構造式を有し、口内炎や咽頭炎などの症状における消毒剤として、医療現場や家庭での使用実績のある抗菌剤である。 Decalinium contained in the composition according to the present invention has the following chemical structural formula, and is an antibacterial agent that has been used as a disinfectant for symptoms such as stomatitis and pharyngitis at medical sites and at home.
本発明に係る組成物において、ＰＧＡとデカリニウムがいかなる状態にあるかは必ずしも明らかではないが、ＰＧＡを構成するグルタミン酸のα−カルボキシ基とデカリニウムの第四級アンモニウムカチオンが静電結合していると考えられる。また、デカリニウムは分子内に２つの第四級アンモニウムカチオンを有することから、１分子のＰＧＡ鎖における２つのα−カルボキシ基と静電結合する可能性の他、２分子のＰＧＡ鎖間を架橋していると考えられる。その結果、本発明に係る組成物は、従来の非架橋ＰＧＡＩＣよりも化学的安定性が高く、水のみならず、低級アルコール等の有機溶媒に対しても不溶性や耐性を示すと考えられる。以下、本発明に係る組成物の主成分であるＰＧＡとデカリニウムの複合体を「ＰＧＡデカリニウム」という場合がある。 In the composition according to the present invention, it is not always clear what state PGA and decalinium are in, but when the α-carboxy group of glutamic acid constituting PGA and the quaternary ammonium cation of decalinium are electrostatically bonded. Conceivable. In addition, since decalinium has two quaternary ammonium cations in the molecule, it has the possibility of electrostatically bonding to two α-carboxy groups in one molecule of PGA chain, and also bridges between two molecules of PGA chain. It is thought that it is. As a result, it is considered that the composition according to the present invention has higher chemical stability than conventional non-crosslinked PGAIC, and exhibits insolubility and resistance not only to water but also to organic solvents such as lower alcohols. Hereinafter, the composite of PGA and decalinium, which are the main components of the composition according to the present invention, may be referred to as “PGA decalinium”.
本発明に係るＰＧＡデカリニウムにおいては、ＰＧＡを構成するグルタミン酸単位に対して半モルもしくは略半モルあるいは任意のモル比のデカリニウムを用いることができるが、過剰な親水性などＰＧＡの有する材料としての欠点を克服するために、デカリニウムにより十分に改質されているものが好適である。より具体的には、ＰＧＡデカリニウムにおけるデカリニウムの割合が、ＰＧＡを構成するグルタミン酸単位に対して０．１倍モル以上であることが好ましく、０．２倍モル以上であることがより好ましく、０．３倍モル以上であることがさらに好ましく、０．４５倍モル以上であることがよりさらに好ましい。特に、ＰＧＡを構成するグルタミン酸単位に対して０．５倍モル以上のデカリニウムを含む完全架橋構造のものが好適である。上記割合の上限は特に制限されないが、同様の理由から１倍モル以下が好ましく、０．８倍モル以下がより好ましく、０．６倍モル以下がよりさらに好ましく、０．５５倍モル以下が特に好ましい。 In the PGA decalinium according to the present invention, decalinium can be used in a molar amount of half or almost half or an arbitrary molar ratio with respect to the glutamic acid unit constituting PGA, but the disadvantages of the material possessed by PGA such as excessive hydrophilicity can be used. In order to overcome this problem, those which have been sufficiently modified with decalinium are preferred. More specifically, the proportion of decalinium in PGA decalinium is preferably at least 0.1 times mol, more preferably at least 0.2 times mol, relative to the glutamic acid unit constituting PGA. It is more preferably at least 3 moles, even more preferably at least 0.45 moles. Particularly, those having a completely crosslinked structure containing 0.5 times or more mol of decalinium with respect to the glutamic acid unit constituting PGA are preferable. The upper limit of the ratio is not particularly limited, but is preferably 1 mol or less, more preferably 0.8 mol or less, still more preferably 0.6 mol or less, particularly preferably 0.55 mol or less for the same reason. preferable.
本発明に係る組成物は、溶媒中、ＰＧＡとデカリニウムの塩を混合するのみで、極めて容易に製造できる。 The composition according to the present invention can be produced very easily only by mixing PGA and a salt of decalinium in a solvent.
ここで使用する溶媒としては、水が好適である。原料であるＰＧＡを良好に溶解できるからであり、また、目的化合物であるＰＧＡデカリニウムは水に対して不溶性であることから、反応後における目的物の単離精製に好都合なためである。但し、メタノールやエタノールなどのアルコール系溶媒；ＴＨＦなどのエーテル系溶媒；ジメチルホルムアミドやジメチルアセトアミドなどのアミド系溶媒などの水溶性有機溶媒を反応液に添加してもよい。しかし、反応終了後におけるＰＧＡデカリニウムの分離を考慮すれば、溶媒としては水のみを用いることが好ましい。 Water is suitable as the solvent used here. This is because PGA, which is a raw material, can be dissolved well, and PGA decalinium, which is a target compound, is insoluble in water, so that it is convenient for isolating and purifying the target compound after the reaction. However, an alcohol-based solvent such as methanol or ethanol; an ether-based solvent such as THF; or a water-soluble organic solvent such as an amide-based solvent such as dimethylformamide or dimethylacetamide may be added to the reaction solution. However, considering the separation of PGA decalinium after completion of the reaction, it is preferable to use only water as the solvent.
原料であるＰＧＡとしては、その塩を用いてもよい。当該塩としては、ナトリウム塩やカリウム塩などのアルカリ金属塩；カルシウム塩やマグネシウム塩などのアルカリ土類金属塩などを挙げることができる。また、塩を用いる場合であっても全てのカルボキシ基が塩となっている必要はなく、その一部のみが塩となっていてもよい。但し、アルカリ土類金属塩などの多価金属塩は、水に対する溶解性が低い場合があり得るので、好適にはＰＧＡのフリー体またはＰＧＡの一価金属塩を用いる。 As PGA as a raw material, a salt thereof may be used. Examples of the salt include alkali metal salts such as sodium salt and potassium salt; and alkaline earth metal salts such as calcium salt and magnesium salt. Even when a salt is used, not all carboxy groups need to be salts, and only some of them may be salts. However, since a polyvalent metal salt such as an alkaline earth metal salt may have low solubility in water, a free form of PGA or a monovalent metal salt of PGA is preferably used.
原料であるデカリニウムの塩は、通常、ハロゲン化物塩として存在する。よって、本発明においては、反応液へデカリニウムの塩を直接添加、或いは当該塩を水溶媒に溶解した上で添加すればよい。デカリニウムの塩はＰＧＡを十分に改質するため、ＰＧＡに対して十分量用いることが好ましい。 The raw material decalinium salt usually exists as a halide salt. Therefore, in the present invention, the salt of decalinium may be directly added to the reaction solution, or may be added after dissolving the salt in an aqueous solvent. Decalinium salt is preferably used in a sufficient amount with respect to PGA in order to sufficiently modify PGA.
本発明のＰＧＡデカリニウムは水不溶性であることから、水溶媒から容易に分離できるため、反応液における各成分の濃度は特に制限されない。例えば、反応液におけるＰＧＡの濃度を０．５ｗ／ｖ％以上、１０ｗ／ｖ％以下程度、デカリニウムの濃度を１．０ｗ／ｖ％以上、１０ｗ／ｖ％以下程度とすることができる。 Since the PGA decalinium of the present invention is insoluble in water and can be easily separated from a water solvent, the concentration of each component in the reaction solution is not particularly limited. For example, the concentration of PGA in the reaction solution can be about 0.5 w / v% or more and about 10 w / v% or less, and the concentration of decalinium can be about 1.0 w / v% or more and about 10 w / v% or less.
反応液は、架橋構造の形成を促進するために適度に加熱することが好ましい。加熱温度は、例えば４０℃以上、８０℃以下程度とすることができる。反応時間は適宜調整すればよいが、通常、３０分間以上、２０時間以下程度とすることができる。 It is preferable that the reaction solution is appropriately heated in order to promote formation of a crosslinked structure. The heating temperature can be, for example, about 40 ° C. or more and 80 ° C. or less. The reaction time may be appropriately adjusted, and can be generally about 30 minutes or more and about 20 hours or less.
本発明のＰＧＡデカリニウムは、水や有機溶媒に不溶であることから、濾過や遠心分離などにより水溶媒および有機溶媒から容易に分離することができる。また、分離したＰＧＡデカリニウムは、水または有機溶媒で洗浄することにより、過剰に用いたＰＧＡまたはデカリニウムの塩、その他の塩を除去することも可能である。また、水溶媒は、アセトンやエタノールなどで洗浄することにより簡便に除去できる。 Since the PGA decalinium of the present invention is insoluble in water or an organic solvent, it can be easily separated from an aqueous solvent and an organic solvent by filtration, centrifugation, or the like. The separated PGA decalinium can be washed with water or an organic solvent to remove excess PGA or decalinium salt and other salts. Further, the water solvent can be easily removed by washing with acetone or ethanol.
本発明のＰＧＡデカリニウムは、水と有機溶媒に対して優れた耐久性を有する。ここで示す有機溶媒は、メタノールやエタノールなどのＣ1-4アルコール；ジエチルエーテルやＴＨＦなどのエーテル系溶媒；ジメチルホルムアミドやジメチルアセトアミドなどのアミド系溶媒；アセトン、メチルエチルケトンなどのケトン系有機溶媒；ペンタン、ヘキサン、ヘプタン、ベンゼン、トルエン、キシレンなどの炭化水素系有機溶媒；塩化メチレン、クロロホルム、四塩化炭素、トリクロロエチレンなどのハロゲン系有機溶媒などが挙げられる。The PGA decalinium of the present invention has excellent durability against water and organic solvents. Examples of the organic solvent include C 1-4 alcohols such as methanol and ethanol; ether solvents such as diethyl ether and THF; amide solvents such as dimethylformamide and dimethylacetamide; ketone organic solvents such as acetone and methyl ethyl ketone; Hexane, heptane, benzene, toluene, xylene and the like; and hydrocarbon-based organic solvents such as methylene chloride, chloroform, carbon tetrachloride and trichloroethylene.
本発明のＰＧＡデカリニウムは、グラム陽性およびグラム陰性のいずれの細菌類に対しても優れた抗菌効果を発揮するのみならず、同時に真菌類に対しても優れた抗菌効果を示し、健康・衛生面で抗細菌性や抗真菌性が要求される分野で広範囲に利用することができる抗細菌剤および／または抗真菌剤として利用できる。 The PGA decalinium of the present invention not only exerts an excellent antibacterial effect on both gram-positive and gram-negative bacteria, but also shows an excellent antibacterial effect on fungi at the same time. And can be used as an antibacterial agent and / or an antifungal agent which can be widely used in fields requiring antibacterial and antifungal properties.
本発明のＰＧＡデカリニウムが抗菌効果を示すグラム陽性細菌の例としては、Ｓｔａｐｈｙｌｏｃｏｃｃｕｓ属、Ｓｔｒｅｐｔｏｃｏｃｃｕｓ属、Ｃｏｒｙｎｅｂａｃｔｅｒｉｕｍ属、Ｂａｃｉｌｌｕｓ属、Ｌｉｓｔｅｒｉａ属、Ｃｌｏｓｔｒｉｄｉｕｍ属、Ｌａｃｔｏｂａｃｉｌｌｕｓ属などが挙げられる。 Examples of Gram-positive bacteria in which the PGA decalinium of the present invention exhibits an antibacterial effect include Staphylococcus, Streptococcus, Corynebacterium, Bacillus, Listeria, Clostridium, Lactobacillus, and the like.
本発明のＰＧＡデカリニウムが抗菌効果を示すグラム陰性細菌の例としては、Ｅｓｃｈｅｒｉｃｈｉａ属、Ｐｓｅｕｄｏｍｏｎａｓ属、Ｓａｌｍｏｎｅｌｌａ属、Ｅｎｔｅｒｏｂａｃｔｅｒ属、Ｎｅｉｓｓｅｒｉａ属、Ｘａｎｔｈｏｍｏｎａｓ属、Ｓｅｒｒａｔｉａ属、Ｃａｍｐｙｌｏｂａｃｔｅｒ属などが挙げられる。 Examples of Gram-negative bacteria in which the PGA decalinium of the present invention exhibits an antibacterial effect include Escherichia, Pseudomonas, Salmonella, Enterobacter, Neisseria, Xanthomonas, Serratia, Campylobacter and the like.
本発明のＰＧＡデカリニウムが抗菌効果を示す真菌の例としては、Ａｂｓｉｄｉａ属、Ｍｕｃｏｒ属、Ｒｈｉｚｏｐｕｓ属などの接合菌門；Ａｓｐｅｒｇｉｌｌｕｓ属、Ｎｅｕｒｏｓｐｏｒａ属、Ｐｅｎｉｃｉｌｌｉｕｍ属、Ｔｒｉｃｈｏｄｅｒｍａ属、Ｎｅｏｓａｒｔｏｒｙａ属、Ｃａｎｄｉｄａ属、Ｐｉｃｈｉａ属、Ｓａｃｃｈａｒｏｍｙｃｅｓ属などの子嚢菌門；Ｔｒａｍｅｔｅｓ属、Ｃｒｙｐｔｏｃｏｃｃｕｓなどの担子菌門；Ａｌｔｅｒｎａｒｉａ属、Ｆｕｓａｒｉｕｍ属、Ｃｌａｄｏｓｐｏｒｉｕｍ属、Ｃｕｒｖｕｌａｒｉａ属、Ａｕｒｅｏｂａｓｉｄｉｕｍ属などの不完全菌類などが挙げられる。 Examples of fungi to which the PGA decalinium of the present invention exhibits an antibacterial effect include zygomycota such as Absidium, Mucor, and Rhizopus; , Saccharomyces, etc .; Ascomycota, Trametes, Cryptococcus, etc .; Incomplete fungi, such as Alternaria, Fusarium, Cladosporium, Curvularia, Aureobasidium and the like.
本発明のＰＧＡデカリニウムは、生分解性を示す上に、水溶性や過剰な吸水性を示さない。また、６０℃付近に明確な融点を有し、且つ融点と熱分解開始点（２６０℃付近）が十分に離れていることから加熱成形が可能である。よって、生分解性のプラスチック材料としても利用することが可能であり、従来の石油由来の化学合成材料にとって代わり得るものである。 The PGA decalinium of the present invention shows biodegradability and does not show water solubility or excessive water absorption. Further, since it has a clear melting point around 60 ° C. and the melting point and the starting point of thermal decomposition (around 260 ° C.) are sufficiently separated, heat molding is possible. Therefore, it can be used also as a biodegradable plastic material, and can replace conventional petroleum-derived chemically synthesized materials.
本発明のＰＧＡデカリニウムは、抗菌性材料の抗菌性有効成分として用いることもできる。本発明のＰＧＡデカリニウムを有効成分として含む抗菌性材料の利用形態としては、高分子樹脂への粉体塗装、マスターバッチブレンドによる複合化などが挙げられる。 The PGA decalinium of the present invention can also be used as an antibacterial active ingredient of an antibacterial material. Examples of the use form of the antibacterial material containing PGA decalinium as an active ingredient of the present invention include powder coating on a polymer resin, compounding by masterbatch blending, and the like.
本発明のＰＧＡデカリニウムを高分子樹脂に配合した抗菌材料として使用する場合、高分子樹脂の種類には特に制約はなく、樹脂組成物の用途などに応じて自由に選ぶことができる。使用し得る樹脂の具体例としては、例えば、塩化ビニル系ポリマー、ウレタン系ポリマー、アクリル系ポリマー、オレフィン系ポリマー、エチレン系ポリマー、プロピレン系ポリマー、アミド系ポリマー、エチレン−酢酸ビニル共重合体、塩化ビニリデン系ポリマー、スチレン系ポリマー、エステル系ポリマー、ナイロン系ポリマー、セルロース誘導体、カーボネート系ポリマー、フッ素系樹脂、シリコーン系樹脂、ビニルアルコール系ポリマー、ビニルエステル系ポリマー、合成ゴム、天然ゴムなどが挙げられる。樹脂組成物には、必要に応じて、可塑剤、充填剤、着色剤（染料、顔料など）、紫外線吸収剤などを適宜配合してもよい。 When the PGA decalinium of the present invention is used as an antibacterial material mixed with a polymer resin, the type of the polymer resin is not particularly limited, and can be freely selected according to the use of the resin composition. Specific examples of resins that can be used include, for example, vinyl chloride-based polymers, urethane-based polymers, acrylic polymers, olefin-based polymers, ethylene-based polymers, propylene-based polymers, amide-based polymers, ethylene-vinyl acetate copolymers, and chlorides. Vinylidene polymer, styrene polymer, ester polymer, nylon polymer, cellulose derivative, carbonate polymer, fluorine resin, silicone resin, vinyl alcohol polymer, vinyl ester polymer, synthetic rubber, natural rubber, etc. . A plasticizer, a filler, a colorant (a dye, a pigment, and the like), an ultraviolet absorber, and the like may be appropriately added to the resin composition as needed.
上記の樹脂組成物は、その用途などに応じて種々の形態に加工することができる。例えば、本発明の樹脂組成物は、押出成形、射出成形、溶液流延法、紡糸法など、それ自体既知の樹脂加工法によって、フィルム状、シート状、板状、繊維状、立体状に成形することができる。例えば、内装材、床材、繊維製品、紙製品、家電製品などに利用することができる。 The above resin composition can be processed into various forms depending on its use and the like. For example, the resin composition of the present invention may be formed into a film, sheet, plate, fiber, or three-dimensional shape by a resin processing method known per se, such as extrusion molding, injection molding, solution casting, and spinning. can do. For example, it can be used for interior materials, flooring materials, textile products, paper products, home appliances, and the like.
本発明に係るポリ−γ−グルタミン酸とデカリニウムを含む組成物は、例えば、ポリ−γ−グルタミン酸を含む溶液を基材に塗布する工程、および、デカリニウムを含む溶液を基材に塗布する工程を含む方法により、基材上に抗菌性被膜として形成することが可能である。 The composition containing poly-γ-glutamic acid and decalinium according to the present invention includes, for example, a step of applying a solution containing poly-γ-glutamic acid to a substrate, and a step of applying a solution containing decalinium to the substrate. Depending on the method, it is possible to form an antimicrobial coating on the substrate.
本発明に係る組成物を材料表面へコーティング加工する場合、レイヤー・バイ・レイヤー法（交互積層法）により加工することができる。即ち、少なくともＰＧＡを含有する溶液で材料表面をコーティングし、続いて、少なくともデカリニウムを含有する溶液をコーティングすることで、材料表面上で架橋型コンプレックスを形成させて加工することができる。本発明のＰＧＡデカリニウムは基材表面上に高分子被膜を形成し、また、水や有機溶剤に不溶である上に、上記のとおり抗真菌性と抗細菌性を示す。よって、本発明のコーティング剤は、レイヤー・バイ・レイヤー法により、持続的な抗真菌性と抗細菌性の両方を示す塗膜や被膜を基材などに形成することが可能になる。即ち、本発明に係るコーティング剤は、少なくともポリ−γ−グルタミン酸を含有する溶液と、少なくともデカリニウムを含有する溶液とを別々に含む。本発明のＰＧＡデカリニウムは基材との接着性を有し、水や有機溶媒に不溶性を示すため、抗菌成分の溶出による消失がなく、持続性の高い抗菌剤として利用できる。 When the composition according to the present invention is coated on a material surface, it can be processed by a layer-by-layer method (alternate lamination method). That is, by coating the surface of the material with a solution containing at least PGA and subsequently coating a solution containing at least decalinium, a crosslinked complex can be formed on the surface of the material and processed. The PGA decalinium of the present invention forms a polymer film on the surface of a substrate, is insoluble in water and organic solvents, and exhibits antifungal and antibacterial properties as described above. Therefore, the coating agent of the present invention can form a coating film or a film exhibiting both continuous antifungal and antibacterial properties on a substrate or the like by the layer-by-layer method. That is, the coating agent according to the present invention separately contains a solution containing at least poly-γ-glutamic acid and a solution containing at least decalinium. The PGA decalinium of the present invention has an adhesive property to a base material and is insoluble in water or an organic solvent. Therefore, the PGA decalinium does not disappear due to elution of an antibacterial component and can be used as a highly persistent antibacterial agent.
ＰＧＡデカリニウムは被膜中に０．１質量％以上含まれていることが好ましく、０．５質量％以上含まれていることがより好ましい。０．１質量％より少ないと抗菌効果が十分に発揮されない恐れがある。一方、上限は特に制限されず、１００質量％のＰＧＡデカリニウム、即ち実質的にＰＧＡデカリニウムのみで被膜を形成してもよい。 PGA decalinium is preferably contained in the coating in an amount of 0.1% by mass or more, more preferably 0.5% by mass or more. If the amount is less than 0.1% by mass, the antibacterial effect may not be sufficiently exerted. On the other hand, the upper limit is not particularly limited, and the coating may be formed with 100% by mass of PGA decalinium, that is, substantially only PGA decalinium.
さらに、本発明のコーティング剤は、ＰＧＡ溶液およびデカリニウム溶液を交互に噴霧する抗真菌抗細菌用噴霧剤として使用することができる。具体的には、住居、病院、公共施設などにおける浴室、流し、衛生機器類などに直接噴霧塗布することにより、細菌やカビの発生を防止することができる。或いは、プラスチック射出成型機の金型内面に噴霧塗布することにより、成型されたプラスチックの表面に間接的に抗真菌剤を転写させ、長期間、壁面やプラスチック表面の細菌やカビの発生を防止することができる。 Further, the coating agent of the present invention can be used as an antifungal / antibacterial spray which alternately sprays a PGA solution and a decalinium solution. Specifically, by spraying directly onto a bathroom, sink, sanitary equipment, or the like in a house, a hospital, a public facility, or the like, the generation of bacteria and mold can be prevented. Alternatively, the antifungal agent is indirectly transferred to the surface of the molded plastic by spray coating on the inner surface of the mold of the plastic injection molding machine, thereby preventing the generation of bacteria and mold on the wall surface and the plastic surface for a long time. be able to.
この場合、塗布しうる基材として、パルプ、セラミックス、金属、金属酸化物、プラスチック、ゴム類、鉱石類、木材などを挙げることができる。具体的には、セラミックスの例として、ガラス、陶磁器、セメント、耐火煉瓦、琺瑯などを挙げることができる。金属の例としては、鉄、アルミニウム、亜鉛、マグネシウム、金、銀、クロム、ゲルマニウム、モリブデン、ニッケル、鉛、白金、ケイ素、チタン、トリウム、タングステンのような単体金属や、炭素鋼、ニッケル鋼、クロム鋼、クロムモリブデン鋼、ステンレス鋼、アルミニウム合金、黄銅、青銅などの合金を挙げることができる。金属酸化物の例としては、アルミナ、シリカ、マグネシア、トリア、ジルコニア、三二酸化鉄、四三酸化鉄、酸化チタン、酸化カルシウム、酸化亜鉛、酸化鉛などを挙げることができる。プラスチックの例としては、ポリ塩化ビニル、ポリエチレン、ポリプロピレン、ポリスチレン、ポリエチレンテレフタレート、ポリビニルアルコール等の汎用プラスチック；ポリアミド、ポリカーボネート、ポリアセタール、ポリフッ化ビニリデン、ポリエーテルサルフォン、ポリアミドイミド等のエンジニアプラスチック；フェノール樹脂、エポキシ樹脂、シリコン樹脂、ポリウレタンなどの熱硬化性樹脂などを挙げることができる。鉱石類としては、大理石、花崗岩などを挙げることができる。 In this case, pulp, ceramics, metals, metal oxides, plastics, rubbers, ores, wood, and the like can be used as the substrate that can be applied. Specifically, examples of ceramics include glass, porcelain, cement, refractory bricks, and enamel. Examples of metals include simple metals such as iron, aluminum, zinc, magnesium, gold, silver, chromium, germanium, molybdenum, nickel, lead, platinum, silicon, titanium, thorium, tungsten, carbon steel, nickel steel, Alloys such as chromium steel, chromium molybdenum steel, stainless steel, aluminum alloy, brass, and bronze can be given. Examples of metal oxides include alumina, silica, magnesia, thoria, zirconia, iron sesquioxide, triiron tetroxide, titanium oxide, calcium oxide, zinc oxide, lead oxide and the like. Examples of plastics include general-purpose plastics such as polyvinyl chloride, polyethylene, polypropylene, polystyrene, polyethylene terephthalate, and polyvinyl alcohol; engineered plastics such as polyamide, polycarbonate, polyacetal, polyvinylidene fluoride, polyether sulfone, and polyamideimide; phenolic resins , An epoxy resin, a silicone resin, and a thermosetting resin such as polyurethane. Examples of ores include marble and granite.
本発明のＰＧＡデカリニウムを溶融紡糸法や荷電紡糸法などによって紡糸し、織編物または不織布などの繊維構造体として使用することができる。 The PGA decalinium of the present invention can be spun by a melt spinning method, a charged spinning method, or the like, and used as a fibrous structure such as a woven or knitted fabric or a nonwoven fabric.
本願は、２０１５年１月２６日に出願された日本国特許出願第２０１５−１２０８７号に基づく優先権の利益を主張するものである。２０１５年１月２６日に出願された日本国特許出願第２０１５−１２０８７号の明細書の全内容が、本願に参考のため援用される。 This application claims the benefit of priority based on Japanese Patent Application No. 2015-12087 filed on January 26, 2015. The entire contents of the specification of Japanese Patent Application No. 2015-12087 filed on Jan. 26, 2015 are incorporated herein by reference.
以下の実施例により、本発明を更に詳細に説明するが、本発明は、これらに何ら限定されるものではない。 The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
実施例１： ＰＧＡデカリニウムの製造
超好塩古細菌ナトリアルバ・エジプチアキア（Ｎ．ａｅｇｙｐｔｉａｃａ）由来の平均分子量１０００ｋＤのポリ−γ−Ｌ−グルタミン酸ナトリウム塩（以下、「ＰＧＡ」と略記する）を精製水に溶解し、２ｗ／ｖ％の溶液とした。当該溶液へ、ＰＧＡを構成するＬ−グルタミン酸のカルボキシ基のモル数に対して０．５倍モルの塩化デカリニウム（和光純薬工業社製，以下、「ＤＥＱ」と略記する）と精製水から８０℃で加温して作製した１ｗ／ｖ％ＤＥＱ水溶液を添加した。その後、６０℃で１時間攪拌した結果、水不溶性材料が生じた。Example 1 Production of PGA Decalinium Poly-γ-L-glutamate sodium salt (hereinafter abbreviated as “PGA”) having an average molecular weight of 1000 kD and derived from the hyperhalophilic archaebacterium Natriaegyptiaca (hereinafter, abbreviated as “PGA”) was purified water. Dissolve to give a 2% w / v solution. To the solution, 80% of mol of decarinium chloride (manufactured by Wako Pure Chemical Industries, Ltd .; hereinafter, abbreviated as “DEQ”) with respect to the number of moles of the carboxy group of L-glutamic acid constituting PGA and purified water was used. A 1 w / v% aqueous DEQ solution prepared by heating at ℃ was added. Thereafter, stirring at 60 ° C. for 1 hour resulted in a water-insoluble material.
得られた水不溶性材料を濾別回収した後、６０℃に加温した精製水で計３回洗浄した。さらに９５％エタノールで洗浄することにより脱水した後、真空乾燥し、粉末としてＰＧＡデカリニウムを回収した。 The obtained water-insoluble material was collected by filtration and washed with purified water heated to 60 ° C. three times in total. Further, after dehydration by washing with 95% ethanol, vacuum drying was performed to recover PGA decalinium as a powder.
ＰＧＡデカリニウムの生成は、13Ｃ−ＮＭＲ法（ＣＰ／ＭＡＳ法）により確認した。ＰＧＡデカリニウムの13Ｃ−ＮＭＲスペクトルを図１に示す。図１のＮＭＲスペクトルでは、ＰＧＡとデカリニウム由来の13Ｃピークが観測され、ＰＧＡデカリニウムの形成が示唆された。また、示差走査熱量計（日立製作所社製「ＤＳＣ７０２０」）を用い、ＰＧＡデカリニウムのＤＳＣ測定を行った。その結果を図２に示す。図２のとおり、６０℃付近に、ＰＧＡ単独とＤＥＱ単独のＤＳＣチャートには見られない、ＰＧＡデカリニウムの溶融点が観測された。The production of PGA decalinium was confirmed by the 13 C-NMR method (CP / MAS method). FIG. 1 shows the 13 C-NMR spectrum of PGA decalinium. In the NMR spectrum of FIG. 1, a 13 C peak derived from PGA and decalinium was observed, indicating the formation of PGA decalinium. Further, DSC measurement of PGA decalinium was performed using a differential scanning calorimeter (“DSC7020” manufactured by Hitachi, Ltd.). The result is shown in FIG. As shown in FIG. 2, at about 60 ° C., a melting point of PGA decalinium, which is not seen in the DSC charts of PGA alone and DEQ alone, was observed.
比較例１： 非架橋型ＰＧＡＩＣ（ＰＧＡ／ＨＤＰ）の製造
特開２０１０−２２２４９６号公報（特許文献２）を参考にして、非架橋型ＰＧＡＩＣ（ＰＧＡ／ＨＤＰ）を製造した。超好塩古細菌ナトリアルバ・エジプチアキア（Ｎ．ａｅｇｙｐｔｉａｃａ）由来の平均分子量１０００ｋＤのポリ−γ−Ｌ−グルタミン酸ナトリウム塩（ＰＧＡ，４０ｇ）を精製水に溶解し、２ｗ／ｖ％の溶液とした。当該溶液へ、６０℃に保温したヘキサデシルピリジニウムブロマイド（ＨＤＰ）の０．２Ｍ水溶液（１５５１ｇ）を加えた。原料であるＰＧＡの水溶液から、ＨＤＰ添加直後に水不溶性材料が形成されることを確認した後、さらに６０℃で４時間保温した。得られた水不溶性材料を濾別回収した後、１０００ｍＬの精製水で計３回洗浄した。さらにアセトンで洗浄することにより脱水した後、真空乾燥し、粉末としてＰＧＡＩＣ（ＰＧＡ／ＨＤＰ，９３ｇ）を回収した。Comparative Example 1: Production of Non-Crosslinked PGAIC (PGA / HDP) A non-crosslinked PGAIC (PGA / HDP) was produced with reference to Japanese Patent Application Laid-Open No. 2010-222496 (Patent Document 2). Poly-γ-L-glutamic acid sodium salt (PGA, 40 g) having an average molecular weight of 1,000 kD derived from the hyperhalophilic archaebacterium Natriegyptiaca (N. aegyptiaca) was dissolved in purified water to give a 2 w / v% solution. To this solution, a 0.2 M aqueous solution of hexadecylpyridinium bromide (HDP) (1551 g) kept at 60 ° C was added. After confirming that a water-insoluble material was formed immediately after the addition of HDP from an aqueous solution of PGA as a raw material, the temperature was further maintained at 60 ° C. for 4 hours. The obtained water-insoluble material was collected by filtration and washed with 1000 mL of purified water a total of three times. Furthermore, after dehydration by washing with acetone, vacuum drying was performed to collect PGAIC (PGA / HDP, 93 g) as a powder.
試験例１： ＰＧＡデカリニウムの耐溶媒耐性試験
上記実施例１で得られたＰＧＡデカリニウムの一般的な溶媒に対する耐久性試験を実施した。比較のため、上記比較例１で製造した非架橋ＰＧＡＩＣ（ＰＧＡ／ＨＤＰ）、および原料であるＰＧＡと塩化デカリニウム（ＤＥＱ）の溶解性も試験した。各固形試料が完全溶解した際に理論上１ｗｔ％になるように、水、エタノール、ジメチルスルホキシド（ＤＭＳＯ）、クロロホルム、アセトン、Ｎ−メチルピロリドン（ＮＭＰ）、ジメチルアセトアミド（ＤＭＡＣ）、ヘキサンの各溶媒を加え、室温で２４時間以上攪拌した後の溶状を目視で判定した。溶解性試験の結果を表１に示す。Test Example 1: Solvent resistance test of PGA decalinium A durability test of the PGA decalinium obtained in Example 1 with respect to a general solvent was performed. For comparison, the solubility of the non-crosslinked PGAIC (PGA / HDP) produced in Comparative Example 1 and the raw materials of PGA and decalinium chloride (DEQ) were also tested. Each solvent of water, ethanol, dimethylsulfoxide (DMSO), chloroform, acetone, N-methylpyrrolidone (NMP), dimethylacetamide (DMAC) and hexane so that each solid sample is theoretically 1 wt% when completely dissolved. Was added, and the dissolution state after stirring at room temperature for 24 hours or more was visually determined. Table 1 shows the results of the solubility test.
表１に示す結果のとおり、本発明に係るＰＧＡデカリニウムは、水の他、一般的な化成プラスチック類の溶解に使用される極性有機溶媒や非極性有機溶媒に対し不溶性であり、高い安定性と耐水性および耐有機溶媒性を有していることが確認された。また、非架橋型のＰＧＡＩＣや原料（ＰＧＡ単独とＤＥＱ単独）と比較しても、有機溶媒耐性に優れていることも確認された。 As shown in Table 1, the PGA decalinium according to the present invention is insoluble in polar organic solvents and non-polar organic solvents used for dissolving general chemical conversion plastics in addition to water, and has high stability. It was confirmed that it had water resistance and organic solvent resistance. Further, it was also confirmed that the organic solvent resistance was superior to non-crosslinked PGAIC and raw materials (PGA alone and DEQ alone).
実施例２： ＰＧＡデカリニウムによる被膜加工紙の作製
ＰＧＡデカリニウムの被膜形成は、レイヤー・バイ・レイヤー法により実施した。具体的には、まず、超好塩古細菌ナトリアルバ・エジプチアキア（Ｎ．ａｅｇｙｐｔｉａｃａ）由来の平均分子量１０００ｋＤのポリ−γ−Ｌ−グルタミン酸ナトリウム塩を精製水に溶解し、２ｗ／ｖ％のＰＧＡ水溶液とした。別途、塩化デカリニウム（ＤＥＱ）を精製水に８０℃で溶解し、１ｗ／ｖ％のＤＥＱ水溶液とした。上記ＰＧＡ水溶液（５００μＬ）に、１ｃｍ×１ｃｍに切断した市販のハンドタオル（日本製紙クレシア社製「クレシアＥＦハンドタオル」，ｎ＝８の平均重量：２．０ｍｇ）を室温で１０分間浸漬し、６０℃で１時間乾燥させた（浸漬乾燥後の平均重量増加量（ｎ＝８）：０．２６ｍｇ）。続いて、上記ＤＥＱ水溶液（４００μＬ）に８０℃で１分間浸漬させ、取り出した後、６０℃で１時間乾燥させた（浸漬乾燥後の平均重量増加量（ｎ＝８）：０．４７ｍｇ）。Example 2: Preparation of coated paper with PGA decalinium PGA decalinium coating was formed by a layer-by-layer method. Specifically, first, a sodium salt of poly-γ-L-glutamate having an average molecular weight of 1,000 kD derived from a hyperhalophilic archaebacterium, Natrialba egyptiaca, is dissolved in purified water, and a 2 w / v% PGA aqueous solution is dissolved in purified water. did. Separately, decalinium chloride (DEQ) was dissolved in purified water at 80 ° C. to obtain a 1 w / v% aqueous DEQ solution. A commercially available hand towel (“Crecia EF Hand Towel” manufactured by Nippon Paper Crecia, average weight of n = 8: 2.0 mg) cut into 1 cm × 1 cm was immersed in the above PGA aqueous solution (500 μL) at room temperature for 10 minutes, It was dried at 60 ° C. for 1 hour (average weight increase after immersion drying (n = 8): 0.26 mg). Then, it was immersed in the DEQ aqueous solution (400 μL) at 80 ° C. for 1 minute, taken out, and dried at 60 ° C. for 1 hour (average weight increase after immersion drying (n = 8): 0.47 mg).
実施例３： ＰＧＡデカリニウムの被膜加工紙の抗菌性試験
抗菌性試験の指標菌として大腸菌ＪＭ１０９標準株を用いた。約１０8個の該指標菌体をＬＢ寒天培地（直径約９ｃｍ）の表面に塗布し、３７℃で最長１週間まで培養した。また、その中央には上記実施例２の被膜加工紙を載置し、かかる接着面と周囲に形成される生育阻止帯（ハロー）の有無から抗菌性を評価した（ＪＩＳ Ｌ１９０２に準拠）。比較のため、無処理のハンドタオル自体（表２中「なし」）、ＰＧＡ水溶液のみに浸漬したもの（表２中「ＰＧＡ」）、ＤＥＱ水溶液のみに浸漬したもの（表２中「ＤＥＱ」）、上記比較例１で作製したＰＧＡ／ＨＤＰのエタノール溶液に浸漬したもの（浸漬乾燥後の平均重量増加量（ｎ＝５）：０．６ｍｇ）を用いて同様に試験した。Example 3: Antibacterial test of PGA decalinium-coated paper An Escherichia coli JM109 standard strain was used as an indicator for the antibacterial test. About 10 8 of the indicator cells were spread on the surface of an LB agar medium (about 9 cm in diameter) and cultured at 37 ° C. for up to one week. In addition, the coated paper of Example 2 was placed at the center thereof, and the antibacterial property was evaluated based on the presence of the growth inhibition zone (halo) formed around the adhesive surface and the periphery (according to JIS L1902). For comparison, an untreated hand towel itself ("none" in Table 2), one immersed in a PGA aqueous solution only ("PGA" in Table 2), and one immersed in a DEQ aqueous solution only ("DEQ" in Table 2) The same test was performed using a sample immersed in the ethanol solution of PGA / HDP prepared in Comparative Example 1 (average weight increase after immersion drying (n = 5): 0.6 mg).
また、以下の条件で各被膜加工紙の耐有機溶媒性を試験した。無処理のハンドタオルまたは各被膜加工紙の試料を、エタノール（１０ｍＬ）、ジメチルスルホキシド（ＤＭＳＯ，５ｍＬ）またはクロロホルム（５ｍＬ）に各試料を３０分間浸漬後、フレッシュな各溶媒の入った容器に移してさらに浸漬を続けるという工程を３回繰り返した。最後に乾熱器で浸漬溶媒を蒸発させ、実験試料を得た。得られた実験試料を用い、上記と同様にして抗菌性を評価した。結果を表２に示す。表２中、「＋」は抗菌性ありを示し、「−」は抗菌性なしを示し、「±」は生育阻止帯が僅かに認められたことを示す。 The organic solvent resistance of each coated paper was tested under the following conditions. A sample of an untreated hand towel or each coated paper was immersed in ethanol (10 mL), dimethyl sulfoxide (DMSO, 5 mL) or chloroform (5 mL) for 30 minutes, and then transferred to a container containing fresh solvents. The step of further immersion was repeated three times. Finally, the immersion solvent was evaporated by a dry heater to obtain an experimental sample. The antibacterial properties were evaluated in the same manner as described above using the obtained experimental samples. Table 2 shows the results. In Table 2, “+” indicates antibacterial activity, “−” indicates no antibacterial activity, and “±” indicates that a growth inhibition zone was slightly observed.
表２に示す結果のとおり、ＰＧＡデカリニウムによる被膜加工紙は、有機溶媒に暴露されても、抗菌性が安定的に維持されることが認められた。 As shown in Table 2, it was recognized that the coated paper made of PGA decalinium stably maintained the antibacterial property even when exposed to an organic solvent.
Claims (10)
ポリ−γ−グルタミン酸を構成するグルタミン酸単位に対するデカリニウムの割合が０．４５倍モル以上であることを特徴とする組成物。 Poly -γ- glutamic acid and dequalinium only including,
A composition characterized in that the ratio of decalinium to glutamic acid units constituting poly-γ-glutamic acid is 0.45 times mol or more .
ポリ−γ−グルタミン酸を構成するグルタミン酸単位に対するデカリニウムの割合を０．４５倍モル以上とすることを特徴とするコーティング剤。 The solution containing at least poly -γ- glutamic acid and, viewed contains a solution containing at least dequalinium,
A coating agent characterized in that the ratio of decalinium to glutamic acid units constituting poly-γ-glutamic acid is 0.45 times or more mol .
ポリ−γ−グルタミン酸を構成するグルタミン酸単位に対するデカリニウムの割合を０．４５倍モル以上とすることを特徴とするコーティング方法。 Applying a solution containing a poly -γ- glutamic acid to a substrate, and, it viewed including the steps of applying a solution containing a dequalinium the substrate,
A coating method, wherein the ratio of decalinium to glutamic acid units constituting poly-γ-glutamic acid is 0.45 times or more mol .
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