JP5603702B2 - Antibacterial composition and use thereof - Google Patents
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本発明は、抗菌性組成物とその用途に関し、より詳細には、広範な抗細菌と抗真菌活性を有するとともに、紫外線照射による変色や着色を抑制可能な抗菌性組成物及びその用途に関する。 The present invention relates to an antibacterial composition and its use, and more particularly to an antibacterial composition having a wide range of antibacterial and antifungal activities and capable of suppressing discoloration and coloring caused by ultraviolet irradiation and use thereof.
近年、銀イオンを利用した殺菌剤、抗菌剤、防腐剤等が開発され、生活用品に幅広く普及している。しかし、銀イオンを利用したものの中には、実際の効果が疑われるものや、水溶性が低いために所望の効果を得る濃度で使用できないものがある。そして、銀イオンは、一般に、紫外線により還元され、変質等が起こることが知られている。特に、銀イオンを配合した殺菌剤や抗菌剤を対象物に塗布して乾燥固形化すると、変色、着色、金属銀析出等により対象物が汚染されることが少なくない。 In recent years, bactericides, antibacterial agents, preservatives and the like using silver ions have been developed and are widely used in daily necessities. However, among those using silver ions, there are those that are suspected of actual effects and those that cannot be used at a concentration that achieves a desired effect due to low water solubility. Then, it is known that silver ions are generally reduced by ultraviolet rays and altered. In particular, when an antibacterial agent or antibacterial agent containing silver ions is applied to an object and dried and solidified, the object is often contaminated by discoloration, coloring, metallic silver deposition, or the like.
高い抗菌活性を維持し、かつ毒性、皮膚剌激性及び粘膜剌激性を低くした殺菌・抗菌剤成分として、銀とイミダゾール類との錯体が知られている（特許文献１〜４）。これらの錯体には、水に難溶で光安定性が低いという問題点がある。 As a bactericidal / antibacterial agent component that maintains high antibacterial activity and has low toxicity, skin irritation and mucosal irritation, complexes of silver and imidazoles are known (Patent Documents 1 to 4). These complexes have a problem that they are hardly soluble in water and have low photostability.
銀とピロリドンカルボン酸、ヒスチジン等との錯体が、水溶性かつ安定であることが見出された（特許文献５〜８、並びに非特許文献１）。これらの錯体も、水に溶かした状態で長期間安定に存在できずに、金属銀の析出や、激しい変色を引き起こす。銀錯体そのものの変色が添加対象物の変色も引き起こし、適用可能な対象が限定されていた。 It has been found that complexes of silver with pyrrolidonecarboxylic acid, histidine and the like are water-soluble and stable (Patent Documents 5 to 8 and Non-Patent Document 1). These complexes also cannot be stably present for a long time in a state dissolved in water, and cause precipitation of metal silver and severe discoloration. The discoloration of the silver complex itself also caused discoloration of the object to be added, limiting the applicable objects.
無機担持型の銀系抗菌剤と、プリン、ピリミジン塩基類、チアベンダゾール等とを含む組成物（特許文献９及び１０）が提案された。これらの組成物は、水溶性に乏しく、銀イオンを有効に使用することが困難であった。 A composition (Patent Documents 9 and 10) containing an inorganic supported silver antibacterial agent and purine, pyrimidine bases, thiabendazole and the like has been proposed. These compositions have poor water solubility, and it has been difficult to effectively use silver ions.
５，５−二置換型ヒダントイン、バルビツール酸等を配位子とする銀錯体（特許文献１１）も考案された。銀イオンを水溶液として利用するためには、配位子を銀に対して１モル当量追加し、さらに高塩基性に調整する必要がある。それでも、十分な変色抑制効果は得られない。 A silver complex (Patent Document 11) having a ligand of 5,5-disubstituted hydantoin, barbituric acid or the like has also been devised. In order to use silver ions as an aqueous solution, it is necessary to add a 1 molar equivalent of a ligand to silver and further adjust the basicity. Nevertheless, a sufficient discoloration suppressing effect cannot be obtained.
そこで、本発明は、広範な抗細菌と抗真菌活性を有するとともに、紫外線等による変色や着色を抑制する耐光性に優れた抗菌性組成物を提供することを目的とする。 Therefore, an object of the present invention is to provide an antibacterial composition having a wide range of antibacterial and antifungal activities and excellent in light resistance that suppresses discoloration and coloring due to ultraviolet rays and the like.
本発明者らは、上記目的を達成するために鋭意検討した結果、酸化銀、銀塩、又は銀錯体のいずれか1種以上の化合物にクレアチニンを一定割合で配合することにより、水溶性が良好で、広範な抗細菌抗真菌スペクトルを有し、紫外線等による変色、着色や析出物の発生を抑制する抗菌性組成物を見出し、本発明を完成させた。すなわち、本発明は、酸化銀、銀塩、又は銀錯体（ただし、２Ｈ−ピラン−２−オン−４，６−ジカルボン酸及びその誘導体の銀塩及び銀錯体を含まない）のいずれか1種以上の化合物とクレアチニンとを配合してなる抗菌性組成物であって、前記化合物中の銀（Ａ）とクレアチニン（Ｂ）とのモル比（Ｂ）／（Ａ）が、２〜８０であることを特徴とする、前記抗菌性組成物を提供する。本明細書において、「２Ｈ−ピラン−２−オン−４，６−ジカルボン酸の誘導体」は２Ｈ−ピラン−２−オン−４，６−ジカルボン酸のモノエステル体、若しくはモノアミド体などを意味する。 As a result of diligent studies to achieve the above object, the present inventors have good water solubility by blending creatinine in a certain ratio with one or more compounds of silver oxide, silver salt, or silver complex. Thus, an antibacterial composition having a broad antibacterial and antifungal spectrum and suppressing discoloration, coloring, and precipitation due to ultraviolet rays or the like has been found, and the present invention has been completed. That is, the present invention is any one of silver oxide, silver salt, or silver complex (however, it does not include silver salt and silver complex of 2H-pyran-2-one-4,6-dicarboxylic acid and its derivatives). An antibacterial composition comprising the above compound and creatinine, wherein the molar ratio (B) / (A) of silver (A) and creatinine (B) in the compound is 2-80. The antibacterial composition is provided. In the present specification, “derivative of 2H-pyran-2-one-4,6-dicarboxylic acid” means a monoester or monoamide of 2H-pyran-2-one-4,6-dicarboxylic acid. .
前記銀塩又は銀錯体は、カルボン酸の銀塩又は銀錯体であることが好ましい。 The silver salt or silver complex is preferably a silver salt or silver complex of a carboxylic acid.
前記カルボン酸は、特に化学式（１）：
で表されるモノカルボン酸である。
The carboxylic acid is particularly preferably represented by chemical formula (1):
It is the monocarboxylic acid represented by these.
前記カルボン酸は、また、化学式（２）：
で表されるものでもよい。
The carboxylic acid also has the chemical formula (2):
It may be represented by
化学式（２）のカルボン酸は、特に化学式（３）：
で表されるカルボン酸であることが好ましい。
The carboxylic acid of the chemical formula (2) is particularly a chemical formula (3):
It is preferable that it is carboxylic acid represented by these.
化学式（２）のカルボン酸は、また、２〜４個のカルボキシル基を有する芳香族カルボン酸又は芳香族複素環カルボン酸であることが好ましい。 The carboxylic acid of the chemical formula (2) is preferably an aromatic carboxylic acid or an aromatic heterocyclic carboxylic acid having 2 to 4 carboxyl groups.
前記カルボン酸は、また、ピルビン酸、グリコール酸、酢酸、酪酸及びサリチル酸からなる群から選ばれる少なくとも一種であってもよい。 The carboxylic acid may be at least one selected from the group consisting of pyruvic acid, glycolic acid, acetic acid, butyric acid, and salicylic acid.
本発明の抗菌性組成物は、前記酸化銀と酸とを含み、酸／銀のモル当量が
０．２〜４であることが好ましい。
The antibacterial composition of the present invention preferably contains the silver oxide and the acid, and the acid / silver molar equivalent is preferably 0.2-4.
本発明は、また、上記抗菌性組成物を含有する除菌剤又は消臭剤を提供する。 The present invention also provides a disinfectant or deodorant containing the antibacterial composition.
本発明は、また、上記抗菌性組成物を含有する洗浄剤を提供する。 The present invention also provides a cleaning agent containing the antibacterial composition.
本発明は、また、上記抗菌性組成物を含有する塗料を提供する。 The present invention also provides a paint containing the antibacterial composition.
本発明は、また、上記抗菌性組成物を含有する接着又は粘着剤を提供する。 The present invention also provides an adhesive or pressure-sensitive adhesive containing the antibacterial composition.
本発明は、また、上記抗菌性組成物を含有する繊維抗菌加工処理剤を提供する。 The present invention also provides a fiber antibacterial processing agent containing the antibacterial composition.
酸化銀、銀塩、又は酸錯体のいずれか１種以上の化合物とクレアチニンとを一定割合で配合した本発明の組成物によれば、良好な水溶性と紫外線等への耐光性が得られる。この特性を利用して、本発明の組成物は、除菌剤や消臭剤、洗浄剤、香粧品、塗料、接着又は粘着剤、繊維抗菌加工処理剤、医薬品や医薬部外品、食品等への使用が期待される。 According to the composition of the present invention in which at least one compound of silver oxide, silver salt, or acid complex and creatinine are blended at a certain ratio, good water solubility and light resistance to ultraviolet rays and the like can be obtained. Utilizing this characteristic, the composition of the present invention can be used as a disinfectant, deodorant, detergent, cosmetic, paint, adhesive or pressure-sensitive adhesive, antibacterial fiber treatment agent, pharmaceutical or quasi-drug, food, etc. Expected to be used for
以下に、本発明の実施の形態をより詳細に説明する。本発明の組成物は、酸化銀、銀塩、又は酸錯体のいずれか１種を必須の成分とする。 Hereinafter, embodiments of the present invention will be described in more detail. In the composition of the present invention, any one of silver oxide, silver salt, and acid complex is an essential component.
銀塩又は銀錯体には、カルボン酸銀、硝酸銀、炭酸銀、硫酸銀、酢酸銀、過塩素酸銀、フッ化銀、塩化銀、塩素酸銀、クロム酸銀、シアン化銀、臭化銀、臭素酸銀、ヨウ化銀、ヨウ素酸銀等が挙げられる。本明細書で、銀塩又は銀錯体を一銀と称する場合は銀イオンが１個結合し、二銀と称する場合は銀イオンが２個結合している。好ましくは、構造によっては銀の変色を著しく抑制可能であるという点で、カルボン酸の銀塩又は銀錯体である。これらは一種単独でも、二種以上併用してもよい。 Silver salts or silver complexes include silver carboxylate, silver nitrate, silver carbonate, silver sulfate, silver acetate, silver perchlorate, silver fluoride, silver chloride, silver chlorate, silver chromate, silver cyanide, silver bromide Silver bromate, silver iodide, silver iodate and the like. In this specification, when a silver salt or a silver complex is referred to as one silver, one silver ion is bonded, and when it is referred to as two silver, two silver ions are bonded. Preferably, it is a silver salt or silver complex of a carboxylic acid in that the discoloration of silver can be remarkably suppressed depending on the structure. These may be used alone or in combination of two or more.
上記カルボン酸の銀塩又は銀錯体を構成するカルボン酸は、特に化学式（１）： The carboxylic acid constituting the silver salt or silver complex of the carboxylic acid is particularly represented by the chemical formula (1):
［式中、Ｒ１は置換又は未置換の炭素数１〜１８個の１価の炭化水素基（ただし、カルボキシル基を除く）を示し、ＸはＯまたはＮＨを示す。］
で表されるモノカルボン酸（以下、グループＩという）である。
[Wherein, R 1 represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 18 carbon atoms (excluding a carboxyl group), and X represents O or NH. ]
Is a monocarboxylic acid represented by the following (hereinafter referred to as Group I).
Ｒ１は、例えば置換又は未置換の炭素数１〜１８個、好ましくは１〜４個の１価の脂肪族炭化水素基、置換又は未置換の炭素数６〜１８個、好ましくは６〜１２個の１価の芳香族炭化水素基、若しくは、置換又は未置換の炭素数２〜１８個、好ましくは２〜１１個の１価の芳香族複素環基である。脂肪族炭化水素基は、直鎖でも分岐鎖でもよい。 R 1 is, for example, a substituted or unsubstituted monovalent aliphatic hydrocarbon group having 1 to 18 carbon atoms, preferably 1 to 4 carbon atoms, substituted or unsubstituted carbon atoms having 6 to 18 carbon atoms, preferably 6 to 12 carbon atoms. Are monovalent aromatic hydrocarbon groups, or substituted or unsubstituted monovalent aromatic heterocyclic groups having 2 to 18 carbon atoms, preferably 2 to 11 carbon atoms. The aliphatic hydrocarbon group may be linear or branched.
前記脂肪族炭化水素基の例としては、メチル基、エチル基、プロピル基等のアルキル基；ビニル基、プロペニル基等のアルケニル基；エチニル基、プロピニル基等のアルキニル基；並びにシクロプロピル基、シクロブチル基等のシクロアルキル基が挙げられる。 Examples of the aliphatic hydrocarbon group include alkyl groups such as methyl group, ethyl group, and propyl group; alkenyl groups such as vinyl group and propenyl group; alkynyl groups such as ethynyl group and propynyl group; and cyclopropyl group and cyclobutyl. And cycloalkyl groups such as groups.
前記芳香族炭化水素基の例としては、フェニル基等の単環芳香族炭化水素基；ナフチル基等の縮合環炭化水素基；並びにビフェニリル基等の環集合炭化水素基が挙げられる。 Examples of the aromatic hydrocarbon group include a monocyclic aromatic hydrocarbon group such as a phenyl group; a condensed ring hydrocarbon group such as a naphthyl group; and a ring assembly hydrocarbon group such as a biphenylyl group.
前記芳香族複素環基の例としては、トリアゾリル基、フラニル基、フリル基、チエニル基、ピロリル基、ピリジル基、ピラジル基、オキサゾリル基、イソオキサゾリル基、チアゾリル基、イソチアゾリル基、イミダゾリル基、ピラゾリル基、キノリル基、イソキノリル基、キノキサリニル基、ベンゾフリル基、ベンゾチエニル基、インドリル基、カルバゾリル基、アクリジニル基、チオフェニル基、ビピリジル基及びオキサジアゾリル基が挙げられる。 Examples of the aromatic heterocyclic group include triazolyl group, furanyl group, furyl group, thienyl group, pyrrolyl group, pyridyl group, pyrazyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, imidazolyl group, pyrazolyl group, Examples include quinolyl group, isoquinolyl group, quinoxalinyl group, benzofuryl group, benzothienyl group, indolyl group, carbazolyl group, acridinyl group, thiophenyl group, bipyridyl group, and oxadiazolyl group.
Ｒ1における、脂肪族炭化水素基、芳香族炭化水素基又は芳香族複素環基の水素原子は、他の置換基で置換されてもよい。置換基の例としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子、オキソ基、アリールオキシ基、アリールオキシカルボニル基、ヒドロキシ基、アルコキシ基、アルコキシカルボニル基、置換アミノ基、イミノ基、ニトロ基、シアノ基、アルキルチオ基、アルキルスルホニル基、アリールチオ基、アリールスルホニル基等が挙げられる。 The hydrogen atom of the aliphatic hydrocarbon group, aromatic hydrocarbon group or aromatic heterocyclic group in R 1 may be substituted with other substituents. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, oxo group, aryloxy group, aryloxycarbonyl group, hydroxy group, alkoxy group, alkoxycarbonyl group, substituted amino group, imino group Group, nitro group, cyano group, alkylthio group, alkylsulfonyl group, arylthio group, arylsulfonyl group and the like.
Ｒ１は、さらに好ましくは、置換又は未置換の主鎖炭素数１〜３個の飽和脂肪族炭化水素基、未置換の主鎖炭素数１〜２個の炭化水素基、若しくは、カルボニル基で置換された主鎖炭素数１〜３個の炭化水素基である。 R 1 is more preferably a substituted or unsubstituted saturated aliphatic hydrocarbon group having 1 to 3 carbon atoms in the main chain, a hydrocarbon group having 1 to 2 carbon atoms in the main chain, or a carbonyl group. It is a substituted hydrocarbon group having 1 to 3 main chain carbon atoms.
Ｒ１は、特に好ましくは、メチル基及びアセチル基である。 R 1 is particularly preferably a methyl group and an acetyl group.
グループＩのカルボン酸の具体例としては、化学式：
アセチルグリシン及びアセトキシ酢酸は、これらの銀塩又は銀錯体とクレアチニンとを含む水溶液を乾燥させた時に光安定性に優れ、透明な固形物が得られる点で特に好ましい。 Acetylglycine and acetoxyacetic acid are particularly preferable in that they are excellent in light stability when a solution containing these silver salts or silver complexes and creatinine is dried, and a transparent solid is obtained.
上記カルボン酸の銀塩又は銀錯体を構成するカルボン酸は、また、化学式（２）：
で表され、分子内に特性基として２つのオキソ基を有し、少なくとも１つがカルボキシル基を構成しているカルボン酸でもよい。
The carboxylic acid constituting the silver salt or silver complex of the carboxylic acid is also represented by the chemical formula (2):
And a carboxylic acid having two oxo groups as characteristic groups in the molecule and at least one of which constitutes a carboxyl group.
Ｒ２は、例えば置換又は未置換の炭素数１〜１８個、好ましくは１〜５個の２価の脂肪族炭化水素基、置換又は未置換の炭素数６〜１８個、好ましくは６〜１２個の２価の芳香族炭化水素基、若しくは、置換又は未置換の炭素数２〜１８個、好ましくは２〜１１個の２価の芳香族複素環基である。脂肪族炭化水素基は、直鎖でも分岐鎖でもよい。 R 2 is a substituted or unsubstituted divalent aliphatic hydrocarbon group having 1 to 18 carbon atoms, preferably 1 to 5 carbon atoms, preferably 6 to 18 carbon atoms, preferably 6 to 12 carbon atoms. A divalent aromatic hydrocarbon group or a substituted or unsubstituted divalent aromatic heterocyclic group having 2 to 18 carbon atoms, preferably 2 to 11 carbon atoms. The aliphatic hydrocarbon group may be linear or branched.
前記脂肪族炭化水素基の例としては、メチレン基、エチレン基、プロピレン基等のアルキレン基；ビニレン基、プロペニレン基等のアルケニレン基；並びにシクロプロピレン基、シクロブチレン基等のシクロアルキレン基が挙げられる。 Examples of the aliphatic hydrocarbon group include alkylene groups such as methylene group, ethylene group and propylene group; alkenylene groups such as vinylene group and propenylene group; and cycloalkylene groups such as cyclopropylene group and cyclobutylene group. .
前記芳香族炭化水素基の例としては、フェニレン基等の単環芳香族炭化水素基；ナフチレン基等の縮合環炭化水素基；並びにビフェニレン基等の環集合炭化水素基が挙げられる。 Examples of the aromatic hydrocarbon group include a monocyclic aromatic hydrocarbon group such as a phenylene group; a condensed ring hydrocarbon group such as a naphthylene group; and a ring assembly hydrocarbon group such as a biphenylene group.
前記芳香族複素環基の例としては、トリアゾリレン基、フラニレン基、フリレン基、チエニレン基、ピロリレン基、ピリジレン基、ピラジレン基、オキサゾリレン基、イソオキサゾリレン基、チアゾリレン基、イソチアゾリレン基、イミダゾリレン基、ピラゾリレン基、キノリレン基、イソキノリレン基、キノキサリニレン基、ベンゾフリレン基、ベンゾチエニレン基、インドリレン基、カルバゾリレン基、アクリジニレン基、チオフェニレン基、ビピリジレン基、オキサジアゾリレン基等が挙げられる。 Examples of the aromatic heterocyclic group include a triazolylene group, a furanylene group, a furylene group, a thienylene group, a pyrrolylene group, a pyridylene group, a pyrazylene group, an oxazolylene group, an isoxazolylene group, a thiazolylene group, an isothiazolylene group, an imidazolylene group, Examples thereof include a pyrazolylene group, a quinolylene group, an isoquinolylene group, a quinoxalinylene group, a benzofurylene group, a benzothienylene group, an indolenylene group, a carbazolylene group, an acridinylene group, a thiophenylene group, a bipyridylene group, and the like.
Ｒ２における、脂肪族炭化水素基、芳香族炭化水素基又は芳香族複素環基の水素原子は、他の置換基で置換されていてもよい。置換基の例としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子、オキソ基、アリールオキシ基、アリールオキシカルボニル基、ヒドロキシ基、アルコキシ基、アルコキシカルボニル基、置換アミノ基、イミノ基、ニトロ基、シアノ基、アルキルチオ基、アルキルスルホニル基、アリールチオ基、アリールスルホニル基等が挙げられる。 The hydrogen atom of the aliphatic hydrocarbon group, aromatic hydrocarbon group or aromatic heterocyclic group in R 2 may be substituted with other substituents. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, oxo group, aryloxy group, aryloxycarbonyl group, hydroxy group, alkoxy group, alkoxycarbonyl group, substituted amino group, imino group Group, nitro group, cyano group, alkylthio group, alkylsulfonyl group, arylthio group, arylsulfonyl group and the like.
Ｒ２は、さらに好ましくは、置換又は未置換の主鎖炭素数１〜４個の飽和脂肪族炭化水素基、置換又は未置換の主鎖炭素数２〜４個の不飽和脂肪族炭化水素基、置換又は未置換の環炭素数６〜１０個の芳香族炭化水素基、若しくは置換又は未置換の環炭素数３〜９個の芳香族複素環基である。 R 2 is more preferably a substituted or unsubstituted saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms in the main chain, or a substituted or unsubstituted unsaturated aliphatic hydrocarbon group having 2 to 4 carbon atoms in the main chain. , A substituted or unsubstituted aromatic hydrocarbon group having 6 to 10 ring carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 3 to 9 ring carbon atoms.
Ｒ２は、特に好ましくはメチレン基、エチレン基、プロピレン基、ブチレン基、ヒドロキシエチレン基、ビニレン基、ビスヒドロキシエチレン基、フェニレン基、ナフチレン基、カルボキシフェニレン基、ジカルボキシフェニレン基、及びピリジレン基が挙げられる。 R 2 is particularly preferably methylene group, ethylene group, propylene group, butylene group, hydroxyethylene group, vinylene group, bishydroxyethylene group, phenylene group, naphthylene group, carboxyphenylene group, dicarboxyphenylene group, and pyridylene group. Can be mentioned.
Ｒ３は、例えば置換又は未置換の炭素数１〜１８個、好ましくは１〜５個の１価の脂肪族炭化水素基、置換又は未置換の炭素数６〜１８個、好ましくは６〜１２個の１価の芳香族炭化水素基、若しくは、置換又は未置換の炭素数２〜１８個、好ましくは２〜１１個の１価の芳香族複素環基である。脂肪族炭化水素基、芳香族炭化水素基、又は芳香族複素環基の例は、Ｒ１で挙げたものと同様である。脂肪族炭化水素基は、直鎖でも分岐鎖でもよい。 R 3 is, for example, a substituted or unsubstituted monovalent aliphatic hydrocarbon group having 1 to 18 carbon atoms, preferably 1 to 5 carbon atoms, substituted or unsubstituted carbon atoms having 6 to 18 carbon atoms, preferably 6 to 12 carbon atoms. Are monovalent aromatic hydrocarbon groups, or substituted or unsubstituted monovalent aromatic heterocyclic groups having 2 to 18 carbon atoms, preferably 2 to 11 carbon atoms. Examples of the aliphatic hydrocarbon group, the aromatic hydrocarbon group, or the aromatic heterocyclic group are the same as those described for R 1 . The aliphatic hydrocarbon group may be linear or branched.
Ｒ３における、脂肪族炭化水素基、芳香族炭化水素基又は芳香族複素環基の水素原子は、他の置換基によって置換されていてもよい。置換基の例は、Ｒ１で挙げたものと同様である。 The hydrogen atom of the aliphatic hydrocarbon group, aromatic hydrocarbon group or aromatic heterocyclic group in R 3 may be substituted with another substituent. Examples of the substituent are the same as those described for R 1 .
Ｒ３は、さらに好ましくは、置換又は未置換の主鎖炭素数１〜３個の飽和脂肪族基、若しくは置換又は未置換の主鎖炭素数２〜４個の不飽和脂肪族基である。 R 3 is more preferably a substituted or unsubstituted saturated aliphatic group having 1 to 3 main chain carbon atoms, or a substituted or unsubstituted unsaturated aliphatic group having 2 to 4 main chain carbon atoms.
Ｒ３は、特に好ましくはヒドロキシ基又はメチル基である。 R 3 is particularly preferably a hydroxy group or a methyl group.
化学式（２）のカルボン酸の好ましい例として、化学式（３）：
で表されるカルボン酸（以下、グループＩＩという）である。
As a preferable example of the carboxylic acid of the chemical formula (2), the chemical formula (3):
It is a carboxylic acid represented by the following (hereinafter referred to as group II).
前記脂肪族炭化水素基の例は、Ｒ2で挙げたものと同様である。脂肪族炭化水素基は、直鎖でも分岐鎖でもよい。Ｒ４における、脂肪族炭化水素基の水素原子は、他の置換基で置換されていてもよい。置換基の例は、Ｒ２に挙げたものと同様である。 Examples of the aliphatic hydrocarbon group are the same as those described for R 2 . The aliphatic hydrocarbon group may be linear or branched. The hydrogen atom of the aliphatic hydrocarbon group in R 4 may be substituted with another substituent. Examples of the substituent are the same as those described for R 2 .
Ｒ４は、さらに好ましくは、主鎖炭素数１〜４個の脂肪族炭化水素基である。 R 4 is more preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms in the main chain.
Ｒ４は、特に好ましくはメチレン基、エチレン基、プロピレン基、ブチレン基、ヒドロキシエチレン基、ビスヒドロキシエチレン基及びビニレン基である。 R 4 is particularly preferably a methylene group, ethylene group, propylene group, butylene group, hydroxyethylene group, bishydroxyethylene group or vinylene group.
グループＩＩのカルボン酸の具体例には、化学式：
特に、アジピン酸、フマル酸、コハク酸及び酒石酸は、これらの銀塩又は銀錯体とクレアチニンとを含む水溶液を乾燥させた時に光安定性に優れた点で好ましい。 In particular, adipic acid, fumaric acid, succinic acid, and tartaric acid are preferable in terms of excellent light stability when an aqueous solution containing these silver salts or silver complexes and creatinine is dried.
化学式（２）で表されるカルボン酸の別の好ましい例として、２個以上のカルボシキル基を有する芳香族カルボン酸又は芳香族複素環カルボン酸（以下、グループＩＩＩという）がある。 Another preferred example of the carboxylic acid represented by the chemical formula (2) is an aromatic carboxylic acid or an aromatic heterocyclic carboxylic acid (hereinafter referred to as group III) having two or more carboxy groups.
グループＩＩＩのカルボン酸の具体例には、化学式：
特に、フタル酸、トリメリット酸、ルチジン酸及びピロメリット酸は、これらの銀塩又は銀錯体とクレアチニンとを含む水溶液が優れた光安定性を有する点で好ましい。 In particular, phthalic acid, trimellitic acid, lutidine acid and pyromellitic acid are preferable in that an aqueous solution containing these silver salts or silver complexes and creatinine has excellent light stability.
また、化学式（１）や化学式（２）で表されないカルボン酸（以下、グループＩＶという）として、化学式：
本発明の組成物のもう一つの必須成分であるクレアチニンは、以下の化学式：
本発明の組成物は、酸化銀、銀塩、又は銀錯体のいずれか1種以上の化合物中の銀（Ａ）とクレアチニン（Ｂ）とのモル比（Ｂ）／（Ａ）が、２〜８０であり、好ましくは３〜８０であり、特に好ましくは３〜４である。上記モル比が２未満であると、抗菌性組成物の溶解状態及び／又は乾固状態での耐光性が改善されない、溶解性が低下するために抗菌性組成物を高濃度に調製できない等の問題がある。上記モル比が高すぎるとクレアチニン濃度増加によるコストアップやクレアチニンの溶解度が問題になる。よって、モル比８０を上限とする。 The composition of the present invention has a molar ratio (B) / (A) of silver (A) to creatinine (B) in any one or more compounds of silver oxide, silver salt, or silver complex is 2 to 2. 80, preferably 3 to 80, particularly preferably 3 to 4. When the molar ratio is less than 2, the light resistance of the antibacterial composition in the dissolved state and / or dryness is not improved, and the antibacterial composition cannot be prepared at a high concentration because the solubility decreases. There's a problem. If the molar ratio is too high, cost increases due to an increase in the concentration of creatinine and solubility of creatinine becomes a problem. Accordingly, the upper limit is a molar ratio of 80.
本発明の組成物は、酸化銀、銀塩、又は銀錯体のいずれか1種以上の化合物とクレアチニンとを水性媒体に添加することにより得られる。別法として、無機酸、カルボン酸等の酸及びクレアチニンを水性媒体に添加し、次いで、硝酸銀、酸化銀等の銀化合物又はその溶液を添加してもよい。また、前記銀化合物及びクレアチニンを水性媒体に溶かした後、前記酸を添加してもよい。水性媒体の例には、水、水とアルコール等の有機媒体との混合物があり、好ましくは水である。 The composition of the present invention can be obtained by adding at least one compound of silver oxide, silver salt, or silver complex and creatinine to an aqueous medium. Alternatively, an acid such as an inorganic acid or a carboxylic acid and creatinine may be added to the aqueous medium, and then a silver compound such as silver nitrate or silver oxide or a solution thereof may be added. The acid may be added after the silver compound and creatinine are dissolved in an aqueous medium. Examples of the aqueous medium include water, a mixture of water and an organic medium such as alcohol, and preferably water.
前記酸化銀を使用する場合、無機酸、カルボン酸等の酸を添加することが溶液状態の耐光性をさらに改善する点で好ましい。酸／銀のモル当量は、好ましくは０．２〜４、より好ましくは１〜４である。 When the silver oxide is used, it is preferable to add an acid such as an inorganic acid or a carboxylic acid from the viewpoint of further improving the light resistance in the solution state. The acid / silver molar equivalent is preferably 0.2-4, more preferably 1-4.
本発明の組成物のｐＨは、通常、１〜１２であり、好ましくは３〜９である。 The pH of the composition of this invention is 1-12 normally, Preferably it is 3-9.
本発明の組成物は、広範な抗細菌及び真菌活性を有する。具体的には、ブドウ球菌、メチシリン耐性黄色ブドウ球菌、レンサ球菌のようなグラム陽性球菌、バシラス属、クロストリジウム属、コリネバクテリウム属、リステリア属、プロピオニバクテリウム属又はアクチノミセス属のようなグラム陽性桿菌等のグラム陽性菌;ナイセリア属又はブランハメラ属のようなグラム陰性球菌、シュードモナス属、大腸菌、腸管出血性大腸菌、サルモネラ菌、赤痢菌、ペスト菌、ヘモフィルス属、ブルセラ属又はボルデテラ属のようなグラム陰性桿菌等のグラム陰性菌:ビブリオ属等のらせん状桿菌;リケッチア:クラミジア;マイコプラズマ等が挙げられる。真菌類としては、カンジタ等の酵母；アスペルギルス、クラドスポリウム、トリコフィトン等のカビ等が挙げられる。特に、スタフィロコッカス・アウレウス亜種アウレウス、エシェリキア・コリ、シュードーモナス・アエルギノサ、サルモネラ・エンテリティディス、ビブリオ・パラハエモリティカス、アスペルギルス・ニゲル、カンジダ・アルビカンス、クラドスポリウム・クラドスポリオイデス、トリコフィトン・ルブルム等に有効である。 The compositions of the present invention have a wide range of antibacterial and fungal activities. Specifically, gram-positive cocci such as staphylococci, methicillin-resistant Staphylococcus aureus, streptococci, grams such as Bacillus, Clostridium, Corynebacterium, Listeria, Propionibacterium or Actinomyces Gram-positive bacteria such as positive gonococci; Gram-negative cocci such as Neisseria or Blanchamella, Pseudomonas, Escherichia coli, Enterohemorrhagic Escherichia coli, Salmonella, Shigella, Pesto, Haemophilus, Brucella or Bordetella Gram-negative bacteria such as negative gonococci: spiral gonococci such as Vibrio; Rickettsia: chlamydia; mycoplasma and the like. Examples of fungi include yeasts such as Candita; molds such as Aspergillus, Cladosporium and Trichophyton. In particular, Staphylococcus aureus subspecies Aureus, Escherichia coli, Pseudomonas aeruginosa, Salmonella enteritidis, Vibrio parahaemoliticus, Aspergillus niger, Candida albicans, Cladospodium cladospolio Effective for Ides, Trichophyton Rubulum, etc.
本発明の組成物が抗菌・殺菌性を発揮するためには、菌種にもよるが、銀の含有量の下限は、通常、０．００５ｍＭ以上であり、好ましくは０．０１ｍＭ以上、特に好ましくは０．０４ｍＭ以上である。含有量が低すぎると充分な抗菌・殺菌性が得られない。また、銀の含有量の上限は、通常、１５０ｍＭ以下、好ましくは５０ｍＭ以下、特に好ましくは２０ｍＭ以下である。含有量が高すぎると不溶物が生じる場合がある。 In order for the composition of the present invention to exhibit antibacterial and bactericidal properties, although depending on the bacterial species, the lower limit of the silver content is usually 0.005 mM or more, preferably 0.01 mM or more, particularly preferably. Is 0.04 mM or more. If the content is too low, sufficient antibacterial and bactericidal properties cannot be obtained. The upper limit of the silver content is usually 150 mM or less, preferably 50 mM or less, particularly preferably 20 mM or less. If the content is too high, insoluble materials may be produced.
本発明の組成物には、上記必須成分の他に、抗菌剤・殺菌剤分野で汎用されている助剤を、本発明の効果を阻害しない範囲で使用することができる。このような助剤の例には、公知の抗菌剤・防かび剤、キレート剤、ｐＨ調整剤、界面活性剤、紫外線吸収剤、抗酸化剤、乳化剤、香料、着色料、水溶性高分子、アルコール類、蛍光増白剤、粘度調整剤、発泡剤等が挙げられる。 In the composition of the present invention, in addition to the above essential components, auxiliary agents widely used in the antibacterial agent / bactericide field can be used as long as the effects of the present invention are not impaired. Examples of such auxiliaries include known antibacterial and antifungal agents, chelating agents, pH adjusters, surfactants, ultraviolet absorbers, antioxidants, emulsifiers, fragrances, colorants, water-soluble polymers, Examples include alcohols, fluorescent brighteners, viscosity modifiers, and foaming agents.
本発明の組成物は、溶液、スプレー、クリーム、ペースト、ゲル、ジェル、粉末、顆粒等の形態で使用することができる。本発明の組成物は、水溶性であることから、水溶液やスプレーとして使用することが特に有利である。 The composition of the present invention can be used in the form of a solution, spray, cream, paste, gel, gel, powder, granule and the like. Since the composition of the present invention is water-soluble, it is particularly advantageous to use it as an aqueous solution or spray.
本発明の組成物は、除菌剤や消臭剤、洗浄剤、香粧品、塗料、接着又は粘着剤、繊維抗菌加工処理剤、医薬品や医薬部外品、食品、飼料、農薬等への抗菌殺菌活性成分として添加することができる。本発明の組成物は、上記用途に用いても優れた耐光性を発揮する。上記用途における組成物の配合量は、銀含有量として、通常、０．００５〜１００ｍＭでよく、好ましくは０．０１〜１０ｍＭ、特に好ましくは０．０４〜４ｍＭである。 The composition of the present invention has antibacterial effects on disinfectants, deodorants, detergents, cosmetics, paints, adhesives or adhesives, textile antibacterial agents, pharmaceuticals and quasi drugs, foods, feeds, agricultural chemicals, etc. It can be added as a bactericidal active ingredient. The composition of the present invention exhibits excellent light resistance even when used in the above applications. The compounding quantity of the composition in the said use may be 0.005-100 mM normally as silver content, Preferably it is 0.01-10 mM, Most preferably, it is 0.04-4 mM.
以下に、本発明の実施例及び比較例を示して、本発明をより詳細に説明する。しかし、本発明は、実施例に限定されるものではない。
〔調製例１〕カルボン酸の銀塩又は銀錯体の調製（その１）
アセチルグリシン０．４７２ｇ（４．０ｍｍｏｌ、和光純薬工業株式会社製）の２０ｍｌ水溶液に、酸化銀０．４５９ｇ（２．０ｍｍｏｌ、シグマアルドリッチジャパン株式会社製）を添加し、１０倍容のアセトン中に滴下し、アセチルグリシン銀の白色沈殿を得た。この沈殿を濾過して回収して乾燥させた。
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples of the present invention. However, the present invention is not limited to the examples.
[Preparation Example 1] Preparation of silver salt or silver complex of carboxylic acid (Part 1)
To a 20 ml aqueous solution of 0.472 g of acetylglycine (4.0 mmol, manufactured by Wako Pure Chemical Industries, Ltd.), 0.459 g of silver oxide (2.0 mmol, manufactured by Sigma Aldrich Japan Co., Ltd.) was added, and 10 times the volume of acetone was added. Was added dropwise to obtain a white precipitate of acetylglycine silver. The precipitate was collected by filtration and dried.
上記アセチルグリシン銀の銀とカルボン酸のモル比を、示差熱−熱重量同時測定装置（ブルカー・エイエックスエス株式会社製ＴＧ−ＤＴＡ２０１０ＳＡ）により測定した。具体的には、空気導入下にて室温から１０℃／分の条件で５５０℃まで加熱し、重量残存分と減少分から銀とカルボン酸のモル比を計算した。結果を表１に示す。 The molar ratio of silver and carboxylic acid of the acetylglycine silver was measured with a differential thermal-thermogravimetric simultaneous measurement device (TG-DTA2010SA manufactured by Bruker AXS Co., Ltd.). Specifically, the mixture was heated from room temperature to 550 ° C. at 10 ° C./min under air introduction, and the molar ratio of silver and carboxylic acid was calculated from the remaining weight and the reduced amount. The results are shown in Table 1.
〔調製例２〜２２〕カルボン酸の銀塩又は銀錯体の調製（その２）
調製例１のカルボン酸及び銀化合物を、表１の化合物又はその溶液に替えた以外は、調製例１と同様の手順で、カルボン酸の銀塩又は銀錯体を調製した。ここで、酸化銀、硝酸銀及びアセトキシ酢酸は、シグマアルドリッチジャパン株式会社製の試薬、アジピン酸は、関東化学株式会社製の試薬、トリメシン酸、ピロメリット酸、ルチジン酸、及びメトキシ酢酸は、東京化成工業株式会社製の試薬を使用した。それ以外の化合物は、和光純薬工業株式会社製の試薬を使用した。得られた銀塩又は銀錯体の銀とカルボン酸のモル比を、調製例１と同様に測定した。結果を表１に示す。
[Preparation Examples 2 to 22] Preparation of silver salt or silver complex of carboxylic acid (Part 2)
A silver salt or silver complex of carboxylic acid was prepared in the same procedure as in Preparation Example 1, except that the carboxylic acid and silver compound in Preparation Example 1 were replaced with the compounds in Table 1 or solutions thereof. Here, silver oxide, silver nitrate and acetoxyacetic acid are reagents manufactured by Sigma-Aldrich Japan Co., Ltd., adipic acid is a reagent manufactured by Kanto Chemical Co., Ltd., trimesic acid, pyromellitic acid, lutidine acid, and methoxyacetic acid are A reagent manufactured by Kogyo Co., Ltd. was used. For other compounds, reagents manufactured by Wako Pure Chemical Industries, Ltd. were used. The molar ratio of silver and carboxylic acid of the obtained silver salt or silver complex was measured in the same manner as in Preparation Example 1. The results are shown in Table 1.
〔実施例１〜４〕酸化銀、銀塩又は銀錯体とクレアチニンとを含む抗菌性組成物
１．抗菌性組成物の調製
硝酸銀０．０２２ｇ（０．１３ｍｍｏｌ）及びクレアチニン０．０５７ｇ（０．５２ｍｍｏｌ、和光純薬工業株式会社）を水４０ｍｌに溶解し、銀濃度が３．２ｍＭであり、そしてクレアチニン／銀のモル比が４の組成物を得た（実施例１）。また、実施例１において、硝酸銀を、硫酸銀０．０２０ｇ（０．０６５ｍｍｏｌ）、炭酸銀０．０１８ｇ（０．０６５ｍｍｏｌ）あるいは酸化銀０．０１５ｇ（０．０６５ｍｍｏｌ）とする以外は実施例１と同様の方法で実施例２〜４の組成物（それぞれ銀濃度：３．２ｍＭ）を調製した。これらの組成物の水溶性は良好であった。
[Examples 1-4] Antibacterial composition containing silver oxide, silver salt or silver complex and creatinine Preparation of antibacterial composition 0.022 g (0.13 mmol) of silver nitrate and 0.057 g (0.52 mmol, Wako Pure Chemical Industries, Ltd.) of silver nitrate were dissolved in 40 ml of water, the silver concentration was 3.2 mM, and creatinine A composition having a silver / silver molar ratio of 4 was obtained (Example 1). Further, in Example 1, silver nitrate was changed to 0.020 g (0.065 mmol), silver carbonate 0.018 g (0.065 mmol), or silver oxide 0.015 g (0.065 mmol). The compositions of Examples 2 to 4 (silver concentration: 3.2 mM, respectively) were prepared in the same manner. The water solubility of these compositions was good.
２．組成物の抗菌性試験
・抗菌性試験
上記４種類の銀塩とクレアチニンとを含む組成物の抗菌性を確認するため、クロカワカビ（Ｃｌａｄｏｓｐｏｒｉｕｍ ｃｌａｄｏｓｐｏｒｉｏｉｄｅｓ、ＪＣＭ ３８９９）に対するＭＩＣ（菌の発育を阻害する最小銀濃度）を測定した。
2. Antibacterial test / antibacterial test of the composition In order to confirm the antibacterial activity of the composition containing the above four kinds of silver salts and creatinine, MIC (minimum silver that inhibits the growth of bacteria) against black mold (Cladosporium cladosporoides, JCM 3899) Concentration).
対照として、水（４０ｍｌ）に硝酸銀０．０２２ｇ（０．１３ｍｍｏｌ）、又は硫酸銀０．０２０ｇ（０．０６５ｍｍｏｌ）、炭酸銀０．０１８ｇ（０．０６５ｍｍｏｌ）、又は酸化銀０．０１５ｇ（０．０６５ｍｍｏｌ）を添加した比較例１、２、３及び４（銀濃度：０．３２ｍＭ）の抗菌性試験も行った。なお、炭酸銀（比較例３）及び酸化銀（比較例４）は水に溶解しないため、試験を実施しなかった。 As a control, 0.022 g (0.13 mmol) of silver nitrate or 0.020 g (0.065 mmol) of silver sulfate, 0.018 g (0.065 mmol) of silver carbonate, or 0.015 g (0. 065 mmol) was added to Comparative Examples 1, 2, 3 and 4 (silver concentration: 0.32 mM). Note that silver carbonate (Comparative Example 3) and silver oxide (Comparative Example 4) were not dissolved in water and therefore were not tested.
表２の組成物を、それぞれ、孔径０．４５μｍのメンブレンフィルター（製品名マイレクスＨＶ、日本ミリポア株式会社製）を通して滅菌した。 Each of the compositions in Table 2 was sterilized through a membrane filter (product name: Milex HV, manufactured by Nihon Millipore Corporation) having a pore diameter of 0.45 μm.
約４５℃に保った感受性測定用培地（ＰＤＡ寒天培地）を用いて最高濃度１０％として２倍希釈の薬剤系列を各２枚ずつ作製し、滅菌シャーレに固化したものを被検物質含有感受性培地とした。対照として、薬剤原液の代わりに滅菌精製水を使用したものについて、同様に各濃度１枚作製し、薬剤不含培地とした。 Using a sensitivity measurement medium (PDA agar medium) maintained at about 45 ° C., a double-diluted drug series with a maximum concentration of 10% was prepared for each two, and solidified in a sterile petri dish, a test substance-containing sensitive medium It was. As a control, one using each sterilized purified water instead of the drug stock solution was prepared in the same manner to prepare a drug-free medium.
被検物質含有感受性培地及び薬剤不含培地の寒天培地表面に、接種用菌液を白金耳で２ｃｍ程度、画線塗抹した（ｎ＝２）。２５±３℃で３〜５日間、それぞれ好気培養を行った。培養後、各被検物質含有感受性培地及び薬剤不含培地について菌の発育の有無を判定し、ＭＩＣを求めた。結果を表２に示す。 The bacterial solution for inoculation was smeared on the surface of the agar medium containing the test substance-containing sensitive medium and the drug-free medium with a platinum loop (n = 2). Aerobic culture was performed at 25 ± 3 ° C. for 3 to 5 days. After the culture, the presence or absence of bacterial growth was determined for each test substance-containing sensitive medium and drug-free medium, and MIC was determined. The results are shown in Table 2.
表２から、本発明の組成物には、硝酸銀や硫酸銀と同様に、抗菌効果を有することが確認された。 From Table 2, it was confirmed that the composition of the present invention has an antibacterial effect in the same manner as silver nitrate and silver sulfate.
３．耐光性試験
実施例１〜４の組成物の耐光性試験を行った。比較のため、比較例１〜４も同様に試験を行った。
3. Light Resistance Test A light resistance test of the compositions of Examples 1 to 4 was performed. For comparison, Comparative Examples 1 to 4 were similarly tested.
（１）溶液状態での耐光性試験
表２の組成物を、孔径０．２０μｍのメンブレンフィルター（製品名：マイレクスＬＧ、日本ミリポア株式会社製）を通して不溶物を除去した。各被検物質１０ｍｌを２０ｍｌのガラス製バイアル瓶に入れ、蓋をせずに高エネルギー紫外光源（東芝ライテック株式会社製殺菌ランプＧＬ−１５、殺菌線出力４．９Ｗ、紫外線放射強度５１μＷ／ｃｍ２）の下に設置した。光源と液面との距離を４ｃｍとした。１２時間毎に、各溶液に変色又は析出物の発生が起こるかを、以下の基準で観察した。結果を表３に示す。
○：変色又は析出物の発生が認められなかった。
×：変色又は析出物の発生が認められた。
(1) Light Resistance Test in Solution State Insoluble matters were removed from the composition shown in Table 2 through a membrane filter (product name: Milex LG, manufactured by Nihon Millipore Corporation) having a pore size of 0.20 μm. 10 ml of each test substance is placed in a 20 ml glass vial, and a high-energy ultraviolet light source (Toshiba Lighttech Co., Ltd. sterilization lamp GL-15, sterilization line output 4.9 W, ultraviolet radiation intensity 51 μW / cm 2 without covering) ). The distance between the light source and the liquid level was 4 cm. Whether or not discoloration or precipitation occurred in each solution every 12 hours was observed according to the following criteria. The results are shown in Table 3.
○: No discoloration or precipitation was observed.
X: Discoloration or generation of precipitates was observed.
（２）乾固状態での耐光性試験
各組成物０．０５ｍｌをスライドグラス上に滴下し、５０℃、減圧下で揮発分を除去して乾燥した試験体を得た。各試験体を前記紫外光源の下に設置した。光源と試験体との距離は６ｃｍに調節した。
(2) Light resistance test in a dry state 0.05 ml of each composition was dropped on a slide glass, and the volatile matter was removed under reduced pressure at 50 ° C. to obtain a dried test specimen. Each specimen was placed under the ultraviolet light source. The distance between the light source and the test specimen was adjusted to 6 cm.
６０分まで変色を、以下の基準で観察した。結果を表３に示す。
☆：透明
◎：半透明
○：白色
×：黄色、褐色、灰色、黒色等に着色
Discoloration was observed up to 60 minutes according to the following criteria. The results are shown in Table 3.
☆: Transparent ◎: Translucent ○: White ×: Colored yellow, brown, gray, black, etc.
比較例１及び２の組成物は、主に乾固状態での耐光性に劣ったが、それにクレアチニンを配合した実施例１及び２の組成物では、溶液及び乾固状態のいずれも耐光性が良好であった。比較例３の組成物は、溶解性が悪く、耐光性試験に供し得なかったが、それにクレアチニンを配合した実施例３の組成物では、溶解性に優れ、溶液及び乾固状態の早期では良好な耐光性を示した。比較例４の組成物は、溶解性が悪く、耐光性試験に供し得なかったが、それにクレアチニンを配合した実施例４の組成物では、溶解性に優れ、乾固状態の早期では良好な耐光性を示した。 The compositions of Comparative Examples 1 and 2 were mainly inferior in light resistance in the dry state, but in the compositions of Examples 1 and 2 in which creatinine was blended, both the solution and the dry state had light resistance. It was good. The composition of Comparative Example 3 was poorly soluble and could not be subjected to a light resistance test, but the composition of Example 3 blended with creatinine was excellent in solubility and good in the early stage of the solution and dryness. Light resistance. The composition of Comparative Example 4 was poorly soluble and could not be subjected to a light resistance test, but the composition of Example 4 in which creatinine was blended with the composition had excellent solubility and good light resistance at an early stage of dryness. Showed sex.
〔実施例５〜８〕クレアチニンの配合量
実施例１において、銀濃度３．２ｍＭを一定としたまま、クレアチニンの濃度を表４に示すように変えた以外は実施例１と同様の手順で組成物を調製した。これらの組成物の耐光性試験を、実施例１と同様の手順で行った。結果を表４に示す。
[Examples 5 to 8] Blending amount of creatinine In Example 1, the composition was made in the same manner as in Example 1 except that the concentration of creatinine was changed as shown in Table 4 while the silver concentration of 3.2 mM was kept constant. A product was prepared. The light resistance test of these compositions was performed in the same procedure as in Example 1. The results are shown in Table 4.
表４より、クレアチニンの配合量は、銀に対して２モル当量以上で耐光性を示すことが判明した。 From Table 4, it became clear that the compounding quantity of creatinine shows light resistance in 2 mol equivalent or more with respect to silver.
〔実施例９〜１５〕酸化銀、クレアチニン及び酸を含む抗菌性組成物
１．抗菌性組成物の調製
実施例４を調製する際に、表５の組成となるよう、さらにアセチルグリシンあるいは硝酸を加え、水で合計４０ｍｌとなるよう調製して組成物を得た。
[Examples 9 to 15] 1. Antibacterial composition containing silver oxide, creatinine and acid Preparation of antibacterial composition When Example 4 was prepared, acetylglycine or nitric acid was further added so as to have the composition shown in Table 5, and the total amount was adjusted to 40 ml with water to obtain a composition.
２．組成物の耐光性試験
各抗菌性組成物の溶液状態での耐光性試験を行った。測定結果を表５に示す。
2. Light Resistance Test of Composition A light resistance test in a solution state of each antibacterial composition was performed. Table 5 shows the measurement results.
表５に示すように、銀化合物にクレアチニンを添加した組成物に、酸を銀に対して０．４〜４モル当量を添加することで、耐光性がより増すことが分かった。 As shown in Table 5, it was found that the light resistance was further increased by adding 0.4 to 4 molar equivalents of acid to silver to a composition obtained by adding creatinine to a silver compound.
３．組成物の抗菌性試験
上記組成物の抗菌性を確認するため、クロカワカビ（Ｃｌａｄｏｓｐｏｒｉｕｍ ｃｌａｄｏｓｐｏｒｉｏｉｄｅｓ、ＪＣＭ ３８９９）に対するＭＩＣを測定した。結果を表６に示す。
3. Antibacterial property test of the composition In order to confirm the antibacterial property of the above-mentioned composition, MIC against black mold (Cladosporium cladosporoides, JCM 3899) was measured. The results are shown in Table 6.
表６から、酸化銀、クレアチニン及び酸からなる本発明の組成物もまた、酸化銀及びクレアチニンから組成物と同様の抗菌活性があることが確認された。 From Table 6, it was confirmed that the composition of the present invention consisting of silver oxide, creatinine and acid also has antibacterial activity similar to that of the composition from silver oxide and creatinine.
〔実施例１６〜１８〕グループＩのカルボン酸の銀塩又は銀錯体とクレアチニンとを含む抗菌性組成物
１．抗菌性組成物の調製
調製例１で得たアセチルグリシン銀０．０７２ｇ（０．３２ｍｍｏｌ）を、クレアチニン０．１４６ｇ（１．３ｍｍｏｌ）とともに水１００ｍｌに溶解させることにより、アセチルグリシン銀３．２ｍＭ及びクレアチニン１３ｍＭを含み、クレアチニン／銀のモル比が４の組成物（実施例１６）を得た。この組成物の水溶性は良好であった。
[Examples 16 to 18] 1. Antibacterial composition containing silver salt or silver complex of carboxylic acid of group I and creatinine Preparation of antibacterial composition 0.072 g (0.32 mmol) of acetylglycine silver obtained in Preparation Example 1 was dissolved in 100 ml of water together with 0.146 g (1.3 mmol) of creatinine, whereby 3.2 mM of acetylglycine silver and A composition containing 13 mM of creatinine and having a creatinine / silver molar ratio of 4 (Example 16) was obtained. The water solubility of this composition was good.
実施例１６のアセチルグリシン銀に代えて、グループＩのアセトキシ酢酸銀又はメトキシ酢酸銀を使用した以外は、実施例１６と同様の手順で実施例１７、１８を得た。 Examples 17 and 18 were obtained in the same manner as in Example 16 except that group I silver acetoxyacetate or silver methoxyacetate was used instead of silver acetylglycine in Example 16.
２．組成物の抗菌性試験
・抗菌性試験（１）
実施例１６の組成物の抗菌性を確認するため、以下の４種の菌種：
黄色ブドウ球菌（Ｓｔａｐｈｙｌｏｃｏｃｃｕｓ ａｕｒｅｕｓ ｓｕｂｓｐ． Ａｕｒｅｕｓ、ＮＢＲＣ１３２７６）、
大腸菌（Ｅｓｃｈｅｒｉｃｈｉａ ｃｏｌｉ、ＮＢＲＣ３９７２）、
クロコウジカビ（Ａｓｐｅｒｇｉｌｌｕｓ ｎｉｇｅｒ、ＮＢＲＣ９４５５）、及び
クロカワカビ（Ｃｌａｄｏｓｐｏｒｉｕｍ ｃｌａｄｏｓｐｏｒｉｏｉｄｅｓ、ＮＢＲＣ ６３４８）
に対するＭＩＣを測定した。対照として、比較例１の硝酸銀を用いた。
2. Antibacterial test / antibacterial test of composition (1)
In order to confirm the antibacterial properties of the composition of Example 16, the following four bacterial species:
Staphylococcus aureus subsp. Aureus, NBRC13276,
E. coli (Escherichia coli, NBRC 3972),
Aspergillus niger (NBRC 9455) and Aspergillus cladosporeoides (NBRC 6348)
MIC was measured. As a control, the silver nitrate of Comparative Example 1 was used.
発育阻止濃度の測定試験は、日本化学療法学会によるＭＩＣ（最小発育阻止濃度）寒天平板希釈法に準じて、以下の手順で行った。ミュラーヒントンＩＩ寒天培地（ベクトン・ディッキンソン社製）にて、上記細菌をそれぞれ３７±３℃で一夜培養した。また、上記真菌は、それぞれ、サブロー・ブドウ糖寒天倍地（日水製薬株式会社製）にて、２５±３℃で５〜１０日間培養した。寒天平板上の被検菌体を滅菌生理食塩水でＭａｃＦａｒｌａｎｄ Ｎｏ．１（細菌は約１０８ｃｆｕ／ｍＬ、真菌は約１０６ｃｆｕ／ｍＬ）相当の濁度に懸濁し、接種用菌液とした。 The measurement test of the growth inhibitory concentration was performed according to the following procedure according to the MIC (minimum growth inhibitory concentration) agar plate dilution method by the Japanese Society of Chemotherapy. The bacteria were cultured overnight at 37 ± 3 ° C. on Muller Hinton II agar medium (Becton Dickinson). The fungi were cultured at 25 ± 3 ° C. for 5 to 10 days in a Sabouraud-glucose agar medium (Nissui Pharmaceutical Co., Ltd.). The test cells on the agar plate were washed with sterilized physiological saline using MacFarland No. 1 (bacteria were about 10 8 cfu / mL, fungi were about 10 6 cfu / mL) and suspended in a turbidity to obtain a bacterial solution for inoculation.
実施例１６の組成物及び比較例１の組成物を、それぞれ、孔径０．４５μｍのメンブレンフィルター（製品名マイレクスＨＶ、日本ミリポア株式会社製）を通して滅菌した。 The composition of Example 16 and the composition of Comparative Example 1 were each sterilized through a membrane filter (product name: Milex HV, manufactured by Nihon Millipore Corporation) having a pore diameter of 0.45 μm.
約４５℃に保った感受性測定用培地（細菌はミュラーヒントンＩＩ寒天培地、真菌はサブロー・ブドウ糖寒天培地）を用いて最高濃度を１０％として２倍希釈の薬剤系列を各２枚ずつ作製し、滅菌シャーレに固化したものを被検物質含有感受性培地とした。対照として、薬剤原液の代わりに滅菌精製水を使用したものについて、同様に各濃度１枚作製し、薬剤不含培地とした。 Using a sensitivity measurement medium kept at about 45 ° C. (bacterial is Muller Hinton II agar medium, fungus is Sabouraud / glucose agar medium), a two-fold diluted drug series is prepared each at a maximum concentration of 10%, A solidified product in a sterile petri dish was used as a test substance-containing sensitive medium. As a control, one using each sterilized purified water instead of the drug stock solution was prepared in the same manner to prepare a drug-free medium.
被検物質含有感受性培地及び薬剤不含培地の寒天培地表面に、接種用菌液を白金耳で２ｃｍ程度画線塗抹した（被検物質含有感受性培地はｎ＝２、薬剤不含培地はｎ＝１）。細菌は３７±３℃で１８〜２０時間、真菌は２５±３℃で３〜５日間、それぞれ好気培養を行った。培養後、各被検物質含有感受性培地及び薬剤不含培地について菌の発育の有無を判定し、ＭＩＣ値を決定した。これらの測定結果から、菌の発育を阻害する銀濃度を算出した結果を表７に示す。 On the surface of the agar medium containing the test substance-containing sensitive medium and the drug-free medium, the inoculum was smeared with a platinum loop for about 2 cm (n = 2 for the test substance-containing sensitive medium, n = for the drug-free medium). 1). The bacteria were aerobically cultured at 37 ± 3 ° C. for 18 to 20 hours, and the fungi were cultured at 25 ± 3 ° C. for 3 to 5 days. After the culture, the presence or absence of bacterial growth was determined for each test substance-containing sensitive medium and drug-free medium, and the MIC value was determined. Table 7 shows the results of calculating the silver concentration that inhibits the growth of bacteria from these measurement results.
表７から、アセチルグリシン銀及びクレアチニンからなる組成物には、硝酸銀と同様に、細菌及び真菌に対して優れた抗菌効果があることを確認できた。 From Table 7, it has confirmed that the composition which consists of silver acetylglycine and creatinine has the antimicrobial effect outstanding with respect to bacteria and fungi similarly to silver nitrate.
・抗菌性試験（２）
グループＩに属するカルボン酸の銀塩又は銀錯体とクレアチニンとを含む組成物の抗菌性を確認するため、クロカワカビ（Ｃｌａｄｏｓｐｏｒｉｕｍ ｃｌａｄｏｓｐｏｒｉｏｉｄｅｓ、ＪＣＭ ３８９９）に対するＭＩＣを、実施例１６に示したのと同様の手順で測定した。対照として、比較例１の硝酸銀を用いた。結果を表８に示す。
・ Antimicrobial test (2)
In order to confirm the antibacterial activity of a composition comprising a silver salt or silver complex of a carboxylic acid belonging to Group I and creatinine, the MIC for black mold (Cladosporium cladosporoides, JCM 3899) was similar to that shown in Example 16. Measured with As a control, the silver nitrate of Comparative Example 1 was used. The results are shown in Table 8.
表８から、グループＩに属するカルボン酸の銀塩又は銀錯体とクレアチニンとからなる組成物には、硝酸銀と同様に、真菌に対して優れた抗菌効果があることを確認できた。また、実施例１６を減圧乾固することで得た、固形状態の組成物を用いた抗菌性試験においても、抗菌効果に違いがなかった。 From Table 8, it has confirmed that the composition which consists of the silver salt of a carboxylic acid which belongs to group I, or a silver complex, and creatinine has the antimicrobial effect excellent with respect to fungi like silver nitrate. Moreover, there was no difference in the antibacterial effect also in the antibacterial test using the solid composition obtained by drying Example 16 under reduced pressure.
３．耐光性試験
実施例１６〜１８の抗菌性組成物の光安定性を確認する耐光性試験を、実施例１と同様の手順で行った。また、比較のため、水に溶解したアセチルグリシン銀、アセトキシ酢酸銀、メトキシ酢酸銀単独の耐光性試験も行った。結果を表９に示す。
3. Light Resistance Test A light resistance test for confirming the light stability of the antibacterial compositions of Examples 16 to 18 was performed in the same procedure as in Example 1. For comparison, light resistance tests were also conducted on acetylglycine silver, silver acetoxyacetate, and silver methoxyacetate alone dissolved in water. The results are shown in Table 9.
表９に示すとおり、アセチルグリシン銀のみからなる比較例６では、溶液及び乾固状態ともに、時間がたつと耐光性が悪化した。アセトキシ酢酸銀のみからなる比較例７では、乾固状態での耐光性が悪化した。メトキシ酢酸銀のみからなる比較例８では、溶液、乾固状態ともに耐光性に劣った。それに対して、グループＩのカルボン酸の銀塩とクレアチニンとからなる組成物は、溶解性に優れるとともに、溶液及び乾固状態での耐光性に優れることが判明した。 As shown in Table 9, in Comparative Example 6 consisting only of silver acetylglycine, the light resistance deteriorated with time in both the solution and the dried state. In Comparative Example 7 consisting only of silver acetoxyacetate, the light resistance in the dry state deteriorated. In Comparative Example 8 consisting only of silver methoxyacetate, the light resistance was inferior in both the solution and the dried state. On the other hand, it has been found that a composition comprising a silver salt of a group I carboxylic acid and creatinine is excellent in solubility and light resistance in a solution and in a dry state.
実施例１７において、クレアチニンに代えて、化学式：
表１０に示すとおり、クレアチニンをグアニン、５−アザシトシン又はヒダントインに変更した比較例では溶解性が劣り、耐光性試験に供せなかった。また、クレアチニンをアセチルアセトングアニジン又は５，５−ジメチルヒダントインに変更した比較例では、溶解性は確保されるものの、溶液状態及び乾固状態での耐光性に劣った。 As shown in Table 10, the comparative example in which creatinine was changed to guanine, 5-azacytosine or hydantoin was inferior in solubility and could not be subjected to a light resistance test. Moreover, in the comparative example which changed creatinine to acetylacetone guanidine or 5, 5- dimethylhydantoin, although solubility was ensured, it was inferior to the light resistance in a solution state and a dry-solid state.
〔実施例１９〜２５〕グループＩのカルボン酸の銀塩又は銀錯体とクレアチニンとの配合量
実施例１６において、アセチルグリシン銀の銀濃度３．２ｍＭを一定としたまま、クレアチニンの濃度を表１１に示すように変えた以外は実施例１６と同様の手順で本発明の組成物を調製した。組成物の水溶性は、いずれの濃度においても良好であった。
[Examples 19 to 25] Compounding amount of silver salt or silver complex of carboxylic acid of group I and creatinine In Example 16, the concentration of creatinine in Table 11 was kept constant while maintaining the silver concentration of acetylglycine silver of 3.2 mM. A composition of the present invention was prepared in the same manner as in Example 16, except that the changes were made as shown in FIG. The water solubility of the composition was good at any concentration.
上記組成物の溶液及び乾固状態での耐光性試験を、実施例１と同様の手順で行った。結果を表１１に示す。 The light resistance test in the solution of the composition and in the dry state was performed in the same procedure as in Example 1. The results are shown in Table 11.
表１１から、グループＩのアセチルグリシン銀とクレアチニンとの配合量は、銀に対してクレアチニン２〜８０モル当量で変色抑制効果を示し、３〜８０モル当量が適当であり、３〜４モル当量が最適であった。 From Table 11, the compounding quantity of the acetylglycine silver of group I and creatinine shows the discoloration inhibitory effect by creatinine 2-80 molar equivalent with respect to silver, 3-80 molar equivalent is suitable, 3-4 molar equivalent Was the best.
〔実施例２６〜３３〕グループＩＩのカルボン酸の銀塩又は銀錯体とクレアチニンとを含む抗菌性組成物
１．抗菌性組成物の調製
調製例２で得たアジピン酸二銀０．０５８ｇ（０．１６ｍｍｏｌ）とクレアチニン０．１４６ｇ（１．３ｍｍｏｌ）とを、水１００ｍｌに溶解させた。組成物の水溶性は良好であった。アジピン酸二銀１．６ｍＭ及びクレアチニン１３ｍＭを含み、クレアチニン／銀のモル比が４の組成物（実施例２６）を得た。
[Examples 26 to 33] 1. Antibacterial composition containing silver salt or silver complex of carboxylic acid of group II and creatinine Preparation of antibacterial composition 0.058 g (0.16 mmol) of disilver adipate obtained in Preparation Example 2 and 0.146 g (1.3 mmol) of creatinine were dissolved in 100 ml of water. The water solubility of the composition was good. A composition (Example 26) containing 1.6 mM disilver adipate and 13 mM creatinine and having a creatinine / silver molar ratio of 4 was obtained.
実施例２６のアジピン酸二銀に代えて、グループＩＩの表１３のカルボン酸の銀塩又は銀錯体を使用した以外は、実施例２６と同様の手順で実施例２７〜３３を得た。カルボン酸の銀塩又は銀錯体中の銀とクレアチニンとのモル比は、実施例２６と同じく４とした。 Examples 27 to 33 were obtained in the same procedure as in Example 26, except that a silver salt or silver complex of a carboxylic acid in Table 13 of Group II was used in place of the disilver adipate of Example 26. The molar ratio of silver and creatinine in the silver salt or silver complex of carboxylic acid was 4 as in Example 26.
２．抗菌性試験
・抗菌性試験（１）
アジピン酸二銀とクレアチニンとからなる組成物の抗菌性試験を、実施例１６と同様の手順で行った。結果を表１２に示す。
2. Antibacterial test / antibacterial test (1)
An antibacterial test of a composition comprising disilver adipate and creatinine was performed in the same procedure as in Example 16. The results are shown in Table 12.
表１２から、グループＩＩのアジピン酸二銀及びクレアチニンからなる本発明の組成物には、硝酸銀と同様に、細菌及び真菌に対して優れた抗菌効果があることを確認できた。 From Table 12, it was confirmed that the composition of the present invention consisting of group II disilver adipate and creatinine had an excellent antibacterial effect against bacteria and fungi as well as silver nitrate.
・抗菌性試験（２）
グループＩＩに属するカルボン酸の銀塩又は銀錯体とクレアチニンとを含む組成物（表１３）の抗菌性を確認するため、クロカワカビ（Ｃｌａｄｏｓｐｏｒｉｕｍ ｃｌａｄｏｓｐｏｒｉｏｉｄｅｓ、ＪＣＭ ３８９９）に対するＭＩＣを測定した。結果を表１３に示す。
・ Antimicrobial test (2)
In order to confirm the antibacterial activity of a composition (Table 13) containing a silver salt or silver complex of a carboxylic acid belonging to Group II and creatinine, the MIC against black mold (Cladosporium cladosporeides, JCM 3899) was measured. The results are shown in Table 13.
表１３から、グループＩＩに属するカルボン酸の銀塩又は銀錯体とクレアチニンとからなる組成物には、硝酸銀と同様に、真菌に対して優れた抗菌効果があることを確認できた。 From Table 13, it has confirmed that the composition which consists of the silver salt or silver complex of carboxylic acid which belongs to the group II, and creatinine has the antimicrobial effect excellent with respect to fungi like silver nitrate.
３．耐光性試験
グループＩＩに属するカルボン酸の銀塩又は銀錯体及びクレアチニンからなる組成物の耐光性試験を実施例１に記載と同様の手順で行った。また、比較のため、水に溶かしたアジピン酸二銀、フマル酸二銀、リンゴ酸二銀、コハク酸二銀、及び酒石酸二銀単独の耐光性試験も行った。結果を表１４に示す。
3. Light Resistance Test A light resistance test of a composition comprising a silver salt or silver complex of a carboxylic acid belonging to Group II and creatinine was performed in the same procedure as described in Example 1. For comparison, light resistance tests were also conducted on disilver adipate, disilver fumarate, disilver malate, disilver succinate, and disilver tartrate dissolved in water. The results are shown in Table 14.
表１４に示すとおり、アジピン酸二銀、フマル酸二銀やコハク酸二銀を単独に用いた比較組成物は、水に溶けにくく耐光性試験に供し得なかった。また、リンゴ酸二銀や酒石酸二銀を単独に用いた組成物は、水溶性であるものの、耐光性に劣った。それに対して、グループＩＩのカルボン酸の銀塩又は銀錯体とクレアチニンとを含む組成物は、水溶性があり耐光性試験に供し得、溶液状態での耐光性に優れた。 As shown in Table 14, the comparative composition using disilver adipate, disilver fumarate or disilver succinate alone was hardly soluble in water and could not be subjected to a light resistance test. Moreover, although the composition using disilver malate or disilver tartrate alone was water-soluble, it was inferior in light resistance. In contrast, a composition containing a silver salt or silver complex of a group II carboxylic acid and creatinine was water-soluble and could be subjected to a light resistance test, and was excellent in light resistance in a solution state.
〔実施例３４〜３９〕グループＩＩＩのカルボン酸の銀塩又は銀錯体とクレアチニンとを含む抗菌性組成物
１．抗菌性組成物の調製
調製例３で得たフタル酸二銀０．０６１ｇ（０．１６ｍｍｏｌ）とクレアチニン０．１４６ｇ（１．３ｍｍｏｌ）とを水１００ｍｌに溶解させた。組成物の水溶性は良好であった。こうして、フタル酸二銀１．６ｍＭ及びクレアチニン１３ｍＭを含み、クレアチニン／銀のモル比が４の組成物（実施例３４）を得た。
Examples 34 to 39 Antibacterial composition comprising silver salt or silver complex of group III carboxylic acid and creatinine Preparation of antibacterial composition 0.061 g (0.16 mmol) of disilver phthalate obtained in Preparation Example 3 and 0.146 g (1.3 mmol) of creatinine were dissolved in 100 ml of water. The water solubility of the composition was good. Thus, a composition (Example 34) containing 1.6 mM disilver phthalate and 13 mM creatinine and having a creatinine / silver molar ratio of 4 was obtained.
実施例３４のフタル酸二銀に代えて、グループＩＩＩの表１６のカルボン酸の銀塩又は銀錯体を使用した以外は、実施例３４と同様の手順で実施例３５〜３９を得た。カルボン酸の銀塩又は銀錯体中の銀とクレアチニンとのモル比は、実施例３４と同じく４とした。 Examples 35 to 39 were obtained in the same procedure as in Example 34 except that the silver salt or silver complex of carboxylic acid in Table 16 of Group III was used instead of disilver phthalate in Example 34. The molar ratio of silver and creatinine in the silver salt or silver complex of carboxylic acid was 4 as in Example 34.
２．抗菌性試験
・抗菌性試験（１）
実施例３４の組成物の抗菌性試験を、実施例１６と同様の手順で行った。結果を表１５に示す。
2. Antibacterial test / antibacterial test (1)
An antibacterial test of the composition of Example 34 was performed in the same procedure as in Example 16. The results are shown in Table 15.
表１５から、グループＩＩＩのフタル酸二銀及びクレアチニンからなる本発明の組成物には、硝酸銀と同様、細菌及び真菌に対して優れた抗菌効果があることを確認した。 From Table 15, it was confirmed that the composition of the present invention consisting of Group III disilver phthalate and creatinine has an excellent antibacterial effect against bacteria and fungi, as well as silver nitrate.
・抗菌性試験（２）
グループＩＩＩに属するカルボン酸の銀塩又は銀錯体とクレアチニンとを含む組成物（表１６）の抗菌性を確認するため、クロカワカビ（Ｃｌａｄｏｓｐｏｒｉｕｍ ｃｌａｄｏｓｐｏｒｉｏｉｄｅｓ、ＪＣＭ ３８９９）に対するＭＩＣを測定した。結果を表１６に示す。
・ Antimicrobial test (2)
In order to confirm the antibacterial activity of a composition (Table 16) containing a silver salt or silver complex of a carboxylic acid belonging to Group III and creatinine, the MIC against black mold (Cladosporium cladosporeides, JCM 3899) was measured. The results are shown in Table 16.
表１６から、グループＩＩＩに属するカルボン酸の銀塩又は銀錯体とクレアチニンとからなる組成物には、硝酸銀と同様に、真菌に対して優れた抗菌効果があることを確認できた。 From Table 16, it has confirmed that the composition which consists of the silver salt of a carboxylic acid which belongs to group III, or a silver complex, and creatinine has the antimicrobial effect excellent with respect to fungi like silver nitrate.
３．耐光性試験
グループＩＩＩのカルボン酸の銀塩又は銀錯体及びクレアチニンからなる抗菌性組成物の耐光性試験を実施例１に記載と同様の手順で行った。比較のため、フタル酸二銀、イソフタル酸二銀、テレフタル酸二銀、トリメリット酸三銀、ピロメリット酸四銀、及びルチジン酸二銀単独の耐光性試験も行った。結果を表１７に示す。
3. Light Resistance Test A light resistance test of an antibacterial composition comprising a silver salt or silver complex of a carboxylic acid of Group III and creatinine was performed in the same procedure as described in Example 1. For comparison, light resistance tests were also conducted on disilver phthalate, disilver isophthalate, disilver terephthalate, trisilver trimellitic acid, tetrasilver pyromellitic acid, and disilver lutizinate alone. The results are shown in Table 17.
表１７に示すとおり、フタル酸二銀を単独に用いた組成物は、時間が経過すると、耐光性が悪化した。イソフタル酸二銀、テレフタル酸二銀、ピロメリット酸四銀、あるいはルチジン酸二銀を単独に用いた組成物は、水に溶けにくく、耐光性試験に供し得なかった。また、トリメリット酸三銀を単独に用いた組成物は、水溶性であったものの、溶液状態での耐光性が悪化した。一方、グループＩＩＩのカルボン酸の銀塩又は銀錯体とクレアチニンとを含む本発明の組成物は、溶解性に優れるとともに、溶液及び乾固状態での耐光性に優れた。 As shown in Table 17, the light resistance of the composition using disilver phthalate alone deteriorated over time. A composition using disilver isophthalate, disilver terephthalate, tetrasilver pyromellitic acid, or disilver lutizinate was difficult to dissolve in water and could not be subjected to a light resistance test. Moreover, although the composition using trimellitic acid trisilver alone was water-soluble, the light resistance in a solution state deteriorated. On the other hand, the composition of the present invention containing a silver salt or silver complex of a group III carboxylic acid and creatinine was excellent in solubility and light resistance in a solution and in a dry state.
〔実施例４０〜４６〕グループＩＩＩのカルボン酸の銀塩又は銀錯体とクレアチニンとの配合量
実施例３４において、フタル酸二銀の銀濃度を１．６ｍＭに一定しにしたまま、クレアチニンの濃度を表に示すように変えた以外は実施例３４と同様の手順で抗菌性組成物を調製した。各抗菌性組成物の溶液及び乾固状態での耐光性試験を行った。結果を表１８に示す。
[Examples 40 to 46] Compounding amount of silver salt or silver complex of carboxylic acid of group III and creatinine In Example 34, while maintaining the silver concentration of disilver phthalate constant at 1.6 mM, the concentration of creatinine The antibacterial composition was prepared in the same procedure as in Example 34, except that was changed as shown in the table. Each antibacterial composition solution and a light resistance test in a dry state were performed. The results are shown in Table 18.
表１８から、グループＩＩＩのフタル酸二銀に対するクレアチニン添加量は、銀に対して２〜８０モル当量で変色抑制効果を示し、３〜８０モル当量が適当であり、３〜４モル当量が最適であった。 From Table 18, the amount of creatinine added relative to the disilver phthalate of Group III is 2 to 80 molar equivalents with respect to silver, showing a discoloration suppressing effect, 3 to 80 molar equivalents is appropriate, and 3 to 4 molar equivalents is optimal. Met.
〔実施例４７〜５１〕グループＩＶのカルボン酸の銀塩又は銀錯体とクレアチニンとを含む抗菌性組成物
１．抗菌性組成物の調製
上記調製例１８〜２２で得たカルボン酸の銀塩又は銀錯体とクレアチニンとを、カルボン酸の銀塩又は銀錯体３．２ｍＭ及びクレアチニン１３ｍＭ（クレアチニン／銀のモル比：４）となるように水に溶解させた（表１９）。いずれの組成物ともに、良好な水溶性を示した。
[Examples 47 to 51] 1. Antibacterial composition containing silver salt or silver complex of carboxylic acid of group IV and creatinine Preparation of antibacterial composition The silver salt or silver complex of carboxylic acid obtained in Preparation Examples 18 to 22 and creatinine were mixed with 3.2 mM of silver salt or silver complex of carboxylic acid and 13 mM of creatinine (creatinine / silver molar ratio: It was dissolved in water so as to be 4) (Table 19). All the compositions showed good water solubility.
２．抗菌性試験
グループＩＶに属するカルボン酸の銀塩又は銀錯体とクレアチニンとを含む組成物の抗菌性を確認するため、クロカワカビ（Ｃｌａｄｏｓｐｏｒｉｕｍ ｃｌａｄｏｓｐｏｒｉｏｉｄｅｓ、ＪＣＭ ３８９９）に対するＭＩＣを測定した。結果を表１９に示す。
2. Antibacterial test In order to confirm the antibacterial activity of a composition containing a silver salt or silver complex of a carboxylic acid belonging to group IV and creatinine, the MIC against black mold (Cladosporium cladosporoides, JCM 3899) was measured. The results are shown in Table 19.
表１９から、グループＩＶに属するカルボン酸の銀塩又は銀錯体とクレアチニンとからなる組成物には、硝酸銀と同様に、真菌に対して優れた抗菌効果があることを確認できた。 From Table 19, it has confirmed that the composition which consists of the silver salt or silver complex of carboxylic acid which belongs to group IV, and creatinine has the antimicrobial effect excellent with respect to fungi similarly to silver nitrate.
３．耐光性試験
上記組成物の耐光性試験を、実施例１と同様の手順で行った。また、比較のため、ピルビン酸銀、酢酸銀、酪酸銀、グリコール酸銀、サリチル酸銀単独の耐光性試験も行った。結果を表２０に示す。
3. Light Resistance Test A light resistance test of the above composition was performed in the same procedure as in Example 1. For comparison, light resistance tests of silver pyruvate, silver acetate, silver butyrate, silver glycolate, and silver salicylate were also performed. The results are shown in Table 20.
表２０に示すとおり、ピルビン酸銀、酢酸銀、酪酸銀、グリコール酸銀を単独に用いた組成物は、溶液状態での耐光性に劣った。サリチル酸銀を単独に用いた組成物は、時間が経過すると、乾固状態での耐光性が低下した。一方、グループＩＶのサリチル酸以外のカルボン酸の銀塩又は銀錯体とクレアチニンとを含む本発明の組成物は、溶液状態での耐光性に優れた。また、サリチル酸銀とクレアチニンとを含む本発明の組成物は乾固状態での耐光性に優れた。 As shown in Table 20, the composition using silver pyruvate, silver acetate, silver butyrate, and silver glycolate alone was inferior in light resistance in a solution state. In the composition using silver salicylate alone, the light resistance in the dry state decreased with time. On the other hand, the composition of the present invention containing a silver salt or silver complex of a carboxylic acid other than group IV salicylic acid and creatinine was excellent in light resistance in a solution state. Moreover, the composition of the present invention containing silver salicylate and creatinine was excellent in light resistance in a dry state.
〔実施例５３〕抗菌性組成物を用いた除菌剤
実施例１７において、アセトキシ酢酸銀及びクレアチニンの濃度を５倍とする以外は、実施例１７と同様の手順で組成物を調製し、アセトキシ酢酸銀濃度１６ｍＭ、そしてクレアチニン／銀のモル比４の組成物（実施例５２）を得た。同様に、比較例７においてアセトキシ酢酸銀の濃度を５倍とする以外は、比較例７と同様の手順で組成物を調製し、アセトキシ酢酸銀濃度１６ｍＭでクレアチニンを含まない組成物（比較例３２）を得た。
[Example 53] Disinfectant using antibacterial composition A composition was prepared in the same manner as in Example 17 except that the concentration of silver acetoxyacetate and creatinine in Example 17 was increased to 5 times. A composition having a silver acetate concentration of 16 mM and a creatinine / silver molar ratio of 4 (Example 52) was obtained. Similarly, a composition was prepared in the same procedure as in Comparative Example 7 except that the concentration of silver acetoxyacetate was 5 times in Comparative Example 7, and a composition containing no creatinine at a silver acetoxyacetate concentration of 16 mM (Comparative Example 32). )
除菌・消臭剤として汎用の９９．５％エタノール８０ｍｌに、実施例５２の組成物を２０ｍｌ添加することにより、アセトキシ酢酸銀濃度３．２ｍＭの除菌剤（実施例５３）を調製した。同様に、９９．５％エタノール８０ｍｌに比較例３２の組成物を２０ｍｌ添加することにより、アセトキシ酢酸銀濃度３．２ｍＭの除菌剤（比較例３３）を調製した。 By adding 20 ml of the composition of Example 52 to 80 ml of general-purpose 99.5% ethanol as a disinfectant / deodorant, a disinfectant having a silver acetoxyacetate concentration of 3.2 mM (Example 53) was prepared. Similarly, 20 ml of the composition of Comparative Example 32 was added to 80 ml of 99.5% ethanol to prepare a disinfectant having a silver acetoxyacetate concentration of 3.2 mM (Comparative Example 33).
実施例５３の除菌剤を透明ガラス容器内で密栓した状態で室温に放置し、外観を観察した。７日後、除菌剤に変色や析出物の発生は認められなかった。よって、除菌剤の安定性が確認された。 The disinfectant of Example 53 was left at room temperature in a sealed state in a transparent glass container, and the appearance was observed. After 7 days, no discoloration or precipitation was observed in the disinfectant. Therefore, the stability of the disinfectant was confirmed.
（溶液状態での耐光性試験）
実施例５３及び比較例３３の除菌剤１０ｍｌを、それぞれ、２０ｍｌのガラス製バイアル瓶に入れ、蓋をせずに前記紫外光源下（光源と液面との距離：４ｃｍ）に設置した。１０分後に変色又は析出物の発生が起こるかを、以下の基準で観察した。結果を表２１に示す。
○：変化なし
×：変色又は析出あり
××：著しい変色又は析出あり
(Light resistance test in solution)
10 ml of the disinfectant of Example 53 and Comparative Example 33 were each placed in a 20 ml glass vial and placed under the ultraviolet light source (distance between the light source and the liquid surface: 4 cm) without a lid. Whether or not discoloration or precipitation occurred after 10 minutes was observed according to the following criteria. The results are shown in Table 21.
○: No change ×: Discoloration or precipitation XX: Significant discoloration or precipitation
（乾燥後の安定性試験）
実施例５３及び比較例３３の除菌剤０．０５ｍｌを、それぞれ、スライドグラス上に滴下し、室温で１日間放置して、揮発分を除去した乾燥試験体を得た。この試験体を室温下で更に３日間放置し、変色を以下の基準で観察した。結果を表２１に示す。
○：変色なし
×：変色あり
(Stability test after drying)
0.05 ml of the disinfectant of Example 53 and Comparative Example 33 was dropped on a slide glass and left at room temperature for 1 day to obtain a dry specimen from which volatile components were removed. This test specimen was left for another 3 days at room temperature, and the color change was observed according to the following criteria. The results are shown in Table 21.
○: No discoloration ×: Discoloration
表２１から、本発明の組成物を含有する除菌剤が優れた耐光性を有することが確認された。 From Table 21, it was confirmed that the disinfectant containing the composition of the present invention has excellent light resistance.
（除菌性能試験）
実施例５３の除菌剤を、塗装鋼板上に０．１ｇ／２５ｃｍ２噴霧をした。室温で、噴霧１時間後及び７日後に、塗装鋼板上の生菌数を環境微生物検査用試薬（製品名：ぺたんチェック（登録商標）１０、栄研科学株式会社製）を用いてカウントした。比較として、９９．５％エタノールを実施例５３と同様の操作で評価した（比較例３４）。結果を表２２に示す。
(Sterilization performance test)
The disinfectant of Example 53 was sprayed on a coated steel plate at 0.1 g / 25 cm 2 . After 1 hour and 7 days after spraying at room temperature, the number of viable bacteria on the coated steel plate was counted using an environmental microorganism testing reagent (product name: Petan Check (registered trademark) 10, manufactured by Eiken Science Co., Ltd.). For comparison, 99.5% ethanol was evaluated in the same manner as in Example 53 (Comparative Example 34). The results are shown in Table 22.
表２２から、７日後の生菌数が未噴霧及びエタノールのみ噴霧した条件より少なかった。よって、エタノールのみ（比較例３４）よりも、除菌剤の除菌性能の持続性があることが確認された。 From Table 22, the number of viable bacteria after 7 days was less than the condition of spraying only with unsprayed and ethanol. Therefore, it was confirmed that the disinfection performance of the disinfectant is more sustainable than ethanol alone (Comparative Example 34).
〔実施例５５〕抗菌性組成物を用いた洗浄剤
実施例５２において、銀塩をアセチルグリシン銀とする以外は、実施例５２と同様の手順で組成物を調製し、アセチルグリシン銀濃度１６ｍＭ、そしてクレアチニン／銀のモル比４の組成物（実施例５４）を得た。同様に、比較例３２において銀塩をアセチルグリシン銀とする以外は、比較例３２と同様の手順で組成物を調製し、アセチルグリシン銀濃度１６ｍＭでクレアチニンを含まない組成物（比較例３５）を得た。市販の液体合成洗剤（製品名：トップ ＮＡＮＯＸ（ナノックス）、ライオン株式会社製）８０ｍｌに、実施例５４の組成物を２０ｍｌ添加することにより、銀濃度３．２ｍＭの洗浄剤を調製した（実施例５５）。同様に、前記液体合成洗剤８０ｍｌに比較例３５の組成物２０ｍｌ添加することにより、銀濃度３．２ｍＭの洗浄剤を調製した（比較例３６）。
[Example 55] Detergent using an antibacterial composition In Example 52, a composition was prepared in the same manner as in Example 52 except that the silver salt was acetylglycine silver, and the acetylglycine silver concentration was 16 mM. A composition having a creatinine / silver molar ratio of 4 (Example 54) was obtained. Similarly, a composition was prepared in the same procedure as in Comparative Example 32 except that the silver salt was changed to silver acetylglycine in Comparative Example 32, and a composition containing no creatinine at an acetylglycine silver concentration of 16 mM (Comparative Example 35). Obtained. A detergent having a silver concentration of 3.2 mM was prepared by adding 20 ml of the composition of Example 54 to 80 ml of a commercially available liquid synthetic detergent (product name: Top NANOX (Nanox), manufactured by Lion Corporation) (Example) 55). Similarly, a detergent with a silver concentration of 3.2 mM was prepared by adding 20 ml of the composition of Comparative Example 35 to 80 ml of the liquid synthetic detergent (Comparative Example 36).
実施例５５の洗浄剤を透明ガラス容器で密栓した状態で室温に放置し、外観を観察した。７日後、洗浄剤に変色や析出物の発生は認められなかったことから、洗浄剤の安定性が確認された。 The cleaning agent of Example 55 was left at room temperature in a state where it was sealed with a transparent glass container, and the appearance was observed. Seven days later, since no discoloration or precipitation was observed in the cleaning agent, the stability of the cleaning agent was confirmed.
実施例５５及び比較例３６の洗浄剤について、実施例５３と同様の方法で、耐光性試験と安定性試験を行った。結果を表２３に示す。 For the cleaning agents of Example 55 and Comparative Example 36, the light resistance test and the stability test were performed in the same manner as in Example 53. The results are shown in Table 23.
表２３から、本発明の組成物を含有する洗浄剤は、優れた耐光性を有することが確認された。 From Table 23, it was confirmed that the cleaning agent containing the composition of the present invention has excellent light resistance.
実施例５５の洗浄剤を水で３，０００倍に希釈して洗濯液とした。この洗濯液３００ｍｌを８ｃｍ×８ｃｍの綿布とともに１０００ｍｌ三角フラスコに入れた。フラスコを回転させて攪拌し、５分間の洗濯に続き、２分間の濯ぎを２回行った。取り出した綿布を室温下で自然乾燥した。乾燥後、綿布に着色が認められるかを観察した。洗濯した綿布に、着色は認められなかった。 The cleaning agent of Example 55 was diluted 3,000 times with water to obtain a washing liquid. 300 ml of this washing liquid was put into a 1000 ml Erlenmeyer flask together with an 8 cm × 8 cm cotton cloth. The flask was rotated and stirred, followed by 5 minutes of washing followed by 2 minutes of rinsing twice. The taken-out cotton cloth was naturally dried at room temperature. After drying, the cotton fabric was observed to be colored. No color was observed on the washed cotton fabric.
〔実施例５６〕抗菌性組成物を用いた塗料
市販の合成樹脂塗料（製品名：水性多用途、株式会社アサヒペン製）８０ｍｌに、実施例５４の組成物を２０ｍｌ添加することにより、銀濃度３．２ｍＭの塗料を調製した（実施例５６）。同様に、前記合成樹脂塗料８０ｍｌに比較例３５の組成物２０ｍｌを添加することにより、銀濃度３．２ｍＭの塗料を調製した（比較例３７）。
[Example 56] Paint using antibacterial composition By adding 20 ml of the composition of Example 54 to 80 ml of a commercially available synthetic resin paint (product name: aqueous versatile, manufactured by Asahi Pen Co., Ltd.), a silver concentration of 3 A 2 mM paint was prepared (Example 56). Similarly, a paint having a silver concentration of 3.2 mM was prepared by adding 20 ml of the composition of Comparative Example 35 to 80 ml of the synthetic resin paint (Comparative Example 37).
実施例５６及び比較例３７の塗料を、透明ガラス容器で密栓した状態で室温に５日間放置して、外観を観察した。比較例３７の塗料は褐変したが、実施例５６の塗料では、変色や析出物の発生は認められなかった。 The paints of Example 56 and Comparative Example 37 were allowed to stand at room temperature for 5 days in a state of being sealed with a transparent glass container, and the appearance was observed. Although the paint of Comparative Example 37 was browned, no discoloration or precipitation was observed in the paint of Example 56.
実施例５６の塗料をＭＤＦ（中質繊維板）上に０．０１４ｍｌ／ｃｍ２塗布し、２０℃で２時間放置し、塗料を硬化させた。塗装後の塗膜に、色合いの変化は認められなかった。 The coating material of Example 56 was applied onto MDF (medium fiber board) at 0.014 ml / cm 2 and allowed to stand at 20 ° C. for 2 hours to cure the coating material. No change in hue was observed in the coated film after painting.
〔実施例５７〕抗菌性組成物を用いた接着剤
市販の特殊変性酢酸ビニル・アクリル共重合樹脂エマルジョン系接着剤（製品名：ＶＷ−Ｈ−１３５、株式会社Ｊ−ケミカル製）８０ｍｌに、実施例５４の組成物を２０ｍｌ添加することにより、銀濃度３．２ｍＭの接着剤を調製した（実施例５７）。同様に、上記エマルジョン系接着剤８０ｍｌに比較例３５の組成物を２０ｍｌ添加することにより、銀濃度３．２ｍＭの接着剤を調製した（比較例３８）。
[Example 57] Adhesive using antibacterial composition Conducted on 80 ml of commercially available specially modified vinyl acetate / acrylic copolymer emulsion adhesive (product name: VW-H-135, manufactured by J-Chemical Co., Ltd.) An adhesive with a silver concentration of 3.2 mM was prepared by adding 20 ml of the composition of Example 54 (Example 57). Similarly, an adhesive having a silver concentration of 3.2 mM was prepared by adding 20 ml of the composition of Comparative Example 35 to 80 ml of the emulsion adhesive (Comparative Example 38).
実施例５７の接着剤を透明ガラス容器で密栓した状態で室温に放置し、外観を観察した。７日後、接着剤に変色や析出物の発生は認められなかったことから、安定性が確認された。 The adhesive of Example 57 was allowed to stand at room temperature in a state of being sealed with a transparent glass container, and the appearance was observed. Seven days later, since no discoloration or precipitation was observed in the adhesive, stability was confirmed.
実施例５７及び比較例３８の接着剤について、実施例５３と同様の方法で、耐光性試験と安定性試験を行った。結果を表２４に示す。 The adhesives of Example 57 and Comparative Example 38 were subjected to a light resistance test and a stability test in the same manner as in Example 53. The results are shown in Table 24.
表２４の結果より、本発明の組成物を含有した接着剤は、優れた耐光性を有することを確認した。 From the results of Table 24, it was confirmed that the adhesive containing the composition of the present invention had excellent light resistance.
実施例５７の接着剤にその架橋剤（製品名：Ｋ−１３２Ｄ、株式会社Ｊ−ケミカル製）を３重量％加えて混合し、混合物をＭＤＦに６５ｇ／ｍ２塗布した。その塗面にオレフィンフィルムを２０℃で４ｋｇｆ／ｃｍ２×２０分の圧力条件で接着させた。その後、浸漬剥離試験を実施した。その結果、抗菌性組成物の代わりに水を添加したものと同様の接着力を示した。 3% by weight of the crosslinking agent (product name: K-132D, manufactured by J-Chemical Corporation) was added to the adhesive of Example 57 and mixed, and the mixture was applied to MDF at 65 g / m 2 . The olefin film was adhered to the coated surface at 20 ° C. under a pressure condition of 4 kgf / cm 2 × 20 minutes. Then, the immersion peeling test was implemented. As a result, the same adhesive strength as that obtained by adding water instead of the antibacterial composition was exhibited.
〔実施例５８〕抗菌性組成物を用いた繊維抗菌加工処理剤
実施例５４の組成物を水で２０倍に希釈して抗菌加工処理剤を調製した（実施例５８）。同様に、比較例３５の組成物を水で２０倍に希釈して抗菌加工処理剤を調製した（比較例３９）。実施例５８又は比較例３９の処理剤を入れたビーカーに８ｃｍ×８ｃｍの綿布を浸漬して抗菌加工処理剤を約０．８ｇ付着させ、１０５℃の乾燥機内で乾燥させた。
[Example 58] Fiber antibacterial processing agent using antibacterial composition An antibacterial processing agent was prepared by diluting the composition of Example 54 20 times with water (Example 58). Similarly, the composition of Comparative Example 35 was diluted 20 times with water to prepare an antibacterial processing agent (Comparative Example 39). An 8 cm × 8 cm cotton cloth was dipped in a beaker containing the treatment agent of Example 58 or Comparative Example 39 to attach about 0.8 g of the antibacterial treatment agent, and dried in a dryer at 105 ° C.
上記の抗菌加工処理した綿布を、前記紫外光源の下（光源と試験体との距離：６ｃｍ）に設置した。３０分後の変色を以下の基準で観察した。結果を表２５に示す。
○：変色なし
×：変色あり
The above-described cotton treated with antibacterial treatment was placed under the ultraviolet light source (distance between the light source and the test piece: 6 cm). The color change after 30 minutes was observed according to the following criteria. The results are shown in Table 25.
○: No discoloration ×: Discoloration
表２５から、本発明の組成物を含有する繊維加工処理剤で抗菌加工処理を施した綿布は、優れた耐光性を有することが確認された。 From Table 25, it was confirmed that the cotton fabric which gave the antibacterial processing with the fiber processing agent containing the composition of this invention has the outstanding light resistance.
Claims (13)
で表されるモノカルボン酸であることを特徴とする、請求項２に記載の抗菌性組成物。 The carboxylic acid has the chemical formula (1):
The antibacterial composition according to claim 2, which is a monocarboxylic acid represented by the formula:
で表される、請求項２に記載の抗菌性組成物。 The carboxylic acid has the chemical formula (2):
The antimicrobial composition of Claim 2 represented by these.
で表されるカルボン酸である、請求項４に記載の抗菌性組成物。 The carboxylic acid has the chemical formula (3):
The antimicrobial composition of Claim 4 which is carboxylic acid represented by these.
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