JP5864290B2 - Antibacterial composition and use thereof - Google Patents
Antibacterial composition and use thereof Download PDFInfo
- Publication number
- JP5864290B2 JP5864290B2 JP2012017591A JP2012017591A JP5864290B2 JP 5864290 B2 JP5864290 B2 JP 5864290B2 JP 2012017591 A JP2012017591 A JP 2012017591A JP 2012017591 A JP2012017591 A JP 2012017591A JP 5864290 B2 JP5864290 B2 JP 5864290B2
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- JP
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- Prior art keywords
- group
- silver
- antibacterial
- composition
- antibacterial composition
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Description
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。一方で、銀イオンは石鹸等に含まれるカルボン酸や水道水等に含まれる塩化物イオン（Cl-）と結合し、不溶性の塩を作る。これらの塩は、光に対する感受性も高く、銀イオンが容易に還元され、金属銀が析出する。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. On the other hand, silver ions combine with carboxylic acid contained in soaps and chloride ions (Cl − ) contained in tap water to form insoluble salts. These salts are highly sensitive to light, silver ions are easily reduced, and metallic silver is precipitated. 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.
従来の抗菌剤は、水道水等に含まれる塩素及び塩化物イオンと化合して沈殿物を形成しやすい。したがって、洗浄剤、化粧品等の商品に抗菌剤を添加すると、沈殿物析出によって商品価値が損なわれることがある。 Conventional antibacterial agents are likely to form precipitates by combining with chlorine and chloride ions contained in tap water and the like. Therefore, when an antibacterial agent is added to products such as cleaning agents and cosmetics, the value of the product may be impaired due to precipitation.
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.
銀イオンを抗菌剤として利用する場合、その使用環境中に最も多く存在する物質は塩化物イオンである。しかし、従来技術は、塩化物イオンに対する対策を施していない。 When silver ion is used as an antibacterial agent, the most abundant substance in the environment of use is chloride ion. However, the prior art does not take measures against chloride ions.
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、耐塩素(耐塩化物イオン)性に優れ、紫外線等による変色や着色を抑制する耐光性に優れる抗菌性組成物を提供することを目的とする。 Thus, the present invention provides an antibacterial composition having a wide range of antibacterial and antifungal activities, excellent in chlorine resistance (chloride ion resistance), and excellent in light resistance that suppresses discoloration and coloring due to ultraviolet rays and the like. With the goal.
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し、かつそのｐHを一定範囲に制御することにより、水溶性が良好で、広範な抗細菌抗真菌スペクトルを有し、塩化物イオンに対して安定であり、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（ｘ＝Ｂ／Ａ）が２以上であり、該抗菌性組成物のクレアチニンと銀の合計を１．０重量％に調整した水溶液のｐＨ（ｙ）が、下記の条件式：
前記ｘは、２以上５０，０００以下であることが好ましい。 The x is preferably 2 or more and 50,000 or less.
本発明は、また、前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、前記抗菌性組成物を含有する化粧品を提供する。 The present invention also provides a cosmetic containing the antibacterial composition.
本発明は、また、前記抗菌性組成物を含有する除菌・消臭剤を提供する。 The present invention also provides a disinfectant / deodorant containing the antibacterial composition.
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一定割合で配合し、かつｐＨを銀とクレアチニンとのモル比に応じて一定の範囲に調整した本発明によれば、耐塩素性と紫外線等への耐光性に優れる水溶性の抗菌剤が得られる。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、化粧品や医薬部外品、食品等への使用が期待される。 According to the present invention, one or more compounds of silver oxide, silver salt, or silver complex and creatinine are blended in a certain ratio, and the pH is adjusted to a certain range in accordance with the molar ratio of silver and creatinine. Thus, a water-soluble antibacterial agent excellent in chlorine resistance and light resistance to ultraviolet rays or the like can be obtained. Utilizing this characteristic, the composition of the present invention can be used as a disinfectant, deodorant, cleaning agent, cosmetic, paint, adhesive or pressure-sensitive adhesive, antibacterial fiber treatment agent, cosmetic 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、銀塩又は銀錯体のいずれか１種を必須の成分とする。 Hereinafter, embodiments of the present invention will be described in more detail. The composition of the present invention contains any one of silver oxide, silver salt, and silver complex as 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、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、そして二銀と称する場合は銀イオンが２個結合しているものを意味する。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 perchlorate, silver fluoride, silver chloride, silver chlorate, silver chromate, silver cyanide, silver bromide, bromic acid Silver, silver iodide, silver iodate, etc. are mentioned. In this specification, when a silver salt or a silver complex is referred to as mono-silver, one silver ion is bonded, and when it is referred to as di-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.
上記銀塩又は銀錯体を構成するカルボン酸は、特に化学式（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):
Is a carboxylic acid represented by (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：
銀に配位して銀塩又は銀錯体を形成する上記カルボン酸以外の化合物の例には、アミノ酸及びその誘導体、カルボン酸型のキレート剤、チオールの様な活性化硫黄、アミン類、窒素含有複素環類、グアニジン、スルホン酸、リン酸などの活性部位を持つ化合物が挙げられる。これらの化合物には、水和物も含まれる。 Examples of compounds other than the above carboxylic acids that coordinate to silver to form silver salts or silver complexes include amino acids and derivatives thereof, carboxylic acid type chelating agents, activated sulfur such as thiols, amines, nitrogen containing Examples thereof include compounds having an active site such as heterocycles, guanidine, sulfonic acid, and phosphoric acid. These compounds also include hydrates.
アミノ酸及びその誘導体としては、グリシン、Ｎ−アセチルグリシン、アラニン、アルギニン、アスパラギン、アスパラギン酸、システイン、グルタミン、グルタミン酸、ヒスチジン、イソロイシン、ロイシン、リシン、メチオニン、フェニルアラニン、プロリン、セリン、トレオニン、トリプトファン、チロシン、バリン等が挙げられる。 As amino acids and derivatives thereof, glycine, N-acetylglycine, alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine , Valine and the like.
カルボン酸型のキレート剤としては、エチレンジアミン４酢酸（ＥＤＴＡ）、Ｐｈｏｓｐｈｏｎｏｂｕｔａｎｅ Ｔｒｉｃａｒｂｏｘｙｌｉｃ ａｃｉｄ（ＰＢＴＣ）等が挙げられる。 Examples of the carboxylic acid type chelating agent include ethylenediaminetetraacetic acid (EDTA) and phosphonobutane tricarboxylic acid (PBTC).
チオールのような活性化硫黄を持つ化合物としては、システイン、シスチン、チオフェノール等が挙げられる。 Examples of the compound having activated sulfur such as thiol include cysteine, cystine, thiophenol and the like.
アミン類を活性部位に持つ化合物としては、尿素、エチレン尿素、グアニン、ヒダントイン、５，５’−ジメチルヒダントイン等が挙げられる。 Examples of the compound having an amine as an active site include urea, ethylene urea, guanine, hydantoin, and 5,5′-dimethylhydantoin.
窒素含有複素環としては、イミダゾール、メラミン等が挙げられる。 Examples of the nitrogen-containing heterocycle include imidazole and melamine.
グアニジンを活性部位にもつ化合物としては、グアニジン硫酸塩、クレアチン等が挙げられる。 Examples of the compound having guanidine in the active site include guanidine sulfate and creatine.
スルホン酸、リン酸を活性部位に持つ化合物として、Ｈｙｄｒｏｘｙｅｔｈｙｌｉｄｅｎｅ Ｄｉｐｈｏｓｐｈｏｎｏｃ Ａｃｉｄ（ＨＥＤＰ），Ｅｔｈｙｌｅｎｅｄｉａｍｉｎｅ
Ｔｅｔｒａ（Ｍｅｔｈｙｌｅｎｅ Ｐｈｏｓｐｈｏｎｉｃ Ａｃｉｄ）（ＥＤＴＭＰ）等が挙げられる
Hydroxyethylidene Diphosphonoc Acid (HEDP), Ethylenediamine as compounds having sulfonic acid and phosphoric acid in the active site
Tetra (Methylene Phosphonic Acid) (EDTMP)
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（ｘ＝Ｂ／Ａ）が、２以上であり、好ましくは６以上であり、特に好ましくは１０以上、さらに好ましくは１５以上である。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／又は耐塩素性が確保できない、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。上限は特にないが、好ましくは５００００以下であり、より好ましくは１００００以下であり、さらに好ましくは３０００以下である。モル比が大きいと抗菌性効果を得るためにクレアチニン濃度が高くなり、溶解性に問題が生じる場合がある。 In the composition of the present invention, the molar ratio (x = B / A) of silver (A) to creatinine (B) in any one or more compounds of silver oxide, silver salt, or silver complex is 2 or more. It is preferably 6 or more, particularly preferably 10 or more, and further preferably 15 or more. When the molar ratio is less than 2, there are problems that the antibacterial composition cannot be ensured in dissolved state and / or chlorine resistance, and the antibacterial composition cannot be prepared at a high concentration because the solubility is lowered. Although there is no upper limit in particular, Preferably it is 50000 or less, More preferably, it is 10,000 or less, More preferably, it is 3000 or less. If the molar ratio is large, the concentration of creatinine is increased to obtain an antibacterial effect, which may cause a problem in solubility.
本発明の抗菌性組成物は、銀に対するクレアチニンのモル比（ｘ）に応じて、塩化物イオンに対して組成物が安定に存在するｐＨ（ｙ）の範囲が異なる。本発明では、以下の条件式：
ｐＨが１１．５以上になると、組成物はＯＥＣＤの基準で腐食性物質として分類される。したがって、好ましいｐＨの範囲は、以下の条件式：
ｐＨが１０．０以上になると光に対する安定性が極端に悪くなることがある。したがって、特に好ましいｐＨの範囲は、以下の条件式：
本発明の組成物は、酸化銀、銀塩、又は銀錯体のいずれか１種以上の化合物とクレアチニンとを水性媒体に添加し、必要に応じてｐＨを調整することにより得られる。各成分の添加の順序は、特に制限されず、例えば無機酸、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。 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 and adjusting the pH as necessary. The order of addition of each component is not particularly limited, and for example, an acid such as an inorganic acid or a carboxylic acid and creatinine may be added to an 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.
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。 Examples of the aqueous medium include water, a mixture of water and an organic medium such as alcohol, and preferably water.
ｐＨ調整剤の例には、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム、水酸化バリウム、水酸化マグネシウム、酸化ナトリウム、酸化カリウム、酸化カルシウム、酸化バリウム、酸化マグネシウム等のアルカリ金属又はアルカリ土類金属の水酸化物又は酸化物、アルギニン、リシン等の塩基性アミノ酸；カルボン酸、硫酸、スルホン酸、リン酸等のオキソ酸；並びにリン酸緩衝液等のｐＨ緩衝液が挙げられる。 Examples of pH adjusters include alkali metals or alkaline earths such as sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, magnesium hydroxide, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide Examples thereof include basic amino acids such as metal hydroxides or oxides, arginine and lysine; oxo acids such as carboxylic acid, sulfuric acid, sulfonic acid and phosphoric acid; and pH buffer solutions such as phosphate buffers.
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, Cladosporia 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、化粧品や医薬部外品、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塩素性を発揮する。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 comprises antibacterial agents such as disinfectants, deodorants, detergents, cosmetics, paints, adhesives or adhesives, textile antibacterial processing agents, cosmetics 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 chlorine 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、以下の実施例に限定されるものではない。 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 following examples.
試薬は、酸化銀（東洋化学工業（株）製）、クレアチニン（有機合成薬品工業（株）製）、クレアチン１水和物（小林香料（株）製）、アセトキシ酢酸（ＡＬＤＲＩＣＨ製）、硝酸銀、１Ｍ ＮａＯＨ水溶液、１Ｍ Ｈ２ＳＯ４水溶液、塩化ナトリウム、アルギニン、リシン、フマル酸、Ｎ−アセチルグリシン、５，５’−ジメチルヒダントイン（以上、和光純薬工業（株）製）、ヒスチジン、メチオニン、イミダゾール、システイン（以上、関東化学（株）製）を使用した。 Reagents are silver oxide (manufactured by Toyo Chemical Industry Co., Ltd.), creatinine (manufactured by Organic Synthetic Chemical Industry Co., Ltd.), creatine monohydrate (manufactured by Kobayashi Fragrance Co., Ltd.), acetoxyacetic acid (manufactured by ALDRICH), silver nitrate, 1M NaOH aqueous solution, 1M H 2 SO 4 aqueous solution, sodium chloride, arginine, lysine, fumaric acid, N-acetylglycine, 5,5′-dimethylhydantoin (manufactured by Wako Pure Chemical Industries, Ltd.), histidine, methionine, Imidazole and cysteine (manufactured by Kanto Chemical Co., Inc.) were used.
また、キレート剤として、ＥＤＴＡ（商品名：キレスト−２００）、HEDP（商品名：キレスト−PH２１０）、ＰＢＴＣ（商品名：キレスト−ＰＨ４３０、以上、キレスト（株）製）を使用した。 Further, EDTA (trade name: Kirest-200), HEDP (trade name: Kirest-PH210), PBTC (trade name: Kirest-PH430, above, manufactured by Kirest Co., Ltd.) were used as chelating agents.
ＰＤＣは、例えば特開２００９−０８２０６４号に記載の製造方法に準じて、糖類を出発物質として、大腸菌ＸＬ１−Ｂｌｕｅ株（ＳＴＲＡＴＥＧＥＮＥ， ＣＡ， ＵＳＡ）にＰＤＣの発酵生産プラスミドｐＣＤＦＤｕｅｔ−ｑｕｔＣ及びｐＵＬＡＢＣを導入した形質転換細胞を培養することで得られた物を使用した。 For example, according to the production method described in JP-A-2009-082064, PDC introduces the PDC fermentation production plasmids pCDFDuet-cutC and pULABC into E. coli XL1-Blue strain (STRATEGENE, CA, USA) using saccharides as a starting material. The product obtained by culturing the transformed cells was used.
［調製例１〜３］
純水１５３．２０ｇにクレアチニン４．２４ｇ、及び酸化銀４．３４ｇを加え、４０℃で１時間反応させた。反応物を吸引濾過し、クレアチニン／銀のモル比が１で、銀濃度２．５％（２３．２ｍｍｏｌ／１００ｇ）の組成物を得た（調製例１）。調製例１において配合量を変えた以外は調製例１と同様の操作によって、表１に示すクレアチニン／銀のモル比の組成物を得た。
[Preparation Examples 1 to 3]
To 153.20 g of pure water, 4.24 g of creatinine and 4.34 g of silver oxide were added and reacted at 40 ° C. for 1 hour. The reaction product was subjected to suction filtration to obtain a composition having a creatinine / silver molar ratio of 1 and a silver concentration of 2.5% (23.2 mmol / 100 g) (Preparation Example 1). A composition with a molar ratio of creatinine / silver shown in Table 1 was obtained in the same manner as in Preparation Example 1, except that the blending amount was changed in Preparation Example 1.
［調製例４〜１７］
調製例１の組成物１０．０ｇに対して純水４０．０ｇを加え、銀濃度０．５％（４．６４ｍｍｏｌ／１００ｇ）の組成物を得た（調製例４）。追加のクレアチニンを添加する以外は、調製例４と同様の操作で、表２に示すクレアチニン／銀のモル比の組成物を得た。
[Preparation Examples 4 to 17]
40.0 g of pure water was added to 10.0 g of the composition of Preparation Example 1 to obtain a composition having a silver concentration of 0.5% (4.64 mmol / 100 g) (Preparation Example 4). A composition having a molar ratio of creatinine / silver shown in Table 2 was obtained in the same manner as in Preparation Example 4 except that additional creatinine was added.
［実施例１〜７２］耐塩素性評価試験（Ｉ）
クレアチニン及び酸化銀からなる抗菌性組成物の耐塩素性試験を、以下のように実施した。
[Examples 1 to 72] Chlorine resistance evaluation test (I)
A chlorine resistance test of an antibacterial composition comprising creatinine and silver oxide was carried out as follows.
（抗菌性組成物のｐＨ調整）
調製例４〜１７で得た抗菌性組成物に、１Ｍ ＮａＯＨ水溶液又は１Ｍ Ｈ２ＳＯ４水溶液を表３〜５に示すｐＨになるように添加して、抗菌性組成物を調製した。
(PH adjustment of antibacterial composition)
To the antibacterial compositions obtained in Preparation Examples 4 to 17, 1M NaOH aqueous solution or 1M H 2 SO 4 aqueous solution was added so as to have the pH shown in Tables 3 to 5 to prepare antibacterial compositions.
（耐塩素性試験Ｉ−１）
上記抗菌性組成物のうち、クレアチニン/銀のモル比が１〜２０の組成物については、塩化物イオン濃度５〜１００ｐｐｍに調整した塩化ナトリウム水溶液１０．０ｇに対し、抗菌性組成物０．５ｇを添加し、混合した。この時、塩化ナトリウム／銀のモル比は０．０６〜１．２２となっている。結果を表３に示す。
(Chlorine resistance test I-1)
Among the antibacterial compositions, for the composition having a creatinine / silver molar ratio of 1 to 20, 0.5 g of the antibacterial composition is used for 10.0 g of an aqueous sodium chloride solution adjusted to a chloride ion concentration of 5 to 100 ppm. Was added and mixed. At this time, the molar ratio of sodium chloride / silver is 0.06 to 1.22. The results are shown in Table 3.
（耐塩素性試験Ｉ−２）
上記抗菌性組成物のうち、クレアチニン/銀のモル比が４０〜８０の組成物については、塩化物イオン濃度５．４〜１０８．１ｐｐｍに調整した塩化ナトリウム水溶液３．７ｇに対し、抗菌性組成物０．５ｇを添加し、混合した。この時、塩化ナトリウム／銀のモル比は０．０６〜１．２２となっている。結果を表４に示す。
(Chlorine resistance test I-2)
Among the antibacterial compositions, the composition having a creatinine / silver molar ratio of 40 to 80 is antibacterial composition against 3.7 g of a sodium chloride aqueous solution adjusted to a chloride ion concentration of 5.4 to 108.1 ppm. 0.5 g of product was added and mixed. At this time, the molar ratio of sodium chloride / silver is 0.06 to 1.22. The results are shown in Table 4.
（耐塩素性試験Ｉ−３）
上記抗菌性組成物のうち、クレアチニン/銀のモル比が１，０００の組成物については、銀濃度を０．０２３ｍｍｏｌ／１００ｇに調整した抗菌性組成物２０．０ｇに、１．０重量％塩化ナトリウム水溶液を塩化物イオン濃度が５〜１００ｐｐｍになるように添加し（１６〜３３０μｌ）、混合した。この時、塩化ナトリウム／銀のモル比は０．６〜１２．２となっている。結果を表５に示す。
(Chlorine resistance test I-3)
Among the antibacterial compositions, for the composition having a creatinine / silver molar ratio of 1,000, 20.0 g of the antibacterial composition adjusted to a silver concentration of 0.023 mmol / 100 g was added to 1.0 wt% chloride. An aqueous sodium solution was added so that the chloride ion concentration was 5 to 100 ppm (16 to 330 μl) and mixed. At this time, the molar ratio of sodium chloride / silver is 0.6 to 12.2. The results are shown in Table 5.
（耐塩素性試験Ｉ−４）
上記抗菌性組成物のうち、クレアチニン/銀のモル比が１０，０００の組成物については、銀濃度を０．００４６ｍｍｏｌ／１００ｇに調整した抗菌性組成物２０．０ｇに、１．０重量％塩化ナトリウム水溶液を塩化物イオン濃度が５〜１００ｐｐｍになるように添加し（１６〜３３０μｌ）、混合した。この時、塩化ナトリウム／銀のモル比は３．０〜６０．９となっている。結果を表５に示す。
(Chlorine resistance test I-4)
Among the antibacterial compositions, for the composition having a creatinine / silver molar ratio of 10,000, 20.0 g of the antibacterial composition having a silver concentration adjusted to 0.0046 mmol / 100 g was added to 1.0 wt% chloride. An aqueous sodium solution was added so that the chloride ion concentration was 5 to 100 ppm (16 to 330 μl) and mixed. At this time, the molar ratio of sodium chloride / silver is 3.0 to 60.9. The results are shown in Table 5.
撹拌後、室温で６０分放置した後、析出物の有無を調べ、沈殿物が析出しない塩化物イオン濃度を求めた。評価は、水溶液に市販のレーザーポインター（波長６５０ｎｍ、クラス２）を照射し、以下の基準：
○ チンダル現象無し（沈殿物が析出しない；耐塩素性有り）
× チンダル現象有り（沈殿物が析出した；耐塩素性無し）
で分類した。結果を表３〜５に示す。
After stirring, the mixture was allowed to stand at room temperature for 60 minutes, and then the presence or absence of precipitates was examined to determine the chloride ion concentration at which no precipitate was deposited. Evaluation is performed by irradiating an aqueous solution with a commercially available laser pointer (wavelength 650 nm, class 2), and the following criteria:
○ No Tyndall phenomenon (precipitate does not deposit; has chlorine resistance)
× With Tyndall phenomenon (precipitate deposited; no chlorine resistance)
Classified by. The results are shown in Tables 3-5.
比較として、銀濃度０．５％（４．６４ｍｍｏｌ／１００ｇ）に調整した硝酸銀水溶液（ｐＨ５．２５）を使用した。上記の耐塩素性評価を実施したところ、耐塩素性を示す塩化物イオン濃度は５ｐｐｍ未満という結果であった（比較例１）。ｐＨ調製を試みたところ、水酸化ナトリウム水溶液を添加することで、沈殿物（灰色〜黒色）が析出し、耐塩素性評価を実施できなかった。 For comparison, an aqueous silver nitrate solution (pH 5.25) adjusted to a silver concentration of 0.5% (4.64 mmol / 100 g) was used. When the above chlorine resistance evaluation was carried out, the chloride ion concentration showing chlorine resistance was less than 5 ppm (Comparative Example 1). When pH adjustment was tried, the precipitate (gray-black) precipitated by adding sodium hydroxide aqueous solution, and chlorine resistance evaluation was not able to be implemented.
［ｐＨ測定］
ダブルジャンクションタイプのpH電極（型名：ＥＬＰ−０６２、東亜ディーケーケー（株）製）、ｐＨメーター（型名：ＨＭ−２５Ｒ、東亜ディーケーケー（株）製）を使用し、電極の内部液は３．３Ｍ−ＫＣｌ水溶液、外筒液は３．３Ｍ−ＫＮＯ３水溶液を用いて、該抗菌性組成物のクレアチニンと銀の合計が１．０重量％水溶液になるように調整してｐＨを測定した。
[PH measurement]
A double junction type pH electrode (model name: ELP-062, manufactured by Toa DK Corporation) and a pH meter (model name: HM-25R, manufactured by Toa DK Corporation) were used. The 3M-KCl aqueous solution and the outer cylinder solution were 3.3M-KNO 3 aqueous solution, and the pH was measured by adjusting the antibacterial composition so that the total amount of creatinine and silver was 1.0 wt% aqueous solution.
表３〜５から、抗菌性組成物は、耐塩素性を得る上で、下記の条件式：
［実施例７３〜１０８］耐塩素性評価試験（ＩＩ）
クレアチニン及び銀塩又は銀錯体からなる抗菌性組成物の耐塩素性試験を、以下の手順で実施した。
[Examples 73 to 108] Chlorine resistance evaluation test (II)
A chlorine resistance test of an antibacterial composition comprising creatinine and a silver salt or a silver complex was carried out according to the following procedure.
純水９４０．４９ｇに、クレアチニン１１５．３９ｇ、及びフマル酸１４．８０ｇを溶解させた後、酸化銀２９．５４ｇを加え、３０℃で１時間反応させ、次いで６０℃に昇温して１時間反応させた。反応物を３０℃で吸引濾過して得られた組成物５０ｇに純水２００ｇを加え、ｐＨを表６に示す値に調整することにより、銀濃度０．５％（４．６４ｍｍｏｌ／１００ｇ）、クレアチニン／銀のモル比が４の抗菌性組成物（比較例１６、実施例７３〜７８）を得た。 After dissolving 115.39 g of creatinine and 14.80 g of fumaric acid in 940.49 g of pure water, 29.54 g of silver oxide was added and reacted at 30 ° C. for 1 hour, then heated to 60 ° C. and heated for 1 hour. Reacted. By adding 200 g of pure water to 50 g of the composition obtained by suction filtration of the reaction product at 30 ° C., and adjusting the pH to the value shown in Table 6, a silver concentration of 0.5% (4.64 mmol / 100 g), Antibacterial compositions having a creatinine / silver molar ratio of 4 (Comparative Example 16, Examples 73 to 78) were obtained.
また、調製例３の組成物（クレアチニン／銀のモル比４）に、銀と塩又は錯体を形成する表６に記載の化合物を添加し、さらに、ｐＨを表６に示す値に調整することにより、クレアチニン及び銀塩又は銀錯体からなり、銀濃度０．５％（４．６４ｍｍｏｌ／１００ｇ）の抗菌性組成物を得た（実施例７９、８０、８２〜１０８）。 Further, the compound shown in Table 6 that forms a salt or complex with silver is added to the composition of Preparation Example 3 (creatinine / silver molar ratio 4), and the pH is adjusted to the value shown in Table 6. Thus, an antibacterial composition comprising creatinine and a silver salt or a silver complex and having a silver concentration of 0.5% (4.64 mmol / 100 g) was obtained (Examples 79, 80, 82 to 108).
また、調製例３の組成物（クレアチニン／銀のモル比４）に、クレアチニン及びフマル酸を添加することで、銀濃度０．５％（４．６４ｍｍｏｌ／１００ｇ）、クレアチニン／銀のモル比が２０の抗菌性組成物（実施例８１）を得た。 Further, by adding creatinine and fumaric acid to the composition of Preparation Example 3 (creatinine / silver molar ratio 4), the silver concentration was 0.5% (4.64 mmol / 100 g) and the molar ratio of creatinine / silver was 20 antimicrobial compositions (Example 81) were obtained.
これらの抗菌性組成物について、実施例１と同様の耐塩素性試験を行い、沈殿物が析出しない塩化物イオン濃度を求めた。結果を表６に示す。表６中の組成物のｐＨの※はｐＨ試験紙（型番：ＴＣ ｐＨ１-１１、Ｗｈａｔｍａｎ社製）で測定した数値である。 About these antibacterial compositions, the chlorine resistance test similar to Example 1 was done, and chloride ion concentration which a deposit does not precipitate was calculated | required. The results are shown in Table 6. The pH * of the compositions in Table 6 is a numerical value measured with a pH test paper (model number: TC pH 1-11, manufactured by Whatman).
表６の結果から、酸化銀を各種銀塩又は錯体に変更した場合でも、抗菌性組成物の耐塩素性が得られることが判明した。 From the results of Table 6, it was found that the chlorine resistance of the antibacterial composition can be obtained even when the silver oxide is changed to various silver salts or complexes.
［実施例１０９〜１１１］耐光性評価試験
表７に示す銀濃度０．５％（４．６４ｍｍｏｌ／１００ｇ）の抗菌性組成物１０ｍｌを、１０ｍｌ容量ガラス製バイアル瓶（型番：SV-１０、日電理化硝子（株）製）に入れ、蓋をせずに高エネルギー紫外光源（殺菌ランプＧＬ−１５、殺菌線出力４．９Ｗ、東芝ライテック（株）製）の下に設置した。その際、光源と液面との距離を４ｃｍ（紫外線放射強度２ｍＷ／ｃｍ２）とした。６時間までは１時間毎に、それ以降は１２、２４、３６、４８時間後の各溶液を観察し、変色又は析出物が発生しない時間（耐光時間）を求めた。結果を表７に示す。
[Examples 109 to 111] Light resistance evaluation test 10 ml of an antibacterial composition having a silver concentration of 0.5% (4.64 mmol / 100 g) shown in Table 7 was placed in a 10 ml capacity glass vial (model number: SV-10, Nidec) The product was placed in Rika Glass Co., Ltd. and installed under a high energy ultraviolet light source (sterilization lamp GL-15, sterilization line output 4.9 W, manufactured by Toshiba Lighting & Technology Co., Ltd.) without a lid. At that time, the distance between the light source and the liquid surface was set to 4 cm (ultraviolet radiation intensity 2 mW / cm 2 ). Each solution was observed every hour up to 6 hours and after 12, 24, 36, and 48 hours thereafter, and the time during which no discoloration or precipitation occurred (light resistance time) was determined. The results are shown in Table 7.
表７の結果から、本発明で特定する範囲内では良好な耐光性を維持できることを確認できたが、より好ましくはｐＨが１０．０未満であることがわかった。 From the results of Table 7, it was confirmed that good light resistance could be maintained within the range specified by the present invention, but it was found that the pH is more preferably less than 10.0.
［実施例１１２〜１１８］抗菌試験（Ｉ）
本発明の抗菌性組成物の抗菌性を確認するため、黒皮カビ（Ｃｌａｄｏｓｐｏｒｉｕｍ ｃｌａｄｏｓｐｏｒｉｏｉｄｅｓ、ＪＣＭ ３８９９）に対する最小発育阻止濃度（ＭＩＣ）を測定し、その時の抗菌性組成物の銀濃度を求めた。
[Examples 112 to 118] Antibacterial test (I)
In order to confirm the antibacterial properties of the antibacterial composition of the present invention, the minimum inhibitory concentration (MIC) against black mold (Cladosporium cladosporeoides, JCM 3899) was measured, and the silver concentration of the antibacterial composition at that time was determined.
表８の抗菌性組成物を、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）製）を通して滅菌した。 Each of the antibacterial compositions in Table 8 was sterilized through a membrane filter (product name: Milex HV, manufactured by Nihon Millipore Co., Ltd.) having a pore diameter of 0.45 μm.
上記菌を、ポテトデキストローズ寒天倍地（ベクトン・ディッキンソン社製）で５〜１０日間培養し、寒天平板上の集落を滅菌リン酸緩衝液でＭａｃＦａｒｌａｎｄ Ｎｏ.Ｉ（約１０６CFU／ｍＬ）相当に懸濁して接種用菌液とした。 The bacterium is cultured in potato dextrose agar medium (Becton Dickinson) for 5 to 10 days, and the colonies on the agar plate are equivalent to MacFarland No. I (about 10 6 CFU / mL) with a sterile phosphate buffer. And inoculated into a bacterial solution for inoculation.
約４５℃に保ったポテトデキストローズ寒天培地を用いて、抗菌性組成物の銀濃度を最高１６０ｐｐｍ（１．４８ｍM）とした２倍希釈系列を各２枚ずつ作製し、滅菌シャーレ（アズワン（株）製）に固化したものを抗菌性組成物含有感受性培地とした。対照として、抗菌性組成物の代わりに滅菌精製水を使用したものについて、同様に１枚作製し、不含培地とした。 Using a potato dextrose agar medium maintained at about 45 ° C., two 2-fold dilution series each having a silver concentration of the antibacterial composition at a maximum of 160 ppm (1.48 mM) were prepared. The solidified product was made into a sensitive medium containing an antibacterial composition. As a control, one using sterilized purified water instead of the antibacterial composition was similarly prepared and used as a non-containing medium.
抗菌性組成物含有感受性培地及び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±１℃で３〜５日間、好気培養を行った。培養後、各抗菌性組成物含有感受性培地及び不含培地について菌の発育の有無を判定し、ＭＩＣ（銀濃度）を求めた。結果を表８に示す。表８中のｐＨの※はｐＨ試験紙で測定した数値である。 The bacterial solution for inoculation was smeared on the surface of the agar medium containing the antibacterial composition-containing sensitive medium and the non-containing medium with a platinum loop (n = 2). Aerobic culture was performed at 25 ± 1 ° C. for 3-5 days. After culturing, the presence or absence of bacterial growth was determined for each of the antimicrobial composition-containing sensitive medium and the non-containing medium, and the MIC (silver concentration) was determined. The results are shown in Table 8. The pH * in Table 8 is a numerical value measured with a pH test paper.
表８の結果から、本特許請求範囲内の抗菌性組成物は十分な抗菌性能を持っていることが判明した。 From the results of Table 8, it was found that the antibacterial composition within the scope of the claims has sufficient antibacterial performance.
［実施例１１９］抗菌試験（ＩＩ）
本発明の抗菌性組成物の抗菌性を確認するため、黒皮カビ（Ｃｌａｄｏｓｐｏｒｉｕｍ ｃｌａｄｏｓｐｏｒｉｏｉｄｅｓ、ＪＣＭ ３８９９）に対する最小殺菌濃度（ＭＢＣ）を測定し、その時の抗菌性組成物の銀濃度を求めた。
[Example 119] Antibacterial test (II)
In order to confirm the antibacterial property of the antibacterial composition of the present invention, the minimum bactericidal concentration (MBC) against black skin mold (Cladosporium cladsporoides, JCM 3899) was measured, and the silver concentration of the antibacterial composition at that time was determined.
表９の抗菌性組成物を、それぞれ、孔径０．４５μｍのメンブレンフィルターを通して滅菌した。 Each of the antibacterial compositions in Table 9 was sterilized through a membrane filter having a pore size of 0.45 μm.
上記菌を、ポテトデキストローズ寒天倍地で５〜１０日間培養し、寒天平板上の集落を滅菌リン酸緩衝液でＭａｃＦａｒｌａｎｄ
Ｎｏ.Ｉ（約１０６CFU／ｍＬ）相当に懸濁して接種用菌液とした。
The above bacteria are cultured in potato dextrose agar medium for 5 to 10 days, and the colonies on the agar plate are washed with a sterilized phosphate buffer solution in MacFarland.
It was suspended in No. I (about 10 6 CFU / mL) and used as a bacterial solution for inoculation.
抗菌性組成物の銀濃度を最高０．６ｐｐｍ（０．００６ｍM）とした１０倍希釈系列を作製し、上記接種用菌液と混合させ、２５℃±１℃で２４時間培養した。対照として、抗菌性組成物の代わりに滅菌精製水を使用したものについて、同様の操作を行った。 A 10-fold dilution series in which the silver concentration of the antibacterial composition was 0.6 ppm (0.006 mM) at the maximum was prepared, mixed with the above inoculum, and cultured at 25 ° C. ± 1 ° C. for 24 hours. As a control, the same operation was carried out for those using sterilized purified water instead of the antibacterial composition.
上記の培養液の１０倍希釈系列を作製し、生菌数を測定し、抗菌性組成物中の生菌数が検出限界未満になったときのMBC（銀濃度）を求めた。生菌数の測定については、ポテトデキストローズ寒天培地を用いて、第十五改正日本薬局方 生菌数測定 カンテン平板混釈法に準じた。結果を表９に示す。 A 10-fold dilution series of the above culture solution was prepared, the number of viable bacteria was measured, and MBC (silver concentration) when the number of viable bacteria in the antibacterial composition was below the detection limit was determined. For the measurement of the viable cell count, the potato dextrose agar medium was used, and the 15th revised Japanese Pharmacopoeia viable cell count measurement was performed according to the Kanten plate pour method. The results are shown in Table 9.
表９の結果から、クレアチン／銀のモル比が大きくても、十分な抗菌・殺菌性能を持っていることが判明した。 From the results of Table 9, it was found that even if the molar ratio of creatine / silver was large, it had sufficient antibacterial and bactericidal performance.
［実施例１２０〜１２１］抗菌試験（ＩＩＩ）
クレアチニン及び銀塩又は銀錯体からなる抗菌性組成物の抗菌試験を以下のようにして行った。
[Examples 120 to 121] Antibacterial test (III)
An antibacterial test of an antibacterial composition comprising creatinine and a silver salt or silver complex was performed as follows.
抗菌性組成物（実施例１１４）の、以下の２種の菌種：
黄色ブドウ球菌（Ｓｔａｐｈｙｌｏｃｏｃｃｕｓ ａｕｒｅｕｓ ｓｕｂｓｐ． ａｕｒｅｕｓ， ＡＴＣＣ６５３８Ｐ）、
大腸菌（Ｅｓｃｈｅｒｉｃｈｉａ ｃｏｌｉ， ＡＴＣＣ８７３９）、
に対するＭＩＣ（銀濃度）を求めた。
The following two bacterial species of the antibacterial composition (Example 114):
Staphylococcus aureus subsp. Aureus, ATCC 6538P,
Escherichia coli (ATCC8739),
The MIC (silver concentration) was determined.
試験は、日本化学療法学会によるＭＩＣ寒天平板希釈法に準じて、以下の手順で行った。普通寒天培地（ベクトン・ディッキンソン社製）にて、上記細菌をそれぞれ３５〜３７℃で１８〜２４時間培養した。寒天平板上の被検菌体を白金耳でかきとり、滅菌生理食塩水で約２．０〜４．０×１０６CFU／ｍＬ相当の濁度に懸濁し、接種用菌液とした。 The test was performed according to the following procedure according to the MIC agar plate dilution method by the Japanese Society of Chemotherapy. The bacteria were cultured at 35 to 37 ° C. for 18 to 24 hours in a normal agar medium (Becton Dickinson). The test cells on the agar plate were scraped with a platinum loop and suspended in sterilized physiological saline to a turbidity equivalent to about 2.0 to 4.0 × 10 6 CFU / mL to obtain a bacterial solution for inoculation.
実施例１１４の組成物を、それぞれ、孔径０．４５μｍのメンブレンフィルターを通して滅菌した。 The composition of Example 114 was sterilized through a membrane filter having a pore size of 0.45 μm.
約４５℃に保った普通寒天培地を用いて抗菌性組成物の銀濃度が最高２０ｐｐｍ（０．１９ｍM）とした２倍希釈系列を各２枚ずつ作製し、滅菌シャーレに固化したものを抗菌性組成物含有感受性培地とした。対照として、抗菌性組成物の代わりに滅菌精製水を使用したものについて、同様に各菌種１枚作製し、不含培地とした。 Using a normal agar medium kept at about 45 ° C, two double dilution series each with a silver concentration of the antibacterial composition having a maximum concentration of 20 ppm (0.19 mM) were prepared and solidified in a sterile petri dish. The composition-containing sensitive medium was used. As a control, one type of each fungus was similarly prepared for the one using sterilized purified water instead of the antibacterial composition, and used as a non-containing medium.
抗菌性組成物含有感受性培地及び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（抗菌性組成物含有感受性培地はｎ＝２、不含培地はｎ＝１）、３５〜３７℃で１８〜２４時間、それぞれ好気培養を行った。培養後、各抗菌性組成物含有感受性培地及び不含培地について菌の発育の有無を判定し、ＭＩＣ（銀濃度）を求めた。結果を表１０に示す。 On the surface of the agar medium containing the antibacterial composition-containing sensitive medium and the non-containing medium, the bacterial solution for inoculation was smeared with a platinum loop for about 2 cm (n = 2 for the antimicrobial composition-containing sensitive medium, n for the non-containing medium) = 1) Aerobic culture was performed at 35-37 ° C. for 18-24 hours. After culturing, the presence or absence of bacterial growth was determined for each of the antimicrobial composition-containing sensitive medium and the non-containing medium, and the MIC (silver concentration) was determined. The results are shown in Table 10.
表１０の結果から、本特許請求範囲内の抗菌性組成物は十分な抗菌性能を持っていることが判明した。 From the results in Table 10, it was found that the antibacterial composition within the scope of the claims has sufficient antibacterial performance.
〔実施例１２２〕抗菌性組成物を用いた洗浄剤（Ｉ）
調製例１２の抗菌性組成物２．０ｇを、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）製）８．０ｇに添加することにより、銀濃度０．９３ｍｍｏｌ／１００ｇの洗浄剤を調製した（実施例１２３）。
[Example 122] Cleaning agent (I) using antibacterial composition
By adding 2.0 g of the antibacterial composition of Preparation Example 12 to 8.0 g of a commercially available liquid synthetic detergent (product name: Top NANOX (Nanox), manufactured by Lion Corporation), the silver concentration is 0.93 mmol / 100 g. A cleaning agent was prepared (Example 123).
比較のため、前記液体合成洗剤８．０ｇに銀濃度０．５％（４．６４ｍｍｏｌ／１００ｇ）に調整した硝酸銀水溶液２．０ｇ添加することにより、銀濃度０．９３ｍｍｏｌ／１００ｇの洗浄剤を調製した（比較例１９）。 For comparison, a cleaning agent having a silver concentration of 0.93 mmol / 100 g was prepared by adding 2.0 g of an aqueous silver nitrate solution adjusted to a silver concentration of 0.5% (4.64 mmol / 100 g) to 8.0 g of the liquid synthetic detergent. (Comparative Example 19).
実施例１２２と比較例１９を透明ガラス容器で密栓した状態で室温に放置し、７日後、外観を観察した。結果を表１１に示す。 Example 122 and Comparative Example 19 were allowed to stand at room temperature in a state of being sealed with a transparent glass container, and the appearance was observed after 7 days. The results are shown in Table 11.
実施例１２２と比較例１９を水道水で３，０００倍に薄めたときの外観を観察した。結果を表１１に示す。 Appearance was observed when Example 122 and Comparative Example 19 were diluted 3,000 times with tap water. The results are shown in Table 11.
〔実施例１２３〕抗菌性組成物を用いた洗浄剤（ＩＩ）
調製例１２の抗菌性組成物２．０ｇを、市販の液体合成洗剤（製品名：アタックneo 抗菌EXパワー、花王（株）製）８．０ｇに添加することにより、銀濃度０．９３ｍｍｏｌ／１００ｇの洗浄剤を調製した（実施例１２４）。
[Example 123] Cleaning agent using antibacterial composition (II)
By adding 2.0 g of the antibacterial composition of Preparation Example 12 to 8.0 g of a commercially available liquid synthetic detergent (product name: Attack Neo Antibacterial EX Power, manufactured by Kao Corporation), the silver concentration is 0.93 mmol / 100 g. A cleaning agent was prepared (Example 124).
比較のため、前記液体合成洗剤８．０ｇに銀濃度０．５％（４．６４ｍｍｏｌ／１００ｇ）に調整した硝酸銀水溶液２．０ｇ添加することにより、銀濃度０．９３ｍｍｏｌ／１００ｇの洗浄剤を調製した（比較例２０）。 For comparison, a cleaning agent having a silver concentration of 0.93 mmol / 100 g was prepared by adding 2.0 g of an aqueous silver nitrate solution adjusted to a silver concentration of 0.5% (4.64 mmol / 100 g) to 8.0 g of the liquid synthetic detergent. (Comparative Example 20).
実施例１２３と比較例２０を透明ガラス容器で密栓した状態で室温に放置し、７日後、外観を観察した。結果を表１２に示す。 Example 123 and Comparative Example 20 were allowed to stand at room temperature in a sealed state with a transparent glass container, and the appearance was observed after 7 days. The results are shown in Table 12.
実施例１２３と比較例２０を水道水で３，０００倍に薄めたときの外観を観察した。結果を表１２に示す。 Appearance was observed when Example 123 and Comparative Example 20 were diluted 3,000 times with tap water. The results are shown in Table 12.
表１１〜１２の結果から、本特許請求範囲内の抗菌性組成物を洗浄剤に配合しても、優れた安定性を示すことが判明した。 From the results of Tables 11 to 12, it was found that even when the antibacterial composition within the scope of the present claims was blended with a cleaning agent, excellent stability was exhibited.
〔実施例１２４〕抗菌性組成物を用いた化粧品
９９．５％エタノール７．５ｇ、レオドールＴＷ−Ｏ１２０Ｖ（花王（株）製）０．１ｇ、グリセリン２．０ｇ、１．０％塩化ナトリウム水溶液０．１ｇ、及び純水８５．３ｇを含む化粧水に、抗菌剤として調製例１２の抗菌性組成物５．０ｇを添加して、銀濃度０．２３ｍｍｏｌ／１００ｇの化粧水を調整した（実施例１２４）。
[Example 124] Cosmetic product using antibacterial composition 7.5 g of ethanol 99.5%, Rheodor TW-O120V (manufactured by Kao Corporation) 0.1 g, glycerin 2.0 g, 1.0% aqueous sodium chloride solution 0 To the lotion containing 0.1 g and 85.3 g of pure water, 5.0 g of the antibacterial composition of Preparation Example 12 was added as an antibacterial agent to prepare a lotion having a silver concentration of 0.23 mmol / 100 g (Example) 124).
比較のため、実施例１２４において、抗菌性組成物のｐＨを５．０に変えた以外は同じ操作で化粧水を調製した（比較例２１）。また、実施例１２４において、抗菌性組成物を銀濃度０．５％（４．６４ｍｍｏｌ／１００ｇ）に調整した硝酸銀水溶液とした以外は、同じ操作で銀濃度０．９３ｍｍｏｌ／１００ｇの化粧水を調整した（比較例２２）。 For comparison, a lotion was prepared in the same manner as in Example 124 except that the pH of the antibacterial composition was changed to 5.0 (Comparative Example 21). Further, in Example 124, a lotion having a silver concentration of 0.93 mmol / 100 g was prepared by the same operation except that the antibacterial composition was an aqueous silver nitrate solution adjusted to a silver concentration of 0.5% (4.64 mmol / 100 g). (Comparative Example 22).
実施例１２４、比較例２１、比較例２２の化粧水を透明ガラス容器で密栓した状態で室温に放置し、７日後、外観を観察した。結果を表１３に示す。 The skin lotions of Example 124, Comparative Example 21, and Comparative Example 22 were allowed to stand at room temperature in a state of being sealed with a transparent glass container, and the appearance was observed after 7 days. The results are shown in Table 13.
表１３の結果から、本特許請求範囲内の抗菌性組成物を化粧品に配合しても、優れた安定性を示すことが判明した。 From the results shown in Table 13, it was found that even when an antibacterial composition within the scope of the present patent claims was added to cosmetics, excellent stability was exhibited.
〔実施例１２５〕抗菌性組成物を用いた接着剤
調製例１２の抗菌性組成物１．０ｇを、市販のメラミン樹脂系接着剤（製品名：ML−０４８WP、（株）Ｊ−ケミカル製）１９．０ｇに添加することにより、銀濃度０．２３ｍｍｏｌ／１００ｇの接着剤を調製した（実施例１２５）。
[Example 125] Adhesive using antibacterial composition 1.0 g of the antibacterial composition of Preparation Example 12 was added to a commercially available melamine resin adhesive (product name: ML-048WP, manufactured by J-Chemical Co., Ltd.). By adding to 19.0 g, an adhesive having a silver concentration of 0.23 mmol / 100 g was prepared (Example 125).
比較のため、前記接着剤１９．０ｇに銀濃度０．５％（４．６４ｍｍｏｌ／１００ｇ）に調整した硝酸銀水溶液１．０ｇ添加することにより、銀濃度０．２３ｍｍｏｌ／１００ｇの接着剤を調製した（比較例２３）。 For comparison, an adhesive having a silver concentration of 0.23 mmol / 100 g was prepared by adding 1.0 g of an aqueous silver nitrate solution adjusted to a silver concentration of 0.5% (4.64 mmol / 100 g) to 19.0 g of the adhesive. (Comparative Example 23).
実施例１２５、比較例２３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、４日後、外観を観察した。結果を表１４に示す。 The adhesives of Example 125 and Comparative Example 23 were sealed at a room temperature with a transparent glass container, and the appearance was observed after 4 days. The results are shown in Table 14.
表１４の結果から、本特許請求範囲内の抗菌性組成物を接着剤に配合しても、優れた安定性を示すことが判明した。 From the results shown in Table 14, it was found that even when an antibacterial composition within the scope of the present claims was blended with an adhesive, excellent stability was exhibited.
〔実施例１２６〕抗菌性組成物を用いた除菌・消臭剤
調製例１２の抗菌性組成物１．０ｇを、市販の液体除菌剤（製品名：アルコール除菌 キッチンクリーナー、フマキラー（株）製）９．０ｇに添加することにより、銀濃度０．４６ｍｍｏｌ／１００ｇの除菌剤を調製した（実施例１２６）。
[Example 126] Disinfectant / deodorant using antibacterial composition 1.0 g of the antibacterial composition of Preparation Example 12 was added to a commercially available liquid disinfectant (product name: alcohol disinfectant kitchen cleaner, Fumakilla (stock) )) Disinfection agent having a silver concentration of 0.46 mmol / 100 g was prepared by adding to 9.0 g (Example 126).
比較のため、前記除菌剤９．０ｇに銀濃度０．５％（４．６４ｍｍｏｌ／１００ｇ）に調整した硝酸銀水溶液１．０ｇ添加することにより、銀濃度０．４６ｍｍｏｌ／１００ｇの除菌剤を調製した（比較例２４）。 For comparison, 1.0 g of an aqueous silver nitrate solution adjusted to a silver concentration of 0.5% (4.64 mmol / 100 g) was added to 9.0 g of the sterilizing agent, thereby removing a sterilizing agent having a silver concentration of 0.46 mmol / 100 g. Prepared (Comparative Example 24).
実施例１２６、比較例２４の除菌剤を透明ガラス容器で密栓した状態で室温に放置し、７日後、外観を観察した。結果を表１５に示す。 The sanitizers of Example 126 and Comparative Example 24 were left at room temperature in a state of being sealed with a transparent glass container, and the appearance was observed after 7 days. The results are shown in Table 15.
表１５の結果から、本特許請求範囲内の抗菌性組成物を除菌・消臭剤に配合しても、優れた安定性を示すことが判明した。 From the results shown in Table 15, it was found that even when the antibacterial composition within the scope of the present patent claims was added to the sterilization / deodorant, excellent stability was exhibited.
Claims (5)
にある（ただし、X=４のとき、Y=８．０を除く。）ことを特徴とする、前記抗菌性組成物。 An antibacterial composition comprising one or more compounds of silver oxide, silver salt, or silver complex and creatinine, wherein the molar ratio of silver (A) to creatinine (B) in the compound The pH (y) of the aqueous solution in which (x = B / A) is 2 or more and the total amount of creatinine and silver of the antibacterial composition is adjusted to 1.0% by weight is as follows:
(However, when X = 4, Y = 8.0 is excluded.) The antibacterial composition described above.
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