JP2017036244A - Inorganic antibacterial composition and use thereof - Google Patents
Inorganic antibacterial composition and use thereof Download PDFInfo
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Abstract
Description
本発明は、無機抗菌性組成物、その用途である無機抗菌性組成物を含む、化粧品、衣料品、樹脂材、セラミック材または金属材に関する。 The present invention relates to an inorganic antibacterial composition and a cosmetic, clothing, resin material, ceramic material or metal material containing the inorganic antibacterial composition which is the application thereof.
無機系抗菌剤は有機系抗菌剤と比較して、耐熱性、耐久性に優れ、不揮発性で効果も持続的である点から現在市場が拡大している。しかし無機系抗菌剤の代表として挙げられる銀は、変色、高価といった問題がある。そこで、人体に安全で安価な無機系抗菌剤として挙げられるのが金属酸化物である。中でも酸化亜鉛は暗所でも抗菌効果を発現し、さらに水中で中性を示すという点から様々な応用が期待される。 Inorganic antibacterial agents are currently expanding the market in that they are superior in heat resistance and durability as compared to organic antibacterial agents, and are non-volatile and durable. However, silver, which is representative of inorganic antibacterial agents, has problems such as discoloration and cost. Thus, metal oxides are listed as inorganic antibacterial agents that are safe and inexpensive for the human body. Among them, zinc oxide is expected to have various applications in that it exhibits an antibacterial effect even in the dark and is neutral in water.
特許文献１は酸化亜鉛薄膜からなることを特徴とする抗菌性材料であるとされており、ドナー元素のドーピングも行えるとしている。しかし、スパッタ法によって形成される膜形状であるため利用範囲が限られ、たとえば化粧品への配合や繊維等への固定には不適当である。 Patent Document 1 is said to be an antibacterial material characterized by comprising a zinc oxide thin film, and it can also be doped with a donor element. However, since the film shape is formed by sputtering, the range of use is limited, and it is unsuitable for, for example, blending into cosmetics or fixing to fibers.
特許文献２は、IIIB族金属元素およびIVB族金属元素から選択される金属元素を含有する、導電性の付与された酸化亜鉛微粒子からなる抗菌・防黴剤を記載する。その製造法として、酸化亜鉛粒子に第二成分金属を添加浸透させる方法が提供されている（［００２２］）。しかし本願出願人の知見では、この製造法ではドナー元素が亜鉛と置換固溶することは困難である。また、酸化亜鉛中に第二成分を置換型固溶させるためには、８００℃以上の高温が必要となり、出発酸化亜鉛がナノサイズの粒子であっても、粒成長することで表面積の低下が著しくなる。 Patent Document 2 describes an antibacterial / antifungal agent comprising zinc oxide fine particles imparted with conductivity, containing a metal element selected from a group IIIB metal element and a group IVB metal element. As a manufacturing method thereof, a method of adding and infiltrating a second component metal into zinc oxide particles is provided ([0022]). However, according to the knowledge of the applicant of the present application, in this production method, it is difficult for the donor element to be substituted and dissolved in zinc. In addition, in order to dissolve the second component in substitutional solid solution in zinc oxide, a high temperature of 800 ° C. or higher is required, and even if the starting zinc oxide is nano-sized particles, the surface growth is reduced by grain growth. It becomes remarkable.
特許文献３では、水を反応溶媒として亜鉛イオン、炭酸イオン、および水酸イオンをpH保持環境で反応させて、生成する塩基性炭酸亜鉛を焼成することにより製造される酸化亜鉛を有効成分とする、抗菌防黴剤が記載されている。この製造方法では亜鉛以外の金属を用いていない。また、この製造法における焼成温度は１５０℃〜４５０℃であると提示されている（［００１３］）。この焼成温度では酸化亜鉛の結晶成長も不十分であり、たとえ亜鉛以外の金属を添加して焼成しても、沈殿物中で固溶の促進がされない。 In Patent Document 3, zinc oxide produced by reacting zinc ions, carbonate ions, and hydroxide ions in a pH-maintaining environment with water as a reaction solvent and firing the resulting basic zinc carbonate is used as an active ingredient. Antibacterial and antifungal agents are described. This manufacturing method uses no metal other than zinc. Moreover, it is proposed that the firing temperature in this production method is 150 ° C. to 450 ° C. ([0013]). At this firing temperature, the crystal growth of zinc oxide is insufficient, and even if a metal other than zinc is added and fired, solid solution is not promoted in the precipitate.
本発明では、耐熱性・耐久性・安全性に優れる特徴を有し、暗所でも効果を発現する安価な無機系抗菌剤として、上記の問題を解決し抗菌効果を格段に向上させた酸化亜鉛粉末、およびその製造法を提供する。 In the present invention, as an inexpensive inorganic antibacterial agent having characteristics excellent in heat resistance, durability and safety and exhibiting an effect even in a dark place, zinc oxide which has solved the above-mentioned problems and has greatly improved the antibacterial effect Powders and methods for their production are provided.
すなわち本発明は、以下を提供する。
（１）モル比でＺｎ/Ａｌ=１超〜１００００、またはモル比でＺｎ/Ｇａ=１超〜１００００である、アルミニウム塩水溶液またはガリウム塩水溶液と、亜鉛塩水溶液、炭酸塩水溶液、およびアルカリ水溶液の沈殿物生成反応で生成される炭酸水和物を７００℃以上の温度で熱処理して得られる無機抗菌性組成物。
（２）前記沈殿物生成反応で得られる沈殿物が、塩基性炭酸亜鉛並びに、亜鉛、アルミニウムおよび・またはガリウムの沈殿物を含む（１）に記載の無機抗菌性組成物。
（３）前記炭酸水和物が下式（１）で表されるハイドロジンカイトまたはその水和物を含有する（１）または（２）に記載の無機抗菌性組成物。
Ｍ４〜６（ＣＯ３）１〜３（ＯＨ）６〜７ （１）
Ｍ：亜鉛元素、アルミニウム、およびガリウムからなる群から選択される少なくとも一つの金属を示す。
（４）上記（１）ないし（３）のいずれかに記載の無機抗菌性組成物および化粧料用担体を含む化粧品。
（５）上記（１）ないし（３）のいずれかに記載の無機抗菌性組成物を繊維に固定する抗菌性繊維または前記抗菌性繊維を用いた抗菌性衣料品。
（６）上記（１）ないし（３）のいずれかに記載の無機抗菌性組成物を含む、または前記無機抗菌性組成物を含むコーティングを有する、樹脂材、セラミック材、または金属材。
（７）上記（１）ないし（３）のいずれか１項に記載の無機抗菌性組成物を含む医薬品、または前記無機抗菌性組成物を含む、または前記無機抗菌性組成物を含むコーティングを有する医療用物品。
That is, the present invention provides the following.
(1) Aluminum salt aqueous solution or gallium salt aqueous solution, zinc salt aqueous solution, carbonate aqueous solution, and alkaline aqueous solution having a molar ratio of Zn / Al = 1 to 10000 or molar ratio of Zn / Ga = 1 to 10000 An inorganic antibacterial composition obtained by heat-treating a carbonic acid hydrate produced by the precipitate formation reaction at a temperature of 700 ° C. or higher.
(2) The inorganic antibacterial composition according to (1), wherein the precipitate obtained by the precipitate generation reaction includes basic zinc carbonate and a precipitate of zinc, aluminum and / or gallium.
(3) The inorganic antibacterial composition according to (1) or (2), wherein the carbonic acid hydrate contains a hydrozincite represented by the following formula (1) or a hydrate thereof.
M 4-6 (CO 3 ) 1-3 (OH) 6-7 (1)
M: At least one metal selected from the group consisting of elemental zinc, aluminum, and gallium.
(4) A cosmetic comprising the inorganic antibacterial composition according to any one of (1) to (3) and a cosmetic carrier.
(5) Antibacterial fiber for fixing the inorganic antibacterial composition according to any one of (1) to (3) to a fiber or an antibacterial clothing using the antibacterial fiber.
(6) A resin material, a ceramic material, or a metal material containing the inorganic antibacterial composition according to any one of (1) to (3) or having a coating containing the inorganic antibacterial composition.
(7) A pharmaceutical comprising the inorganic antibacterial composition according to any one of the above (1) to (3), or a coating containing the inorganic antibacterial composition or containing the inorganic antibacterial composition Medical article.
本発明の無機抗菌性組成物は、塩基性炭酸亜鉛から脱水、脱炭酸することで得られる従来の酸化亜鉛に比べ、大腸菌などの菌類の増殖を防止し、かつ死滅能力に優れた抗菌剤である。 The inorganic antibacterial composition of the present invention is an antibacterial agent that prevents the growth of fungi such as Escherichia coli and is superior in killing ability compared to conventional zinc oxide obtained by dehydration and decarboxylation from basic zinc carbonate. is there.
１．本発明の無機抗菌性組成物
本発明は、モル比でＺｎ/Ａｌ=１超〜１００００、またはモル比でＺｎ/Ｇａ=１超〜１００００である、アルミニウム塩水溶液またはガリウム塩水溶液と、亜鉛塩水溶液、炭酸塩水溶液、およびアルカリ水溶液の沈殿物生成反応で生成される炭酸水和物を７００℃以上の温度で熱処理して得られる無機抗菌性組成物（以下、本発明の組成物ということがある）である。
以下で説明するように、本発明の組成物は、亜鉛酸化物にアルミニウムまたはガリウムがドープされた組成物である。その特徴は焼成前の前駆体の形態に特徴があり、その製造条件は、亜鉛塩水溶液、炭酸塩水溶液、アルミニウムまたはガリウム塩水溶液、およびアルカリ剤を混合し、水溶液のｐＨを一定に保持して攪拌して沈殿物を生成する反応時に一定に保持される異なるｐＨ値によって結晶性の異なる前駆体が生成され、異なる前駆体を焼成するとそれぞれ異なる亜鉛酸化物が得られる。
1. Inorganic antibacterial composition of the present invention The present invention relates to an aluminum salt aqueous solution or gallium salt aqueous solution having a molar ratio of Zn / Al = 1 to 10000, or a molar ratio of Zn / Ga = 1 to 10000, and a zinc salt. An inorganic antibacterial composition (hereinafter referred to as the composition of the present invention) obtained by heat-treating a carbonate hydrate produced by a precipitate formation reaction of an aqueous solution, an aqueous carbonate solution, and an alkaline aqueous solution at a temperature of 700 ° C. or higher. Yes).
As will be described below, the composition of the present invention is a composition in which zinc oxide is doped with aluminum or gallium. Its characteristics are characterized by the form of the precursor before calcination, and the production conditions are as follows: a zinc salt aqueous solution, a carbonate aqueous solution, an aluminum or gallium salt aqueous solution, and an alkali agent are mixed, and the pH of the aqueous solution is kept constant. Precursors with different crystallinity are produced by different pH values that are kept constant during the reaction to produce precipitates by stirring, and different precursors are obtained by calcining different precursors.
沈殿物の形態を決定する具体的な製造条件は、パラメーターを以下のＩ、IIとすると、
Ｉ組成
１． モル比で、Ｚｎ/Ａｌ=５以上、Ｚｎ/Ｇａ=１０以上
２． モル比で、Ｚｎ/Ａｌ=１超〜５未満、Ｚｎ/Ｇａ=１超〜１０未満
II沈殿反応時のｐＨ
ａ． 低ｐＨ、ｐＨ７．５未満、
ｂ． 好適ｐＨ、ｐＨ７．５〜９．５、
ｃ． 高ｐＨ、ｐＨ９．５超、
で表すことができる。
１）沈殿反応時のｐＨがａで組成が１の場合：ａ−１または、
沈殿反応時のｐＨがａで組成が２の場合：ａ−２
この条件では、炭酸水和物としては結晶性の低い混合物である。
２）沈殿反応時のｐＨがｂで組成が１の場合：ｂ−１
この条件では、前駆体がハイドロジンカイト単相（９０質量％以上）であり、
Ｍ４〜６（ＣＯ３）１〜３（ＯＨ）６〜７ （１）で示され、Ｍが亜鉛元素およびアルミニウム元素、または亜鉛元素およびガリウム元素である。ここで、Ｍ：亜鉛元素、アルミニウム、およびガリウムからなる群から選択される少なくとも一つの金属を示す。モル比でＺｎ/Ａｌ=５以上であり、またはモル比でＺｎ/Ｇａ=１０以上である、モル比の上限は大きくなるほど前駆体がドープ金属の少ない炭酸亜鉛主体のハイドロジンカイトが得られドープ金属の効果が見られなくなる。ドープ金属を前駆体中のハイドロジンカイト相に入れることはドープ金属量が少なくなると製造が困難（確実なドーピングが困難となり、抗菌能にバラツキが生じる）になるので、Ｚｎ/Ａｌ、またはＺｎ/Ｇａのモル比の上限は１００００以下が好ましく、より好ましくは１０００以下である。
３）沈殿反応時のｐＨがｂで組成が２の場合：ｂ−２
この条件では、亜鉛アルミ炭酸水酸化物、および亜鉛ガリウム炭酸水酸化物の異相が存在し、焼成によってスピネル相であるＺｎＡｌ２Ｏ４、ＺｎＧａ２Ｏ４、およびＡｌ２Ｏ３、Ｇａ２Ｏ３などの存在も認められた。このことから、これら異相が粒界に析出することで、導電性が劣化し、抗菌能の低下も認められた。
４）沈殿反応時のｐＨがｃで組成が１の場合：ｃ−１または、
沈殿反応時のｐＨがｃで組成が２の場合：ｃ−２
この条件では、前駆体に水酸化物、酸化物の異相が認められた。
The specific production conditions for determining the form of the precipitate are as follows:
I composition In molar ratio, Zn / Al = 5 or more, Zn / Ga = 10 or more. In molar ratio, Zn / Al = 1 to less than 5, Zn / Ga = 1 to more than 1 to less than 10
II pH during precipitation reaction
a. Low pH, less than 7.5,
b. Preferred pH, pH 7.5-9.5,
c. High pH, above pH 9.5,
Can be expressed as
1) When the pH during precipitation reaction is a and the composition is 1: a-1 or
When the pH during the precipitation reaction is a and the composition is 2: a-2
Under these conditions, the carbonate hydrate is a mixture having low crystallinity.
2) When pH during precipitation reaction is b and composition is 1: b-1
Under these conditions, the precursor is a hydrozincite single phase (90% by mass or more),
M 4-6 (CO 3 ) 1-3 (OH) 6-7 (1), where M is a zinc element and an aluminum element, or a zinc element and a gallium element. Here, M represents at least one metal selected from the group consisting of zinc element, aluminum, and gallium. The molar ratio of Zn / Al = 5 or more, or the molar ratio of Zn / Ga = 10 or more. As the upper limit of the molar ratio is increased, a zinc carbonate-based hydrozincite containing less precursor metal is obtained. The effect of will not be seen. Incorporation of the doped metal into the hydrozincite phase in the precursor is difficult to manufacture if the amount of the doped metal is small (reliable doping becomes difficult and the antibacterial activity varies), so Zn / Al or Zn / Ga The upper limit of the molar ratio is preferably 10,000 or less, more preferably 1000 or less.
3) When the pH during the precipitation reaction is b and the composition is 2: b-2
Under this condition, there are different phases of zinc aluminum carbonate hydroxide and zinc gallium carbonate hydroxide, and ZnAl 2 O 4 , ZnGa 2 O 4 , Al 2 O 3 , and Ga 2 O 3 which are spinel phases by firing. The existence of such was also recognized. From these facts, these heterogeneous phases were precipitated at the grain boundaries, whereby the conductivity was deteriorated and the antibacterial ability was also lowered.
4) When the pH during the precipitation reaction is c and the composition is 1: c-1 or
When the pH during the precipitation reaction is c and the composition is 2: c-2
Under these conditions, hydroxides and oxide heterogeneous phases were observed in the precursor.
酸化亜鉛の抗菌メカニズムには諸説あり、亜鉛イオンが細胞膜を破壊する機構、酸化亜鉛表面から発生する過酸化水素が細菌のDNAまたは酵素等を損傷して死滅させる機構等が考えられている。本発明者はこのうち、過酸化水素発生による抗菌性発現の効果が大きいと考え、本発明に至った。この過酸化水素は、酸化亜鉛が持つキャリアが粒子表面で酸素や水と接触することにより発生する。よって、組成物中の電子の数であるキャリア濃度の増加、キャリア移動度の向上を促すことで過酸化水素発生量が高まり、抗菌活性が向上すると考えることができる。 There are various theories on the antibacterial mechanism of zinc oxide, and the mechanism by which zinc ions destroy cell membranes, the mechanism by which hydrogen peroxide generated from the surface of zinc oxide damages and kills bacterial DNA or enzymes, etc. are considered. Of these, the present inventor considered that the effect of the antibacterial expression due to the generation of hydrogen peroxide was great, and led to the present invention. This hydrogen peroxide is generated when the carrier of zinc oxide comes into contact with oxygen or water on the particle surface. Therefore, it can be considered that by increasing the carrier concentration, which is the number of electrons in the composition, and improving the carrier mobility, the amount of hydrogen peroxide generated is increased and the antibacterial activity is improved.
このキャリア濃度の増加、移動度の向上を実現するため、酸化亜鉛へのＡｌ、Ｇａの分子レベルでのドーピング、および固溶の促進、結晶性の向上がなされるような製造法の発明にいたった。 In order to realize this increase in carrier concentration and improvement in mobility, the invention of a manufacturing method in which zinc oxide is doped with Al and Ga at the molecular level, solid solution is promoted, and crystallinity is improved. It was.
２．本発明の無機抗菌性組成物の製造方法
（沈殿物の製造）
本発明の無機抗菌性組成物は、アルミニウムおよび・またはガリウムの存在下で、亜鉛塩水溶液、炭酸塩水溶液、およびアルカリ水溶液の沈殿物生成反応で生成される前駆体の炭酸水和物を焼成して得られる。前駆体の炭酸水和物は、亜鉛塩水溶液、炭酸塩水溶液、およびアルカリ水溶液の沈殿物生成反応によって得られる反応物、および未反応物としての原料、副生物および原料から混入する不純物の混合物である。
好ましくは、アルミニウムおよび・またはガリウムの金属塩水溶液と亜鉛塩水溶液とを、ＺｎとＡｌの割合が、モル比でＺｎ/Ａｌ=１超〜１００００、またはＺｎとＧａの割合がモル比でＺｎ/Ｇａ=１超〜１００００の範囲で混合する。ただし未反応物を予想してＡｌまたはＧａを過剰量用いることができる。混合する際に、鉱化材またはｐＨ調製剤としての炭酸ナトリウム、炭酸水素ナトリウム、水酸化ナトリウム水溶液を用い、炭酸水素ナトリウム水溶液のｐＨを６．５〜１０．５、好ましくは７．５〜９．５の範囲で一定値に保ち攪拌する状態で、金属塩水溶液と炭酸塩水溶液の混合液に、水酸化ナトリウム水溶液を滴下し、アルカリ沈殿法によって生成される沈殿物を得る。
沈殿物は、炭酸水和物を含む沈殿物であり、好ましくは塩基性炭酸亜鉛並びに、亜鉛、アルミニウムおよび・またはガリウムの沈殿物を含む。より好ましくは焼成工程のための前駆体としてハイドロジンカイトを主成分として有する沈殿物を得るのが好ましい。
金属塩水溶液を滴下後、１０〜３０時間攪拌後、吸引濾過による固液分離、真空乾燥するのが好ましい。原料の炭酸源、亜鉛源、および鉱化材は後述するものに限定されるものではない。炭酸源には（ＮＨ４）ＣＯ３、Ｎａ２ＣＯ３、好ましくは、ＮａＨ（ＣＯ３）水溶液が挙げられ、亜鉛源は硫酸亜鉛、塩化亜鉛、酢酸亜鉛、硝酸亜鉛の中から選択され、鉱化材としてＮＨ３、またはＮａＯＨの使用が挙げられる。Ａｌ源，Ｇａ源は、硫酸塩、塩化塩、酢酸塩、硝酸塩から選択される。
焼成工程の前駆体としてのより好ましい沈殿物は、下式（１）で表されるハイドロジンカイトまたはその水和物を含有する。
Ｍ４〜６（ＣＯ３）１〜３（ＯＨ）６〜７ （１）
Ｍ：亜鉛元素、アルミニウム、およびガリウムからなる群から選択される少なくとも一つの金属を示す。
ハイドロジンカイトの存在は沈殿物をＸ線分析し、ＸＲＤ（Ｘ−線回折法）のピークによって確認できる。
（焼成処理）
上記のアルカリ沈殿法で得られた沈殿物（前駆体）を、７００℃以上、好ましくは１０００℃超から１３００℃以下の温度、さらに好ましくは１１００℃〜１２５０℃の温度で大気中などの酸化性雰囲気で熱処理して、ＺｎとＡｌの割合が、モル比でＺｎ/Ａｌ=１超〜１００００、またはＺｎとＧａの割合がモル比でＺｎ/Ｇａ=１超〜１００００である無機抗菌性組成物を得る。
焼成処理は、前駆体をペレットに成型して行ってもよく、ペレットを作成することなく、粉体のまま焼成してもよい。
2. Production method of inorganic antibacterial composition of the present invention (production of precipitate)
The inorganic antibacterial composition of the present invention is obtained by calcining a precursor carbonate hydrate produced by a precipitation reaction of an aqueous zinc salt solution, an aqueous carbonate solution, and an aqueous alkaline solution in the presence of aluminum and / or gallium. Obtained. Precursor carbonate hydrate is a mixture of reactants obtained by the precipitation reaction of aqueous zinc salt solution, aqueous carbonate solution, and aqueous alkaline solution, and impurities mixed from raw materials, by-products and raw materials as unreacted materials. is there.
Preferably, the metal salt aqueous solution and the zinc salt aqueous solution of aluminum and / or gallium are used in a Zn / Al ratio of Zn / Al = 1 to 10,000 in terms of a molar ratio, or a Zn / Ga ratio in terms of a Zn / Al ratio of Zn / Al. Mix in the range of more than Ga = 1 to 10,000. However, an excess amount of Al or Ga can be used in anticipation of unreacted substances. When mixing, sodium carbonate, sodium bicarbonate, or sodium hydroxide aqueous solution as mineralizer or pH adjuster is used, and the pH of the sodium bicarbonate aqueous solution is 6.5 to 10.5, preferably 7.5 to 9 A sodium hydroxide aqueous solution is dropped into a mixed solution of an aqueous metal salt solution and an aqueous carbonate solution while stirring at a constant value in the range of 0.5 to obtain a precipitate produced by an alkaline precipitation method.
The precipitate is a precipitate containing carbonate hydrate, and preferably includes a basic zinc carbonate and a precipitate of zinc, aluminum and / or gallium. More preferably, a precipitate having hydrozincite as a main component as a precursor for the firing step is preferably obtained.
After dropwise addition of the aqueous metal salt solution, the mixture is preferably stirred for 10 to 30 hours, followed by solid-liquid separation by suction filtration and vacuum drying. The raw material carbonic acid source, zinc source, and mineralizer are not limited to those described below. The carbonate source includes (NH 4 ) CO 3 , Na 2 CO 3 , preferably an aqueous NaH (CO 3 ) solution, wherein the zinc source is selected from zinc sulfate, zinc chloride, zinc acetate, zinc nitrate, Use of NH 3 or NaOH as the chemical material is mentioned. The Al source and the Ga source are selected from sulfate, chloride, acetate, and nitrate.
A more preferred precipitate as a precursor of the firing step contains a hydrozincite represented by the following formula (1) or a hydrate thereof.
M 4-6 (CO 3 ) 1-3 (OH) 6-7 (1)
M: At least one metal selected from the group consisting of elemental zinc, aluminum, and gallium.
Presence of hydrozincite can be confirmed by X-ray analysis of the precipitate and a peak of XRD (X-ray diffraction method).
(Baking process)
Oxidizing the precipitate (precursor) obtained by the above alkaline precipitation method at a temperature of 700 ° C. or higher, preferably more than 1000 ° C. to 1300 ° C., more preferably 1100 ° C. to 1250 ° C. An inorganic antibacterial composition having a Zn / Al ratio of Zn / Al = 1 to 10,000 or a Zn / Ga ratio of Zn / Ga = 1 to 10,000 in a molar ratio after heat treatment in an atmosphere. Get.
The baking treatment may be performed by molding the precursor into pellets, or may be performed as it is without forming pellets.
３．本発明の無機抗菌性組成物の用途
本発明の組成物の用途は限定されない。具体的に例示すれば以下が例示できる。
（１）本発明の無機抗菌性組成物は、創傷治療剤と共に用いることで、抗菌性のある安全性、保存性の高い医薬品とすることができる。また創傷被覆材中に混合または表面に塗布して有用な医療品として用いることができる。
（２）本発明の無機抗菌性組成物は、化粧料用担体と共に用いることで、抗菌性のある安全性、保存性の高い化粧品とすることができる。
化粧料用担体品を例示すれば、清浄用化粧品、頭髪化粧品、基礎化粧品、メークアップ化粧品、芳香化粧品、日焼け化粧品、日焼け止め化粧品、爪化粧品、アイライナー化粧品、口唇化粧品、口腔化粧品、入浴用化粧品を例示することができる。特にＵＶＡカット化粧料においては、酸化亜鉛の紫外線吸収が期待できるなど、より好適な利用方法である。
3. Use of the inorganic antibacterial composition of the present invention The use of the composition of the present invention is not limited. Specific examples include the following.
(1) By using the inorganic antibacterial composition of the present invention together with a wound treatment agent, it can be made into a pharmaceutical product having antibacterial safety and high storage stability. It can also be used as a useful medical product by mixing in a wound dressing or applying to a surface.
(2) The inorganic antibacterial composition of the present invention can be used together with a cosmetic carrier to make a cosmetic product having antibacterial safety and high storage stability.
Examples of cosmetic carrier products include cleaning cosmetics, hair cosmetics, basic cosmetics, makeup cosmetics, aromatic cosmetics, tanning cosmetics, sunscreen cosmetics, nail cosmetics, eyeliner cosmetics, lip cosmetics, oral cosmetics, bath cosmetics Can be illustrated. Particularly in UVA cut cosmetics, it is a more preferred method of use because it can be expected to absorb ultraviolet rays of zinc oxide.
具体的には、クレンジング、石鹸、液体ボディー洗浄、洗髪用化粧品類、シャンプー、リンス、ヘアーローション、ヘアーエッセンス、ヘアークリーム、ヘアートリートメント、ヘアーカラーリング剤、毛髪仕上げ用化粧品、育毛剤、化粧水、美容液類、化粧クリーム、乳液、パック、ジェル、マスク、エッセンス、ボディーローション、ボディークリーム、ひげ剃り用化粧料、ハンドケア剤、ファンデーション、チークメイクアップ、香水、コロン、日焼け止めクリーム、サンケア製品、マニキュア、美爪剤、アイメイクアップベース、アイメイクアップ、リップメイクアップ、口紅、歯磨き剤、洗口剤、浴用剤、さらに点眼液、座薬等に本発明の無機抗菌性組成物を含有させることができる。 Specifically, cleansing, soap, liquid body washing, cosmetics for hair washing, shampoo, rinsing, hair lotion, hair essence, hair cream, hair treatment, hair coloring agent, cosmetics for hair finishing, hair restorer, lotion, Beauty lotion, cosmetic cream, milky lotion, pack, gel, mask, essence, body lotion, body cream, shaving cosmetics, hand care agent, foundation, teak makeup, perfume, cologne, sun cream, sun care product, nail polish , Nail polish, eye makeup base, eye makeup, lip makeup, lipstick, toothpaste, mouthwash, bath preparation, eye drops, suppositories, and the like may contain the inorganic antibacterial composition of the present invention. it can.
（３）本発明の無機抗菌性組成物は、繊維に固定して抗菌性繊維、または前記抗菌性繊維を用いた抗菌性衣料品に用いれば有用性が高い。
繊維としては、天然繊維、合成繊維、ガラス繊維や金属繊維等の無機繊維を使用することができ、中でも溶融紡糸が可能な熱可塑性樹脂の合成繊維が好ましく使用される。合成繊維を形成する熱可塑性樹脂の例としては、ポリエステル、ポリアミド、ポリオレフィン、アクリル、ビニロン、ポリスチレン、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリ乳酸、シルク、セルロース等を挙げることができ、用途等に応じて選択して使用することができる。また、複数種を組み合わせて使用してもよい。具体的には、たとえば、無機抗菌性組成物とバインダー樹脂との分散液を、繊維に含浸して乾燥させる方法が例示できる。
(3) The inorganic antibacterial composition of the present invention is highly useful when it is fixed to fibers and used for antibacterial fibers or antibacterial clothing using the antibacterial fibers.
As the fibers, natural fibers, synthetic fibers, inorganic fibers such as glass fibers and metal fibers can be used, and among them, thermoplastic resin synthetic fibers capable of melt spinning are preferably used. Examples of thermoplastic resins that form synthetic fibers include polyester, polyamide, polyolefin, acrylic, vinylon, polystyrene, polyvinyl chloride, polyvinylidene chloride, polylactic acid, silk, cellulose, etc. Can be selected and used. Moreover, you may use combining multiple types. Specifically, for example, a method of impregnating a fiber with a dispersion of an inorganic antibacterial composition and a binder resin and drying it can be exemplified.
バインダー樹脂としては、ホットメルトパウダー、ラテックス、および水分散型エマルジョンよりなる群から選ばれる１種または２種以上の成分を含んでいても良く、市販の材料の中から適当なものを使用する事ができる。その具体例として、ホットメルトパウダーとしては、ポリエチレン、エチレン酢酸ビニル共重合樹脂（ＥＶＡ）、ポリエステル、ポリアミド等が挙げられる。ラテックスとしては、ＳＢＲ，ＮＢＲ，ポリウレタン等のゴム系ラテックス、ポリアクリレート、ポリ酢酸ビニル、エチレン酢酸ビニル共重合樹脂（ＥＶＡ）等の樹脂系ラテックス等が挙げられる。また水分散型エマルジョンとしては、アクリル系、アクリルスチレン系、アクリルシリコン系、ポリウレタン系、ポリエステル系、ポリアミド系等を挙げることができる。これらのバインダー樹脂の中で無機抗菌性組成物を水分散体として繊維基材に含浸塗布させるためには、水分散型エマルジョンが特に好ましく使用できる。 The binder resin may contain one or more components selected from the group consisting of hot melt powders, latexes, and water-dispersed emulsions, and use appropriate materials from commercially available materials. Can do. Specific examples of the hot melt powder include polyethylene, ethylene vinyl acetate copolymer resin (EVA), polyester, and polyamide. Examples of the latex include rubber latexes such as SBR, NBR, and polyurethane, and resin latexes such as polyacrylate, polyvinyl acetate, and ethylene vinyl acetate copolymer resin (EVA). Examples of the water-dispersed emulsion include acrylic, acrylic styrene, acrylic silicon, polyurethane, polyester, and polyamide. Among these binder resins, in order to impregnate and apply the inorganic antibacterial composition as a water dispersion to a fiber base material, a water dispersion emulsion can be particularly preferably used.
本発明の無機抗菌性組成物を繊維に固定する抗菌性繊維または抗菌性繊維を用いた抗菌性衣料品としては、一般の衣料品の他に、建築用繊維製品、不織布製品が挙げられ、床材、壁材として無機抗菌性組成物を有する材料が有用である。また、建築や自動車部品としてのエアフィルター用途等に好適に用いることができる。特に、建築材料、自動車キャビン内では、本発明の無機抗菌性組成物を含む抗菌性繊維を好適に用いることができる。 The antibacterial fiber or the antibacterial clothing using the antibacterial fiber for fixing the inorganic antibacterial composition of the present invention to the fiber includes, in addition to general clothing products, architectural textile products and non-woven fabric products. A material having an inorganic antibacterial composition as a material or wall material is useful. Moreover, it can use suitably for the air filter use etc. as a building or an automotive part. In particular, antibacterial fibers containing the inorganic antibacterial composition of the present invention can be suitably used in building materials and automobile cabins.
（４）さらに、本発明の無機抗菌性組成物は、無機抗菌性組成物を含む、または前記無
機抗菌性組成物を含むコーティングを有する、樹脂材、セラミック材、または金属材の用途に有用である。具体的には、本発明の無機抗菌性組成物は、樹脂材、セラミック材、または金属材中に含有されて、抗菌性材料として用いることができる。また、樹脂バインダーに混合されて、樹脂パネル、セラミックパネル、金属パネルなどにコーティングされて用いられれば、構造部材を抗菌性にすることができるので有用である。
(4) Furthermore, the inorganic antibacterial composition of the present invention is useful for the use of a resin material, a ceramic material, or a metal material containing the inorganic antibacterial composition or having a coating containing the inorganic antibacterial composition. is there. Specifically, the inorganic antibacterial composition of the present invention is contained in a resin material, a ceramic material, or a metal material and can be used as an antibacterial material. Moreover, if it is mixed with a resin binder and coated on a resin panel, ceramic panel, metal panel or the like, it is useful because the structural member can be made antibacterial.
（５）また、本発明の無機抗菌性組成物を含む医薬品としては、創傷治癒剤等の外用薬
に、用いることができ、または本発明の無機抗菌性組成物を含む、または前記無機抗菌性組成物を含むコーティングを有する医療用物品としては、創傷治癒剤に用いられる創傷被覆材が例示できる。
(5) Moreover, as a pharmaceutical containing the inorganic antibacterial composition of this invention, it can be used for external preparations, such as a wound healing agent, or contains the inorganic antibacterial composition of this invention, or the said inorganic antibacterial Examples of the medical article having a coating containing the composition include a wound dressing used for a wound healing agent.
以下に実施例を用いて本発明を具体的に説明するが、本発明は実施例に限定されない。 EXAMPLES The present invention will be specifically described below using examples, but the present invention is not limited to the examples.
＜本発明の無機抗菌性組成物の製造＞
反応容器に０．０４Ｍ炭酸水素ナトリウム水溶液を５００ｍＬ調整し、これとは別に滴下反応溶液として硝酸亜鉛と硝酸アルミニウムを混合して全モル濃度を０．１Ｍとした金属塩水溶液を１０００ｍＬ用意した。ｐＨ調製液として３０質量％水酸化ナトリウム水溶液を準備した。
ポンプを接続したｐＨコントローラを用いて、上記の炭酸水素ナトリウム溶液のｐＨを９．０に保ち攪拌を行った状態で、金属塩水溶液および水酸化ナトリウム水溶液を滴下した。金属塩水溶液を全て滴下した後、反応液は２０時間攪拌させた。
２０時間攪拌後、反応液を遠心分離によって固液分離し、得られた固体は水洗、遠心分離を３回繰り返した。このように洗浄した沈殿物を真空乾燥して塩基性炭酸亜鉛を得た。
この塩基性炭酸亜鉛をプレス機にてφ２０ｍｍ、重さ２ｇのペレットに成型した後、このペレットを１２００℃、４時間の条件で焼成を行った。
<Production of inorganic antibacterial composition of the present invention>
Separately, 500 mL of a 0.04M sodium hydrogen carbonate aqueous solution was prepared in the reaction vessel, and 1000 mL of a metal salt aqueous solution having a total molar concentration of 0.1 M was prepared by mixing zinc nitrate and aluminum nitrate as a dropping reaction solution. A 30% by mass aqueous sodium hydroxide solution was prepared as a pH adjusting solution.
Using a pH controller connected to a pump, a metal salt aqueous solution and a sodium hydroxide aqueous solution were added dropwise with stirring while maintaining the pH of the sodium bicarbonate solution at 9.0. After all the metal salt aqueous solution was dropped, the reaction solution was stirred for 20 hours.
After stirring for 20 hours, the reaction solution was subjected to solid-liquid separation by centrifugation, and the obtained solid was washed with water and centrifuged three times. The precipitate thus washed was vacuum-dried to obtain basic zinc carbonate.
The basic zinc carbonate was molded into a pellet having a diameter of 20 mm and a weight of 2 g with a press machine, and the pellet was fired at 1200 ° C. for 4 hours.
＜抗菌性評価サンプルの製造＞
（実施例１）
前記製造条件にて、ｐＨを９．０に保持、０．１Ｍ金属塩水溶液が、亜鉛とアルミニウムのモル比は１９９／１（９９．５：０．５）であり、焼成温度を１２００℃として製造した。
（実施例２）
前記製造条件にて、ｐＨを９．０に保持、０．１Ｍ金属塩水溶液が、亜鉛とガリウムのモル比が９９／１（９９：１．０）であり、焼成温度を１２００℃として製造した。
（実施例３）
前記製造条件にて、ｐＨを９．０に保持、０．１Ｍ金属塩水溶液が、亜鉛とアルミニウムのモル比は１９９／１（９９．５：０．５）であり、焼成温度を１０００℃として製造した。
<Manufacture of antibacterial evaluation samples>
Example 1
Under the above manufacturing conditions, the pH is maintained at 9.0, the 0.1M metal salt aqueous solution has a zinc / aluminum molar ratio of 199/1 (99.5: 0.5), and the firing temperature is 1200 ° C. Manufactured.
(Example 2)
Under the above manufacturing conditions, the pH was maintained at 9.0, and the 0.1M metal salt aqueous solution was manufactured at a molar ratio of zinc to gallium of 99/1 (99: 1.0) and a firing temperature of 1200 ° C. .
(Example 3)
Under the above manufacturing conditions, the pH is maintained at 9.0, the 0.1M metal salt aqueous solution has a zinc to aluminum molar ratio of 199/1 (99.5: 0.5), and the firing temperature is 1000 ° C. Manufactured.
（実施例４）
前記製造条件にて、ｐＨを９．０に保持、０．１Ｍ金属塩水溶液が、亜鉛とアルミニウムのモル比は１９９／１（９９．５：０．５）であり、焼成温度を１３００℃として製造した。
（実施例５）
前記製造条件にて、ｐＨを９．０に保持、０．１Ｍ金属塩水溶液が、亜鉛とアルミニウムのモル比は９／１（９０：１０）であり、焼成前の前駆体の組成がハイドロジンカイト単相でない、亜鉛アルミニウム炭酸水酸化物を含む前駆体を焼成温度を１２００℃として製造した。
（実施例６）
前記製造条件にて、ｐＨを９．０に保持、０．１Ｍ金属塩水溶液が、亜鉛とガリウムのモル比は４／１（８０：２０）であり、焼成前の前駆体の組成がハイドロジンカイト単相でない、亜鉛ガリウム炭酸水酸化物を含む前駆体を焼成温度を１２００℃として製造した。
Example 4
Under the above manufacturing conditions, the pH is maintained at 9.0, the 0.1M metal salt aqueous solution has a molar ratio of zinc to aluminum of 199/1 (99.5: 0.5), and the firing temperature is 1300 ° C. Manufactured.
(Example 5)
Under the above manufacturing conditions, pH is maintained at 9.0, 0.1M metal salt aqueous solution has a zinc / aluminum molar ratio of 9/1 (90:10), and the precursor composition before firing is hydrozincite. A precursor containing zinc aluminum carbonate hydroxide that is not a single phase was produced at a firing temperature of 1200 ° C.
(Example 6)
Under the above manufacturing conditions, pH is maintained at 9.0, 0.1M metal salt aqueous solution has a zinc / gallium molar ratio of 4/1 (80:20), and the precursor composition before firing is hydrozincite. A precursor containing zinc gallium carbonate hydroxide that is not a single phase was produced at a firing temperature of 1200 ° C.
（比較例１）
実施例３と同様の条件で、ただし焼成温度を４００℃として製造した。
（比較例２）
実施例３と同様の条件で、ただし焼成温度を６００℃として製造した。
（比較例３）
前記製造条件にて、ｐＨを９．０に保持、０．１Ｍ金属塩水溶液が、亜鉛とアルミニウムのモル比が１/１（５０：５０）であり、焼成前の前駆体の組成がハイドロジンカイト単相でない、亜鉛アルミニウム炭酸水酸化物である異相が支配的な前駆体に対して焼成温度を１２００℃として製造した。
（比較例４）
前記製造条件にて、ｐＨを９．０に保持、０．１Ｍ金属塩水溶液が、亜鉛とガリウムのモル比が１/１（５０：５０）であり、焼成前の前駆体の組成がハイドロジンカイト単相でない、亜鉛ガリウム炭酸水酸化物である異相が支配的な前駆体に対して焼成温度を１２００℃として製造した。
(Comparative Example 1)
It was manufactured under the same conditions as in Example 3, except that the firing temperature was 400 ° C.
(Comparative Example 2)
It was manufactured under the same conditions as in Example 3, except that the firing temperature was 600 ° C.
(Comparative Example 3)
Under the above production conditions, pH is maintained at 9.0, 0.1M metal salt aqueous solution has a zinc / aluminum molar ratio of 1/1 (50:50), and the composition of the precursor before firing is hydrozincite. It was manufactured at a firing temperature of 1200 ° C. with respect to a precursor in which a different phase, which is not a single phase and is zinc aluminum carbonate hydroxide, is dominant.
(Comparative Example 4)
Under the above manufacturing conditions, pH is maintained at 9.0, 0.1M metal salt aqueous solution has a zinc / gallium molar ratio of 1/1 (50:50), and the composition of the precursor before firing is hydrozincite. It was manufactured at a firing temperature of 1200 ° C. with respect to a precursor in which a heterogeneous phase which is not a single phase and is zinc gallium carbonate hydroxide is dominant.
＜比表面積＞
上記のサンプルは全て熱処理後、メノウ乳鉢にて粉砕を行った。それぞれのサンプルのＢＥＴ比表面積を表１に表す。
<Specific surface area>
All the above samples were pulverized in an agate mortar after heat treatment. The BET specific surface area of each sample is shown in Table 1.
＜抗菌性評価試験法＞
上記のサンプルに対して乾熱滅菌を１８０℃で２時間行い、１０ｇ/Ｌに調製して試験液とした。図１に示すように大腸菌（E.coli NBRC 3972）に対する上記サンプルの抗菌性効果を評価した。この試験液中に細菌懸濁液（１０７ＣＦＵｍｌ−１）を加え、暗所において３７℃で２０分間振とうした。対照として、サンプルを用いない細菌懸濁液をコントロールとした。振とう後の混合液は、普通寒天培地に５０μＬずつ播種し、３７℃で２４時間培養した。培養後、寒天培地に形成されたコロニー数をＮ’ＣＦＵ/ｍＬとし計測した。同様に、コントロールの寒天培地からコロニー数Ｎ０ＣＦＵ/ｍＬとし計測した。
＜結果＞
測定された菌数から、抗菌剤の効力として使用される死滅速度定数kを以下の式を用いて計算した。死滅速度定数とは、酸化亜鉛粉末の濃度を一定としたとき、酸化亜鉛と細菌懸濁液の処理時間と細菌の生存率から求められる以下の値である。
<Antimicrobial evaluation test method>
The above sample was sterilized by dry heat at 180 ° C. for 2 hours to prepare 10 g / L as a test solution. As shown in FIG. 1, the antibacterial effect of the sample against E. coli NBRC 3972 was evaluated. Bacterial suspension (10 7 CFU ml −1 ) was added to this test solution and shaken at 37 ° C. for 20 minutes in the dark. As a control, a bacterial suspension without a sample was used as a control. The mixed solution after shaking was seeded on a normal agar medium in an amount of 50 μL and cultured at 37 ° C. for 24 hours. After culturing, the number of colonies formed on the agar medium was counted as N′CFU / mL. Similarly, the colony number N 0 CFU / mL was counted from a control agar medium.
<Result>
From the measured number of bacteria, the kill rate constant k used as the antimicrobial efficacy was calculated using the following formula. The death rate constant is the following value obtained from the treatment time of zinc oxide and bacterial suspension and the survival rate of bacteria when the concentration of zinc oxide powder is constant.
なお抗菌活性の指標を表すに際して、Ｎ０/Ｎ＝Ｎ０ＣＦＵ/ｍＬ／Ｎ’ＣＦＵ/ｍＬとして測定し、ｋをそれぞれのサンプルのBET比表面積で割った表面積あたりの死滅速度定数としてｋ’で表し、表２に示す。 In expressing the index of antibacterial activity, N 0 / N = N 0 CFU / mL / N′CFU / mL was measured, and k ′ was determined as a death rate constant per surface area obtained by dividing k by the BET specific surface area of each sample. And shown in Table 2.
実施例、比較例の評価
実施例の抗菌性組成物は、大腸菌に対しての抗菌活性が著しく向上した。抗菌活性の性能指標である、表面積あたりの死滅速度定数ｋ’が比較例の組成物と比べて２．７倍〜１６３倍と格段に向上した。したがって本発明の酸化亜鉛粉末である無機抗菌性組成物は、抗菌剤として有用である。
Evaluation of Examples and Comparative Examples The antibacterial compositions of the examples have significantly improved antibacterial activity against E. coli. The killing rate constant k ′ per surface area, which is a performance index of antibacterial activity, was markedly improved from 2.7 times to 163 times compared to the composition of the comparative example. Therefore, the inorganic antibacterial composition which is the zinc oxide powder of the present invention is useful as an antibacterial agent.
本発明の無機抗菌剤組成物は、大腸菌などの菌類の増殖を防止し、かつ死滅能力に優れた抗菌剤である。本発明の無機抗菌剤組成物を化粧品、衣料品、および家具類、建材などに、粉体として材料中に添加、またはコーティング材中に添加して用いることで、耐熱性・耐久性・安全性に優れるという特徴を有し、暗所でも効果を発現する安価な無機系抗菌剤として利用される。また、食料品中に添加、または食料品の包装材中に添加して用いることで暗所でも効果を発現する安価な無機系抗菌剤として工業的有用性が高い。 The inorganic antibacterial agent composition of the present invention is an antibacterial agent that prevents the growth of fungi such as Escherichia coli and has excellent killing ability. By using the inorganic antibacterial agent composition of the present invention as a powder in cosmetics, clothing, furniture, building materials, etc., or by adding it to a coating material, heat resistance, durability and safety It is used as an inexpensive inorganic antibacterial agent that has excellent characteristics and exhibits effects even in the dark. In addition, it is highly industrially useful as an inexpensive inorganic antibacterial agent that exhibits an effect even in a dark place by being added to foodstuffs or added to foodstuff packaging materials.
Claims (7)
Ｍ４〜６（ＣＯ３）１〜３（ＯＨ）６〜７ （１）
Ｍ：亜鉛元素、アルミニウム、およびガリウムからなる群から選択される少なくとも一つの金属を示す。 The inorganic antibacterial composition according to claim 1 or 2, wherein the carbonate hydrate contains a hydrozincite represented by the following formula (1) or a hydrate thereof.
M 4-6 (CO 3 ) 1-3 (OH) 6-7 (1)
M: At least one metal selected from the group consisting of elemental zinc, aluminum, and gallium.
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