JP2006312609A - Antimicrobial composition, antimicrobial molding, solution containing antimicrobial composition, detergent and straw mat used as surface of tatami mat - Google Patents
Antimicrobial composition, antimicrobial molding, solution containing antimicrobial composition, detergent and straw mat used as surface of tatami mat Download PDFInfo
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- JP2006312609A JP2006312609A JP2005136366A JP2005136366A JP2006312609A JP 2006312609 A JP2006312609 A JP 2006312609A JP 2005136366 A JP2005136366 A JP 2005136366A JP 2005136366 A JP2005136366 A JP 2005136366A JP 2006312609 A JP2006312609 A JP 2006312609A
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- antibacterial
- antibacterial composition
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- WJCNZQLZVWNLKY-UHFFFAOYSA-N thiabendazole Chemical compound S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 0.000 claims abstract description 18
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- Floor Finish (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
本発明は、有機系抗菌剤および無機系抗菌剤を含有する抗菌性組成物、および、この抗菌性組成物を含有する抗菌性成形体、抗菌性組成物含有溶液、洗浄剤、ならびに畳表に関する。 The present invention relates to an antibacterial composition containing an organic antibacterial agent and an inorganic antibacterial agent, and an antibacterial molded article containing the antibacterial composition, an antibacterial composition-containing solution, a cleaning agent, and a tatami mat.
細菌などの原核生物、カビ、酵母などの真核生物、さらには藻類などの微生物を除去や忌避する抗菌性組成物として、各微生物に対して２種類以上の薬剤を組み合わせることで、相乗効果が得られることが知られている。すなわち、２種類以上の薬剤を併用することで、抗菌スペクトルが拡大したり、最小生育阻止濃度（ＭＩＣ値：Minimum Inhibitory Concentrationの略）（ｐｐｍ）が各薬剤を単独使用する場合に比して減少したりするといった相乗効果を奏する。そして、異なる種類の薬剤を併用する方法として、有機系抗菌剤および無機系抗菌剤を用いる構成が知られている（例えば、特許文献１参照）。 As an antibacterial composition that removes or repels prokaryotes such as bacteria, eukaryotes such as fungi and yeast, and microorganisms such as algae, a synergistic effect can be obtained by combining two or more drugs against each microorganism. It is known to be obtained. In other words, by using two or more drugs together, the antibacterial spectrum is expanded, and the minimum growth inhibitory concentration (MIC value: Abbreviation for Minimum Inhibitory Concentration) (ppm) is reduced compared to when each drug is used alone. There is a synergistic effect. And the structure using an organic type antimicrobial agent and an inorganic type antimicrobial agent is known as a method of using together a different kind of chemical | medical agent (for example, refer patent document 1).
この特許文献１に記載のものは、銀、銅、亜鉛などの金属成分と、この金属成分以外の無機酸化物とからなり抗菌・防黴・防藻性作用を有する無機酸化物微粒子と、チアゾール系化合物およびイミダゾール系化合物のうちの少なくともいずれか一方の有機系抗菌・防黴・防藻剤と、を含有している。そして、無機酸化物微粒子は、分散性や被処理物の表面色調などに及ぼす影響により、平均粒子径を５００ｎｍ以下としている。また、無機酸化物微粒子の含有量は、併用する効果のために０．００１重量％以上としている。 The thing of this patent document 1 consists of inorganic oxide microparticles | fine-particles which consist of metal components, such as silver, copper, and zinc, and inorganic oxides other than this metal component, and have antibacterial / antifungal / algaeproof action, and thiazole And an organic antibacterial / antifungal / algae-proofing agent of at least one of the organic compound and the imidazole compound. The inorganic oxide fine particles have an average particle diameter of 500 nm or less due to the influence on the dispersibility and the surface color tone of the object to be processed. Further, the content of the inorganic oxide fine particles is set to 0.001% by weight or more for the effect of combined use.
ところで、抗菌性組成物は、生活環境中に使用されるものであることから、例えば、被処理物に抗菌性組成物を塗布するなどの際に皮膚に付着したり、抗菌性組成物を塗布あるいは含有した成形体に利用者が接触したりしても、かぶれるなどの人体に影響がない薬剤を用いる必要がある。また、抗菌性組成物を塗布あるいは含有した成形体を例えば焼却処理する際に、ダイオキシンなどの有害物質が発生しない薬剤を用いる必要がある。 By the way, since the antibacterial composition is used in the living environment, for example, when the antibacterial composition is applied to the object to be treated, it adheres to the skin or the antibacterial composition is applied. Or it is necessary to use the chemical | medical agent which does not have influence on the human body, such as a rash, even if a user contacts the containing molded object. In addition, when a molded body on which an antibacterial composition is applied or contained, for example, is incinerated, it is necessary to use a chemical that does not generate harmful substances such as dioxins.
一方、抗菌性組成物を調製する際や抗菌性組成物を含有する成形体を成形する際などの製造工程において、混合する際の容器や整形時の金型など、製造設備の腐食を生じない薬剤が望ましい。すなわち、製造設備に耐腐食性の材料を用いるなど、製造設備に特別な装置が必要となって製造設備の構築性が低下したりコストが増大したりするなどの不都合が生じない薬剤を対象とすることが望ましい。 On the other hand, in the manufacturing process such as when preparing an antibacterial composition or when molding a molded article containing the antibacterial composition, corrosion of manufacturing equipment such as a container for mixing and a mold for shaping does not occur. Drugs are desirable. In other words, it is intended for drugs that do not cause inconveniences such as the use of a corrosion-resistant material for the manufacturing equipment, which requires special equipment in the manufacturing equipment, and the construction efficiency of the manufacturing equipment is reduced or the cost is increased. It is desirable to do.
しかしながら、上述した特許文献１に記載のような従来の有機系および無機系を併用して効果を得る抗菌性組成物として、組み合わせによって十分な相乗効果が発揮できず、限られた微生物にのみしか相乗効果が得られない。すなわち、抗菌スペクトルを大きく拡大できない。さらには、抗菌スペクトルが拡大する抗菌性を発揮させるためには、ＭＩＣ値が増大、すなわち添加量が増大し、効率的な抗菌作用が得られないとともに、添加量の増大による成形体の成形性が困難となるなどの不都合も生じるおそれがある。また、２−（ｎ−オクチル）−４−イソチアゾール−３−オン（略称ＯＩＴ）などのアレルギ性物質も用いられている。 However, as an antibacterial composition that obtains an effect by using a combination of conventional organic and inorganic systems as described in Patent Document 1 described above, a sufficient synergistic effect cannot be exhibited by the combination, and only for limited microorganisms. A synergistic effect cannot be obtained. That is, the antibacterial spectrum cannot be greatly expanded. Furthermore, in order to exhibit antibacterial properties with an expanded antibacterial spectrum, the MIC value is increased, that is, the amount added is increased, an efficient antibacterial action cannot be obtained, and the moldability of the molded product due to the increased amount added Inconveniences such as difficulty may occur. In addition, allergic substances such as 2- (n-octyl) -4-isothiazol-3-one (abbreviation OIT) are also used.
本発明の目的は、抗菌作用が発揮される微生物の種類が多く効率的な抗菌作用が得られ人体や環境に影響のない抗菌性組成物および抗菌性成形体、抗菌性組成物含有溶液、洗浄剤、および、畳表を提供することにある。 An object of the present invention is to provide an antibacterial composition and an antibacterial molded article, an antibacterial composition-containing solution, a washing, which have many kinds of microorganisms that exhibit an antibacterial action, and have an effective antibacterial action and do not affect the human body or the environment. It is to provide an agent and a tatami mat.
本発明に記載の抗菌性組成物は、イミダゾール系の有機系抗菌剤から選ばれた少なくとも２種と、無機系抗菌剤と、からなることを特徴とする。
この発明では、少なくとも２種のイミダゾール系の有機系抗菌剤と、無機系抗菌剤とを併用、特に少なくとも２種のイミダゾール系の有機抗菌性抗菌剤のみと、無機系抗菌剤とを併用しているので、皮膚刺激性が認められず、かつ、相乗効果による低い最小育成素子濃度（ＭＩＣ値）でも格段に広い抗菌スペクトルが得られ、効率よく高い抗菌作用が容易に得られる。
従来は、抗菌スペクトルを広げるには、化学的に異種な抗菌剤を用いることが必要であるが、本発明では、イミダゾール系単一の抗菌剤の組み合わせにより、著しく広い抗菌スペクトルを達成している。これは、公知知見からは全く予想できない効果である。
なお、本発明において、「抗菌性（抗菌効果）」とは、真菌や細菌などの菌類の生育や繁殖を阻止するといった抗菌効果そのものに加え、防カビ・抗カビ効果や、防藻効果といったものも含むものである。
The antibacterial composition described in the present invention is characterized by comprising at least two kinds selected from imidazole-based organic antibacterial agents and an inorganic antibacterial agent.
In the present invention, at least two types of imidazole organic antibacterial agents and inorganic antibacterial agents are used in combination, and in particular, at least two types of imidazole organic antibacterial agents are used in combination with inorganic antibacterial agents. Therefore, skin irritation is not recognized, and an extremely wide antibacterial spectrum can be obtained even at a low minimum growth element concentration (MIC value) due to a synergistic effect, and a high antibacterial action can be easily obtained efficiently.
Conventionally, in order to broaden the antibacterial spectrum, it is necessary to use chemically different antibacterial agents, but in the present invention, an extremely wide antibacterial spectrum is achieved by a combination of imidazole-based single antibacterial agents. . This is an effect that cannot be predicted from known knowledge.
In the present invention, “antibacterial effect (antibacterial effect)” refers to an antibacterial / antifungal effect, an antialgal effect, in addition to the antibacterial effect itself such as inhibiting the growth and reproduction of fungi such as fungi and bacteria. Is also included.
そして、本発明では、前記イミダゾール系の有機系抗菌剤から選ばれた２種は、ベンゾイミダゾール環にチアゾリル基を有するものと、ベンゾイミダゾール環にカーバメート基を有するものとであることが好ましい。
本発明では、イミダゾール系の有機系抗菌剤として、ベンゾイミダゾール環にチアゾリル基を有するものとカーバメート基を有するものとの２種、特に２種のみを併用するので、同一のイミダゾール系でも、人体や環境に影響がなく、かつ、相乗効果による低いＭＩＣ値でも格段に広い抗菌スペクトルが得られるという抗菌作用が容易に得られ、特にこれらの併用により顕著な抗菌性が得られる。
In the present invention, the two kinds selected from the imidazole organic antibacterial agents are preferably those having a thiazolyl group in the benzimidazole ring and those having a carbamate group in the benzimidazole ring.
In the present invention, as an imidazole-based organic antibacterial agent, two types, one having a thiazolyl group in the benzimidazole ring and one having a carbamate group, in particular, only two types are used in combination. The antibacterial action that a remarkably broad antibacterial spectrum can be obtained even with a low MIC value due to a synergistic effect is easily obtained, and remarkable antibacterial property is obtained particularly by the combination thereof.
さらに、本発明では、前記ベンゾイミダゾール環にチアゾリル基を有するものは、２−（４−チアゾリル）−１Ｈ−ベンゾイミダゾールであり、前記ベンゾイミダゾール環にカーバメート基を有するものは、２−ベンゾイミダゾールカルバミン酸メチルであることが好ましい。
本発明では、ベンゾイミダゾール環にチアゾリル基を有する２−（４−チアゾリル）−１Ｈ−ベンゾイミダゾールと、カーバメート基を有する２−ベンゾイミダゾールカルバミン酸メチルとの２種を併用するので、特に併用による相乗効果にて顕著な抗菌性が得られる。さらに、これら２−（４−チアゾリル）−１Ｈ−ベンゾイミダゾールと、２−ベンゾイミダゾールカルバミン酸メチルとは、比較的に製造しやすく入手が容易で、既に利用されている材料で安全性が認められたものであることから、容易に利用できる。
Furthermore, in this invention, what has a thiazolyl group in the said benzimidazole ring is 2- (4-thiazolyl) -1H-benzimidazole, and what has a carbamate group in the said benzimidazole ring is 2-benzimidazole carbamine. Preference is given to methyl acid.
In the present invention, two types of 2- (4-thiazolyl) -1H-benzimidazole having a thiazolyl group in the benzimidazole ring and methyl 2-benzimidazole carbamate having a carbamate group are used in combination. A remarkable antibacterial property is obtained by the effect. Furthermore, these 2- (4-thiazolyl) -1H-benzimidazoles and methyl 2-benzimidazole carbamate are relatively easy to produce and readily available, and safety has been recognized in the materials already used. Therefore, it can be used easily.
また、本発明では、前記無機系抗菌剤は、銀系抗菌剤と酸化亜鉛とのうちの少なくともいずれか一方であることが好ましい。
本発明では、無機系抗菌剤として、イミダゾール系の有機系抗菌剤との相乗効果が得られる銀系抗菌剤と酸化亜鉛とのうちの少なくともいずれか一方を用いるので、顕著な抗菌性が容易に得られる。そして、銀系抗菌剤と酸化亜鉛とを併用することにより、銀系抗菌剤および酸化亜鉛自体による抗菌作用とともに、これら同一の無機系抗菌剤でも併用することで抗菌作用の相乗効果も得られ、より顕著な抗菌性が容易に得られる。
In the present invention, the inorganic antibacterial agent is preferably at least one of a silver antibacterial agent and zinc oxide.
In the present invention, as the inorganic antibacterial agent, at least any one of a silver antibacterial agent and zinc oxide capable of obtaining a synergistic effect with an imidazole organic antibacterial agent is used, so that remarkable antibacterial properties are easily obtained. can get. And by using silver antibacterial agent and zinc oxide together, together with the antibacterial action by silver antibacterial agent and zinc oxide itself, the synergistic effect of antibacterial action can also be obtained by using these same inorganic antibacterial agents together, More remarkable antibacterial properties can be easily obtained.
さらに、本発明では、前記銀系抗菌剤は、銀を担持したジルコニウムまたはその塩あるいはゼオライトであることが好ましい。
本発明では、銀系抗菌剤として銀を担持したジルコニウムまたはその塩あるいはゼオライトを用いるので、貴金属である銀が抗菌作用を発揮する必要最小限の量となり、効率よく無機系抗菌剤による抗菌作用が得られるとともに有機系抗菌剤との抗菌作用の相乗効果が得られ、コストの低減も容易に図れる。
Furthermore, in the present invention, the silver antibacterial agent is preferably zirconium carrying silver, a salt thereof, or zeolite.
In the present invention, zirconium supporting silver or a salt thereof or zeolite is used as the silver antibacterial agent, so that silver, which is a noble metal, becomes a necessary minimum amount to exert the antibacterial action, and the antibacterial action by the inorganic antibacterial agent is efficiently performed. As a result, a synergistic effect of the antibacterial action with the organic antibacterial agent is obtained, and the cost can be easily reduced.
また、本発明では、前記無機系抗菌剤は、前記銀を担持したジルコニウムまたはその塩あるいはゼオライトと前記酸化亜鉛との配合割合が、質量比で１：１〜１：１０であることが好ましい。
本発明では、銀を担持したジルコニウムまたはその塩あるいはゼオライトと、酸化亜鉛とを併用するので、同一の無機系抗菌剤でも併用による抗菌作用の相乗効果が得られ、より顕著な抗菌性が得られる。さらに、無機系抗菌剤自体による抗菌作用と、無機系抗菌剤の併用による抗菌作用の相乗効果と、有機系抗菌剤との抗菌作用の相乗効果とが損なわれることなく、貴金属である銀の使用量が低減し、コストの低減がより容易に図れる。そして、銀を担持したジルコニウムまたはその塩あるいはゼオライトと酸化亜鉛との配合割合が、質量比で１：１〜１：１０であることから、抗菌性が損なわれることなく適切に銀の使用量が低減する。
ここで、銀を担持したジルコニウムまたはその塩あるいはゼオライトと酸化亜鉛との配合割合が、質量比で１：１より酸化亜鉛が少なくなると、銀の使用量の低減による十分なコストの低減が得られにくくなる。また、銀の酸化による変色が問題となるおそれもある。一方、質量比で１：１０より酸化亜鉛が多くなると、銀による十分な抗菌作用が得られにくくなるおそれがある。したがって、銀を担持したジルコニウムまたはその塩あるいはゼオライトと酸化亜鉛との配合割合を質量比で１：１〜１：１０とすることが好ましい。
In the present invention, it is preferable that the inorganic antibacterial agent has a mass ratio of 1: 1 to 1:10 of the zirconium carrying the silver or a salt thereof or zeolite and the zinc oxide.
In the present invention, since zirconium or a salt or zeolite carrying silver is used in combination with zinc oxide, the same inorganic antibacterial agent can provide a synergistic effect of antibacterial action by the combined use, and more remarkable antibacterial properties can be obtained. . Furthermore, the use of silver, a precious metal, without compromising the synergistic effect of the antibacterial effect of the inorganic antibacterial agent itself, the antibacterial effect of the combined use of the inorganic antibacterial agent, and the antibacterial effect of the organic antibacterial agent The amount is reduced and the cost can be reduced more easily. And since the compounding ratio of the zirconium which supported silver, its salt or zeolite, and zinc oxide is 1: 1-1: 10 by mass ratio, the usage-amount of silver is appropriately used, without impairing antibacterial property. To reduce.
Here, when the amount of zirconium supported on silver or a salt thereof or zeolite and zinc oxide is less than 1: 1 in terms of mass ratio, sufficient cost reduction can be obtained by reducing the amount of silver used. It becomes difficult. In addition, discoloration due to silver oxidation may be a problem. On the other hand, when zinc oxide is more than 1:10 by mass ratio, there is a possibility that sufficient antibacterial action due to silver cannot be obtained. Therefore, it is preferable that the mixing ratio of zirconium carrying silver or a salt thereof or zeolite and zinc oxide is 1: 1 to 1:10 by mass ratio.
さらに、本発明では、前記イミダゾール系の有機系抗菌剤と前記無機系抗菌剤との配合割合は、質量比で１：１〜５：１であることが好ましい。
本発明では、イミダゾール系の有機系抗菌剤と無機系抗菌剤との配合割合を、質量比で１：１〜５：１とすることで、有機系抗菌剤や無機系抗菌剤自体の抗菌作用とともに、有機系抗菌剤と無機系抗菌剤との併用による顕著な抗菌作用の相乗効果が適切に得られる。
ここで、有機系抗菌剤と無機系抗菌剤との配合割合が、質量比で１：１より有機系抗菌剤が少なくなると、少ないＭＩＣ値での抗菌スペクトルの拡大が得られなくなるおそれがある。一方、質量比で５：１より有機系抗菌剤が多くなると、無機系抗菌剤に比して初期抗菌性能が遅く抗菌性能の持続性が低減しやすい有機系抗菌剤の割合が多くなり、使用当初から長期間に亘って安定した顕著な抗菌性が得られなくなるおそれがある。したがって、ベンゾイミダゾール系の有機系抗菌剤と無機系抗菌剤との配合割合を、質量比で１：１〜５：１とすることが好ましい。
Furthermore, in this invention, it is preferable that the mixture ratio of the said imidazole type organic antibacterial agent and the said inorganic type antibacterial agent is 1: 1-5: 1 by mass ratio.
In the present invention, the mixing ratio of the imidazole organic antibacterial agent and the inorganic antibacterial agent is 1: 1 to 5: 1 by mass ratio, so that the antibacterial action of the organic antibacterial agent or the inorganic antibacterial agent itself is achieved. At the same time, a remarkable synergistic effect of the antibacterial action by the combined use of the organic antibacterial agent and the inorganic antibacterial agent is appropriately obtained.
Here, if the organic antibacterial agent and the inorganic antibacterial agent are mixed in an organic antibacterial agent with a mass ratio of less than 1: 1, the antibacterial spectrum may not be expanded with a small MIC value. On the other hand, when the amount of organic antibacterial agent is larger than 5: 1 by mass ratio, the proportion of organic antibacterial agents that are slow in initial antibacterial performance and easy to reduce the durability of antibacterial performance is higher than inorganic antibacterial agents There is a risk that stable antibacterial properties that are stable over a long period from the beginning cannot be obtained. Therefore, it is preferable that the blending ratio of the benzimidazole organic antibacterial agent and the inorganic antibacterial agent is 1: 1 to 5: 1 by mass ratio.
また、本発明では、ハロゲン化合物を含まず、実質的に水に不溶であることが好ましい。
本発明では、上述の本発明の抗菌性組成物として、ハロゲン化合物を含まず、実質的に水に不溶とすることで、仮に本発明の抗菌性組成物やこの抗菌性組成物を含有する成形体や溶液などを焼却などのために加熱しても、例えばダイオキシンなどの有害物質が発生するなどの不都合が生じない。さらに、水に不溶であることから、例えば雨露に曝されるなどの使用条件でも流れ落ちて長期間安定した抗菌性を提供できなくなるなどの不都合がなく、樹脂材料と良好に混合されて抗菌性を有した成形体を提供することが容易となり、汎用性の向上も容易に図れる。
Moreover, in this invention, it is preferable that a halogen compound is not included but it is substantially insoluble in water.
In the present invention, the antibacterial composition of the present invention described above does not contain a halogen compound and is substantially insoluble in water, so that the antibacterial composition of the present invention and a molding containing the antibacterial composition are temporarily included. Even if the body or solution is heated for incineration, there is no inconvenience such as generation of harmful substances such as dioxin. Furthermore, since it is insoluble in water, there is no inconvenience such as being unable to provide stable antibacterial properties for a long period of time even under operating conditions such as being exposed to rain dew, and it is well mixed with resin materials to provide antibacterial properties. It becomes easy to provide a molded body having the same, and versatility can be easily improved.
本発明に記載の抗菌性成形体は、上述した本発明の抗菌性組成物を含有したことを特徴とする。
この本発明では、上述した抗菌性組成物を含有するので、本発明における人体や環境に影響がなく、かつ、相乗効果による低いＭＩＣ値でも格段に広い抗菌スペクトルが得られ、効率よく高い抗菌作用が容易に得られるという効果を奏する成形体を提供でき、成形体自体が顕著な抗菌性を奏するので、利用が容易となる。
The antibacterial molded article described in the present invention is characterized by containing the above-described antibacterial composition of the present invention.
Since the antibacterial composition described above is contained in the present invention, the human body and the environment in the present invention are not affected, and a much wider antibacterial spectrum is obtained even with a low MIC value due to a synergistic effect. Can be provided easily, and the molded body itself exhibits remarkable antibacterial properties, which makes it easy to use.
そして、本発明では、上述した本発明の抗菌性成形体は、抗菌性組成物を０．０１質量％以上１０．０質量％以下で含有されたことが好ましい。
本発明では、抗菌性組成物の含有量を０．０１質量％以上１０．０質量％以下とすることで、例えば強度や外観などの特性を損なうことなく顕著な抗菌性を発揮する成形体として提供できる。
ここで、抗菌性組成物の含有量が０．０１質量％より少なくなると、少ないＭＩＣ値での抗菌スペクトルの拡大が得られにくくなり、十分な抗菌性を発揮できなくなるおそれがある。一方、抗菌性組成物の含有量が１０．０質量％より多くなると、成形体の特性が損なわれたり、成形時における作業性が低下したりするなどの不都合を生じるおそれがある。したがって、抗菌性組成物の含有量を０．０１質量％以上１０．０質量％以下とすることが好ましい。
And in this invention, it is preferable that the antimicrobial molded object of this invention mentioned above contained 0.01 mass% or more and 10.0 mass% or less of the antimicrobial composition.
In the present invention, as a molded article that exhibits remarkable antibacterial properties without impairing properties such as strength and appearance, for example, by setting the content of the antibacterial composition to 0.01% by mass or more and 10.0% by mass or less. Can be provided.
Here, when the content of the antibacterial composition is less than 0.01% by mass, it is difficult to obtain an expansion of the antibacterial spectrum with a small MIC value, and there is a possibility that sufficient antibacterial properties cannot be exhibited. On the other hand, when the content of the antibacterial composition is more than 10.0% by mass, there is a possibility that the characteristics of the molded body are impaired or the workability at the time of molding is deteriorated. Therefore, the content of the antibacterial composition is preferably 0.01% by mass or more and 10.0% by mass or less.
また、本発明の抗菌性成形体では、成形体全質量に対して無機系抗菌剤が０．５質量％未満の割合で含有される状態に抗菌性組成物を含有し、社団法人繊維評価技術協議会で規定された殺菌活性値（一般用途）を、以下の条件としていることが好ましい。
ｌｏｇ（Ａ／Ｃ）≧０
Ａ：接種直後の標準布の菌数
Ｃ：１８時間培養後の加工布の生菌数
菌種：黄色ブドウ球菌と肺炎桿菌
本発明では、成形体中に本発明の抗菌性組成物を配合したときに、その成形体中に含まれる無機系抗菌剤が０．５質量％未満であっても、社団法人繊維評価技術協議会で規定された殺菌活性値がｌｏｇ（Ａ／Ｃ）≧０を満たし、広い抗菌スペクトルを示し低いＭＩＣ値の抗菌効果を発揮する。
特に、無機系抗菌剤が０．０５質量％以上、好ましくは０．１質量％以上とすることで、この抗菌効果が良好に発揮される。このような抗菌性組成物が低濃度でも、本発明の抗菌性組成物は、従来の抗菌性組成物では到底得られない広い抗菌スペクトルを示し低いＭＩＣ値の優れた抗菌効果を示す。
In the antibacterial molded article of the present invention, the antibacterial composition is contained in a state in which the inorganic antibacterial agent is contained in a proportion of less than 0.5% by mass with respect to the total mass of the molded article, and the fiber evaluation technology The bactericidal activity value (general use) defined by the council is preferably set as the following conditions.
log (A / C) ≧ 0
A: Bacteria count of standard cloth immediately after inoculation C: Viable count of processed cloth after 18 hours of cultivation Bacterial species: Staphylococcus aureus and Klebsiella pneumoniae In the present invention, the antibacterial composition of the present invention was blended in the molded body Sometimes, even if the inorganic antibacterial agent contained in the molded body is less than 0.5% by mass, the bactericidal activity value defined by the Fiber Evaluation Technology Council is log (A / C) ≧ 0. Satisfies and exhibits a broad antibacterial spectrum and exhibits an antibacterial effect with a low MIC value.
In particular, when the inorganic antibacterial agent is 0.05% by mass or more, preferably 0.1% by mass or more, this antibacterial effect is exhibited well. Even when such an antibacterial composition has a low concentration, the antibacterial composition of the present invention exhibits a broad antibacterial spectrum that cannot be obtained by conventional antibacterial compositions, and exhibits an excellent antibacterial effect with a low MIC value.
本発明に記載の抗菌性組成物含有溶液は、上述した本発明の抗菌性組成物が溶液中に分散されたことを特徴とする。
この発明では、上述した抗菌性組成物を溶液中に均一に分散せしめたので、溶液中の菌類との接触効果が向上し、抗菌性組成物が低濃度でも十分な抗菌効果を発揮し、本発明における人体や環境に影響がなく、かつ、相乗効果による低いＭＩＣ値でも格段に広い抗菌スペクトルが得られ、効率よく高い抗菌作用が容易に得られるという効果を奏する抗菌性の溶液を提供できる。さらに、溶液自体が顕著な抗菌性を奏するので、利用が容易となり、汎用性も容易に向上する。
なお、本発明の抗菌性組成物を配合する溶液は、水や有機溶媒、油、塗料などの液状有機化合物、および、これらの混合物のいずれでも構わないが、特に床や壁に塗るクリーナやワックスなどのように、人が触れる可能性がある製品に使用する場合は、安全面や環境負荷を低くすることを考慮して、水または水を主成分とする溶液にすることが好ましい。
The antibacterial composition-containing solution described in the present invention is characterized in that the above-described antibacterial composition of the present invention is dispersed in a solution.
In this invention, since the above-mentioned antibacterial composition is uniformly dispersed in the solution, the contact effect with the fungi in the solution is improved, and the antibacterial composition exhibits a sufficient antibacterial effect even at a low concentration. It is possible to provide an antibacterial solution that does not affect the human body and the environment in the invention, and that can provide an extremely broad antibacterial spectrum even with a low MIC value due to a synergistic effect, and that can easily obtain a high antibacterial action efficiently. Furthermore, since the solution itself exhibits remarkable antibacterial properties, it is easy to use and versatility is easily improved.
The solution for blending the antibacterial composition of the present invention may be any of water, organic solvents, oils, liquid organic compounds such as paints, and mixtures thereof, particularly cleaners and waxes applied to floors and walls. Thus, when used for a product that may be touched by humans, it is preferable to use water or a solution containing water as a main component in consideration of reducing safety and environmental burden.
そして、本発明の抗菌性組成物含有溶液では、使用時における抗菌性組成物の濃度が１０ｐｐｍ以上１０００ｐｐｍ以下で分散されたことが好ましい。
この発明では、抗菌性組成物の濃度を１０ｐｐｍ以上１０００ｐｐｍ以下としているので、低いＭＩＣ値でも広い抗菌スペクトルを示す良好な抗菌作用を効率よく発揮する。すなわち、本発明の抗菌性組成物は、１０ｐｐｍ以上１０００ｐｐｍ以下の低濃度でも、十分な抗菌効果を発揮する。
ここで、抗菌性組成物の濃度が１０ｐｐｍより低くなると、少ないＭＩＣ値での抗菌スペクトルの拡大が得られにくくなり十分な抗菌性を発揮できなくなるおそれがある。一方、抗菌性組成物の濃度が１０００ｐｐｍより高くなると、抗菌性組成物の配合量の増大によるコストの増大に対して抗菌効果の増大が大きくなく、経済効果が低減するので好ましくない。また、均一分散が難しくなるおそれもある。したがって、抗菌性組成物の濃度を１０ｐｐｍ以上１０００ｐｐｍ以下とする。
And in the antibacterial composition containing solution of this invention, it is preferable that the density | concentration of the antibacterial composition at the time of use was disperse | distributed by 10 ppm or more and 1000 ppm or less.
In the present invention, since the concentration of the antibacterial composition is 10 ppm or more and 1000 ppm or less, a good antibacterial action exhibiting a wide antibacterial spectrum is efficiently exhibited even at a low MIC value. That is, the antibacterial composition of the present invention exhibits a sufficient antibacterial effect even at a low concentration of 10 ppm to 1000 ppm.
Here, when the concentration of the antibacterial composition is lower than 10 ppm, it is difficult to obtain an expansion of the antibacterial spectrum with a small MIC value, and there is a possibility that sufficient antibacterial properties cannot be exhibited. On the other hand, if the concentration of the antibacterial composition is higher than 1000 ppm, the increase in the antibacterial effect is not large with respect to the increase in cost due to the increase in the amount of the antibacterial composition, and the economic effect is reduced. Further, uniform dispersion may be difficult. Therefore, the concentration of the antibacterial composition is set to 10 ppm or more and 1000 ppm or less.
また、本発明の抗菌性組成物含有溶液では、本発明の抗菌性組成物の濃度が０．１質量％以上５０質量％以下の溶液で、製造、輸送、保管することが経済的、手間を省くうえで好ましい。
この濃度の溶液は、前記した濃度に希釈して用いる所謂マスターバッチとして用いることが通常である。
ここで、０．１質量％未満では、マスターバッチとしての効果があまり無く、５０質量％を超えると、溶液中で抗菌性組成物が均一に分散し難くなる。したがって、抗菌性組成物の濃度を０．１質量％以上５０質量％以下とする。
In the antibacterial composition-containing solution of the present invention, it is economical and troublesome to manufacture, transport, and store the antibacterial composition of the present invention in a solution having a concentration of 0.1% by mass to 50% by mass. This is preferable for saving.
The solution having this concentration is usually used as a so-called master batch which is diluted to the above-described concentration.
Here, if it is less than 0.1% by mass, there is not much effect as a masterbatch, and if it exceeds 50% by mass, the antibacterial composition is difficult to uniformly disperse in the solution. Therefore, the concentration of the antibacterial composition is 0.1% by mass or more and 50% by mass or less.
本発明に記載の洗浄剤は、上述した本発明の抗菌性組成物含有溶液を含有していることを特徴とする。
本発明では、上述した抗菌性組成物含有溶液を含有したので、本発明における人体や環境に影響がなく、かつ、相乗効果による低いＭＩＣ値でも格段に広い抗菌スペクトルが得られ、効率よく高い抗菌作用が容易に得られるという効果を奏する洗浄剤を提供できる。さらに、洗浄の際に上述した抗菌効果が得られるとともに洗浄後に菌類の発生も抑制でき、使い勝手が向上する。
The cleaning agent described in the present invention is characterized by containing the above-described antibacterial composition-containing solution of the present invention.
In the present invention, since the antibacterial composition-containing solution described above is contained, the human body and the environment in the present invention are not affected, and a remarkably broad antibacterial spectrum is obtained even with a low MIC value due to a synergistic effect. It is possible to provide a cleaning agent having an effect that the action can be easily obtained. Furthermore, the antibacterial effect described above can be obtained at the time of washing, and the generation of fungi can be suppressed after washing, improving usability.
本発明に記載の畳表は、上述した本発明の抗菌性組成物を含有するフィルムにより形成することを特徴とする。
本発明の畳表では、上述した抗菌性組成物を含有したフィルムにより形成しているので、本発明における人体や環境に影響がなく、かつ、相乗効果による低いＭＩＣ値でも格段に広い抗菌スペクトルが得られ、効率よく高い抗菌作用が容易に得られるという効果を奏する畳表を提供できる。さらに、凹凸があり菌類が発生しやすく人体が直接接触する畳表でも良好な抗菌効果が得られる。
The tatami mat described in the present invention is formed by a film containing the antibacterial composition of the present invention described above.
Since the tatami mat of the present invention is formed of a film containing the above-mentioned antibacterial composition, the human body and the environment in the present invention are not affected, and a significantly broad antibacterial spectrum can be obtained even with a low MIC value due to a synergistic effect. Thus, it is possible to provide a tatami mat that has an effect of efficiently obtaining a high antibacterial action. In addition, a good antibacterial effect can be obtained even with a tatami mat that is uneven and prone to fungi and is in direct contact with the human body.
以下、本発明の抗菌性組成物を含有する抗菌性成形体である抗菌性樹脂シートに係る一実施の形態について説明する。
なお、本実施の形態における抗菌性成形体として、シート状に形成した構成について説明するが、シート状に限らず、各種形状に構成したもの、さらには単層シートに限らず、多層構造のシート形状としたものとしてもよい。また、樹脂成形体に限らず、例えばコンクリートなどの無機成形体などとして適用してもよい。
Hereinafter, an embodiment of an antibacterial resin sheet which is an antibacterial molded article containing the antibacterial composition of the present invention will be described.
In addition, although the structure formed in the sheet form is demonstrated as an antibacterial molded object in this Embodiment, it is not restricted to a sheet form, What was comprised in various shapes, Furthermore, it is not restricted to a single layer sheet, The sheet | seat of multilayer structure It is good also as what was made into the shape. Moreover, you may apply not only as a resin molding but as inorganic moldings, such as concrete, for example.
〔抗菌性樹脂シートの構成〕
抗菌性樹脂シートは、特に適用制限はないが、例えば、微生物である菌類（真菌類、細菌類、藻類など）が繁殖しやすい環境に使われる部品や部位、具体的には、壁紙、合成皮革、畳における畳表の裏面側など、各種用途に直接、あるいは被取付部の表面に接着あるいは貼着、挾持するなどして利用される。
[Configuration of antibacterial resin sheet]
There are no particular restrictions on the application of antibacterial resin sheets. For example, parts and parts used in environments where fungi (fungi, bacteria, algae, etc.), which are microorganisms, are easy to reproduce, specifically wallpaper, synthetic leather It is used for various applications such as the back side of the tatami mat surface in tatami mats, or by adhering, sticking, or holding onto the surface of the attached portion.
そして、抗菌性樹脂シートは、例えば、樹脂材料が、射出成形法、押出成形法、ブロー成形法、インフレーション成形法などの公知の成形方法を用いてシート状に成形されたものである。 The antibacterial resin sheet is obtained by, for example, molding a resin material into a sheet shape using a known molding method such as an injection molding method, an extrusion molding method, a blow molding method, or an inflation molding method.
また、抗菌性樹脂シートは、例えば樹脂材料に本発明の抗菌性組成物を適宜配合して混合し、混練などにより略均一組成に一体化して、上述したように公知の成形方法を用いてシート状に成形されている。この抗菌性樹脂シートは、詳細は後述する抗菌性組成物を０．０１質量％以上１０．０質量％以下で含有することが好ましく、０．０５質量％以上２．０質量％以下で含有することが特に好ましい。
ここで、抗菌性組成物の含有量が０．０１質量％より少なくなると、十分な抗菌性を発揮できなくなるおそれがある。一方、抗菌性組成物の含有量を１０．０質量％より多くしても、抗菌性能はほとんど変化がない一方、例えば成形体となる抗菌性樹脂シートの強度が低下したり、表面の平滑性などの外観が損なわれるなどの特性に影響を及ぼしたり、成形時における作業性や成形性などが低下したりするなどの不都合を生じるおそれがある。このように、必要最小限の含有量で十分な抗菌性を発揮させつつ、抗菌性組成物の含有量の増大によるコストの増大を抑えるため、抗菌性組成物の含有量を０．０１質量％以上１０．０質量％以下にすることが好ましい。
In addition, the antibacterial resin sheet is prepared by, for example, appropriately mixing and mixing the antibacterial composition of the present invention with a resin material, and integrating it into a substantially uniform composition by kneading or the like, and using a known molding method as described above. It is shaped into a shape. The antibacterial resin sheet preferably contains an antibacterial composition, which will be described later in detail, in an amount of 0.01% by mass to 10.0% by mass, and 0.05% by mass to 2.0% by mass. It is particularly preferred.
Here, if the content of the antibacterial composition is less than 0.01% by mass, sufficient antibacterial properties may not be exhibited. On the other hand, even if the content of the antibacterial composition is more than 10.0% by mass, the antibacterial performance is hardly changed. On the other hand, for example, the strength of the antibacterial resin sheet used as a molded body is reduced or the surface smoothness is reduced. This may adversely affect the properties such as the appearance of the product, and may cause inconveniences such as deterioration in workability and moldability during molding. Thus, in order to suppress the increase in cost due to the increase in the content of the antibacterial composition while exhibiting sufficient antibacterial properties with the minimum necessary content, the content of the antibacterial composition is 0.01% by mass. It is preferable to set it to 10.0 mass% or less.
そして、抗菌性樹脂シート、また多層構造とした場合における表層側に設けられる層として用いられる樹脂材料としては、特に制限はないが、ポリエチレン系樹脂、ポリプロピレン系樹脂、ポリウレタン系樹脂、ポリカーボネート系樹脂、ポリスチレン系樹脂、ポリエチレンテレフタレートなどのポリエステル系樹脂、ナイロン（ポリアミド）系樹脂、アクリル樹脂、ポリ塩化ビニル樹脂、アクリロニトリル−ブタジエン−スチレン（Acrylonitorile-Butadiene-Styrene：ＡＢＳ）樹脂などの樹脂材料の一種を単独で、または二種以上を組み合わせて使用することができる。
なお、結晶性樹脂であれば、結晶化度が比較的に低い樹脂材料を用いることが好ましい。すなわち、結晶化度が低い樹脂材料の方が、樹脂材料中に存在する抗菌性組成物による抗菌作用が発揮されやすくなるためである。
And as an antibacterial resin sheet, and a resin material used as a layer provided on the surface layer side in the case of a multilayer structure, there is no particular limitation, polyethylene-based resin, polypropylene-based resin, polyurethane-based resin, polycarbonate-based resin, A single resin material such as polystyrene resin, polyester resin such as polyethylene terephthalate, nylon (polyamide) resin, acrylic resin, polyvinyl chloride resin, acrylonitrile-butadiene-styrene (ABS) resin, etc. Or in combination of two or more.
In the case of a crystalline resin, it is preferable to use a resin material having a relatively low crystallinity. That is, the resin material having a lower crystallinity is more likely to exhibit the antibacterial effect of the antibacterial composition present in the resin material.
（抗菌性組成物）
抗菌性樹脂シートに含有される抗菌性組成物は、イミダゾール系の有機系抗菌剤のみから選ばれた２種と、無機系抗菌剤と、からなるものである。
この抗菌性組成物は、後述する表２ないし表７に示す微生物である菌類（真菌類、細菌類、藻類など）に対して、低いＭＩＣ値でも抗菌効果を奏し格段に広い抗菌スペクトルを示す。
すなわち、ＭＩＣ値を５０ｐｐｍ以下と厳しいレベルとしても、真菌類２１４種、細菌類１３１種、藻類２７種（現時点で確認済み）を示す。
(Antimicrobial composition)
The antibacterial composition contained in the antibacterial resin sheet is composed of two kinds selected from only imidazole-based organic antibacterial agents and an inorganic antibacterial agent.
This antibacterial composition exhibits an antibacterial effect even with a low MIC value against fungi (fungi, bacteria, algae, etc.), which are microorganisms shown in Tables 2 to 7, which will be described later.
That is, even when the MIC value is a severe level of 50 ppm or less, 214 species of fungi, 131 species of bacteria, and 27 species of algae (confirmed at present) are shown.
イミダゾール系の有機系抗菌剤としては、例えばベンゾイミダゾールカルバミン酸化合物、イオウ原子含有ベンゾイミダゾール化合物、ベンゾイミダゾールの環式化合物誘導体などが例示できる。 Examples of imidazole organic antibacterial agents include benzimidazole carbamic acid compounds, sulfur atom-containing benzimidazole compounds, and cyclic compound derivatives of benzimidazoles.
ベンゾイミダゾールカルバミン酸化合物としては、１Ｈ−２−ベンゾイミダゾールカルバミン酸メチル、１−ブチルカルバモイル−２−ベンゾイミダゾールカルバミン酸メチル、６−ベンゾイル−１Ｈ−２−ベンゾイミダゾールカルバミン酸メチル、６−（２−チオフェンカルボニル）−１Ｈ−２−ベンゾイミダゾールカルバミン酸メチルなどが例示できる。
イオウ原子含有ベンゾイミダゾール化合物としては、１Ｈ−２−チオシアノメチルチオベンゾイミダゾール、１−ジメチルアミノスルフォニル−２−シアノ−４−ブロモ−６−トリフロロメチルベンゾイミダゾールなどが例示できる。
ベンゾイミダゾールの環式化合物誘導体としては、２−（４−チアゾリル）−１Ｈ−ベンゾイミダゾール、２−（２−クロロフェニル）−１Ｈ−ベンゾイミダゾール、２−（１−（３，５−ジメチルピラゾリル））−１Ｈ−ベンゾイミダゾール、２−（２−フリル）−１Ｈ−ベンゾイミダゾールなどが例示できる。
Examples of the benzimidazole carbamate compound include methyl 1H-2-benzimidazole carbamate, methyl 1-butylcarbamoyl-2-benzimidazole carbamate, methyl 6-benzoyl-1H-2-benzimidazole carbamate, 6- (2- Examples include thiophenecarbonyl) -1H-2-benzimidazole carbamate methyl.
Examples of the sulfur atom-containing benzimidazole compound include 1H-2-thiocyanomethylthiobenzimidazole and 1-dimethylaminosulfonyl-2-cyano-4-bromo-6-trifluoromethylbenzimidazole.
As cyclic compound derivatives of benzimidazole, 2- (4-thiazolyl) -1H-benzimidazole, 2- (2-chlorophenyl) -1H-benzimidazole, 2- (1- (3,5-dimethylpyrazolyl)) Examples thereof include -1H-benzimidazole and 2- (2-furyl) -1H-benzimidazole.
そして、イミダゾール系の有機抗菌剤としては、イミダゾール系の有機系抗菌剤のみから選ばれた少なくとも２種のみを併用する。同一のイミダゾール系でも、異なる２種を併用することにより、微生物に対して抗菌作用の相乗効果が得られ、特に、ベンゾイミダゾール環にチアゾリル基を有するものと、ベンゾイミダゾール環にカーバメート基を有するものと、を使用することが、顕著な相乗効果が得られることから好ましい。
チアゾリル基としては、例えば２−チアゾリル、４−チアゾリル、５−チアゾリルなどが例示できる。また、カーバメート基としては、このカーバメート基における炭化水素基が、例えば、メチル、エチル、ｎ−２プロピル、ｉｓｏ−プロピル、などのアルキル基が好ましく、特にメチル基あるいはエチル基を有するものが特に好ましい。
具体的には、チアゾリル基を有するものとして、２−（４−チアゾリル）−１Ｈ−ベンゾイミダゾール（チアベンダゾール：Thiabendazole(ＴＢＺ)）などが例示できる。また、カーバメート基を有するものとして、メチル−２−ベンゾイミダゾールカルバミン酸メチル（カルベンダジム：Carbendazim(ＢＣＭ)）、エチル−２−ベンゾイミダゾールカルバミン酸メチルなどが例示できる。特に、２−（４−チアゾリル）−１Ｈ−ベンゾイミダゾールと、２−ベンゾイミダゾールカルバミン酸メチルとは、熱的安定性が比較的に高く、特に樹脂成形体として利用することが容易であり、また例えばグレープフルーツやオレンジ、バナナなどの防かび剤（食品添加物）としても既に利用され、人体への影響が比較的に小さい材料として確認されたものであることから、特に好ましい。
And as an imidazole type organic antibacterial agent, only at least 2 sorts chosen only from an imidazole type organic antibacterial agent are used together. Even in the same imidazole system, by using two different types together, a synergistic effect of antibacterial action against microorganisms can be obtained, especially those having a thiazolyl group in the benzimidazole ring and those having a carbamate group in the benzimidazole ring Is preferable because a remarkable synergistic effect is obtained.
Examples of the thiazolyl group include 2-thiazolyl, 4-thiazolyl, 5-thiazolyl and the like. Further, as the carbamate group, the hydrocarbon group in the carbamate group is preferably an alkyl group such as methyl, ethyl, n-2 propyl, iso-propyl, etc., and particularly preferably has a methyl group or an ethyl group. .
Specifically, 2- (4-thiazolyl) -1H-benzimidazole (thiabendazole (TBZ)) and the like can be exemplified as those having a thiazolyl group. Examples of those having a carbamate group include methyl-2-benzimidazole carbamate methyl (carbendazim (BCM)), ethyl-2-benzimidazole carbamate methyl, and the like. In particular, 2- (4-thiazolyl) -1H-benzimidazole and methyl 2-benzimidazole carbamate have relatively high thermal stability, and are particularly easy to use as a resin molded body. For example, it is particularly preferable because it has already been used as a fungicide (food additive) such as grapefruit, orange and banana, and has been confirmed as a material having a relatively small influence on the human body.
そして、これらイミダゾール系の有機系抗菌剤はハロゲンを含まないため、抗菌性組成物や抗菌性成形体である抗菌性樹脂シートを例えば焼却処理した場合であってもダイオキシンなどの有害物質が生成せず、環境への影響がなく好ましい。また、抗菌性組成物を樹脂材料に含有させて抗菌性樹脂シートを成形する場合に成形金型などの製造ラインにおける金属部品を腐食するなどの不都合が生じず、製造設備に特別な材料を用いた装置が不要で製造設備の簡略化や製造性の向上、装置コストの低減なども容易に得ることができるので好ましい。
また、これらイミダゾール系の有機系抗菌剤は実質的に水に不溶であるため、例えば雨露に曝されるなどの使用条件でも流れ落ちて長期間安定した抗菌性を提供できなくなるなどの不都合がない。さらに、樹脂材料と良好に混合されて抗菌性を有した成形体を提供することが容易となり、汎用性の向上も容易に図ることができる。
These imidazole-based organic antibacterial agents do not contain halogens, so that even if the antibacterial resin sheet, which is an antibacterial composition or an antibacterial molded article, is incinerated, for example, no harmful substances such as dioxin are generated. It is preferable because it does not affect the environment. In addition, when an antibacterial composition is contained in a resin material to form an antibacterial resin sheet, there is no inconvenience such as corrosion of metal parts in a production line such as a molding die, and a special material is used for manufacturing equipment. This is preferable because it eliminates the need for a conventional apparatus and simplifies manufacturing facilities, improves manufacturability, and reduces apparatus costs.
In addition, since these imidazole organic antibacterial agents are substantially insoluble in water, there is no inconvenience such as being unable to provide stable antibacterial properties for a long period of time even under use conditions such as exposure to rain. Furthermore, it becomes easy to provide a molded article that is well mixed with a resin material and has antibacterial properties, and versatility can be easily improved.
一方、無機系抗菌剤としては、亜酸化銅、銅粉、チオシアン酸銅、炭酸銅、塩化銅、硫酸銅、酸化亜鉛、硫酸亜鉛、硫酸ニッケル、銅−ニッケル合金などの無機金属化合物や、リン酸ジルコニウム、金属を担持したゼオライト、またはその塩であるリン酸ジルコニウムなどを使用することができる。特に、金属として銀または銅を担持したリン酸ジルコニウムが好ましく、より好ましくは抗菌性の高い銀系抗菌剤である銀を担持したリン酸ジルコニウムを使用する。なお、銀系抗菌剤としては、担持した形態に限らず、金属単体の銀なども対象とすることができる。
銀や銅といった金属を担持したリン酸ジルコニウムやゼオライトは、人体への安全性に優れ、抗菌速度も速く抗菌性能に優れているとともに、リン酸ジルコニウムやゼオライトに貴金属である銀を担持させることによるコストの低減などが得られるために好ましい。
特に、銀担持リン酸ジルコニウムやゼオライトを利用する場合、酸化亜鉛を併用することがより好ましい。銀担持リン酸ジルコニウムと酸化亜鉛との併用により、銀担持リン酸ジルコニウム自体および酸化亜鉛自体の抗菌作用とともに、同一の無機系である無機系抗菌剤でも併用による抗菌作用の相乗効果が得られ、より顕著な抗菌性が得られることから好ましい。さらに、酸化亜鉛との併用により、銀担持リン酸ジルコニウムやゼオライトの含有量を低減でき、貴金属である銀の使用量の低減によりコストの低減も容易に得られるので好ましい。また、銀の酸化による変色を防ぐこともできる。
On the other hand, inorganic antibacterial agents include cuprous oxide, copper powder, copper thiocyanate, copper carbonate, copper chloride, copper sulfate, zinc oxide, zinc sulfate, nickel sulfate, copper-nickel alloy and other inorganic metal compounds, phosphorus Zirconate acid, metal-supported zeolite, or zirconium phosphate which is a salt thereof can be used. In particular, zirconium phosphate supporting silver or copper as a metal is preferable, and more preferably, zirconium phosphate supporting silver which is a silver antibacterial agent having high antibacterial properties is used. The silver antibacterial agent is not limited to the supported form, and silver as a single metal can also be targeted.
Zirconium phosphate and zeolite supporting metals such as silver and copper have excellent safety to human body, fast antibacterial speed and excellent antibacterial performance, and by supporting silver which is noble metal on zirconium phosphate and zeolite This is preferable because cost reduction can be obtained.
In particular, when silver-supported zirconium phosphate or zeolite is used, it is more preferable to use zinc oxide in combination. With the combination of silver-supported zirconium phosphate and zinc oxide, the antibacterial action of silver-supported zirconium phosphate itself and zinc oxide itself, as well as the synergistic effect of the antibacterial action of the combined inorganic antibacterial agent, It is preferable because more remarkable antibacterial properties can be obtained. Furthermore, the combined use with zinc oxide is preferable because the content of silver-supported zirconium phosphate and zeolite can be reduced, and the reduction in cost can be easily obtained by reducing the amount of silver used as a noble metal. Moreover, the discoloration by silver oxidation can also be prevented.
そして、抗菌性組成物は、イミダゾール系の有機系抗菌剤と無機系抗菌剤との配合割合を、質量比で１：１〜５：１、特に２：１とすることが好ましい。
ここで、有機系抗菌剤と無機系抗菌剤との配合割合が質量比で１：１より有機系抗菌剤が少なくなると、少ないＭＩＣ値での抗菌スペクトルの拡大が得られなくなるおそれがある。一方、質量比で５：１より有機系抗菌剤が多くなると、無機系抗菌剤に比して初期抗菌性能が遅く抗菌性能の持続性が低減しやすい有機系抗菌剤の割合が多くなり、使用当初から長期間に亘って安定した顕著な抗菌性が得られなくなるおそれがある。このことから、ベンゾイミダゾール系の有機系抗菌剤と無機系抗菌剤との配合割合を、質量比で１：１〜５：１とし、有機系抗菌剤や無機系抗菌剤自体の抗菌作用とともに、有機系抗菌剤と無機系抗菌剤との併用による顕著な抗菌作用の相乗効果を適切に発揮させることが好ましい。
In the antibacterial composition, the mixing ratio of the imidazole organic antibacterial agent and the inorganic antibacterial agent is preferably 1: 1 to 5: 1, particularly 2: 1 in terms of mass ratio.
Here, if the organic antibacterial agent and the inorganic antibacterial agent are mixed at a mass ratio of less than 1: 1, the antibacterial spectrum may not be expanded with a small MIC value. On the other hand, when the amount of organic antibacterial agent is larger than 5: 1 by mass ratio, the proportion of organic antibacterial agents that are slow in initial antibacterial performance and easy to reduce the durability of antibacterial performance is higher than inorganic antibacterial agents There is a risk that stable antibacterial properties that are stable over a long period from the beginning cannot be obtained. From this, the blending ratio of the benzimidazole organic antibacterial agent and the inorganic antibacterial agent is 1: 1 to 5: 1 by mass ratio, together with the antibacterial action of the organic antibacterial agent and the inorganic antibacterial agent itself, It is preferable to appropriately exhibit a synergistic effect of remarkable antibacterial action by the combined use of an organic antibacterial agent and an inorganic antibacterial agent.
また、イミダゾール系の有機系抗菌剤として、２−（４−チアゾリル）−１Ｈ−ベンゾイミダゾールと、２−ベンゾイミダゾールカルバミン酸メチルとを併用する場合、これらの配合割合を質量比で１：１〜５：１とすることが好ましい。
ここで、２−（４−チアゾリル）−１Ｈ−ベンゾイミダゾールと、２−ベンゾイミダゾールカルバミン酸メチルとの配合割合が質量比で１：１より２−（４−チアゾリル）−１Ｈ−ベンゾイミダゾールが少なくなる、あるいは５：１より２−（４−チアゾリル）−１Ｈ−ベンゾイミダゾールが多くなると、低いＭＩＣ値で抗菌作用を示す抗菌スペクトルの数が減少、すなわち抗菌性組成物の添加量が増大するおそれがある。このことから、２−（４−チアゾリル）−１Ｈ−ベンゾイミダゾールと、２−ベンゾイミダゾールカルバミン酸メチルとの配合割合を質量比で１：１〜５：１とすることが好ましい。
In addition, when 2- (4-thiazolyl) -1H-benzimidazole and methyl 2-benzimidazole carbamate are used in combination as an imidazole-based organic antibacterial agent, the mixing ratio thereof is 1: 1 to 1 by mass ratio. 5: 1 is preferable.
Here, the mixing ratio of 2- (4-thiazolyl) -1H-benzimidazole and methyl 2-benzimidazole carbamate is less than 1: 1 by mass ratio of 2- (4-thiazolyl) -1H-benzimidazole. Or when the amount of 2- (4-thiazolyl) -1H-benzimidazole is larger than 5: 1, the number of antibacterial spectra exhibiting antibacterial activity at a low MIC value may be decreased, that is, the amount of the antibacterial composition added may be increased. There is. From this, it is preferable that the mixing ratio of 2- (4-thiazolyl) -1H-benzimidazole and methyl 2-benzimidazole carbamate is 1: 1 to 5: 1.
さらに、無機系抗菌剤として、銀を担持したリン酸ジルコニウムやゼオライトと酸化亜鉛とを併用する場合、これらの配合割合を質量比で好ましくは１：１〜１：１０、より好ましくは約１：２とする。
ここで、銀担持リン酸ジルコニウムやゼオライトと酸化亜鉛との配合割合が質量比で１：１より酸化亜鉛が少なくなると、貴金属である銀の使用量の低減による十分なコストの低減が得られにくくなる。また、銀の酸化による変色も防止できる。一方、質量比で１：１０より酸化亜鉛が多くなると、銀による十分な抗菌作用が得られにくくなって、抗菌性組成物の添加量が増大するおそれがある。このことから、銀担持リン酸ジルコニウムやゼオライトと酸化亜鉛との配合割合を質量比で１：１〜１：１０として、併用による顕著な抗菌作用の相乗効果を適切に発揮させることが好ましい。
Furthermore, when silver phosphate-supported silver phosphate or zeolite and zinc oxide are used in combination as an inorganic antibacterial agent, the mixing ratio thereof is preferably 1: 1 to 1:10, more preferably about 1: 2.
Here, when the mixing ratio of silver-supported zirconium phosphate or zeolite and zinc oxide is less than 1: 1 by mass ratio, it is difficult to obtain a sufficient cost reduction due to a reduction in the amount of silver used as a noble metal. Become. Also, discoloration due to silver oxidation can be prevented. On the other hand, when the zinc oxide is more than 1:10 by mass ratio, it is difficult to obtain a sufficient antibacterial action by silver, and the addition amount of the antibacterial composition may increase. For this reason, it is preferable that the compounding ratio of silver-supported zirconium phosphate or zeolite and zinc oxide is 1: 1 to 1:10 by mass ratio to appropriately exhibit a synergistic effect of remarkable antibacterial action by the combined use.
〔実施の形態の作用効果〕
このような本発明の抗菌性組成物によれば、ハロゲン基を有さず皮膚刺激性が認められない少なくとも２種のイミダゾール系の有機系抗菌剤と、無機系抗菌剤とを併用しているので、有機系抗菌剤と無機系抗菌剤との併用による相乗効果に加え、同一のイミダゾール系でも２種の有機系抗菌剤、特に２種のみを併用することによる相乗効果を得ることができる。
このため、仮に抗菌性組成物が皮膚に付着したり、抗菌性組成物を含有する成形体に利用者や製造者が接触したりしても、かぶれるなどの人体に影響がなく、また焼却処理などの際にダイオキシンなどの有害物質が発生せず、環境汚染を良好に抑制でき、人体や環境に影響がなく安全性に優れた良好な抗菌作用を提供できる。さらに、２種のイミダゾール系の有機系抗菌剤自体および無機系抗菌剤自体の抗菌作用とともに、単独では繁殖を阻止できなかった菌類に対しても、有機系抗菌剤および無機系抗菌剤の併用による相乗効果の抗菌性を示し、低いＭＩＣ値でも格段に広い抗菌スペクトルが得られ、効率よく高い抗菌作用を容易に得ることができる。
[Effects of Embodiment]
According to such an antibacterial composition of the present invention, an inorganic antibacterial agent is used in combination with at least two kinds of imidazole organic antibacterial agents that do not have a halogen group and do not have skin irritation. Therefore, in addition to the synergistic effect by the combined use of the organic antibacterial agent and the inorganic antibacterial agent, a synergistic effect can be obtained by using two types of organic antibacterial agents, particularly only two types, even in the same imidazole type.
For this reason, even if the antibacterial composition adheres to the skin or the user or manufacturer comes into contact with the molded body containing the antibacterial composition, there is no effect on the human body such as rash, and incineration treatment In this case, no harmful substances such as dioxin are generated, and environmental pollution can be well controlled, and a good antibacterial action excellent in safety can be provided without affecting the human body and the environment. In addition to the antibacterial action of the two imidazole organic antibacterial agents themselves and the inorganic antibacterial agent itself, the combination of the organic antibacterial agent and the inorganic antibacterial agent is also effective for fungi that could not be prevented from propagating alone. It exhibits a synergistic antibacterial effect, and a much broader antibacterial spectrum can be obtained even at a low MIC value, and a high antibacterial action can be easily obtained efficiently.
そして、本発明の抗菌性組成物によれば、イミダゾール系の有機系抗菌剤として、ベンゾイミダゾール環にチアゾリル基を有するものとカーバメート基を有するものとの２種を併用するので、同一のゾイミダゾール系でも、人体や環境に影響がなく、かつ、相乗効果による低いＭＩＣ値でも格段に広い抗菌スペクトルが得られるという抗菌作用が容易に得られ、特にこれらの併用により顕著な抗菌性が得られる。
特に、ベンゾイミダゾール環にチアゾリル基を有する２−（４−チアゾリル）−１Ｈ−ベンゾイミダゾールと、カーバメート基を有する２−ベンゾイミダゾールカルバミン酸メチルとの２種を併用するので、併用による相乗効果にて顕著な抗菌性を発揮できる。さらに、これら２−（４−チアゾリル）−１Ｈ−ベンゾイミダゾールおよび２−ベンゾイミダゾールカルバミン酸メチルは、比較的に製造しやすく入手が容易で、既に利用されている材料で安全性が認められたものであることから、容易に利用でき、汎用性を向上できる。
According to the antibacterial composition of the present invention, since two types of imidazole organic antibacterial agents, one having a thiazolyl group and one having a carbamate group in the benzimidazole ring, are used in combination. Even in the system, an antibacterial action is obtained that does not affect the human body and the environment, and that a much broader antibacterial spectrum can be obtained even with a low MIC value due to a synergistic effect.
In particular, since two types of 2- (4-thiazolyl) -1H-benzimidazole having a thiazolyl group in the benzimidazole ring and methyl 2-benzimidazole carbamate having a carbamate group are used in combination, Can exhibit remarkable antibacterial properties. Furthermore, these 2- (4-thiazolyl) -1H-benzimidazole and methyl 2-benzimidazole carbamate are relatively easy to produce and readily available, and have been confirmed to be safe from materials that have already been used. Therefore, it can be easily used and versatility can be improved.
また、本発明の抗菌性組成物によれば、無機系抗菌剤として、イミダゾール系の有機系抗菌剤との相乗効果が得られる銀担持リン酸ジルコニウムと酸化亜鉛とのうちの少なくともいずれか一方を用いるので、顕著な抗菌性が容易に得られる。特に、銀担持リン酸ジルコニウムと酸化亜鉛とを併用することにより、銀担持リン酸ジルコニウム自体および酸化亜鉛自体による抗菌作用とともに、これら同一系である無機系抗菌剤でも、併用することで抗菌作用の相乗効果も得られ、より顕著な抗菌性を発揮できる。また、銀担持リン酸ジルコニウムと酸化亜鉛との併用により、抗菌性を損なうことなく、貴金属である銀の使用量を低減でき、コストをより容易に低減できる。
さらに、高い抗菌性を示す銀の使用形態として、リン酸ジルコニウムに銀を担持させた形態としている。このため、必要最小限の量で貴金属である銀による抗菌作用を発揮でき、無機系抗菌剤による抗菌作用および有機系抗菌剤との抗菌作用の相乗効果を効率よく発揮でき、コストをより容易に低減できる。
Further, according to the antibacterial composition of the present invention, as the inorganic antibacterial agent, at least one of silver-supported zirconium phosphate and zinc oxide capable of obtaining a synergistic effect with the imidazole organic antibacterial agent is used. Since it is used, remarkable antibacterial properties can be easily obtained. In particular, when silver-supported zirconium phosphate and zinc oxide are used in combination, the antibacterial effect of silver-supported zirconium phosphate itself and zinc oxide itself, as well as these inorganic antibacterial agents, which are the same system, can be used together. A synergistic effect is also obtained, and more remarkable antibacterial properties can be exhibited. In addition, the combined use of silver-supported zirconium phosphate and zinc oxide makes it possible to reduce the amount of silver used as a noble metal without impairing antibacterial properties, and to reduce costs more easily.
Furthermore, as a usage form of silver exhibiting high antibacterial properties, a form in which silver is supported on zirconium phosphate is used. For this reason, the antibacterial effect of silver, which is a noble metal, can be exerted in the minimum necessary amount, and the synergistic effect of the antibacterial effect of an inorganic antibacterial agent and the antibacterial effect of an organic antibacterial agent can be efficiently exhibited, making cost easier Can be reduced.
〔実施の形態の変形例〕
なお、以上に説明した態様は、本発明の一態様を示したものであって、本発明は、前記した実施形態に限定されるものではなく、本発明の目的および効果を達成できる範囲内での変形や改良が、本発明の内容に含まれるものであることはいうまでもない。また、本発明を実施する際における具体的な構造および形状などは、本発明の目的および効果を達成できる範囲内において、他の構造や形状などとしても問題はない。
[Modification of Embodiment]
The aspect described above shows one aspect of the present invention, and the present invention is not limited to the above-described embodiment, and within the scope of achieving the objects and effects of the present invention. Needless to say, the modifications and improvements are included in the contents of the present invention. In addition, the specific structure and shape in carrying out the present invention may be used as other structures and shapes within the scope of achieving the object and effect of the present invention.
すなわち、本発明の抗菌性組成物として抗菌性樹脂シートの成形体に含有させた構成について例示したが、上述したように、シート状に限らず、フィルム、繊維、射出成形体、ブロー成形体などの各種成形体であってもよく、例えば、畳である化学畳、壁紙、合成皮革、床材などに使用できる。
なお、例えば畳表としては、上述した抗菌性組成物をあらかじめ分散したポリオレフィン樹脂をインフレーション成形によりフィルムに成形し、このフィルムを紙縒り状にねじって繊維形態に整え、各繊維を織り込んで畳表として仕上げるなどが例示できる。
That is, although the composition contained in the molded article of the antibacterial resin sheet was exemplified as the antibacterial composition of the present invention, as described above, it is not limited to the sheet form, but a film, fiber, injection molded article, blow molded article, etc. For example, it can be used for chemical tatami mats, wallpaper, synthetic leather, flooring, and the like.
For example, as a tatami mat, a polyolefin resin in which the above-described antibacterial composition is dispersed in advance is formed into a film by inflation molding, the film is twisted into a paper shape to prepare a fiber form, and each fiber is woven and finished as a tatami mat. Can be illustrated.
また、本発明の抗菌性組成物を、溶液中に略均一分散させて使用すると、溶液中の菌、黴、藻などとの接触効率がよくなるため、特に低濃度、例えば使用時の抗菌性組成物の濃度が１０ｐｐｍ以上１０００ｐｐｍ以下の溶液でも、実用上問題なく使用できる、すなわち十分な抗菌効果が得られ、経済性および安全性に優れている。
そして、溶液に入れて使用する用途としては、例えば、クーリングタワーなどの冷却水や、衣類用洗剤などの洗浄剤、あるいは旋盤などの工作機械の潤滑油などへ添加して抗菌作用を発揮させたりするなど、抗菌のために各部位に適用できる。
Further, when the antibacterial composition of the present invention is used in a substantially uniform dispersion in a solution, the contact efficiency with bacteria, sputum, algae, etc. in the solution is improved. Even a solution having an object concentration of 10 ppm or more and 1000 ppm or less can be used practically without problems, that is, a sufficient antibacterial effect can be obtained, and the economy and safety are excellent.
And as an application to be used in the solution, for example, it is added to cooling water such as a cooling tower, a detergent such as a laundry detergent, or a lubricating oil of a machine tool such as a lathe to exert an antibacterial effect. It can be applied to each part for antibacterial.
また、シート状の形態に限らず、例えば樹脂部品の成形体としたり、樹脂繊維として形成したり、この樹脂繊維の織布や不織布など、いずれの形態とすることもできる。
さらには、樹脂部材に限らず、例えば生コンクリートに添加して生成したコンクリート製品や、木片などと接着剤とともに混合して板状に成形した合板などとして適用することもできる。
また、具体的用途として、エアコンやカーエアコンの風路やドレン部位、洗濯機や冷蔵庫、食器乾燥機、便座、浄水器、トイレケース付きブラシなどの住宅設備機器、繊維製品（エプロン、布巾、病院制服、家具張地、カーテンなど）、まな板、水切り袋、風呂マットや風呂桶などの水廻り製品や風呂・台所などの水回り部位、建築クレーナ、内外装塗料、車両内装材、カーペット、クーリングタワーの冷却水流路の部位や用水路、花壇や花瓶などに広く適用することができる。
Further, the present invention is not limited to a sheet form, and may be any form such as a molded part of a resin component, a resin fiber, a woven fabric or a nonwoven fabric of the resin fiber.
Furthermore, the present invention is not limited to the resin member, and may be applied as, for example, a concrete product produced by adding to ready-mixed concrete, a plywood formed by mixing with a piece of wood and an adhesive and forming into a plate shape.
Specific applications include air conditioners and car air conditioners, drainage parts, washing machines, refrigerators, tableware dryers, toilet seats, water purifiers, brushes with toilet cases, textile products (aprons, cloths, hospitals, etc.) Uniforms, furniture upholstery, curtains, etc.), cutting boards, draining bags, watering products such as bath mats and bath tubs, watering parts such as baths and kitchens, architectural cleaners, interior and exterior paints, vehicle interior materials, carpets, and cooling towers The present invention can be widely applied to parts of cooling water passages, irrigation canals, flower beds and vases.
さらに、抗菌性組成物として、２種のイミダゾール系の有機系抗菌剤と、無機系抗菌剤とからなる構成としたが、不可避的に混入する物質が混入する構成も対象となることは言うまでもない。また、成形体の基材となる合成樹脂や溶媒、または磁石として利用するための磁性粉体、あるいは繊維強化プラスチック（Fiber Reinforced Plastic：ＦＲＰ）などのように成形体の強度向上のためのガラスファイバや樹脂ファイバ、インクなどの顔料など、抗菌性組成物の各成分と機能干渉せずに独立して機能する添加部材を加えた構成としても対象とすることができる。 Furthermore, the antibacterial composition is composed of two kinds of imidazole-based organic antibacterial agents and inorganic antibacterial agents, but it goes without saying that a configuration in which substances that are inevitably mixed are also included. . Also, glass fiber for improving the strength of the molded body such as synthetic resin and solvent as the base material of the molded body, magnetic powder for use as a magnet, or fiber reinforced plastic (FRP). It is also possible to use a configuration in which additive members that function independently without interfering with each component of the antibacterial composition, such as pigments such as resin fibers and ink, are added.
なお、塗布や散布などにより抗菌性組成物を含有する抗菌性成形体としての塗膜を形成する場合、塗膜を形成する樹脂として、例えば、ウレタン系樹脂、アクリル系樹脂、ポリエステル系樹脂、ビニル系樹脂などの公知の溶剤系、水系、ＵＶ硬化型の種々の材料を使用することができる。また、抗菌性組成物を含有させたこれらの材料を成形体に対して塗工するには、スプレーコーティング、ナイフコーティング、グラビアコーティング、フローコーティング、ダイコーティング、コンマコーティングなどの各種コーティング手段や、スクリーン印刷、パッド印刷、オフセット印刷などの各種印刷手段を、使用する材料の種類や目的に応じて適宜選択することができる。
さらに、本発明の抗菌性組成物を、ポリウレタン系樹脂、不飽和ポリエステル樹脂、アクリル樹脂、ビニル樹脂などの水系樹脂溶液やエマルジョンに含有させて、ディッピング加工剤、繊維吸尽加工剤、コーティング剤などの塗布材料として使用してもよい。
In addition, when forming a coating film as an antibacterial molded article containing an antibacterial composition by coating or spraying, as the resin forming the coating film, for example, urethane resin, acrylic resin, polyester resin, vinyl Various known solvent-based, water-based, and UV-curable materials such as resin can be used. In addition, in order to apply these materials containing antibacterial compositions to molded products, various coating means such as spray coating, knife coating, gravure coating, flow coating, die coating, comma coating, screens, etc. Various printing means such as printing, pad printing, and offset printing can be appropriately selected according to the type and purpose of the material to be used.
Furthermore, the antibacterial composition of the present invention is contained in a water-based resin solution or emulsion such as polyurethane resin, unsaturated polyester resin, acrylic resin, vinyl resin, and the like, dipping agent, fiber exhaust agent, coating agent, etc. It may be used as a coating material.
また、イミダゾール系の有機系抗菌剤としては、２−（４−チアゾリル）−１Ｈ−ベンゾイミダゾールと、２−ベンゾイミダゾールカルバミン酸メチルとに限らず、上述した各種ベンゾイミダゾール系の組成物を組み合わせた構成として適用することができる。
さらに、各配合割合についても、利用部位や用途などに対応して適宜設定することができる。
In addition, the imidazole organic antibacterial agent is not limited to 2- (4-thiazolyl) -1H-benzimidazole and methyl 2-benzimidazole carbamate, and the above-described various benzimidazole compositions are combined. It can be applied as a configuration.
Furthermore, each blending ratio can also be set as appropriate in accordance with the use site and application.
その他、本発明の実施における具体的な構造および形状などは、本発明の目的を達成できる範囲で他の構造等としてもよい。 In addition, the specific structure, shape, and the like in the implementation of the present invention may be other structures as long as the object of the present invention can be achieved.
以下、実施例および比較例などを挙げて、本発明をより具体的に説明するが、本発明は実施例などの内容に何ら限定されるものではない。 EXAMPLES Hereinafter, although an Example, a comparative example, etc. are given and this invention is demonstrated more concretely, this invention is not limited to the content, such as an Example, at all.
〔実験１〕
（実施例１および比較例１，２）
表１に記載される処方の各成分を混合して、実施例１および比較例１，２の抗菌性組成物を調製した。
なお、比較例１の構成は、実施例１において無機系抗菌剤を配合せず、各成分を等量（１／２）ずつ混合したものである。また、比較例２の構成は、実施例１において有機系抗菌剤を配合せず、実施例１における無機系抗菌剤の各成分と同一の成分にて適宜配合したものである（銀担持リン酸ジルコニウム３３質量％、酸化亜鉛６７質量％）。
[Experiment 1]
(Example 1 and Comparative Examples 1 and 2)
The antibacterial compositions of Example 1 and Comparative Examples 1 and 2 were prepared by mixing the components of the formulation described in Table 1.
In addition, the structure of the comparative example 1 does not mix | blend an inorganic type antibacterial agent in Example 1, but mixes each component by equal amount (1/2). Further, the constitution of Comparative Example 2 is one in which the organic antibacterial agent is not blended in Example 1, but is appropriately blended with the same components as those of the inorganic antibacterial agent in Example 1 (silver-supported phosphoric acid) Zirconium 33% by mass, zinc oxide 67% by mass).
（抗菌性組成物の処方）
（試験方法）
抗菌性組成物の抗菌性能試験を実施した。
抗菌性能試験としては、実施例１および比較例１，２で得られた抗菌性組成物について、下記の試験方法に従って最小生育阻止濃度（ＭＩＣ値：ｐｐｍ）を測定し、抗菌性能を評価した。
(Test method)
An antibacterial performance test of the antibacterial composition was performed.
As the antibacterial performance test, the antibacterial compositions obtained in Example 1 and Comparative Examples 1 and 2 were measured for the minimum growth inhibitory concentration (MIC value: ppm) according to the following test method to evaluate the antibacterial performance.
(１)抗菌性組成物を所定の濃度（１０００ｐｐｍ、１００ｐｐｍ、５０ｐｐｍなど）となるように、ジメチルスルホキシドで希釈して抗菌剤懸濁液を調製した。
(２)９ｃｍシャーレに、１２１℃で２０分オートクレーブ殺菌した寒天培地を９ｍｌ流し込み、(１)で調製した抗菌剤懸濁液を１ｍｌ添加して攪拌した。そして、シャーレを室温で放置して、寒天培地を固化させた。
(３)また、別途、１×１０6ＣＦＵ／ｍｌとなるように試験菌株を希釈して、この試験菌株と４０℃で保温した減菌済０．９％寒天培地５ｍｌとを混合して、試験菌株含有寒天溶液を調製した。
(４)(２)の寒天培地上に(３)で調製した試験菌株含有寒天溶液を重層して、固化させた。インキュベータ内にて、真菌は２７℃、７２時間培養後、また、細菌は３０℃、２４時間培養後それぞれ生育を確認した。このうち、試験菌が生育しない培地の中でもっとも抗菌性組成物の濃度の低いものを最低生育阻止濃度（ＭＩＣ値：ｐｐｍ）とした。結果を表２〜表７に示す。
(1) The antibacterial composition was diluted with dimethyl sulfoxide so as to have a predetermined concentration (1000 ppm, 100 ppm, 50 ppm, etc.) to prepare an antibacterial agent suspension.
(2) 9 ml of an agar medium autoclaved at 121 ° C. for 20 minutes was poured into a 9 cm petri dish, and 1 ml of the antibacterial agent suspension prepared in (1) was added and stirred. The petri dish was allowed to stand at room temperature to solidify the agar medium.
(3) Separately, the test strain is diluted to 1 × 10 6 CFU / ml, and this test strain is mixed with 5 ml of a sterilized 0.9% agar medium kept at 40 ° C. A test strain-containing agar solution was prepared.
(4) The test strain-containing agar solution prepared in (3) was overlaid on the agar medium of (2) and solidified. In the incubator, the fungus was cultured at 27 ° C. for 72 hours, and the bacteria were cultured at 30 ° C. for 24 hours. Of these, the medium with the lowest concentration of the antibacterial composition among the media in which the test bacteria did not grow was defined as the minimum growth inhibitory concentration (MIC value: ppm). The results are shown in Tables 2 to 7.
（結果：真菌類（１））
（結果：真菌類（２））
（結果：真菌類（３））
（結果：細菌類（１））
（結果：細菌類（２））
（結果：藻類）
通常、固形分への添加濃度は、ＭＩＣ値の１００倍以上であることから、経済性や安全性などを考慮して、ＭＩＣ値が５０ｐｐｍ以下を本実施例と定義した。
すなわち、社団法人繊維評価技術協議会の定義（規格値）は８００ｐｐｍ以下ならば抗菌剤として合格レベルであるが、８００ｐｐｍの１００倍では８質量％配合することとなり、経済性や抗菌性成形物あるいは抗菌性溶液としての物性的にも影響が生じるおそれがある。
上述したように、表２ないし表７に示す結果からわかるように、実施例１の抗菌性組成物はいずれの試験菌類（真菌類、細菌類、藻類）に対しても、ＭＩＣ値が５０ｐｐｍ以下であり、極めて低い濃度で多くの各種試験菌類の増殖を阻止することができた。このように、実施例１の抗菌性組成物が幅広い抗菌スペクトルを有し、幅広い菌類に対しても効果的に対応することが可能であることが確認できた。
Usually, since the concentration added to the solid content is 100 times or more of the MIC value, the MIC value is defined as 50 ppm or less in consideration of economy and safety.
In other words, the definition (standard value) of the Japan Textile Evaluation Technology Council is a pass level as an antibacterial agent if it is 800 ppm or less, but if it is 100 times 800 ppm, 8% by mass will be blended. The physical properties of the antibacterial solution may also be affected.
As described above, as can be seen from the results shown in Tables 2 to 7, the antibacterial composition of Example 1 has an MIC value of 50 ppm or less for any test fungus (fungi, bacteria, algae). It was possible to inhibit the growth of many various test fungi at extremely low concentrations. Thus, it was confirmed that the antibacterial composition of Example 1 has a broad antibacterial spectrum and can effectively cope with a wide range of fungi.
〔実験２〕
（試料）
本発明の抗菌性成形体として、畳表を作製し、抗菌性について比較評価した。
実施例２として、実施例１の抗菌性組成物を０．２質量％でポリオレフィン樹脂に混合・混練し、インフレーション成形によりポリオレフィンフィルムを作製し、繊維状に成形した後、畳表に織り上げたものとした。
比較例３として、市販抗菌剤であるチアベダゾールを０．２質量％の配合割合で、実施例２と同様にしてポリオレフィンの畳表を作製したものとした。比較例４として、銀担持ゼオライト（シナネンセオミック（商品名））を０．２質量％の配合割合、比較例５として、銀担持ゼオライト（シナネンセオミック（商品名））を１．０質量％の配合割合で、実施例２と同様にしてポリオレフィンの畳表を作製したものとした。比較例６としては、抗菌剤を配合せずに、実施例２と同様にしてポリオレフィンの畳表を作製したものとした。
[Experiment 2]
(sample)
A tatami mat was prepared as the antibacterial molded article of the present invention, and the antibacterial properties were comparatively evaluated.
As Example 2, 0.2% by mass of the antibacterial composition of Example 1 was mixed and kneaded with a polyolefin resin, a polyolefin film was produced by inflation molding, formed into a fiber, and then woven into a tatami surface. did.
As Comparative Example 3, a polyolefin tatami table was prepared in the same manner as in Example 2 at a blending ratio of 0.2% by mass of thiabedazole, which is a commercially available antibacterial agent. As Comparative Example 4, 0.2% by mass of silver-supported zeolite (Sinanentheomic (trade name)) is used, and as Comparative Example 5, 1.0% by mass of silver-supported zeolite (Sinanen Theomic (trade name)). In the same manner as in Example 2, the tatami mat surface of polyolefin was prepared. As Comparative Example 6, a polyolefin tatami mat was prepared in the same manner as in Example 2 without blending an antibacterial agent.
（評価方法）
（１）無機塩培地の調製
表８に示す無機塩培地を調製し、これを１２１℃で２０分間オートクレーブ殺菌後、苛性ソーダ水溶液（ＮａＯＨ水溶液）によりｐＨが６．０〜６．５となるように調整した。
(Evaluation methods)
(1) Preparation of inorganic salt medium An inorganic salt medium shown in Table 8 was prepared, and after autoclaving at 121 ° C. for 20 minutes, the pH was adjusted to 6.0 to 6.5 with an aqueous caustic soda solution (NaOH aqueous solution). It was adjusted.
（無機塩培地）
（２）混合胞子液の調製
以下の表９に示した菌株からなるカビの胞子を減菌水に懸濁させ、ろ過して濃度が約１×１０6ｃｅｌｌ／ｍｌの混合胞子液を調製した。なお、胞子の懸濁には、ラウリル硫酸ナトリウムを用いて分散を行うようにした。
(2) Preparation of mixed spore solution Mold spores composed of the strains shown in Table 9 below were suspended in sterilized water and filtered to prepare a mixed spore solution having a concentration of about 1 × 10 6 cells / ml. . The spore suspension was dispersed using sodium lauryl sulfate.
（菌株の種類）
（３）（１）で調製した無機塩培地に（２）で調製した混合胞子液をまいた後、上から実施例２、比較例３，４をサイズ５０ｍｍ×５０ｍｍに切断した試験片のそれぞれを載せた後、温度を２８℃、湿度を８５％ＲＨ以上とした状態で２８日間カビを培養させた。そして、カビの生育状況を目視で確認し、表１０に示す判定基準を用いて評価した。その結果を表１１に示す。
また、実施例２および比較例２〜６について、社団法人繊維評価技術協議会で規定され菌種として黄色ブドウ球菌における殺菌活性値（一般用途）についても比較評価した。その結果を表１１に合わせて示す。
(3) After sprinkling the mixed spore solution prepared in (2) on the inorganic salt medium prepared in (1), each of the test pieces obtained by cutting Example 2 and Comparative Examples 3 and 4 into a size of 50 mm × 50 mm from above. Then, the mold was cultured for 28 days in a state where the temperature was 28 ° C. and the humidity was 85% RH or more. And the growth condition of mold | fungi was confirmed visually and it evaluated using the criteria shown in Table 10. The results are shown in Table 11.
Moreover, about Example 2 and Comparative Examples 2-6, the bactericidal activity value (general use) in Staphylococcus aureus as a bacterial species prescribed | regulated by the corporation fiber evaluation technical meeting was also comparatively evaluated. The results are also shown in Table 11.
（判定基準）
（評価結果）
この表１１に示すように、本発明の抗菌性組成物を含有する畳表は、従来の防かび剤であるチアベンダゾール配合品の畳表よりも明確に強い防かび性を発揮することが認められた。また、実施例２については、社団法人繊維評価技術協議会で規定された殺菌活性値（一般用途）についても、ｌｏｇ（Ａ／Ｃ）≧０（Ａ：接種直後の標準布の菌数、Ｃ：１８時間培養後の加工布の生菌数）を満たし、抗菌評価（殺菌活性値）も良好であった。 As shown in Table 11, it was recognized that the tatami mat containing the antibacterial composition of the present invention exhibits a fungicide that is clearly stronger than the tatami mat of the thiabendazole compound that is a conventional fungicide. Moreover, about Example 2, also about the bactericidal activity value (general use) prescribed | regulated by the corporation fiber evaluation technical meeting, log (A / C)> = 0 (A: the number of bacteria of the standard cloth immediately after inoculation, C : Viable count of processed cloth after 18 hours of culture) and antibacterial evaluation (bactericidal activity value) was also good.
〔実験３〕
（試料）
本発明の抗菌性組成物含有溶液として、洗浄剤である床面処理剤としての床用ワックスを調製し、抗菌性について比較評価した。
試料としては、プロペラ式攪拌機により、エチルアルコール、下記の界面活性剤、および実施例１の抗菌性組成物を投入して十分に攪拌し、抗菌性組成物含有溶液を調製した。配合比は、エチルアルコール６８質量％、実施例１の抗菌性組成物３０質量％、上述の界面活性剤２質量％とした。
なお、界面活性剤は、脂肪族高級アルコールエチレンオキサイド付加物を１質量％、直鎖アルキルベンゼンスルホン酸１質量％の混合物である。
[Experiment 3]
(sample)
As the antibacterial composition-containing solution of the present invention, floor wax as a floor surface treatment agent, which is a cleaning agent, was prepared and comparatively evaluated for antibacterial properties.
As a sample, ethyl alcohol, the following surfactant, and the antibacterial composition of Example 1 were charged with a propeller-type stirrer and stirred sufficiently to prepare an antibacterial composition-containing solution. The blending ratio was 68% by mass of ethyl alcohol, 30% by mass of the antibacterial composition of Example 1, and 2% by mass of the surfactant described above.
The surfactant is a mixture of 1% by mass of aliphatic higher alcohol ethylene oxide adduct and 1% by mass of linear alkylbenzene sulfonic acid.
（試験方法）
（１）上述した方法で調製した抗菌性組成物含有溶液と、市販の床用ワックス（横浜油脂工業製 商品名：ＬＩＮＤＡ スーパーハードコート）とを、プロペラ式攪拌機を用いて適宜攪拌混合し、クリーナワックスを調製した。このクリーナワックスは、抗菌性組成物の配合量が、このクリーンワックスの乾燥後の含有率として、０質量％、０．０５質量％および０．２質量％となる状態に調製した。
（２）ポリエチレンシートに（１）で調製したクリーナワックスを７０ｇ／ｍ2となる状態に均一塗布し、自然乾燥し、試験片とした。なお、乾燥後の目付は、約１８ｇ／ｍ2であった。そして、各試験片の社団法人繊維評価技術協議会で規定され菌種として黄色ブドウ球菌、肺炎桿菌およびメチシリン・レジスタント・スタヒロコッカス・アウレウス（ＭＲＳＡ）における殺菌活性値（一般用途）についても比較評価した。その結果を表１２に示す。
(Test method)
(1) The antibacterial composition-containing solution prepared by the above-described method and a commercially available wax for flooring (trade name: LINDA Super Hard Coat, manufactured by Yokohama Oils & Fats Industries Co., Ltd.) are appropriately stirred and mixed using a propeller-type stirrer. A wax was prepared. This cleaner wax was prepared so that the content of the antibacterial composition was 0% by mass, 0.05% by mass, and 0.2% by mass as the content of the clean wax after drying.
(2) The cleaner wax prepared in (1) was uniformly applied to a polyethylene sheet in a state of 70 g / m 2 and naturally dried to obtain a test piece. The basis weight after drying was about 18 g / m 2 . In addition, the bactericidal activity values (general use) of Staphylococcus aureus, Klebsiella pneumoniae and Methicillin resistant Stahirococcus aureus (MRSA) as the bacterial species specified by the Japan Textile Evaluation Technology Council for each specimen are also compared. evaluated. The results are shown in Table 12.
（評価方法）
評価方法は、上述した実験２の評価方法と同様に実施した。すなわち、表８に示す無機塩培地に表９に示す混合胞子液をまいた後、作製した試験片を載せ、温度を２８℃、湿度を８５％ＲＨ以上とした状態で２８日間カビを培養させた。そして、カビの生育状況を目視で確認し、上述した表１０に示す判定基準を用いて評価した。その結果を、表１３に示す。
(Evaluation methods)
The evaluation method was the same as the evaluation method of Experiment 2 described above. That is, after spreading the mixed spore solution shown in Table 9 on the inorganic salt medium shown in Table 8, the prepared test piece was placed, and the mold was cultured for 28 days in a state where the temperature was 28 ° C. and the humidity was 85% RH or more. It was. And the growth condition of mold | fungi was confirmed visually and it evaluated using the criteria shown in Table 10 mentioned above. The results are shown in Table 13.
（殺菌活性性値）
（評価結果）
これら表１２および表１３に示すように、抗菌性組成物を０．０５質量％の低濃度でも殺菌効果が認められ、０．２質量％配合した塗板では、抗菌性および抗カビ性とも、非常に優れていることが認められた。 As shown in Table 12 and Table 13, the antibacterial effect was observed even at a low concentration of 0.05% by mass of the antibacterial composition. It was found to be excellent.
Claims (16)
無機系抗菌剤と、からなる
ことを特徴とした抗菌性組成物。 At least two selected from imidazole-based organic antibacterial agents;
An antibacterial composition comprising an inorganic antibacterial agent.
前記イミダゾール系の有機系抗菌剤から選ばれた２種は、ベンゾイミダゾール環にチアゾリル基を有するものと、ベンゾイミダゾール環にカーバメート基を有するものとである
ことを特徴とした抗菌性組成物。 The antibacterial composition according to claim 1,
Two types selected from the imidazole organic antibacterial agents are those having a thiazolyl group in the benzimidazole ring and those having a carbamate group in the benzimidazole ring.
前記イミダゾール環にチアゾリル基を有するものは、２−（４−チアゾリル）−１Ｈ−ベンゾイミダゾールであり、
前記ベンゾイミダゾール環にカーバメート基を有するものは、２−ベンゾイミダゾールカルバミン酸メチルである
ことを特徴とした抗菌性組成物。 An antibacterial composition according to claim 2,
What has a thiazolyl group in the imidazole ring is 2- (4-thiazolyl) -1H-benzimidazole,
What has a carbamate group in the said benzimidazole ring is methyl 2-benzimidazole carbamate. The antibacterial composition characterized by the above-mentioned.
前記無機系抗菌剤は、銀系抗菌剤と酸化亜鉛とのうちの少なくともいずれか一方である
ことを特徴とした抗菌性組成物。 The antibacterial composition according to any one of claims 1 to 3,
The antibacterial composition, wherein the inorganic antibacterial agent is at least one of a silver antibacterial agent and zinc oxide.
前記銀系抗菌剤は、銀を担持したジルコニウムまたはその塩あるいはゼオライトである
ことを特徴とした抗菌性組成物。 An antibacterial composition according to claim 4,
The antibacterial composition characterized in that the silver-based antibacterial agent is zirconium carrying a silver, a salt thereof, or a zeolite.
前記無機系抗菌剤は、前記銀を担持したジルコニウムまたはその塩あるいはゼオライトと前記酸化亜鉛との配合割合が、質量比で１：１〜１：１０である
ことを特徴とした抗菌性組成物。 An antibacterial composition according to claim 5,
The antibacterial composition characterized in that the inorganic antibacterial agent has a mass ratio of 1: 1 to 1:10 of zirconium carrying a silver or a salt thereof or zeolite and the zinc oxide.
前記イミダゾール系の有機系抗菌剤と前記無機系抗菌剤との配合割合は、質量比で１：１〜５：１である
ことを特徴とした抗菌性組成物。 The antibacterial composition according to any one of claims 1 to 6,
The mixing ratio of the imidazole organic antibacterial agent and the inorganic antibacterial agent is 1: 1 to 5: 1 by mass ratio.
ハロゲン化合物を含まず、実質的に水に不溶である
ことを特徴とした抗菌性組成物。 The antibacterial composition according to any one of claims 1 to 7,
An antibacterial composition characterized by being free of halogen compounds and substantially insoluble in water.
ことを特徴とした抗菌性成形体。 An antibacterial molded article comprising the antibacterial composition according to any one of claims 1 to 8.
前記抗菌性組成物は、０．０１質量％以上１０．０質量％以下で含有された
ことを特徴とした抗菌性成形体。 The antibacterial molded article according to claim 9,
The antibacterial composition is contained in an amount of 0.01% by mass or more and 10.0% by mass or less.
前記無機系抗菌剤が全体質量に対して０．５質量％未満の割合で含有される状態に前記抗菌性組成物が含有され、
社団法人繊維評価技術協議会で規定された殺菌活性値（一般用途）が、以下の条件である
ｌｏｇ（Ａ／Ｃ）≧０
Ａ：接種直後の標準布の菌数
Ｃ：１８時間培養後の加工布の生菌数
菌種：黄色ブドウ球菌と肺炎桿菌
ことを特徴とした抗菌性成形体。 The antibacterial molded article according to claim 9 or 10,
The antibacterial composition is contained in a state where the inorganic antibacterial agent is contained in a proportion of less than 0.5% by mass with respect to the total mass,
The bactericidal activity value (general use) specified by the Japan Textile Evaluation Technology Council is the following condition: log (A / C) ≧ 0
A: Number of bacteria in standard cloth immediately after inoculation C: Number of viable bacteria in processed cloth after 18 hours of cultivation Bacterial species: Staphylococcus aureus and Klebsiella pneumoniae
ことを特徴とした抗菌性組成物含有溶液。 An antibacterial composition-containing solution, wherein the antibacterial composition according to any one of claims 1 to 8 is dispersed in the solution.
前記抗菌性組成物は、濃度が０．１質量％以上５０質量％以下で分散された
ことを特徴とした抗菌性組成物含有溶液。 An antibacterial composition-containing solution according to claim 12,
The antibacterial composition-containing solution, wherein the antibacterial composition is dispersed at a concentration of 0.1% by mass to 50% by mass.
使用時における前記抗菌性組成物の濃度が１０ｐｐｍ以上１０００ｐｐｍ以下に希釈可能に分散された
ことを特徴とした抗菌性組成物含有溶液。 An antibacterial composition-containing solution according to claim 12,
The antibacterial composition-containing solution, wherein the concentration of the antibacterial composition at the time of use is 10 ppm or more and 1000 ppm or less so as to be diluted.
ことを特徴とした洗浄剤。 A cleaning agent comprising the antibacterial composition-containing solution according to any one of claims 12 to 14.
ことを特徴とした畳表。 A tatami mat formed of a film containing the antibacterial composition according to any one of claims 1 to 8.
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| JP2005136366A JP4713937B2 (en) | 2005-05-09 | 2005-05-09 | Antibacterial composition, antibacterial molded article, antibacterial composition-containing solution, cleaning agent, and tatami mat |
| KR1020077000894A KR101105182B1 (en) | 2004-07-13 | 2005-07-12 | Antibacterial composition, antibacterial molding, solution containing antibacterial composition, detergent, surface of tatami mat and tatami mat |
| CN2005800236371A CN101005762B (en) | 2004-07-13 | 2005-07-12 | Antibacterial composition, antibacterial molding, solution containing antibacterial composition, detergent, surface of tatami mat and tatami mat |
| PCT/JP2005/012834 WO2006006594A1 (en) | 2004-07-13 | 2005-07-12 | Antibacterial composition, antibacterial molding, solution containing antibacterial composition, detergent, surface of tatami mat and tatami mat |
| EP05765698A EP1779727A4 (en) | 2004-07-13 | 2005-07-12 | Antibacterial composition, antibacterial molding, solution containing antibacterial composition, detergent, surface of tatami mat and tatami mat |
| US11/632,271 US20080138385A1 (en) | 2004-07-13 | 2005-07-12 | Antibacterial Composition, Antibacterial Molding, Solution Containing Antibacterial Composition, Detergent, Surface of Tatami Mat and Tatami Mat |
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| WO2023286394A1 (en) * | 2021-07-16 | 2023-01-19 | 日本曹達株式会社 | Harmful organism control composition |
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