JP2013216596A - Antimicrobial agent, antimicrobial agent dispersion, and antimicrobial-treated product using the same - Google Patents
Antimicrobial agent, antimicrobial agent dispersion, and antimicrobial-treated product using the same Download PDFInfo
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- JP2013216596A JP2013216596A JP2012086969A JP2012086969A JP2013216596A JP 2013216596 A JP2013216596 A JP 2013216596A JP 2012086969 A JP2012086969 A JP 2012086969A JP 2012086969 A JP2012086969 A JP 2012086969A JP 2013216596 A JP2013216596 A JP 2013216596A
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- antibacterial agent
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- 239000006185 dispersion Substances 0.000 title claims abstract description 80
- 239000004599 antimicrobial Substances 0.000 title abstract description 9
- 230000000845 anti-microbial effect Effects 0.000 title abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 99
- 239000011941 photocatalyst Substances 0.000 claims abstract description 54
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 31
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 claims abstract description 18
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- 230000000844 anti-bacterial effect Effects 0.000 claims description 56
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- MYPYJXKWCTUITO-LYRMYLQWSA-O vancomycin(1+) Chemical compound O([C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=C2C=C3C=C1OC1=CC=C(C=C1Cl)[C@@H](O)[C@H](C(N[C@@H](CC(N)=O)C(=O)N[C@H]3C(=O)N[C@H]1C(=O)N[C@H](C(N[C@@H](C3=CC(O)=CC(O)=C3C=3C(O)=CC=C1C=3)C([O-])=O)=O)[C@H](O)C1=CC=C(C(=C1)Cl)O2)=O)NC(=O)[C@@H](CC(C)C)[NH2+]C)[C@H]1C[C@](C)([NH3+])[C@H](O)[C@H](C)O1 MYPYJXKWCTUITO-LYRMYLQWSA-O 0.000 description 2
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
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Abstract
Description
本発明は、酸化ジルコニウム粒子を含有する抗菌剤、抗菌剤分散液、およびこれを用いた抗菌加工製品に関する。 The present invention relates to an antibacterial agent containing zirconium oxide particles, an antibacterial agent dispersion, and an antibacterial processed product using the same.
抗菌剤としては、一般に有機系抗菌剤および無機系抗菌剤が知られている。有機系抗菌剤は、効果の持続期間が１〜２ヶ月程度と短く、また部材の表面に抗菌性を付与する場合、有機系抗菌剤では使用中に抗菌性能が低下するとの不具合もある。
一方、無機系抗菌剤としては、銀イオン、銅イオンなどを含む抗菌剤が知られている。しかし、銀イオンや銅イオンは、光、熱、共存物質などの影響を受けやすいという問題点がある。
As antibacterial agents, organic antibacterial agents and inorganic antibacterial agents are generally known. The organic antibacterial agent has a short duration of effect of about 1 to 2 months, and when the antibacterial property is imparted to the surface of the member, the organic antibacterial agent has a problem that the antibacterial performance is lowered during use.
On the other hand, antibacterial agents containing silver ions, copper ions and the like are known as inorganic antibacterial agents. However, silver ions and copper ions have a problem that they are easily affected by light, heat, coexisting substances, and the like.
また、光触媒作用を利用した抗菌剤も知られており、特許文献１には、酸化タングステンからなる抗菌剤が開示されている。この抗菌剤は、酸化タングステンの光触媒作用により、光照射下では高い抗菌性能を発揮する。 Further, an antibacterial agent using a photocatalytic action is also known, and Patent Document 1 discloses an antibacterial agent made of tungsten oxide. This antibacterial agent exhibits high antibacterial performance under light irradiation due to the photocatalytic action of tungsten oxide.
しかし、酸化タングステンからなる抗菌剤は、暗所下では十分な抗菌性能を発揮せず、暗所下において抗菌性能を発揮させるには、２４時間以上もの時間を要する。さらに、屋内では、蛍光灯に紫外線吸収剤を含むアクリルカバーなどを装着して用いることが多く、そのような環境下では抗菌性能が低下するという問題もある。 However, an antibacterial agent made of tungsten oxide does not exhibit sufficient antibacterial performance in the dark, and takes 24 hours or more to exhibit the antibacterial performance in the dark. Further, indoor use is often performed by attaching an acrylic cover containing an ultraviolet absorber to a fluorescent lamp, and there is a problem that the antibacterial performance deteriorates in such an environment.
したがって、暗所や紫外線をカットした蛍光灯の光照射でも、高い抗菌性能を発揮する抗菌剤が求められている。 Therefore, an antibacterial agent that exhibits high antibacterial performance even under light irradiation of a fluorescent lamp that cuts off a dark place or ultraviolet rays is demanded.
本発明の課題は、暗所でも高い抗菌性能を発揮し、かつ可視光照射下ではより高い抗菌性能を発揮し、病原菌などの菌を死滅させることができる抗菌剤を提供することにある。 An object of the present invention is to provide an antibacterial agent that exhibits high antibacterial performance even in a dark place and exhibits higher antibacterial performance under visible light irradiation, and can kill bacteria such as pathogenic bacteria.
本発明者らは、上記課題を解決するべく鋭意検討を行った結果、以下の構成からなる解決手段を見出し、本発明を完成するに至った。
（１）１０〜１００ｎｍの平均粒子径を有する酸化ジルコニウム粒子を含有する、抗菌剤。
（２）前記酸化ジルコニウム粒子が非晶質である、（１）に記載の抗菌剤。
（３）前記酸化ジルコニウム粒子が、１０〜１００質量％の割合で含有される、（１）または（２）に記載の抗菌剤。
（４）光触媒粒子をさらに含有する、（１）〜（３）のいずれかに記載の抗菌剤。
（５）前記光触媒粒子の表面に、貴金属または貴金属前駆体が担持されている、（４）に記載の抗菌剤。
（６）前記貴金属が、Ｃｕ、Ｐｔ、Ａｕ、Ｐｄ、Ａｇ、Ｒｕ、ＩｒおよびＲｈからなる群より選択される少なくとも１種である、（５）に記載の抗菌剤。
（７）前記光触媒粒子が、酸化タングステン粒子である、（４）〜（６）のいずれかに記載の抗菌剤。
（８）上記（１）〜（７）のいずれかに記載の抗菌剤を含有する、抗菌剤分散液。
（９）上記（１）〜（７）のいずれかに記載の抗菌剤を含有する抗菌剤層が表面に形成された、抗菌加工製品。
（１０）上記（８）の抗菌剤分散液を基材表面に塗工して、抗菌剤層を形成する工程を含む、抗菌加工製品の製造方法。
As a result of intensive studies to solve the above problems, the present inventors have found a solution means having the following configuration, and have completed the present invention.
(1) An antibacterial agent containing zirconium oxide particles having an average particle diameter of 10 to 100 nm.
(2) The antibacterial agent according to (1), wherein the zirconium oxide particles are amorphous.
(3) The antibacterial agent according to (1) or (2), wherein the zirconium oxide particles are contained at a ratio of 10 to 100% by mass.
(4) The antibacterial agent according to any one of (1) to (3), further containing photocatalytic particles.
(5) The antibacterial agent according to (4), wherein a noble metal or a noble metal precursor is supported on the surface of the photocatalyst particles.
(6) The antibacterial agent according to (5), wherein the noble metal is at least one selected from the group consisting of Cu, Pt, Au, Pd, Ag, Ru, Ir, and Rh.
(7) The antibacterial agent according to any one of (4) to (6), wherein the photocatalyst particles are tungsten oxide particles.
(8) An antibacterial agent dispersion containing the antibacterial agent according to any one of (1) to (7).
(9) An antibacterial processed product in which an antibacterial agent layer containing the antibacterial agent according to any one of (1) to (7) is formed on the surface.
(10) A method for producing an antibacterial processed product, comprising a step of coating the antibacterial agent dispersion liquid of (8) above on a substrate surface to form an antibacterial agent layer.
本発明によれば、暗所でも高い抗菌性能を発揮し、かつ可視光照射下ではより高い抗菌性能を発揮し、病原菌などの菌を死滅させることができるという効果が得られる。 ADVANTAGE OF THE INVENTION According to this invention, the effect of exhibiting high antibacterial performance also in dark place, and exhibiting higher antibacterial performance under visible light irradiation, and killing microbes, such as a pathogenic microbe, is acquired.
以下、本発明について、詳細に説明する。
本発明の抗菌剤は、１０〜１００ｎｍの平均粒子径を有する酸化ジルコニウム粒子を含有する。平均粒子径が１００ｎｍを超える場合、基材に塗布した際に、酸化ジルコニウム粒子を最蜜充填に近い状態で塗工できず、塗膜の密着性が損なわれる可能性がある。一方、平均粒子径が１０ｎｍ未満の場合、分散安定性に優れる分散液を得るには、酸化ジルコニウム粒子の濃度を極めて薄くしなければならず、抗菌性を発現するのに十分な塗工量を得るのが困難になる。
Hereinafter, the present invention will be described in detail.
The antibacterial agent of the present invention contains zirconium oxide particles having an average particle size of 10 to 100 nm. When the average particle diameter exceeds 100 nm, when applied to a substrate, zirconium oxide particles cannot be applied in a state close to honey filling, and the adhesion of the coating film may be impaired. On the other hand, when the average particle diameter is less than 10 nm, in order to obtain a dispersion having excellent dispersion stability, the concentration of the zirconium oxide particles must be extremely thin, and a coating amount sufficient to develop antibacterial properties is required. It becomes difficult to obtain.
１０〜１００ｎｍの平均粒子径を有する酸化ジルコニウム粒子であれば、特に限定されず、Ｘ線回折測定において結晶質のものでも非晶質のものでもよい。基材への塗工後、より密着性に優れる塗膜が得られる点で、非晶質のものが好ましい。
また、本発明の抗菌剤は、酸化ジルコニウム粒子を、好ましくは１０〜１００質量％の割合で含有する。酸化ジルコニウム粒子がこのような割合で含有されると、より高い抗菌性能が発揮される。酸化ジルコニウム粒子は、より好ましくは１５〜１００質量％の割合で含有される。
酸化ジルコニウム粒子は、例えば、水に分散した酸化ジルコニウムゾルの形態で市販されているものを用いてもよい。このような市販品としては、例えば、ＺＳＬ−１０Ｔ（第一稀元素化学工業（株）製）、ＺＲ−３０ＢＦ（日産化学工業（株）製）などが挙げられる。これらの中でも、鉱酸（硝酸など）を含むＺＳＬ−１０Ｔを用いることが好ましい。
The zirconium oxide particles are not particularly limited as long as they have an average particle diameter of 10 to 100 nm, and may be crystalline or amorphous in the X-ray diffraction measurement. An amorphous thing is preferable at the point from which the coating film which is more excellent in adhesiveness is obtained after the coating to a base material.
Moreover, the antibacterial agent of this invention contains a zirconium oxide particle preferably in the ratio of 10-100 mass%. When the zirconium oxide particles are contained in such a ratio, higher antibacterial performance is exhibited. The zirconium oxide particles are more preferably contained in a proportion of 15 to 100% by mass.
As the zirconium oxide particles, for example, those commercially available in the form of a zirconium oxide sol dispersed in water may be used. Examples of such commercially available products include ZSL-10T (Daiichi Rare Element Chemical Co., Ltd.), ZR-30BF (Nissan Chemical Co., Ltd.), and the like. Among these, it is preferable to use ZSL-10T containing a mineral acid (such as nitric acid).
本発明の抗菌剤は、分散媒に分散した状態で分散液（抗菌剤分散液）として用いることができる。分散媒は、特に限定されず、通常、水を主成分とする水性溶媒が用いられる。具体的には、分散媒は、水単独であってもよく、水と有機溶媒との混合溶媒であってもよい。水と有機溶媒との混合溶媒を用いる場合、水の含有量は４０質量％以上であることが好ましく、５０質量％以上であることがより好ましい。有機溶媒としては、例えば、水溶性アルコール（メタノール、エタノール、ｎ−プロパノール、イソプロパノール、ｎ−ブタノール、イソブタノール、ｓｅｃ−ブタノール、ｔｅｒｔ−ブタノールなど）、酢酸エチル、アセトン、メチルエチルケトンなどが挙げられる。なお、有機溶媒は、単独で用いてもよいし、２種以上を併用してもよく、例えば、上記のような酸化ジルコニウムゾルの市販品を用いる場合、この酸化ジルコニウムゾルに有機溶剤を添加してもよい。 The antibacterial agent of the present invention can be used as a dispersion (antibacterial agent dispersion) in a state of being dispersed in a dispersion medium. A dispersion medium is not specifically limited, Usually, the aqueous solvent which has water as a main component is used. Specifically, the dispersion medium may be water alone or a mixed solvent of water and an organic solvent. When a mixed solvent of water and an organic solvent is used, the content of water is preferably 40% by mass or more, and more preferably 50% by mass or more. Examples of the organic solvent include water-soluble alcohols (methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, etc.), ethyl acetate, acetone, methyl ethyl ketone, and the like. In addition, an organic solvent may be used independently and may use 2 or more types together, for example, when using the commercial item of the above zirconium oxide sol, an organic solvent is added to this zirconium oxide sol. May be.
抗菌剤分散液において、分散媒の含有量は、抗菌剤１００質量部に対して、通常３００〜２００００質量部、好ましくは５００〜１００００質量部である。分散媒がこのような範囲で含有される場合、抗菌剤が沈降しにくく、また容積効率の点でも好ましい。 In the antibacterial agent dispersion, the content of the dispersion medium is usually 300 to 20000 parts by mass, preferably 500 to 10000 parts by mass with respect to 100 parts by mass of the antibacterial agent. When the dispersion medium is contained in such a range, the antibacterial agent is unlikely to settle, and is preferable from the viewpoint of volume efficiency.
本発明の抗菌剤は、光触媒粒子をさらに含有してもよい。通常の抗菌剤では、抗菌作用により菌は死滅するが、基材表面に菌の死骸は残存する。このような場合、死骸の上に菌が付着すると、その菌は抗菌剤と接触しにくくなるため、死滅させることが困難となる。
一方、光触媒粒子が含有されると、光触媒作用により生成する活性酸素種により菌の死骸は完全に分解される。したがって、基材表面に菌の死骸が堆積しにくくなり、長期間にわたって高い抗菌性能を発揮することが可能となる。
The antibacterial agent of the present invention may further contain photocatalyst particles. In a normal antibacterial agent, bacteria are killed by an antibacterial action, but dead bodies of the bacteria remain on the surface of the substrate. In such a case, if bacteria adhere to the dead body, it becomes difficult for the bacteria to come into contact with the antibacterial agent, making it difficult to kill them.
On the other hand, when the photocatalyst particles are contained, the dead bodies of the fungus are completely decomposed by the active oxygen species generated by the photocatalytic action. Therefore, it becomes difficult for bacteria dead bodies to accumulate on the surface of the base material, and high antibacterial performance can be exhibited over a long period of time.
光触媒粒子は、光（例えば紫外線、可視光線など）の照射により光触媒作用を発現する半導体であり、具体的には、特定の結晶構造を有する金属元素と、酸素、窒素、硫黄およびフッ素の少なくとも１種とからなる化合物などが挙げられる。金属元素としては、例えば、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｗ、Ｍｎ、Ｔｃ、Ｒｅ、Ｆｅ、Ｃｏ、Ｎｉ、Ｒｕ、Ｒｈ、Ｐｄ、Ｏｓ、Ｉｒ、Ｐｔ、Ｃｕ、Ａｇ、Ａｕ、Ｚｎ、Ｃｄ、Ｇａ、Ｉｎ、Ｔｌ、Ｇｅ、Ｓｎ、Ｐｂ、Ｂｉ、Ｌａ、Ｃｅなどが挙げられる。
化合物としては、これら金属の１種類または２種類以上の酸化物、窒化物、硫化物、酸窒化物、酸硫化物、窒弗化物、酸弗化物、酸窒弗化物などが挙げられる。これらの中でも、酸化チタン、酸化タングステンなどが好ましく、とりわけ室内光の大部分を占める可視光の照射でも高い活性を示すことから、酸化タングステンや、Ｃｕ、Ｆｅなどを担持した酸化チタンがさらに好ましく、これらの中でも酸化タングステンが特に好ましい。なお、光触媒粒子は単独で用いてもよく、２種類以上を併用してもよい。
The photocatalyst particles are a semiconductor that exhibits a photocatalytic action when irradiated with light (for example, ultraviolet rays and visible rays). Specifically, the photocatalyst particles are a metal element having a specific crystal structure and at least one of oxygen, nitrogen, sulfur, and fluorine. Examples include compounds composed of seeds. Examples of metal elements include Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, and Cu. , Ag, Au, Zn, Cd, Ga, In, Tl, Ge, Sn, Pb, Bi, La, Ce, and the like.
Examples of the compound include one or more oxides, nitrides, sulfides, oxynitrides, oxysulfides, nitrofluorides, oxyfluorides, and oxynitrofluorides of these metals. Among these, titanium oxide, tungsten oxide, and the like are preferable, and in particular, titanium oxide supporting tungsten oxide, Cu, Fe, and the like is more preferable because it shows high activity even in the irradiation of visible light that occupies most of the indoor light. Among these, tungsten oxide is particularly preferable. In addition, a photocatalyst particle may be used independently and may use 2 or more types together.
酸化タングステンは、光触媒作用を有する粒子状の酸化タングステン粒子であれば、特に限定されず、例えば、三酸化タングステン（ＷＯ3）粒子などが挙げられる。なお、酸化タングステン粒子は、単独で用いてもよく、２種以上を併用してもよい。
酸化タングステン粒子の粒子径は、特に限定されない。例えば、光触媒という用途の観点から、平均粒子径で、通常５０〜２００ｎｍ、好ましくは８０〜１３０ｎｍである。
The tungsten oxide is not particularly limited as long as it is particulate tungsten oxide particles having a photocatalytic action, and examples thereof include tungsten trioxide (WO 3 ) particles. The tungsten oxide particles may be used alone or in combination of two or more.
The particle diameter of the tungsten oxide particles is not particularly limited. For example, from the viewpoint of use as a photocatalyst, the average particle size is usually 50 to 200 nm, preferably 80 to 130 nm.
光触媒粒子は、分散媒に分散した状態で分散液として用いてもよい。分散媒としては、上述の抗菌剤分散液で説明した分散媒が用いられる。 You may use a photocatalyst particle as a dispersion liquid in the state disperse | distributed to the dispersion medium. As the dispersion medium, the dispersion medium described in the above antibacterial agent dispersion is used.
光触媒分散液において、分散媒の含有量は、光触媒粒子１００質量部に対して、通常２００〜２００００質量部、好ましくは３００〜１００００質量部である。分散媒がこのような範囲で含有される場合、光触媒粒子が沈降しにくく、また容積効率の点でも好ましい。 In the photocatalyst dispersion, the content of the dispersion medium is usually 200 to 20000 parts by mass, preferably 300 to 10,000 parts by mass with respect to 100 parts by mass of the photocatalyst particles. When the dispersion medium is contained in such a range, the photocatalyst particles are unlikely to settle, and this is preferable from the viewpoint of volume efficiency.
本発明において、酸化ジルコニウム粒子と光触媒粒子との混合は、以下の方法によって行われる。
（ｉ）酸化ジルコニウム粒子含有分散液および光触媒分散液を別々に調製し、これらを混合する方法。
（ｉｉ）酸化ジルコニウム粒子含有分散液を調製し、そこに光触媒粒子を添加して、媒体撹拌式分散機などの分散機を用いて分散処理を行う方法。
（ｉｉｉ）光触媒分散液を調製し、そこに酸化ジルコニウム粒子を添加して、媒体撹拌式分散機などの分散機を用いて分散処理を行う方法。
（ｉｖ）酸化ジルコニウム粒子および光触媒粒子を混合し、そこに水などの分散媒を添加して、媒体撹拌式分散機などの分散機を用いて分散処理を行う方法。
In the present invention, the mixing of the zirconium oxide particles and the photocatalyst particles is performed by the following method.
(I) A method of separately preparing a zirconium oxide particle-containing dispersion and a photocatalyst dispersion and mixing them.
(Ii) A method of preparing a dispersion containing zirconium oxide particles, adding photocatalyst particles thereto, and performing a dispersion treatment using a dispersing machine such as a medium stirring type dispersing machine.
(Iii) A method of preparing a photocatalyst dispersion liquid, adding zirconium oxide particles thereto, and performing a dispersion treatment using a dispersing machine such as a medium stirring type dispersing machine.
(Iv) A method in which zirconium oxide particles and photocatalyst particles are mixed, a dispersion medium such as water is added thereto, and dispersion treatment is performed using a dispersion machine such as a medium stirring type dispersion machine.
本発明の抗菌剤に光触媒粒子を含有させる場合、光触媒粒子は、酸化ジルコニウム粒子１００質量部に対して、好ましくは９５０質量部以下、より好ましくは８００質量部以下の割合で含有される。 When the photocatalyst particles are contained in the antibacterial agent of the present invention, the photocatalyst particles are preferably contained at a ratio of 950 parts by mass or less, more preferably 800 parts by mass or less with respect to 100 parts by mass of the zirconium oxide particles.
光触媒粒子には、好ましくは貴金属または貴金属前駆体が担持されている。本明細書において、貴金属とは、光触媒粒子の表面に担持されて電子吸引性を発揮し得る化合物を意味し、貴金属単体だけではなく、貴金属の酸化物、水酸化物なども包含される。また、貴金属の前駆体とは、光触媒粒子の表面で貴金属に遷移し得る化合物（例えば、光照射により貴金属に還元される化合物）を意味し、貴金属の硝酸塩、硫酸塩、ハロゲン化物、有機酸塩、炭酸塩、リン酸塩などが挙げられる。貴金属が光触媒粒子の表面に担持されて存在すると、光の照射により伝導帯に励起された電子と価電子帯に生成した正孔との再結合が抑制され、光触媒作用をより高めることができる。 The photocatalyst particles preferably carry a noble metal or a noble metal precursor. In the present specification, the noble metal means a compound that is supported on the surface of the photocatalyst particle and can exhibit electron withdrawing property, and includes not only a noble metal alone but also an oxide or hydroxide of the noble metal. The precursor of the noble metal means a compound that can transition to the noble metal on the surface of the photocatalyst particles (for example, a compound that is reduced to the noble metal by light irradiation), and the nitrate, sulfate, halide, organic acid salt of the noble metal. , Carbonate, phosphate and the like. When the noble metal is supported on the surface of the photocatalyst particles, recombination between electrons excited in the conduction band by irradiation of light and holes generated in the valence band is suppressed, and the photocatalytic action can be further enhanced.
貴金属としては、好ましくはＣｕ、Ｐｔ、Ａｕ、Ｐｄ、Ａｇ、Ｒｕ、Ｉｒ、およびＲｈからなる群より選択される少なくとも１種が挙げられる。より好ましくは、Ｃｕ、ＰｔおよびＡｕからなる群より選択される少なくとも１種である。 The noble metal is preferably at least one selected from the group consisting of Cu, Pt, Au, Pd, Ag, Ru, Ir, and Rh. More preferably, it is at least one selected from the group consisting of Cu, Pt and Au.
貴金属または貴金属前駆体を光触媒粒子に担持させる場合、貴金属または貴金属前駆体は、金属原子換算で、光触媒粒子１００質量部に対して、通常０．００５〜０．６質量部、好ましくは０．０１〜０．４質量部の割合で用いられる。このような割合で貴金属または貴金属前駆体が光触媒粒子に担持される場合、光触媒の活性がより向上する。 When the noble metal or noble metal precursor is supported on the photocatalyst particles, the noble metal or noble metal precursor is usually 0.005 to 0.6 parts by mass, preferably 0.01, based on 100 parts by mass of the photocatalyst particles in terms of metal atoms. It is used at a ratio of ˜0.4 parts by mass. When the noble metal or the noble metal precursor is supported on the photocatalyst particles at such a ratio, the activity of the photocatalyst is further improved.
貴金属の前駆体を光触媒粒子分散液に添加する場合、その添加後、光触媒粒子分散液に光照射を行うのが好ましい。照射する光としては、光触媒粒子のバンドギャップ以上のエネルギーを有する光であれば特に限定されず、可視光線でも紫外線でもよい。光触媒粒子分散液に光照射を行うことにより、光励起によって生成した電子によって前駆体が還元されて貴金属となり、光触媒粒子の表面に担持される。なお、光触媒粒子分散液に光照射を行なわなくても、得られた分散液により形成された抗菌剤層中の光触媒粒子に光が照射された時点で貴金属へ変換されるため、その光触媒能が損なわれることはない。光照射は、前駆体を光触媒粒子分散液に添加後であれば、どの段階で行ってもよい。
また、貴金属の前駆体を光触媒粒子分散液に添加する場合、より効率よく貴金属に転化させる目的で、光照射の前に、本発明の効果を損なわない範囲で、メタノール、エタノール、シュウ酸などを光触媒粒子分散液に加えてもよい。
When a noble metal precursor is added to the photocatalyst particle dispersion, it is preferable to irradiate the photocatalyst particle dispersion with light after the addition. The light to be irradiated is not particularly limited as long as the light has energy higher than the band gap of the photocatalyst particles, and may be visible light or ultraviolet light. By irradiating the photocatalyst particle dispersion with light, the precursor is reduced by electrons generated by photoexcitation to become a noble metal, and is supported on the surface of the photocatalyst particles. Even if the photocatalyst particle dispersion is not irradiated with light, it is converted to a noble metal at the time when the photocatalyst particles in the antibacterial agent layer formed by the obtained dispersion are irradiated with light. It will not be damaged. The light irradiation may be performed at any stage as long as the precursor is added to the photocatalyst particle dispersion.
In addition, when a noble metal precursor is added to the photocatalyst particle dispersion, methanol, ethanol, oxalic acid, and the like may be added to the noble metal within a range that does not impair the effects of the present invention before light irradiation. It may be added to the photocatalyst particle dispersion.
本発明の抗菌加工製品は、上述の抗菌剤を含有する抗菌剤層が表面に形成されている。なお、基材（製品）と抗菌剤層との密着性を向上させる目的で、必要に応じて、抗菌剤層と基材（製品）との間に下地層を形成してもよい。
下地層は、変性シリコーンや変成シリコーンポリマーを含む下地層形成用コート液を基材表面に塗布することによって形成される。変性シリコーンや変成シリコーンポリマーとは、シリコーンの骨格構造であるポリシロキサンの側鎖、末端に有機基を導入したものである。導入する有機基によって、アクリル変性シリコーン、アラルキル変成シリコーン、フェニル変成シリコーン、フェノール変成シリコーン、ポリエーテル変成シリコーン、カルビノール変性シリコーン、カルボキシル変性シリコーン、高級脂肪酸エステル変性シリコーン、長鎖アルキル変性シリコーン、モノアミン変性シリコーン、ジアミン変性シリコーン、ハイドロジェン変成シリコーンなどが挙げられ、本発明においては、いずれも下地層形成用コート液として用いることができる。 このような下地層形成用コート液として、例えば、ビストレイターＮＲＣ−３５０Ａ（日本曹達（株）製）、ビストレイターＮＲＣ−３１７Ａ（日本曹達（株）製）、ビストレイターＮＲＣ−３１８Ａ（日本曹達（株）製）、ビストレイターＮＲＣ−３００（日本曹達製）、ビストレイターＮＲＣ−３００Ａ（日本曹達（株）製）、ビストレイターＮＤＣ−１５０ＡおよびビストレイターＮＤＣ−１５５Ａ（日本曹達（株）製）、などが挙げられる。
抗菌剤層および下地層の膜厚は、特に制限されるものではなく、その用途などに応じて、適宜設定すればよい。通常、２０ｎｍ〜３ｍｍ程度の範囲である。
As for the antibacterial processed product of this invention, the antibacterial agent layer containing the above-mentioned antibacterial agent is formed in the surface. In addition, you may form a base layer between an antimicrobial agent layer and a base material (product) as needed for the purpose of improving the adhesiveness of a base material (product) and an antimicrobial agent layer.
The underlayer is formed by applying an underlayer-forming coating solution containing a modified silicone or a modified silicone polymer to the substrate surface. The modified silicone and the modified silicone polymer are those in which an organic group is introduced into the side chain and terminal of polysiloxane which is a silicone skeleton structure. Depending on the organic group to be introduced, acrylic modified silicone, aralkyl modified silicone, phenyl modified silicone, phenol modified silicone, polyether modified silicone, carbinol modified silicone, carboxyl modified silicone, higher fatty acid ester modified silicone, long chain alkyl modified silicone, monoamine modified Examples thereof include silicone, diamine-modified silicone, and hydrogen-modified silicone. In the present invention, any of them can be used as a coating solution for forming an underlayer. As such a base layer forming coating solution, for example, Vistraiter NRC-350A (manufactured by Nippon Soda Co., Ltd.), Vistraitor NRC-317A (manufactured by Nippon Soda Co., Ltd.), Vistraiter NRC-318A (Nihon Soda ( Co., Ltd.), Vistraiter NRC-300 (Nihon Soda Co., Ltd.), Vistraiter NRC-300A (Nihon Soda Co., Ltd.), Vistraitor NDC-150A and Vistraiter NDC-155A (Nihon Soda Co., Ltd.), Etc.
The film thicknesses of the antibacterial agent layer and the base layer are not particularly limited, and may be set as appropriate according to the application. Usually, it is in the range of about 20 nm to 3 mm.
抗菌剤層は、基材（製品）の内表面または外表面であれば、どの部分に形成されていてもよく、特に、菌が接触しやすい面に形成されていることが好ましく、さらに光触媒粒子が含有される場合には、光（可視光線）が照射される面に形成されていることが好ましい。基材（製品）の材質は、形成される抗菌剤層を実用に耐え得る強度で保持できる限り、特に限定されず、例えば、プラスチック、金属、セラミックス、木材、コンクリート、紙など、あらゆる材料からなる製品を対象にすることができる。
さらに、プラスチックの基材としては、例えばポリ塩化ビニル系樹脂、ＡＢＳ系樹脂、ＡＥＳ系樹脂、ポリアクリル系樹脂、ポリウレタン系樹脂、ポリエチレンテレフタレート、非結晶性ポリエチレンテレフタレートコポリマー、完全非晶性ポリエステル系樹脂、ポリカーボネート、ポリエチレン、ポリプロピレンなどが挙げられる。
本発明の抗菌加工製品としては、具体的には建築資材（天井材、タイル、ガラス、壁紙、壁材、床など）、自動車内装材（自動車インストルメントパネル、自動車用シート、自動車用天井材、自動車用ガラスなど）、家電製品（冷蔵庫、エアコンなど）、繊維製品（衣類、カーテンなど）、不特定多数の人が接触する物品（電車のつり革、デスクマット、テーブルクロス、エレベーターのボタン、階段や廊下の手摺など）などが挙げられる。
The antibacterial agent layer may be formed on any part as long as it is the inner surface or the outer surface of the base material (product). In particular, the antibacterial agent layer is preferably formed on a surface that is easily contacted by bacteria. When it contains, it is preferable to form in the surface where light (visible light) is irradiated. The material of the base material (product) is not particularly limited as long as the antibacterial agent layer to be formed can be held at a strength that can be practically used, and is made of any material such as plastic, metal, ceramics, wood, concrete, and paper. Can target products.
Furthermore, as a plastic substrate, for example, polyvinyl chloride resin, ABS resin, AES resin, polyacrylic resin, polyurethane resin, polyethylene terephthalate, amorphous polyethylene terephthalate copolymer, completely amorphous polyester resin , Polycarbonate, polyethylene, polypropylene and the like.
Specifically, the antibacterial processed product of the present invention includes building materials (ceiling materials, tiles, glass, wallpaper, wall materials, floors, etc.), automotive interior materials (automotive instrument panels, automotive seats, automotive ceiling materials, Automotive glass, etc.), household appliances (refrigerators, air conditioners, etc.), textile products (clothing, curtains, etc.), articles that are in contact with an unspecified number of people (train straps, desk mats, tablecloths, elevator buttons, stairs) And handrails in hallways).
本発明の抗菌加工製品は、例えば、抗菌剤分散液を基材表面に塗工して、抗菌剤層を形成することによって得られる。抗菌剤分散液に含まれる分散媒は、通常、乾燥（自然乾燥、熱風乾燥など）などによって揮発させる。
さらに、下地層を設ける場合、下地層は公知の方法で形成される。例えば、基材（製品）の表面に、下地層形成用コート液をグラビアコーティング、リバースコーティング、刷毛ロールコーティング、スプレーコーティング、キスコーティング、ダイコーティング、ディッピング、バーコーティング、アプリケーターなどの公知の方法で塗布し、コート液中の分散媒を揮発させればよい。この下地層の上に、抗菌剤分散液を同様の方法で塗布、乾燥して抗菌剤層を形成すればよい。
The antibacterial processed product of the present invention can be obtained, for example, by applying an antibacterial agent dispersion to the surface of a substrate to form an antibacterial agent layer. The dispersion medium contained in the antibacterial agent dispersion liquid is usually volatilized by drying (such as natural drying or hot air drying).
Furthermore, when providing an underlayer, the underlayer is formed by a known method. For example, the coating solution for forming the underlayer is applied to the surface of the substrate (product) by a known method such as gravure coating, reverse coating, brush roll coating, spray coating, kiss coating, die coating, dipping, bar coating, applicator, etc. Then, the dispersion medium in the coating solution may be volatilized. The antibacterial agent dispersion may be applied and dried on the underlayer in the same manner to form an antibacterial agent layer.
本発明の抗菌加工製品は、屋外はもちろん、屋内においても高い抗菌性能を発揮する。さらに、光触媒粒子を含有する場合は、蛍光灯、ナトリウムランプ、白色ＬＥＤ、有機ＥＬなどのような可視光源からの光しか受けない屋内環境においても、可視光線の照射によって長期間にわたり高い抗菌性能を発揮する。 The antibacterial processed product of the present invention exhibits high antibacterial performance not only outdoors but also indoors. In addition, when it contains photocatalyst particles, it has high antibacterial performance over a long period of time by irradiation with visible light even in an indoor environment that only receives light from a visible light source such as a fluorescent lamp, sodium lamp, white LED, and organic EL. Demonstrate.
したがって、本発明の抗菌剤分散液を、例えば、建築資材（天井材、タイル、ガラス、壁紙、壁材、床など）、自動車内装材（自動車インストルメントパネル、自動車用シート、自動車用天井材、自動車用ガラスなど）、家電製品（冷蔵庫、エアコンなど）、繊維製品（衣類、カーテンなど）、不特定多数の人が接触する物品（電車のつり革、デスクマット、テーブルクロス、エレベーターのボタン、階段や廊下の手摺など）などに塗布して乾燥させると、長期に渡り、大腸菌、炭疽菌、結核菌、コレラ菌、ジフテリア菌、破傷風菌、ペスト菌、赤痢菌、ボツリヌス菌、多剤耐性アシネトバクター、多剤耐性緑膿菌、ＮＤＭ−１産生多剤耐性菌、メシチリン耐性黄色ブドウ球菌、バンコマイシン耐性腸球菌、レジオネラ菌などの病原菌の数を低減させることができる。 Therefore, the antibacterial agent dispersion of the present invention can be used, for example, for building materials (ceiling materials, tiles, glass, wallpaper, wall materials, floors, etc.), automotive interior materials (automotive instrument panels, automotive seats, automotive ceiling materials, Automotive glass, etc.), household appliances (refrigerators, air conditioners, etc.), textile products (clothing, curtains, etc.), articles that are in contact with an unspecified number of people (train straps, desk mats, tablecloths, elevator buttons, stairs) And dried on a long time, such as E. coli, anthrax, tuberculosis, cholera, diphtheria, tetanus, plague, shigella, botulinum, multidrug-resistant Acinetobacter, The number of pathogenic bacteria such as multidrug resistant Pseudomonas aeruginosa, NDM-1 producing multidrug resistant bacteria, methicillin resistant Staphylococcus aureus, vancomycin resistant enterococci, Legionella It is possible to Gensa.
以下、実施例および比較例を挙げて本発明を具体的に説明するが、本発明はこれらの実施例に限定されるものではない。なお、実施例および比較例における各物性の測定および抗菌性活性の評価については、以下の方法で行った。 EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to these Examples. In addition, about the measurement of each physical property in an Example and a comparative example, and evaluation of antibacterial activity, it performed with the following method.
（結晶型）
結晶型は、Ｘ線回折装置（（株）リガク製の「ＲＩＮＴ２０００／ＰＣ」）を用いてＸ線回折スペクトルを測定し、そのスペクトルから決定した。
（ＢＥＴ比表面積）
ＢＥＴ比表面積は、比表面積測定装置（湯浅アイオニクス（株）製の「モノソーブ」）を用い、窒素吸着法によって測定した。
（平均粒子径）
平均粒子径（分散粒子径ｄ５０）は、マイクロトラックＵＰＡ粒度分析計（日機装（株）製）を用いて、動的散乱法により累積５０％径を測定した。
（密着性）
抗菌剤層の密着性は、２４ｍｍ幅の粘着セロハンテープ（ニチバン（株）製）を抗菌剤層の表面に貼着させて素早く剥したときに、抗菌剤層が同時に剥れるか否かによって評価した。
(Crystal type)
The crystal type was determined from an X-ray diffraction spectrum measured by using an X-ray diffractometer (“RINT2000 / PC” manufactured by Rigaku Corporation).
(BET specific surface area)
The BET specific surface area was measured by a nitrogen adsorption method using a specific surface area measuring device (“Monosorb” manufactured by Yuasa Ionics Co., Ltd.).
(Average particle size)
For the average particle size (dispersed particle size d50), a 50% cumulative size was measured by a dynamic scattering method using a Microtrac UPA particle size analyzer (manufactured by Nikkiso Co., Ltd.).
(Adhesion)
The adhesion of the antibacterial agent layer is evaluated by whether or not the antibacterial agent layer is peeled off simultaneously when a 24 mm wide adhesive cellophane tape (manufactured by Nichiban Co., Ltd.) is attached to the surface of the antibacterial agent layer and quickly peeled did.
（抗菌性活性の測定）
抗菌剤層を表面に形成したポリエチレンテレフタレート（ＰＥＴ）フィルムを用いて、大腸菌の生菌数を測定することにより評価した。抗菌剤層には、予め紫外線強度が１ｍＷ／ｃｍ2となるように（トプコン社製紫外線強度計「ＵＶＲ−２」に同社製受光部「ＵＤ−３６」を取り付けて測定）、ブラックライトを用いて紫外線を１６時間照射し、これを抗菌性活性測定用試料とした。
次に、この抗菌性活性測定用試料を用いて、日本工業規格ＪＩＳ Ｒ １７０２：２００６「ファインセラミックス−光照射下での光触媒抗菌加工製品の抗菌性試験方法・抗菌効果」１０フィルム密着法に基づく方法で行った。すなわち、抗菌剤層に大腸菌（Escherichia coli NBRC3972）の菌液（生菌数：３．０×１０5個）を播種し、被覆フィルムを載せて密着させ、これを室温（２５±５℃）、暗所もしくは可視光照射下で６時間保存し、試料検体１個当たりの生菌数を測定した。
未塗工のポリエチレンフィルムについても同様の操作を行い、生菌数を測定した。なお、抗菌性活性測定用試料を２つ用いて同時に行い、これら２つの生菌数の平均値で評価を行った。抗菌活性値は以下の式で求めた。抗菌活性値が２以上であれば、一般的に抗菌活性を発現しているといえる。
抗菌活性値＝ｌｏｇ（Ｎ0／Ｎ）
Ｎ0：未塗工のポリエチレンフィルムで評価を６時間行った後の生菌数の平均値
Ｎ：抗菌剤塗工フィルムで評価を６時間行った後の生菌数の平均値
可視光の照射は、市販の白色蛍光灯を光源とし、アクリル樹脂板（日東樹脂工業（株）製「Ｎ１６９」）を通して、被覆フィルムを載せた抗菌剤層の上から、蛍光灯に含まれる可視光のみが照射されるようにして行った。照射は、抗菌剤層近傍で５００ルクス（トプコン社製照度計「ＩＬＬＵＭＩＮＡＣＥ ＭＥＴＥＲ ＩＭ−３」で測定）となるように行った。可視光照射６時間後の生菌数が少ないものほど、大腸菌の抗菌性、すなわち光触媒活性が高いと言える。
(Measurement of antibacterial activity)
Evaluation was carried out by measuring the number of viable Escherichia coli using a polyethylene terephthalate (PET) film having an antibacterial agent layer formed on the surface. For the antibacterial agent layer, black light is used so that the ultraviolet intensity is 1 mW / cm 2 in advance (measured by attaching a UV receiver “UD-36” to Topcon's UV intensity meter “UVR-2”). The sample was irradiated with ultraviolet rays for 16 hours and used as a sample for measuring antibacterial activity.
Next, using this antibacterial activity measurement sample, based on Japanese Industrial Standard JIS R 1702: 2006 "Fine Ceramics-Antibacterial Test Method / Antimicrobial Effect of Photocatalytic Antibacterial Products Under Light Irradiation" 10 Film Adhesion Method Went in the way. That is, the antibacterial layer is inoculated with Escherichia coli NBRC3972 bacterial solution (viable cell count: 3.0 × 10 5 ), placed on a coated film, and brought into close contact with it at room temperature (25 ± 5 ° C.). It was stored for 6 hours in the dark or under visible light irradiation, and the number of viable bacteria per sample specimen was measured.
The same operation was performed on the uncoated polyethylene film, and the viable cell count was measured. In addition, it carried out simultaneously using two samples for antimicrobial activity measurement, and evaluated by the average value of these two viable cell counts. The antibacterial activity value was determined by the following formula. If the antibacterial activity value is 2 or more, it can be said that the antibacterial activity is generally expressed.
Antibacterial activity value = log (N 0 / N)
N 0 : Average number of viable cells after evaluation for 6 hours with an uncoated polyethylene film N: Average value of viable cells after evaluation with an antibacterial agent coated film for 6 hours Visible light irradiation Uses a commercially available white fluorescent lamp as a light source, and irradiates only visible light contained in the fluorescent lamp through an acrylic resin plate (“N169” manufactured by Nitto Resin Kogyo Co., Ltd.) on the antibacterial agent layer on which the coating film is placed. I went there. Irradiation was performed so as to be 500 lux in the vicinity of the antibacterial agent layer (measured with a illuminometer “ILLUMINACE METER IM-3” manufactured by Topcon Corporation). It can be said that the smaller the number of viable bacteria 6 hours after irradiation with visible light, the higher the antibacterial activity of E. coli, that is, the photocatalytic activity.
（実施例１）
樹脂基材としてＰＥＴフィルム（厚み１００μｍ）に、下地層形成用コート液（日本曹達（株）製、商品名：ＮＲＣ−３５０Ａ）をバーコーター（３番）で塗布し、４０℃で１分間乾燥して、フィルムの上に下地層を形成した。
次いで、平均粒子径２４ｎｍの非晶質酸化ジルコニウムゾル（濃度１０質量％、商品名：ＺＳＬ−１０Ｔ、第一稀元素化学工業（株）製）に、２−プロパノール、酢酸エチルおよび水を添加して混合し、抗菌剤分散液を得た。この抗菌剤分散液には、２質量％の非晶質酸化ジルコニウム粒子、２０質量％の２−プロパノール、２０質量％の酢酸エチル、および５８質量％の水が含まれる。この抗菌剤分散液を、上記下地層に箱型アプリケーター（液厚２１μｍ）を用いて塗布し、４０℃で１分間乾燥して抗菌剤塗工フィルムを得た。
Example 1
As a resin base material, a coating film for forming an underlayer (made by Nippon Soda Co., Ltd., trade name: NRC-350A) is applied to a PET film (thickness: 100 μm) with a bar coater (No. 3) and dried at 40 ° C. for 1 minute. Then, an underlayer was formed on the film.
Next, 2-propanol, ethyl acetate and water were added to an amorphous zirconium oxide sol having an average particle size of 24 nm (concentration: 10% by mass, trade name: ZSL-10T, manufactured by Daiichi Rare Element Chemical Co., Ltd.). And mixed to obtain an antibacterial agent dispersion. The antibacterial agent dispersion contains 2% by weight of amorphous zirconium oxide particles, 20% by weight of 2-propanol, 20% by weight of ethyl acetate, and 58% by weight of water. This antibacterial agent dispersion was applied to the underlayer using a box-type applicator (liquid thickness: 21 μm) and dried at 40 ° C. for 1 minute to obtain an antibacterial agent-coated film.
このフィルムの抗菌剤層の密着性を評価したところ、抗菌剤層の剥がれは見られなかった。
このフィルムの抗菌活性を評価したところ、暗所で６時間保存したときの生菌数は２．１×１０3個であった。また、未塗工のポリエチレンフィルムで同様の操作を行うと、生菌数は６．５×１０5個であった。これらの値から、抗菌活性値は２．５（ｌｏｇ６．５×１０5／２．１×１０3）となる。結果を表１に示す。
When the adhesion of the antibacterial agent layer of this film was evaluated, no peeling of the antibacterial agent layer was observed.
When the antibacterial activity of this film was evaluated, the number of viable bacteria when stored in the dark for 6 hours was 2.1 × 10 3 . Moreover, when the same operation was performed with an uncoated polyethylene film, the viable cell count was 6.5 × 10 5 . From these values, the antibacterial activity value is 2.5 (log 6.5 × 10 5 /2.1×10 3 ). The results are shown in Table 1.
（比較例１）
抗菌剤分散液を塗工しなかったこと以外は、実施例１と同様の手順で抗菌活性を評価した。暗所で６時間保存したときの生菌数は１．５×１０5個であった。また、未塗工のポリエチレンフィルムで同様の操作を行うと、生菌数は６．５×１０5個であった。これらの値から、抗菌活性値は０．６（ｌｏｇ６．５×１０5／１．５×１０5）となる。結果を表１に示す。
(Comparative Example 1)
Antibacterial activity was evaluated in the same procedure as in Example 1 except that the antibacterial agent dispersion was not applied. The number of viable bacteria when stored in the dark for 6 hours was 1.5 × 10 5 . Moreover, when the same operation was performed with an uncoated polyethylene film, the viable cell count was 6.5 × 10 5 . From these values, the antibacterial activity value is 0.6 (log 6.5 × 10 5 /1.5×10 5 ). The results are shown in Table 1.
実施例１と比較例１とを比べると、非晶質酸化ジルコニウム粒子を塗工した実施例１の方が、大腸菌に対して高い抗菌性能を発揮することがわかる。 Comparing Example 1 and Comparative Example 1, it can be seen that Example 1 coated with amorphous zirconium oxide particles exhibits higher antibacterial performance against E. coli.
次に、光触媒分散液を併用した場合の効果を検証した。 Next, the effect when the photocatalyst dispersion was used in combination was verified.
（製造例１）
酸化タングステン粒子と分散媒としての水とを混合して混合物を得た。湿式媒体撹拌ミルを用いてこの混合物に分散処理を施し、濃度４２質量％の酸化タングステン粒子分散液を得た。
得られた酸化タングステン粒子分散液における酸化タングステン粒子の平均粒子径は１８０ｎｍであった。また、この分散液の一部を真空乾燥して固形分を得たところ、得られた固形分のＢＥＴ比表面積は３０ｍ2／ｇであった。なお、分散処理前の混合物についても同様に真空乾燥して固形分を得、分散処理前の混合物の固形分と分散処理後の固形分について、Ｘ線回折スペクトルをそれぞれ測定して比較したところ、同じピーク形状であり、分散処理による結晶型の変化は見られなかった。得られた分散液を２０℃で２４時間保管しても、保管中に固液分離は見られなかった。
この酸化タングステン粒子分散液にヘキサクロロ白金酸（Ｈ2ＰｔＣｌ6）の水溶液をヘキサクロロ白金酸が白金原子換算で酸化タングステン粒子１００質量部に対して０．１２質量部となるように加え、さらに分散液全体に対するメタノールの濃度が１．０質量％となるようにメタノールを添加した。その後、撹拌しながら低圧水銀灯を照射することにより、光電着法により酸化タングステン粒子の表面に白金粒子を担持し、白金担持酸化タングステン粒子を光触媒粒子とする光触媒分散液を得た。
この光触媒分散液を２０℃で２４時間保管しても、保管後に固液分離は見られなかった。また、この分散液中の固形分濃度は２６質量％であった。
(Production Example 1)
Tungsten oxide particles and water as a dispersion medium were mixed to obtain a mixture. This mixture was subjected to a dispersion treatment using a wet medium stirring mill to obtain a tungsten oxide particle dispersion having a concentration of 42% by mass.
The average particle diameter of the tungsten oxide particles in the obtained tungsten oxide particle dispersion was 180 nm. Moreover, when a part of this dispersion was vacuum-dried to obtain a solid content, the BET specific surface area of the obtained solid content was 30 m 2 / g. In addition, when the mixture before the dispersion treatment was similarly vacuum-dried to obtain a solid content, and the solid content of the mixture before the dispersion treatment and the solid content after the dispersion treatment were measured and compared, The peak shape was the same, and no change in crystal form due to dispersion treatment was observed. Even when the obtained dispersion was stored at 20 ° C. for 24 hours, solid-liquid separation was not observed during storage.
An aqueous solution of hexachloroplatinic acid (H 2 PtCl 6 ) is added to the tungsten oxide particle dispersion so that hexachloroplatinic acid is 0.12 parts by mass with respect to 100 parts by mass of tungsten oxide particles in terms of platinum atoms, and further the dispersion Methanol was added so that the concentration of methanol with respect to the whole was 1.0% by mass. Thereafter, irradiation with a low-pressure mercury lamp while stirring was carried out to obtain a photocatalyst dispersion liquid in which platinum particles were supported on the surface of tungsten oxide particles by a photo-deposition method, and the platinum-supported tungsten oxide particles were used as photocatalyst particles.
Even when this photocatalyst dispersion was stored at 20 ° C. for 24 hours, no solid-liquid separation was observed after storage. Moreover, the solid content concentration in this dispersion liquid was 26 mass%.
（製造例２）
製造例１で得た光触媒分散液を撹拌しながら、そこに実施例１で使用した非晶質酸化ジルコニウムゾル（ＺＳＬ−１０Ｔ）と水と２−プロパノールとを添加して、抗菌剤分散液を得た。この抗菌剤分散液には、２質量％の非晶質酸化ジルコニウム粒子、８質量％の白金担持酸化タングステン粒子、４０質量％の２−プロパノール、および５０質量％の水が含まれる。
(Production Example 2)
While stirring the photocatalyst dispersion obtained in Production Example 1, the amorphous zirconium oxide sol (ZSL-10T) used in Example 1, water and 2-propanol were added thereto, and the antibacterial agent dispersion was prepared. Obtained. The antibacterial agent dispersion contains 2% by mass of amorphous zirconium oxide particles, 8% by mass of platinum-supported tungsten oxide particles, 40% by mass of 2-propanol, and 50% by mass of water.
（実施例２）
実施例１で使用した抗菌剤分散液の代わりに、製造例２で得られた抗菌剤分散液を用いたこと以外は、実施例１と同様の手順で抗菌剤性フィルムを得た。このフィルムの抗菌剤層の密着性を評価したところ、抗菌剤層の剥がれは見られなかった。このフィルムの抗菌活性を評価したところ、暗所で６時間保存したときの生菌数は１．８×１０2個であった。また、未塗工のポリエチレンフィルムで同様の操作を行うと、生菌数は５．５×１０5個であった。これらの値から、抗菌活性値は３．５（ｌｏｇ５．５×１０5／１．８×１０2）となる。結果を表１に示す。
(Example 2)
An antibacterial film was obtained in the same procedure as in Example 1 except that the antibacterial dispersion obtained in Production Example 2 was used instead of the antibacterial dispersion used in Example 1. When the adhesion of the antibacterial agent layer of this film was evaluated, no peeling of the antibacterial agent layer was observed. When the antibacterial activity of this film was evaluated, the number of viable bacteria when stored in the dark for 6 hours was 1.8 × 10 2 . Moreover, when the same operation was performed with an uncoated polyethylene film, the viable cell count was 5.5 × 10 5 . From these values, the antibacterial activity value is 3.5 (log 5.5 × 10 5 /1.8×10 2 ). The results are shown in Table 1.
次いで、可視光照射を６時間行ったときの生菌数は１０個未満であった。また、未塗工のポリエチレンフィルムで同様の操作を行うと、生菌数は５．８×１０5個であった。これらの値から、抗菌活性値は４．８（ｌｏｇ５．８×１０5／１０）となる。結果を表１に示す。なお、抗菌活性値の算出においては、可視光照射６時間後の生菌数を１０個とした。 Subsequently, the viable cell count was less than 10 when visible light irradiation was performed for 6 hours. Moreover, when the same operation was performed with an uncoated polyethylene film, the number of viable bacteria was 5.8 × 10 5 . From these values, the antibacterial activity value is 4.8 (log5.8 × 10 5/10 ). The results are shown in Table 1. In the calculation of the antibacterial activity value, the number of viable bacteria after 10 hours of visible light irradiation was set to 10.
（比較例２）
高純度ケイ酸エチルと２−プロパノールとを混合し、そこに水を添加してバインダーを調製した。バインダー中の成分の質量比は、２：８．６：１（高純度ケイ酸エチル：２−プロパノール：水）であった。次いで、水を加えて濃度を２４質量％に調整した製造例１の光触媒分散液９．８ｇに、バインダー６ｇと２−プロパノール１．６ｇとを混合して光触媒含有塗工液を得た。この光触媒含有塗工液には、１３．５質量％の白金担持酸化タングステン粒子、１．５質量％の高純度ケイ酸エチル（ＳｉＯ2換算）、３５質量％の２−プロパノール、４．６質量％のエタノール（高純度ケイ酸エチル由来）、および４５．４質量％の水が含まれる。
製造例２で得られた抗菌剤分散液の代わりに、上記の光触媒含有塗工液を用いたこと以外は、実施例２と同様の手順で抗菌剤性フィルムを得た。このフィルムの抗菌剤層（光触媒層）の密着性を評価したところ、抗菌剤層（光触媒層）の剥がれは見られなかった。このフィルムの抗菌活性を評価したところ、暗所で６時間保存したときの生菌数は３．０×１０5個であった。また、未塗工のポリエチレンフィルムで同様の操作を行うと、生菌数は５．５×１０5個であった。これらの値から、抗菌活性値は０．３（ｌｏｇ５．５×１０5／３．０×１０5）となる。結果を表１に示す。
(Comparative Example 2)
High purity ethyl silicate and 2-propanol were mixed, and water was added thereto to prepare a binder. The mass ratio of the components in the binder was 2: 8.6: 1 (high purity ethyl silicate: 2-propanol: water). Next, 6 g of binder and 1.6 g of 2-propanol were mixed with 9.8 g of the photocatalyst dispersion liquid of Production Example 1 whose concentration was adjusted to 24 mass% by adding water to obtain a photocatalyst-containing coating liquid. In this photocatalyst-containing coating solution, 13.5% by mass of platinum-supported tungsten oxide particles, 1.5% by mass of high-purity ethyl silicate (in terms of SiO 2 ), 35% by mass of 2-propanol, 4.6% by mass % Ethanol (from high purity ethyl silicate) and 45.4% by weight water.
Instead of the antibacterial agent dispersion obtained in Production Example 2, an antibacterial film was obtained in the same procedure as in Example 2 except that the photocatalyst-containing coating solution was used. When the adhesion of the antibacterial agent layer (photocatalyst layer) of this film was evaluated, peeling of the antibacterial agent layer (photocatalyst layer) was not observed. When the antibacterial activity of this film was evaluated, the number of viable bacteria when stored in the dark for 6 hours was 3.0 × 10 5 . Moreover, when the same operation was performed with an uncoated polyethylene film, the viable cell count was 5.5 × 10 5 . From these values, the antibacterial activity value is 0.3 (log 5.5 × 10 5 /3.0×10 5 ). The results are shown in Table 1.
次いで、可視光照射を６時間行ったときの生菌数は１０個未満であった。また、未塗工のポリエチレンフィルムで同様の操作を行うと、生菌数は５．８×１０5個であった。これらの値から、抗菌活性値は４．８（ｌｏｇ５．８×１０5／１０）となる。結果を表１に示す。なお、抗菌活性値の算出においては、可視光照射６時間後の生菌数を１０個とした。 Subsequently, the viable cell count was less than 10 when visible light irradiation was performed for 6 hours. Moreover, when the same operation was performed with an uncoated polyethylene film, the number of viable bacteria was 5.8 × 10 5 . From these values, the antibacterial activity value is 4.8 (log5.8 × 10 5/10 ). The results are shown in Table 1. In the calculation of the antibacterial activity value, the number of viable bacteria after 10 hours of visible light irradiation was set to 10.
実施例２と比較例２とを比べると、可視光照射下での抗菌性能はほぼ同等である。しかし、暗所所での抗菌性能は、非晶質酸化ジルコニウム粒子を含む実施例２の方が著しく高い抗菌性能を発揮することがわかる。 When Example 2 and Comparative Example 2 are compared, the antibacterial performance under visible light irradiation is almost the same. However, it can be seen that the antibacterial performance in a dark place is significantly higher in Example 2 containing amorphous zirconium oxide particles.
（参考例１）
天井を構成する天井材の表面に、実施例１で用いた抗菌剤分散液または製造例２の抗菌剤分散液を塗布して抗菌剤層を形成し、抗菌剤層を形成してから約６時間後、天井材の表面に存在する病原菌を調べると、実施例１および２の結果から、９９％以上が死滅していると推察される。
なお、病原菌は、大腸菌、炭疽菌、結核菌、コレラ菌、ジフテリア菌、破傷風菌、ペスト菌、赤痢菌、ボツリヌス菌、多剤耐性アシネトバクター、多剤耐性緑膿菌、ＮＤＭ−１産生多剤耐性菌、メシチリン耐性黄色ブドウ球菌、バンコマイシン耐性腸球菌、レジオネラ菌などであり、以下の参考例２〜９も同様である。
(Reference Example 1)
The antibacterial agent dispersion liquid used in Example 1 or the antibacterial agent dispersion liquid of Production Example 2 was applied to the surface of the ceiling material constituting the ceiling to form an antibacterial agent layer, and after forming the antibacterial agent layer, about 6 When the pathogenic bacteria existing on the surface of the ceiling material were examined after a time, it was estimated from the results of Examples 1 and 2 that 99% or more had been killed.
The pathogenic bacteria are Escherichia coli, anthrax, tuberculosis, cholera, diphtheria, tetanus, plague, shigella, botulinum, multidrug-resistant Acinetobacter, multidrug-resistant Pseudomonas aeruginosa, and NDM-1-producing multidrug resistant Examples include bacteria, methicillin-resistant Staphylococcus aureus, vancomycin-resistant enterococci, Legionella, and the following reference examples 2 to 9.
（参考例２）
屋内の壁面に施工されたタイルの表面に、実施例１で用いた抗菌剤分散液または製造例２の抗菌剤分散液を塗布して抗菌剤層を形成し、抗菌剤層を形成してから約６時間後、タイルの表面に存在する病原菌を調べると、実施例１および２の結果から、９９％以上が死滅していると推察される。
(Reference Example 2)
After applying the antibacterial agent dispersion liquid used in Example 1 or the antibacterial agent dispersion liquid of Production Example 2 to form the antibacterial agent layer on the surface of the tile constructed on the indoor wall surface, and forming the antibacterial agent layer About 6 hours later, when the pathogenic bacteria present on the surface of the tile were examined, it was estimated from the results of Examples 1 and 2 that 99% or more had been killed.
（参考例３）
窓ガラスの屋内側の表面に、実施例１で用いた抗菌剤分散液または製造例２の抗菌剤分散液を塗布して抗菌剤層を形成し、抗菌剤層を形成してから約６時間後、窓ガラスの屋内側の表面に存在する病原菌を調べると、実施例１および２の結果から、９９％以上が死滅していると推察される。
(Reference Example 3)
About 6 hours after forming the antibacterial agent layer by applying the antibacterial agent dispersion liquid used in Example 1 or the antibacterial agent dispersion liquid of Production Example 2 to the indoor side surface of the window glass. Later, when the pathogenic bacteria present on the indoor surface of the window glass were examined, it was estimated from the results of Examples 1 and 2 that 99% or more had been killed.
（参考例４）
壁紙の表面に、実施例１で用いた抗菌剤分散液または製造例２の抗菌剤分散液を塗布して抗菌剤層を形成し、抗菌剤層を形成してから約６時間後、壁紙の表面に存在する病原菌を調べると、実施例１および２の結果から、９９％以上が死滅していると推察される。
(Reference Example 4)
On the surface of the wallpaper, the antibacterial agent dispersion liquid used in Example 1 or the antibacterial agent dispersion liquid of Production Example 2 was applied to form an antibacterial agent layer, and about 6 hours after the antibacterial agent layer was formed, When the pathogenic bacteria existing on the surface are examined, it is estimated from the results of Examples 1 and 2 that 99% or more are dead.
（参考例５）
屋内の床面の表面に、実施例１で用いた抗菌剤分散液または製造例２の抗菌剤分散液を塗布して抗菌剤層を形成し、抗菌剤層を形成してから約６時間後、床面の表面に存在する病原菌を調べると、実施例１および２の結果から、９９％以上が死滅していると推察される。
(Reference Example 5)
About 6 hours after the antibacterial agent layer was formed by applying the antibacterial agent dispersion liquid used in Example 1 or the antibacterial agent dispersion liquid of Production Example 2 to the surface of the indoor floor surface. When the pathogenic bacteria existing on the surface of the floor surface are examined, it is estimated from the results of Examples 1 and 2 that 99% or more have been killed.
（参考例６）
自動車用インストルメントパネル、自動車用シート、自動車の天井材などの自動車内装材の表面に、実施例１で用いた抗菌剤分散液または製造例２の抗菌剤分散液を塗布して抗菌剤層を形成し、抗菌剤層を形成してから約６時間後、自動車内装材の表面に存在する病原菌を調べると、実施例１および２の結果から、９９％以上が死滅していると推察される。
(Reference Example 6)
An antibacterial agent layer is formed by applying the antibacterial agent dispersion liquid used in Example 1 or the antibacterial agent dispersion liquid of Production Example 2 to the surface of an automobile interior material such as an instrument panel, an automobile seat, or an automobile ceiling material. About 6 hours after the formation of the antibacterial agent layer, when the pathogenic bacteria present on the surface of the automobile interior material are examined, it is estimated from the results of Examples 1 and 2 that 99% or more have been killed. .
（参考例７）
エアコンの表面に、実施例１で用いた抗菌剤分散液または製造例２の抗菌剤分散液を塗布して抗菌剤層を形成し、抗菌剤層を形成してから約６時間後、エアコンの表面に存在する病原菌を調べると、実施例１および２の結果から、９９％以上が死滅していると推察される。
(Reference Example 7)
The antibacterial agent dispersion liquid used in Example 1 or the antibacterial agent dispersion liquid of Production Example 2 was applied to the surface of the air conditioner to form an antibacterial agent layer, and about 6 hours after the formation of the antibacterial agent layer, When the pathogenic bacteria existing on the surface are examined, it is estimated from the results of Examples 1 and 2 that 99% or more are dead.
（参考例８）
冷蔵庫の表面に、実施例１で用いた抗菌剤分散液または製造例２の抗菌剤分散液を塗布して抗菌剤層を形成し、抗菌剤層を形成してから約６時間後、冷蔵庫の表面に存在する病原菌を調べると、実施例１および２の結果から、９９％以上が死滅していると推察される。
(Reference Example 8)
The antibacterial agent dispersion liquid used in Example 1 or the antibacterial agent dispersion liquid of Production Example 2 was applied to the surface of the refrigerator to form an antibacterial agent layer, and about 6 hours after the antibacterial agent layer was formed, When the pathogenic bacteria existing on the surface are examined, it is estimated from the results of Examples 1 and 2 that 99% or more are dead.
（参考例９）
タッチパネル、電車のつり革、デスクマット、テーブルクロス、エレベーターのボタン、階段や廊下の手摺、カーテンなど不特定多数の人が接触する基材表面に、実施例１で用いた抗菌剤分散液または製造例２の抗菌剤分散液を塗布して抗菌剤層を形成し、抗菌剤層を形成してから約６時間後、これらの基材表面に存在する病原菌を調べると、実施例１および２の結果から、９９％以上が死滅していると推察される。
(Reference Example 9)
The antibacterial agent dispersion or production used in Example 1 on the surface of a base material that is touched by an unspecified number of people, such as touch panels, train straps, desk mats, table cloths, elevator buttons, stairs and corridors, and curtains The antibacterial agent dispersion of Example 2 was applied to form an antibacterial agent layer, and about 6 hours after the formation of the antibacterial agent layer, the pathogens present on these substrate surfaces were examined. From the results, it is estimated that more than 99% are dead.
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