JP2022109198A - Abrasion protective agent and abrasion protective film with photocatalytic activity mode - Google Patents

Abstract

[Problem] Equipped with a photocatalytic activity mode that prevents rough skin, removes dirt, bacteria, and viruses, and fixes and sustains sterilizing, antibacterial, antiviral, sterilizing, deodorizing, and antifungal effects in any environment through photocatalytic action. Provides an abrasion protection agent and an abrasion protection film. The present invention includes one or more photocatalyst liquids, a plurality of supported metals or metal liquids and compounds dispersed in the photocatalyst liquid, silicon and silicon compounds, a peracetic acid preparation, a plurality of nanocelluloses, a saccharide containing sugar, To provide an abrasion protectant characterized by containing algae and pulp, and further to provide a cylindrical or prismatic illumination and a photocatalytic activity mode arranged concentrically with a container filled with the abrasion protectant. [Selection diagram] Figure 11

Description

The present invention is a simple method of irradiating light from a light source attached to a rubbing protective agent in order to prevent bacterial and viral infections in humans, and is a constant sterilization, antibacterial, antiviral, deodorant, and antifungal effect by photocatalytic activity. and methods for inactivating viruses.

Titanium oxide, which is most commonly used in photocatalysts, generates active oxygen when exposed to ultraviolet light. In particular, OH radicals are much more powerful than chlorine, hypochlorous acid, hydrogen peroxide, and ozone, which are widely used for disinfection and sterilization. In addition to converting carbon dioxide gas into non-toxic substances with its strong oxidizing power, it destroys coenzymes such as coenzyme A in bacterial cells, enzymes that act on the respiratory system, cancer cells, etc., decomposing organic matter, and killing bacteria and mold. It can also decompose toxins and viruses, exhibit antibacterial and antiviral effects, and stop the growth of bacteria and mold and the adhesion of viruses. Due to these actions, almost all harmful organic substances such as various harmful chemical substances and airborne chemical substances such as malodorous substances, and bacteria and viruses that adhere to fibers and the human body can be easily decomposed and decomposed by light irradiation. can be rendered harmless. In recent years, in addition to photocatalysts that require ultraviolet light, visible-light-responsive photocatalysts that can obtain a photocatalytic effect even with room light or the like are widely used and frequently used.

The skin's primary function is to reduce water loss, protect against abrasive effects and microbes, and act as a permeable barrier to the environment. In order of layers, the surface layer (stratum corneum, thickness of about 10-20 μm), epidermis layer (thickness about 50=100 μm), dermis layer (thickness about 1-2 mm), subcutaneous tissue (thickness about 1-2 mm) ), and the barrier to percutaneous absorption lies within the stratum corneum, the thinnest component of the skin. The pH of the skin on the hands is naturally kept acidic and has the function of suppressing the growth of bacteria. It is clear that it causes proliferation of bacteria and colonization of viruses. Due to the current spread of new coronavirus infections, community-acquired infections in familiar places such as restaurants and medical facilities, as well as welfare facilities, have been reported one after another.[Non-Patent Document 20] The survival period of the virus has been elucidated above, and it has been concluded that the need for hand hygiene as a countermeasure against infection will be the future control of virus infection, but as shown in [Non-Patent Document 16], Skin dryness, skin thickening, and loss of pattern are high in hand sanitizers, and after using hand sanitizers containing moisturizing ingredients, redness, thinning, fissures, periungual fissures, and eczema have been reported. When a person develops rough hands, dermatitis, etc., not only Staphylococcus aureus but also Gram-negative bacteria, which originally adheres transiently, may colonize, and many nosocomial infections caused by them have been reported. Therefore, rough hands are a big problem that cannot be neglected from the perspective of infection prevention, and it has been pointed out that rough hands cause a decrease in the compliance rate of hand washing for humans. Although no significant difference was observed when comparing the presence or absence of rough hands in the hands, the hand sanitizer containing moisturizing ingredient (Lipijua) showed a slight improvement trend when compared with the hand rough symptoms, and the feeling of use was good and the dryness was quick. It is considered that it can be used efficiently, and it is said that moisturizing is the most effective measure to prevent rough hands, and that daily skin care is also important.

Japanese Patent No. 2783339 Japanese Patent No. 2517874 Japanese Patent No. 6576996 Japanese Patent No. 6184108 Japanese Patent Application Laid-Open No. 2002-308712 JP 2014-113576 A Japanese Patent Application No. 2020-46968 JP 2016-10724 A Patent No. 6359865 publication Japanese Patent No. 6427334

パルプの性質と紙の強度 十条製紙株式会社研究所 奥杏一 熱帯樹林の成分と利用（２）大原誠資 熱帯林業Ｎｏ３９ １９９７年 光触媒応用技術 橋本和仁 ２００７年７月２５日 東京図書株式会社 光触媒のすべて 藤嶋昭 ２０１７年１１月２２日 ダイヤモンド社 抗菌薬剤感受性試験結果に基づく銅イオン溶液の抗菌・殺菌作用過程 石田恒雄 日本微生物生態学会誌 ３１巻２号４５－４６ ２０１６年 はじめて出会う細胞の分子生物学 伊藤明夫 株式会社岩波書店２００６年８月２９日 可視光下での金属酸化物の抗ウイルス活性に関する試験 砂田香矢乃、畑山靖佳、永井武、石黒斉 ＫＩＳＴＥＣ研究報告２０１９ ２０１９年７月 錯体粉末の熱分解による酸化タングステンナノ粒子の作製 山下洋子、原田智洋、牧野晃久 粉体および粉末治金 ５９ Ｎｏ６ Ｐ３３３ ２０１２年 常識は覆るのか？！光触媒反応における酸素の還元機構 大谷文章、阿部竜 化学レビュー（第６回）光触媒化学 化学，６３（９），１９－２３ ２００８年９月 光触媒標準研究法 光触媒反応系の開発と成果の発表 大谷文章 東京図書株式会社 ２０１７年１２月１５日 人間の手指の摩擦特性の解析 嶋田明広 韓鉱庸 川村貞夫 計測自動制御学会論文集１９９６年 Ｖｏ．３２ Ｎｏ１２ 粉体層の摩擦特性に及ぼす粒子形状および粒径の影響 廣田満昭他 粉体工学会誌／粉体工学会［編］ １９８６年 Ｖｏｌ．２３ Ｎｏ．９ 速乾性手指消毒剤と手荒れの評価潤い成分配合手指消毒剤使用前後の比較 龍口さだ子 第Ｖ群１９席 Ｐ７３～７６ 手指消毒による手荒れと除菌効果の検討 高森スミ 久家智子 ▲辻▼明良 日環感 １９９２年 Ｖｏ１．７ ｎｏ．２ 粉体粒子の形状 竹林敬 色材基礎講座第ＸＩ講 １９９５年 ５２－５８ 光殺菌速度に及ぼす装置材料の影響 八木下将史他 秋田高専研究紀要第４４号 ２００８年１１月３０日 ヒトの皮膚上に存在する新型コロナウイルスとインフルエンザ ウイルスの生存評価 ＣＯＶＩＤ－１９における手指衛生の重要性 京都府立医科大学 大学院医学研究科 Ｃｌｉｎｉｃａｌ Ｉｎｆｅｃｔｉｏｕｓ Ｄｉｓｅａｓｅｓ ２０２０年１０月３日 Photocatalyst material development, industrial application and international standardization Hiroshi Taoda Bio-related application of photocatalyst technology Kazuya Nakata Fujiko Giken Technical Report "Creating" No. 26

Properties of Pulp and Strength of Paper Kyoichi Oku Research Institute, Jujo Paper Co., Ltd. Components and Uses of Tropical Forests (2) Seisuke Ohara Tropical Forestry No.39 1997 Photocatalytic Application Technology Kazuhito Hashimoto July 25, 2007 Tokyo Tosho Co., Ltd. All about photocatalyst Akira Fujishima November 22, 2017 Diamond Company Antibacterial and bactericidal action process of copper ion solution based on the results of antibacterial drug susceptibility test Tsuneo Ishida Journal of Microbial Ecology, Vol.31, No.2, 45-46 2016 Molecular Biology of Cells Encountered for the First Time Akio Ito Iwanami Shoten Co., Ltd. August 29, 2006 Test on antiviral activity of metal oxides under visible light Kayano Sunada, Yasuyoshi Hatayama, Takeshi Nagai, Hitoshi Ishiguro KISTEC Research Report 2019 July 2019 Production of Tungsten Oxide Nanoparticles by Thermal Decomposition of Complex Powder Yoko Yamashita, Tomohiro Harada, Akihisa Makino Powder and Powder Metallurgy 59 No6 P333 2012 Will common sense be overturned? ! Oxygen Reduction Mechanism in Photocatalytic Reaction Fumiaki Otani, Ryu Abe Kagaku Review (6th) Photocatalytic Chemistry Chemistry, 63(9), 19-23 September 2008 Photocatalyst standard research method Development of photocatalytic reaction system and presentation of results Fumiaki Otani Tokyo Tosho Co., Ltd. December 15, 2017 Analysis of Friction Characteristics of Human Fingers Akihiro Shimada Koyong Han Sadao Kawamura Transactions of the Society of Instrument and Control Engineers 1996 Vo. 32 No. 12 Effect of Particle Shape and Particle Size on Friction Characteristics of Powder Bed Mitsuaki Hirota et al., Journal of Japan Society of Powder Technology/Japan Society of Powder Technology [ed.] 1986 Vol. 23 No. 9 Quick-drying hand sanitizer and evaluation of rough hands Comparison before and after using hand sanitizer containing moisturizing ingredients Sadako Tatsuguchi Group V 19th seat P73-76 Investigation of rough hands and sterilization effect by hand disinfection Sumi Takamori Tomoko Kuge Tsuji Akira Nichikankan 1992 Vo1.7 no. 2 Shape of Powder Particles Takashi Takebayashi Color Material Basic Lecture No. XI 1995 52-58 Influence of equipment material on photo-sterilization rate Masafumi Yagishita et al. Research Bulletin of Akita College of Technology No.44 November 30, 2008 Survival assessment of novel coronavirus and influenza virus present on human skin Importance of hand hygiene in COVID-19 Kyoto Prefectural University of Medicine Graduate School of Medicine Clinical Infectious Diseases October 3, 2020

The problem that the invention is trying to solve

However, the photocatalyst solutions and non-photocatalyst solutions shown in [Patent Document 1] to [Patent Document 5] are generally limited to walls and floors assuming substrates, residential and industrial applications, etc. The balance between the light intensity and the adsorbed substances is important for photocatalysts, which are assumed to be used on the skin, textiles, places frequently used in the house, and fixed objects used by an unspecified number of people. Titanium oxide alone requires ultraviolet rays of several tens of μW/cm ² to several hundreds of μW/cm ² or more. Unless nitrogen-doped titanium oxide, molybdenum, or metal ions that respond to There is room for improvement. In addition, when a general photocatalyst solution that exhibits oxidative decomposition and sterilization power is applied to the skin or fibers of the hands, it decomposes and kills bacteria and viruses when UV irradiation is stable, but the target substance does not reach the surface. It has been said that photocatalysts, which cannot cause reactions such as decomposition unless they come, cannot be applied to the human body, fibers, etc., where it is difficult to immobilize the photocatalyst solution due to the adsorbed substances and changes in the environment in which they are used. In the first place, photocatalysts do not produce bactericidal, antibacterial, or antiviral effects without light irradiation, and active oxygen such as OH radicals has a short life, and the antibacterial effect cannot be exhibited unless bacteria come near titanium oxide. If titanium oxide is buried in a carrier or binder, it is difficult for light to reach it and the antibacterial effect is reduced.

Furthermore, photocatalytic reactions have the disadvantage that reactions such as decomposition cannot occur unless the target substance comes to the surface. However, since activated carbon does not transmit light, the reaction does not occur if the photocatalyst is in the shadow of the activated carbon. However, there is also a drawback that it cannot be used. In addition, it is difficult to obtain a stable effect of the photocatalyst in the absence of light at night. Visible light-responsive photocatalysts, which are effective for the total decomposition of water (H ₂ O → H ₂ + 1/2 O ₂ ), which is a photo-chemical energy conversion system, cannot be used for instantaneous oxidative decomposition reactions of organic compounds. [Non-Patent Document 12] also describes that a phenomenon that cannot be explained only by comparing the structure) and the standard electrode potential occurs.

In addition, peracetic acid is a colorless and transparent liquid with a pungent acetic acid odor. As an acetic acid preparation, it is mainly used for sterilization, sterilization, and disinfection of medical instruments at a concentration of 0.2% to 0.3%. It is a disinfectant with low sensitization/allergenicity and mutagenicity to the human body, and exhibits the strongest antibacterial effect. Viruses and the like can be killed in a short period of time within 5 minutes. The peracetic acid formulation is a mixture containing peracetic acid, hydrogen peroxide, acetic acid, octanoic acid (peroctanoic acid), 1-hydroxyethylidene-1.1-diphosphonic acid (hereinafter referred to as HEDP), and the like. Compared to chlorine-based disinfectants, which are often used as disinfectants, peracetic acid preparations are less inactivated by contact with organic matter and have been found to have no residue. However, due to its strong oxidizing power, it causes corrosion in iron, copper, brass, etc. For metal ions, it decomposes into acetic acid and oxygen, or hydrolyzes. As a result, it is characterized by being decomposed into acetic acid and hydrogen peroxide, but in [Patent Document 9] and [Patent Document 10], non-corrosive peroxide formulations that suppress the occurrence of corrosion of metals such as iron have also been developed. .

Furthermore, in the event of an epidemic of bacterial or viral infections, hand disinfection is generally the most familiar, simple and important means, and if the number of bacteria etc. is reduced considerably, both substantial and non-substantial active ingredients can be maintained. Since it is well known that disinfectants are active, when disinfectants are used frequently, the symptoms appear in the order of dryness, hardening, cracks, disappearance of marks, erythema, and itching. Since it also has a dehydrating effect, it will degrease the surface of the skin, removing both sebum and moisture, which can easily lead to rough hands, leading to the growth of pathogenic bacteria and becoming a breeding ground for bacteria. put away. For example, when alcohol is applied to the skin, it has an immediate bactericidal effect, but because it is highly volatile and has no persistence (residuality), the effect disappears in just a few minutes, and it is often difficult to maintain hygiene. It is known that the use of disinfectants is essential, and it is known that it often causes rough hands and is accompanied by allergic symptoms, so there are situations where the use of disinfectants is refrained. Although many reports have been made on the bactericidal effect and antibacterial activity of antiseptic agents in hand disinfection, there are few reports on the relationship between rough hands and sterilization effects, and there is room for further investigation. [Non-Patent Document 17] also reported physicochemical evaluation methods such as morphological evaluation by the replica method, measurement of transepidermal water loss, and measurement of sebum content, and performed measurement of skin water loss and transsebum content, and image analysis. However, the current situation is that sufficient results have not been obtained and have not yet been reported.

In view of the above-mentioned problems, the problem of the present invention is to respond to the usage environment of consumers. Metal compounds such as peroxide preparations and molybdenum oxide, which are constantly effective regardless of the environment in which they are used, such as light conditions, nanocellulose with moisturizing and protective action with conductivity, seaweed, algae and anti-allergic action. In addition to using a composite material that is a mixture of allantoin, pulp fine powder, and silicon, it is possible to effectively activate the catalytic reaction by irradiating ultraviolet light in a photocatalytic activity mode, and the peelability of the photocatalyst that enters the gaps between the skin and fibers, and the inside (hand skin). Intermolecular force acts on the fiber side (hereafter referred to as the bulk side) and the surface side (hereafter referred to as the surface), and the molecular density on the bulk side is overwhelmingly high, so the molecules existing on the surface are always drawn to the bulk side. Using surface tension, which is one of the surfactants, and quick-drying due to friction of fine pulp powder, adsorption of oxygen in the air, and adsorption and immobilization of silicon, it can be applied not only to the human body such as hands, but also to fibers and solid objects. By applying or spraying, the protective agent is adsorbed and fixed, and instantly removes bacteria and viruses, has bactericidal action, antibacterial, antiviral, disinfecting, deodorizing, and antifungal effects, and protects the skin from roughening. The purpose is to provide the drug

Therefore, in order to solve the above problems, the present invention is configured as follows.
(1) Instantaneous sterilization and disinfection, including in the air, with a peroxide formulation, and at the same time, a superhydrophilic photocatalyst solution and a non-hydrophilic microparticle pulp mixed with nanocellulose. A photocatalytic protective agent with a photocatalytic activity mode (hereinafter referred to as protective agent) that adsorbs and fixes a photocatalyst solution that uses a type of adsorption and fixation action to the gaps of the human skin, exfoliates, decomposes, sterilizes, and inactivates bacteria and viruses that adhere to the skin. .
(2) Sterilization, antibacterial, antiviral, sterilization, deodorizing, antifungal, and moisturizing protection by applying the above protective agent to keep the environment sanitary and in an environment where bleaching of bacteria and viruses and adhesion and growth of bacteria are difficult to occur. A rubbing protective film (hereinafter referred to as a protective film) that provides an action (hereinafter referred to as a rubbing action).
(3) The protective agent contains a photocatalyst material, and by irradiating light from a light source to a container through which a light source can easily pass, such as quartz glass or a light-transmitting resin, photocatalytic activity can be constantly obtained, and bacteria A protective agent that sterilizes and inactivates viruses. However, the container is not limited to quartz glass.
(4) A protective agent that provides moisturizing and protective effects on the skin by the tasteless, odorless and safe hydrophilic nanocellulose and saccharides described in (1) above.
(5) Infiltration, coating, and quick drying by the rubbing method by rubbing two or more kinds of non-hydrophilic microparticle fine pulps with different particle sizes described in (1) above, anti-allergic action by allantoin, and cooling by citric acid dispersion A protective agent that provides cooling and pain relief.
(6) The protective agent according to the above (1), (2) and (3), which has a rubbing effect on fibers and solids and a protective film for sterilization, antibacterial, antiviral, sterilizing, deodorizing, and antifungal properties.
(7) The protective agent according to (3) above, wherein the wavelength of the photocatalytic activity mode is ultraviolet light of 200 to 400 nm depending on the photocatalytic material in the protective agent.
(8) The protective agent according to (3) above, wherein the photocatalyst material in the protective agent contains a visible light-responsive material, and the light from the light source has a wavelength of 360 to 830 nm in the visible region.
(9) The protective agent according to (3) above, wherein the light source with a wavelength of 200 to 400 nm is black light, LED, or organic EL.

The titanium oxide used in the present invention is at least one of anatase-type titanium oxide, brookite-type titanium oxide, and rutile-type titanium oxide having high photocatalytic activity, but is not limited thereto.

The nanocellulose used in the present invention is a particulate powder or liquid having a concentration of about 6% or less, but not limited to 6%.

The nanocellulose used in the present invention is composed of cellulose-based polymer fibers having an average fiber diameter (D) of 3 nm to 100 nm and a moisturizing liquid at a weight ratio of cellulose-based polymer fiber:moisturizing liquid = 1:1 to 1:20. , but the weight ratio is not limited.

The protective agent of the present invention includes, for example, micro-sized fine powder of paper pulp from which cellulose fibers are separated and extracted, cyclodextrin, glucose, fructose, sucrose, maltose, lactose and glycerin, dipropylene glycol, polyethylene glycol (for example, number average molecular weight 120 to 20,000), polyglycerin (for example, number average molecular weight 120 to 20,000), glycol-based solvents such as butylene glycol, polyhydric alcohols such as xylitol and maltitol, polysaccharides such as chondroitin sulfate and hyaluronic acid, collagen sterol esters such as hydroxydistearate, organic acid salts such as sodium lactate, and diglycerin adducts. Among these, polyhydric alcohols and nanocellulose, which is highly hydrophilic to the skin, contain fine-grained pulp to prevent the moisturizing agent from locally infiltrating only the sprayed area. It is preferable to distribute the moisturizing agent throughout the area, and one or two or more selected from them are suitable.

The seaweeds and algae used in the present invention are, for example, at least one or more powders or liquids of Akamoku and Nemacystus decipiens, but are not limited.

The titanium oxide and tungsten oxide used in the protective agent of the present invention are in the form of powder, water dispersion or gel, and may be photocatalyst materials and visible light responsive photocatalyst materials that are generally manufactured, processed and sold, and are at least one type. is not limited.

Molybdenum used in the protective agent of the present invention includes, but is not limited to, one or more powders or liquids of sodium molybdate and molybdenum trioxide in addition to molybdenum.

The concentrations of the copper ion water and the copper liquid of the present invention are 0.2 mg to 0.3 mg, respectively, but their use is optional.

The peroxide formulation of the present invention may be a liquid peroxide formulation that is generally manufactured and sold. PBio acryl, but not limited to.

Stabilizers contained in the peracetic acid formulation of the present invention include hydroxy-carbonate-based organic sequestering agents such as citric acid, glycolic acid, gluconic acid and salts thereof, amino-carbonate-based agents such as EDTA and acetate. , ethylene, diamine, tetra-, and trinitric acetic acid, and hydroxy-aminocarbonates such as hydroxy, ethylene, diamine, and tetraacetic acid.

The preservative of the protective agent of the present invention is one or more powders or liquids of hexanediol, potassium sorbate and calcium sorbate. Use is optional.

Antioxidants for the protective agent of the present invention include diptyrylhydroxytoluene (BHT), t-butylhydroxyanisole (BHA), tocopherols (vitamin E), ascorbic acids (vitamin C), erythorbic acids, chlorogenic acid, catechin, Gallic acid powder or liquid is one or more, but the presence or absence of use is not limited.

The allantoin used in the protective agent of the present invention is powder or liquid, but the presence or absence of use is not limited.

When the protective agent of the present invention is used on the human body other than the hands, for example, on the heels of the feet, it can improve ringworm fungi such as athlete's foot. There is no limitation on the use site of However, when it is used in the oral cavity other than the eyeball, the content of the photocatalyst is preferably in the range of 0.01% to 0.004%, and is of course harmless.

Fibers to which the protective agent of the present invention is applied or sprayed include wood and natural fibers such as plant fibers (cellulose polymers), animal fibers (protein polymers), mineral fibers and chemical fibers such as inorganic fibers and refined fibers. (Natural polymer), regenerated fiber (natural polymer), semi-synthetic fiber (semi-synthetic polymer), synthetic fiber (synthetic polymer) (hereafter referred to as fiber) materials, and products and merchandise manufactured from them but not limited to them.

As solids to which the protective agent of the present invention is applied or sprayed, the principle of adding titanium oxide has already been used by dentists as dental hygiene. and metals such as keys and coins, paper products such as banknotes, newspapers, stationery, etc., tableware such as chopsticks and cups, housing-related items such as doorknobs, toilets, bathrooms, bedding, etc., audios such as CDs, DVDs, etc., but not limited to them. .

In addition, general disinfectants or sterilization/antibacterial agents that have an irritating odor and only temporary effects deprive the skin of both sebum and moisture. , Chlorines and alcohols that are likely to be hotbeds for bacterial growth, but without using them, it is sterilizing, disinfecting, sterilizing, antibacterial, antiviral, sterilizing, deodorizing, antifungal, etc. and moisturizing.・Protective agents that can simultaneously obtain water retention, adhesiveness, etc. by using the rubbing method are difficult to apply and spray, not only in situations where it can be applied and sprayed on a daily basis, but also when sleeping, bedridden, working, nursing, etc. It is a protective agent and a protective film whose effect is continuously maintained immediately after application and spraying even under circumstances. However, indigenous bacteria that always live in humans and prevent the growth of invading bacteria from the outside, and good indigenous bacteria that protect from ultraviolet rays and create healthy skin, prevent the growth of bad indigenous bacteria and become a source of infection if you are healthy. However, if the resistance is weakened, infection may occur, and even if they are killed with peracetic acid preparations or photocatalytic activity, the rubbing action of pulp and the moisturizing and protective action of nanocellulose can be obtained at the same time. Since the protective agent works regardless of the physical condition, safer and more stable use becomes possible.

この場合、Ｃｉは各成分の平均曝露濃度を示し、Ｔｉは各成分の許容濃度を示す。ただし有害物質の許容濃度の基準は職場における環境原因による労働者の健康障害を予防するための手引きに用いられることを目的とし、日本産業衛生学会が勧告している。In addition, nanocellulose is blended with the photocatalyst solution and used, but this figure for the permissible concentration of the mixed substance is for the case where the substance exists alone in the air, and is exposed to two or more substances. If there is no evidence showing that addition does not hold, the toxicity of two or more Assuming that they are additive, it has been shown that it is appropriate to judge that exposure exceeds the permissible concentration when the value of I calculated by the following formula exceeds 1.

In this case, Ci indicates the average exposure concentration of each component and Ti indicates the permissible concentration of each component. However, the standards for permissible concentrations of hazardous substances are recommended by the Japan Society for Occupational Health for the purpose of being used as a guide for preventing health problems for workers due to environmental causes in the workplace.

In addition, molybdenum oxide (MoO3) is one of the metal compounds other than copper compounds and silver compounds that are known to have high antibacterial and antiviral activity. It is believed to have antiviral activity against both non-enveloped and enveloped viruses. Furthermore, a visible light responsive photocatalyst material (Mo/TiO), which is a combination of molybdenum oxide and titanium oxide, is known to have higher antiviral activity under white fluorescent lamp irradiation than under dark conditions, and the present invention By adding and using these protective agents, it is possible to obtain deactivation by a photocatalyst without fail.

り、本発明の保護剤に混合後に噴霧すると、微生物と接触し、遊離した活性酸素が細胞内の酵素にある－ＳＨ基やＳ－Ｓ結合を破壊して不活性化をしたり、発生したラジカルが膜組成を酸化し細胞膜を破壊して殺菌作用を起こし、反応後は酢酸・水・酸素に分解され残留毒性も無く安全に使用できる。過酢酸製剤は芽胞菌を含む細菌、真菌、ウイルス等、ほぼすべての微生物に対して幅広い効果を示し、過酸化水素よりも強い殺菌力を持つことが古くか

有量で安定して高い効果を発揮する。過酸化水素が０．８０％、過酢酸が０．０６％であるため、医薬用外劇物に該当せず、使用前の希釈調製も不要となる。生分解性が有り、残留

等の医療用具の滅菌消毒剤として認可されており皮膚毒性や感作性物質も無い事から本発明の保護剤で人体の手肌にも使用が可能となる。但し、過酢酸製剤は鉄や銅、酸化タングステンに使用すると腐食する性質と金属イオン水に対し分解作用がある事から、保護剤中の銅イオンや銅水溶液等の濃度に対してキレート剤含有の過酢酸製剤またはキレート剤の混合使用している。

Therefore, when sprayed after being mixed with the protective agent of the present invention, it comes into contact with microorganisms, and the released active oxygen destroys -SH groups and S-S bonds in enzymes in cells to inactivate or generate them. Radicals oxidize the membrane composition, destroy cell membranes, and cause a bactericidal effect. Peracetic acid preparations show a wide range of effects against almost all microorganisms, including bacteria, fungi, and viruses, including spore-forming bacteria, and have long been known to have stronger sterilizing power than hydrogen peroxide.

Stable and highly effective in large quantities. Since hydrogen peroxide is 0.80% and peracetic acid is 0.06%, it does not correspond to non-medical deleterious substances and does not require dilution preparation before use. Biodegradable and residual

It is approved as a sterilizing and disinfecting agent for medical instruments, such as medical devices, and has no skin toxicity or sensitization. However, since peracetic acid is corrosive when used on iron, copper, and tungsten oxide, and has a decomposing effect on metal ion water, the concentration of copper ions and copper aqueous solution in the protective agent should not be affected by the concentration of chelating agents. You are using a peracetic acid preparation or a mixture of chelating agents.

為、本発明の保護剤に混合して使用しても良い。また過酢酸製剤の溶液は酸化チタン入り微粒子パルプに浸潤した状態で塗布・噴霧され、乾燥に至るまで残留する持続性の高いものである。In addition, acetic acid and hydrogen peroxide react again to form peracetic acid even in peracetic acid preparations distributed in Japan. Ac

Therefore, it may be used by mixing with the protective agent of the present invention. Further, the peracetic acid preparation solution is applied and sprayed in a state of being soaked in the fine particle pulp containing titanium oxide, and remains in the form of a highly persistent solution until it dries.

Furthermore, the peracetic acid preparation, which maintains an equilibrium state, is effective against all microorganisms such as bacterial spores, tubercle bacillus, viruses, filamentous fungi, and general bacteria, and can kill viruses in a short time of less than 5 minutes. In environments where the catalytic reaction of photocatalysts is difficult to obtain from air or in environments where instantaneous sterilization is required such as in the air, it acts as a sterilizer, antibacterial, antiviral, disinfectant, and disinfectant instead of photocatalysts, and is effective regardless of the environment. is obtained. However, when containing metal ions, a chelating agent is mixed.

Regarding the use of a chelating agent, if the protective agent contains metal ions such as copper ions, it is necessary to prevent decomposition even when the peracetic acid formulation is mixed and to maintain an equilibrium state. A stable complex is formed by sandwiching metal ions, and the metal ions are inactivated in the protective agent due to the action of blocking and hiding state. Demonstrates the effectiveness of the inherent antibacterial and antiviral effects of metal ions.

In addition, in the field of application of photocatalysts, combinations with other technologies have been attempted with flexible ideas, not limited to photocatalytic reactions. Focusing on sustaining the photocatalyst effect such as sterilization and antibacterial other than that, when using the particle size of fine particle pulp containing titanium oxide in the situation where the protective agent is sprayed and applied to the hand skin and the rubbing method by rubbing with fingers. , The coefficient of friction, which is an index of the friction effect on the skin of the hand, is expressed by the ratio of the tangential force to the normal force. greater than 2.5. It can be seen that the coefficient of friction of human fingers is quite large compared to the fact that the coefficient of friction between many metals is approximately between 0.6 and 1.2 in the experimental results. From this, it is thought that humans can generate forces at various angles from their fingertips, and can select the optimal solution from many redundant solutions. As a result, a fine movement of the finger as a whole is realized, resulting in a development that cannot be explained by a constant coefficient of friction. It was found that the frictional characteristics of human fingers differ depending on the direction of friction, and that the coefficient of friction in the direction in which the finger scratches an object is greater than that in the opposite direction. Therefore, the friction on the finger surface is considered to be affected by the contact area in addition to the vertical load. Moreover, the structure of human finger skin is different from that of general skin, and the presence of fingerprints in particular is unique to fingers, which is not found on other body parts. Human fingertips have nails, which increase the rigidity of the fingertips and improve the efficiency of work with the fingers. The friction coefficient of the fingertip is also considered to change due to the physical properties of the finger itself depending on the measurement direction.

In addition, human fingers are covered with relatively soft tissue, and there are nails on the back of the fingers, which are thought to increase the rigidity of the fingertips when compressive stress acts on them. The effect of nails is large in the range where the inside of the skin is hardened. As for the finger posture, the greater the posture, the greater the force acting on the nail via the internal tissue of the fingertip, and the more compressive stress acts, resulting in a wider range of hardening of the fingertip. As the tissue hardens, it is expected that the shear strength will increase, resulting in higher frictional forces. That is, it is considered that the softness of the fingertip and the presence of the nail are involved in the cause of the tendency, and that these actions change the state of the fingertip surface and internal tissue. Therefore, the coefficient of friction of a human finger is approximately in the range of 0.5 to 3, which is considerably larger than that of metal-to-metal friction, and the coefficient of friction of a human finger increases as the longitudinal load decreases. Furthermore, the coefficient of friction of a human finger depends on the structure of the human finger, particularly the presence of the nail and the softness of the fingertip tissue. The coefficient of friction changes depending on the direction of friction and increases depending on the direction, but this tendency becomes more pronounced as the finger posture increases. Based on these data and the coefficient of friction of the research theory, etc., the rubbing effect due to friction can be obtained, and the details will be described later in [0037] to [0040].

The nano-sized to μm-sized titanium oxide-containing microparticle pulp used in the present invention takes advantage of its non-hydrophilic property that it is not compatible with water, and the liquefied hydrophilic nanocellulose can be used in a superhydrophilic photocatalyst solution or peracetic acid preparation. The non-hydrophilic microparticle pulp containing titanium oxide is surrounded and adhered in a mixed state, and when it is applied or sprayed, the microparticles of the microparticle pulp containing titanium oxide are released from the infiltration state, The function of the original non-hydrophilic pulp microparticles, that is, the friction of the microparticle pulp containing titanium oxide, which maintains the hardness of the pulp without being affected by other ingredients even after long-term mixing, prevents liquid dripping and protects hands. Considering the large friction coefficient of , it is essential to use a coating method in which the fine particle pulp containing titanium oxide is wet and dried while the moisture of the photocatalyst solution is evenly transferred to the coating film by rubbing with fingers when using the skin. be. In other words, the non-hydrophilic fine particle pulp containing titanium oxide is a carrier for adsorbing bacteria and viruses to be decomposed and sterilized. A rubbing method using a protective agent plays an important role.

In the first place, regarding the shape factor of powder particles, when a factor related to particle shape is included in a certain functional relationship that represents the properties or phenomena of a group of particles, it is extracted as one factor and used as one factor. It can be granular, spherical, cubic, plate-like, flake-like, column-like, rod-like, needle-like, fibrous, massive, spongy, horn-like, horn-like, round-like, and the like. The shape factor is determined by uniformity, sufficiency, sphericity, circularity, roundness, surface index, volume shape factor, surface area shape factor, specific surface area shape factor, etc., and is based on powder physical properties related to shape. It is shown in [Non-Patent Document 18] that there are bulk density measurements and Stokes measurements that perform evaluations that are directly linked to specific purposes. There is a fairly close relationship between shape and particle size. There is Furthermore, in the structure of the secondary particles, several or more unit particles (primary particles) that are considered to be crystallographically single aggregate to form composite particles (secondary particles). The force between particles when they aggregate can be broadly divided into those due to chemical bonding force and those due to physical van der Waalska and magnetic attraction. The former is difficult to separate, and aggregated particles are treated as unit particles. or agglomerates, and the latter are called collective particles or aggregates in which the primary particles are relatively easily dispersed. Distinguishing between the two is difficult only from the geometrical form under a microscope, and physical methods such as the sedimentation method are used to distinguish between the two. be done. For example, in titanium oxide used for white pigments, several cubic primary particles of about 0.3 μm are aggregated, and it is impossible to distinguish between aggregates and aggregates based on this alone. 0.8 .mu.m, and the average values obtained by the adsorption method and the permeation method are almost the same. It is considered that the primary particles are condensed during the production process of the titanium oxide powder, and the primary particles may aggregate with their crystal axes aligned to form aggregates or agglomerates. Particles of vanadium pentoxide (V205) sol are filamentous, and it is well known that these gather with their fiber axes (long axes) aligned to form so-called tactoids, and such parallel aggregates are iron hydroxide (FeOOH), It is also found in aluminum hydroxide (AlOOH) and tungsten trioxide (WO3). Calcium carbonate obtained by the synthesis method usually has a spindle shape of 2-3 μm, but in special cases, it becomes cubic ultrafine particles of 0.05 μm. It seems to be a single particle with Particles obtained by solid-state reactions such as decomposition, reduction, and oxidation from large crystals sometimes exhibit aggregates that have the shape of the original crystals, and such agglomerated particles are sometimes called ghost particles. Many of the metal powders obtained by reduction of metal oxides have such particles. The crystal axis of the grain has a certain crystallographic relationship with the mother crystal, and the topotactic reaction.Furthermore, when observing the grain surface as a fine structure of the grain with a simple industrial test electron microscope, it is found that the sintered powder is The size and shape of crystal grains differ depending on the conditions of production and additives, which greatly affects physical properties. Even if you take only one method, the particle size distribution will be unknown if the particle shape is completely ignored. It is preferred to use a powder.

In addition, the force between particles due to adhesion exerts a pulling force between particles that are in contact with each other and between particles in the vicinity. and reduce the independence of the particles. These mechanisms have the effect of limiting the independence between particles, and generally the stronger their effect, the lower the flow properties of the powder. Therefore, the particles, which are starting to dry or have a fixed amount of particle powder on the skin, palms, fingertips, etc. that are wet with water, are connected with each other, and even if they are tried to be shaken off, they strongly resist, and it is necessary to shake off several times. become. In addition, there is a misconception that small particle size powders have strong adhesion, but this is not always true, in this case the mass of individual particles is small and therefore the relative cohesive force to gravity is Since the scale is large, the absolute value of the cohesive force may be small, but the gravitational force acting on the particles is also small. In other words, because the cohesive force is large, the powder that is the aggregate is worked on by the particles and the aggregated group, making it difficult to fall off. Under these circumstances, the contact area increases depending on the number of contact points, the contact pressure, and the extensibility of the particles themselves. The goal is to optimize the properties of such powders to suit critical processes and applications so that they can effectively enhance adhesion when the process design and composition are optimized. . Furthermore, the frictional properties of powder are related to properties related to individual particles such as particle shape, particle size and its distribution, particle material and the presence or absence of surface adsorbed substances, and layers as particle aggregates such as void ratio and packing structure. The frictional behavior of the powder bed is considered to be very complicated, and the relationship between the dynamic friction angle, which is the property of the aggregate of particles, and the shape and particle size, which are the properties of individual particles. The relationship is discussed in [15]. According to this, the internal friction angle of the powder bed is affected by the shape and particle diameter of the particles, but at the same time it is also affected by the material of the particles and the adsorbed substances on the surface. In order to avoid the influence of factors other than the shape of the particles on the friction characteristics of the layer, if the material and particle size are almost the same but the shape is different, the friction characteristics of the particles will depend on the shape if the material and particle size are the same. However, when a layer of flat particles is _sheared , the particles are oriented in the shear direction in the limit state where the shear displacement is large. The friction characteristics of the layer are considered to have a strong correlation with the particle shape. can be roughly estimated from the circularity or Wadell's sphericity, and it has been proven that the flatter the particle, the smaller the friction, and the bulkier the particle, the greater the friction. In some cases, one or two or more kinds of fine particle pulp containing titanium oxide are used.

In addition, when mixed with the hydrophilic nanocellulose that wraps the superhydrophilic photocatalyst solution, the fine particle pulp containing titanium oxide, in which the entire particle is wrapped, prevents the liquid from dripping during coating and spraying, as well as the fine particles of the pulp. When the protective agent released from the hydrophilic component and adhering to the skin is rubbed with the fingers, the non-hydrophilic microparticle pulp containing titanium oxide coats the photocatalyst solution component while rubbing the photocatalyst solution. Since it is not necessary to wipe off the protective agent with a handkerchief, towel, or other fibrous material, it is hygienic and can be used anywhere. Of course, since the pulp fine particles are nanometer to micrometer sized, even if they are rubbed together, the pulp components cannot be seen. It becomes a carrier for , and the antibacterial and antiviral effects of hands and solids can be sustained by separation and destruction by rubbing the skin and fibers and deposition of photocatalytic active ingredients during drying. Therefore, the human fingertip has a static friction coefficient of 1.5 or more, and in some cases exceeds 2.5 due to its flexibility, and the friction coefficient between many metals is approximately between 0.6 and 1.2. The coefficient of friction of the human finger is considerably larger than that of the human finger.

The above-mentioned coating method using the friction of the fine particle pulp containing titanium oxide does not break the hydrogen bonds of the fine particle pulp, for example, when titanium oxide is agglomerated and fine particle pulp is added, and the area directly in contact with titanium oxide can be reduced. , For example, by maintaining particle hardness with titanium oxide-containing microparticle pulp using titanium oxide W-10 provided by Ishihara Sangyo Co., Ltd., the friction action after spraying or coating the protective agent is maintained, and a protective film is formed. If the skin of the hands or the like is irradiated with ultraviolet light or visible light, bacteria and viruses adhering to the surface of the skin are decomposed and a rubbing action is obtained. However, as for titanium dioxide, in addition to W-10, it is considered effective to use ST-K211, MPT-623 for visible light, platinum compound-supported titanium oxide, water dispersion STS-427, etc. Sakai Chemical Industry Co., Ltd. etc., titanium oxide powder or water dispersion of each company may be used without limitation.

Furthermore, in [Non-Patent Document 3], the effectiveness of virus inactivation by the photocatalytic reaction of titanium oxide non-woven fabric has been partially recognized based on the results of development experiments, and definitive reports are under consideration. However, even when the protective agent of the present invention in which the liquefied catalyst is activated is applied or sprayed onto the surface of clothes, masks, etc., the oxygen adsorption action of the microparticle pulp containing titanium oxide and the action of attaching it to fingers and the like are used. The transition and fixation of the rubbing effect can be expected to suppress bacteria and viruses by the activated photocatalytic action.

In addition, the photocatalyst solution activated by the photocatalytic activity mode can obtain a coating and rubbing action regardless of the environment in which it is used, such as ultraviolet rays and visible light, so by using it as a protective agent, the activity of the photocatalyst cannot be obtained. A rubbing effect can be obtained as a protective film even in an environment such as sleeping.

In addition, molybdenum oxide (MoO3) is one of the compounds exhibiting antibacterial and antiviral activity, and is considered to have antiviral activity against both non-enveloped and enveloped viruses. , A visible-light-responsive photocatalyst material (Mo/TiO2) that combines molybdenum oxide and titanium oxide has been shown to have higher antiviral activity under white fluorescent lamp irradiation than under dark conditions. Molybdenum oxide (MoO3) is contained in the photocatalyst solution or the like even in the protective agent of the invention, so that continuous antibacterial and antiviral action can be obtained.

Furthermore, calcium silicate, which is one of the silicon salts, has long been used as a raw material for pharmaceuticals (listed in the Standards for Pharmaceutical Additives and the Standards for Quasi-Drug Ingredients), as an adsorbent for oily or oil-soluble vitamins, powdered crude drug extracts, etc. In general, in addition to nano-sized pores represented by the specific surface area, macropores have the ability to absorb and retain liquid, and their capacity is proportional to the volume of macropores. Since it is thought that the ability will increase or decrease, even with the protective agent of the present invention, when it is sprayed and applied to the skin of the hands or fibers, the calcium silicate to which the fine-particle pulp is adsorbed is adsorbed and fixed in the form of a protective film, while the use of calcium silicate Utilizing the characteristics of hardening the surface by volume and highly disintegrating properties of the coating, it is adsorbed by bacteria and viruses attached to the surface of the skin of the hands, etc., and is applied by a rubbing method that utilizes the friction of microparticle pulp containing titanium oxide. It is a protective agent with high rubbing action.

On the other hand, ultraviolet light is a type of light with a shorter wavelength (=higher energy) than visible light. It is UV-C with a wavelength of 290 nm. The peak of the sterilization effect by ultraviolet light is about 260 nm, and the short wavelength of 375 nm of UV-LED and 315 nm to 400 nm of fluorescent tube type cannot be used for virus inactivation. At present, sterilization lamps that emit UC-V around 260 nm and UV-CLEDs are on the market, but their effectiveness in inactivating viruses has not been verified. The photocatalyst activation mode of the present invention is just a device for activating the photocatalyst of the sprayed protective agent, and the virus inactivation is effected by the activated protective agent. It is applied to palliative treatment, etc., and is used for skin diseases, tuberculosis, and surgical therapy, and is known to be effective for the human body.

Moreover, it is already known that photocatalysts act upon irradiation with ultraviolet rays from sunlight, and the reaction speed of photocatalysts is light intensity×absorption intensity×reaction efficiency. At present, as shown in [Patent Document 6], various developments have been made even in the visible light responsive type, and photocatalytic action has been recognized. visible light is not necessarily required. The photocatalytic activity mode attached to the protective agent is for the purpose of photocatalytic activity in the protective agent. It is a very important device that can improve and stabilize the rubbing effect by activating the protective agent by the photocatalytic activation mode before and after work to wear it or in an environment where hand washing with water is not possible. In the case of rutile-type titanium dioxide, the wavelength peak of ultraviolet rays, which is known to be most effective for photocatalyst activity, is said to be 380 nm or less. Not limited to choose.

Since the photocatalytic activity mode of the present invention utilizes the above-described ultraviolet irradiation, the container (including the spray port) filled with the protective agent is made of quartz, polyethylene, polypropylene, fluorinated ethylene propylene (FEP), perfluoroalkoxy (PFA). , a fluorocarbon polymer, an acrylic resin, and the like, but are not limited to these as long as they are materials that transmit ultraviolet rays. However, when the photocatalytic activation mode is not used, the material of the filling container is not limited to whether or not it transmits ultraviolet rays, and is optional.

It is the figure which showed the antiviral effect by a photocatalyst reaction. FIG. 2 is a diagram showing the mechanism of virus inactivation by photocatalytic reaction. FIG. 4 is a diagram showing a state in which photocatalyst titanium oxide adheres to spaces between fibers and pulp particles adhering to fibers. It is the figure which showed the mechanism which kills E. coli with a photocatalyst. FIG. 2 shows the antiviral activity of metal oxides. FIG. 4 is a diagram showing a comparison of friction coefficients depending on directions; FIG. 4 is a diagram showing the dependence of shear strength on contact pressure; It is the figure which showed contact pressure and a coefficient of friction. FIG. 10 is a diagram showing results of least-squares approximation of the error between human finger contact and elastic contact experimental values. FIG. 4 is a diagram showing the dependence of the coefficient of friction on the normal; FIG. 2 is a cross-sectional view showing an example of a photocatalytic activation mode; FIG. 2 is a cross-sectional view showing an example of a photocatalytic activation mode during use; It is the perspective view which showed an example of the photocatalyst activation mode.

Furthermore, the size of bacteria and viruses that cause infectious diseases is 1 to 10 μm for bacteria and 0.02 to 0.2 μm for viruses, so there is a large difference. Bacteria are single-celled microorganisms that self-replicate. Viruses have a simple structure consisting of a nucleic acid and a membrane that envelops it. It parasitizes and self-replicates other organisms (including lodgings). Hemagglutinin (HA), a protein on the surface of these viruses, adheres to, invades, unshells, synthesizes, matures, and releases human (host) cells, and repeats to proliferate in the body. Since the protein is denatured, it cannot be adsorbed, and it does not enter the human body (host) and multiply the nucleic acid. Therefore, at this stage, the virus is inactivated (infected) by a photocatalytic reaction. In other words, in order to prevent these intrusion mechanisms, the hands and fingers should be sterilized, sterilized, disinfected, or antibacterially and disinfected to prevent invasion of viruses and the like. However, this is not the case when the virus is artificially inserted into the eyes, mouth, nose, wounds, etc. Moreover, as shown in Fig. 2, the photocatalytic reaction decomposes the membrane structure of the virus, damages the nucleic acid (RNA), which is the genetic information inside, and finally completely decomposes the virus-derived organic matter. In addition, the strong oxidative decomposition power of photocatalysts not only inactivates bacteria that are ten times larger than viruses, but also completely decomposes them as organic matter. In view of these facts, in order to obtain strong oxidative decomposition of the photocatalyst, it is most important to irradiate the photocatalyst with ultraviolet rays to make the active state constant, and the photocatalyst activity mode protective agent of the present invention made it possible. The reaction mechanism of the photocatalyst is different from other sterilization, antibacterial, and antiviral agents. As shown in Fig. 4, the reaction mechanism of the photocatalyst is non-selective, regardless of the opponent, such as bacteria and viruses. Since it also leads to the difficulty of producing resistant bacteria as a result, it becomes a hybrid protective agent that allows the sprayed or applied protective agent to vaporize on the hand skin, enabling rubbing action and moisturizing protection at the same time.

In addition, after making the particle shape of titanium oxide into a confetti type, etc., apatite, which is a substance that constitutes bones and teeth and has excellent biocompatibility and does not have photocatalytic activity, is coated on the surface like the horn of a confetti. , This konpeito-shaped grain is also developed and sold, and by using it, titanium oxide particles are immersed in a simulated body fluid with a composition close to that of human body fluid, and the surface of the titanium oxide is maintained at a temperature close to body temperature. By using a photocatalyst solution that is prepared by naturally forming apatite so that bones and teeth can be formed in the body as a protective agent, there is no need to coat titanium oxide with apatite, making it a cheaper and more effective protective agent. .

The titanium oxide used in the photocatalyst solution is natural anatase-type titanium oxide (hereinafter referred to as photocatalyst solution) or brookite-type titanium oxide or rutile-type titanium oxide (hereinafter referred to as photocatalyst solution) with a bandgap of 3.2 eV and a high photocatalytic activity of about 388 nm in terms of wavelength. However, the photocatalyst solution has the property of forming a non-conductive film, which has excellent corrosion resistance and sufficient adhesion. In addition, it has been reported that the strong oxidizing power of photocatalytic titanium oxide not only decomposes and removes surface stains, but also inactivates bacteria, viruses, filamentous fungi, cancer cells, etc., including Moraxella. In addition, the antimicrobial properties of titanium oxide, which is not limited to specific bacteria, have been actively applied to the fields of medicine, medical care, and sanitary materials. Since this effect utilizes a photocatalytic reaction, the basic concept of coating is the same as for self-cleaning applications that mainly utilize decomposition activity. It is known to have antibacterial and antiviral properties, and titanium oxide has a strong feature against nitric acid and chromium, and can be specialized for oxidative decay and forming a thin film in the gaps of the skin of the hands. At the same time, the energy of the surface tension of the micro-powder pulp that enters the gaps between the attached dirt is added to sterilize, peel and decompose the bacteria and viruses, and the unnecessary substances are removed. It becomes a protective agent that can obtain a strong effect by being able to eliminate it.

Furthermore, since the photocatalyst component in the protective agent does not change before and after the catalytic reaction, it can be used semi-permanently unless the particles are washed away. For example, if it is applied to the skin of the hand or to the fabric of a mask, it will gradually inactivate the attached virus, and if the filter of an air purifier etc. is processed with photocatalyst and the air is blown after irradiating it with light, it will become droplets and aerosols. Studies have also been conducted to make it possible to inactivate the contained virus, and in order to obtain a higher effect of the photocatalyst continuously, radicals such as active oxygen can be generated by irradiation with light such as ultraviolet rays in any environment. The protective agent of the present invention is more effective because it is important to quickly produce it to inactivate viruses and eliminate bacteria.

ここで、γ_Ｓ、γ_ＳＬはそれぞれ平滑な固体表面における固体表面の表面自由エネルギー、固液界面の界面エネルギーである。これを平滑な表面での接触角θを用いて表すとＷｅｎｚｅｌの式が得られる。

この式から表面粗さが大きくなると、接触角θ_ｒはθ＜９０°のときにはθより小さくなり、θ＞９０°のときには逆に大きくなる。即ち、固体表面のラフネスが大きくなることで、親水的な表面はより親水的になり、撥水的な表面はより撥水的になる。酸化チタン表面に微構造を付与することにより、光誘起親水化特性が向上したり、暗所における超親水性状態の維持性向上が公知されている。さらに、異種金属酸化物光触媒との複合化による高活性化として、酸化チタンと酸化タングステンを積層した薄膜の光誘起親水化は、酸化タングステンを下地にして酸化チタンを積層した薄膜では、酸化チタン単独では親水化しないような光照射条件下でも超親水性状態が得られる。酸化タングステンの伝導帯の下端および価電子帯の上端は、酸化チタンに比べてそれぞれエネルギー的により深い位置にある。そのため、光照射を行うと酸化チタンで生じた励起電子は酸化タングステン側に、酸化タングステンで生じた正孔は酸化チタン側にそれぞれ電荷移動する。このことは酸化チタン自体の光電荷分離効率の向上に繋がるとともに酸化チタン表面で利用できる正孔が増えることになり、光誘起親水化反応が促進されたものになる他、酸化タングステンのハンドキャップは２．８ｅＶで可視光も一部利用できることが高活性化につながり、酸化タングステンをアイランド状に酸化チタン表面に析出させた系でも高活性化が達成されている。一般的に、光触媒酸化分解反応の量子効率は数～数十％であるのに対し、光誘起親水化反応は０．１％にも満たない非常に低い数値が出され、酸化チタン表面の親水化の有利となる条件を付与させることで、光誘起親水化に利用される正孔の数を倍加させても酸化分解反応の量子効率は低下させずに維持ができる。In addition, as an example of a superhydrophilic photocatalyst that responds to weak ultraviolet rays and visible light, the wettability of solid surfaces is governed not only by chemical properties that give surface free energy, but also by physical properties such as surface roughness. If the roughness of the solid surface increases and the surface area increases r times, the surface free energy of the solid surface and the interfacial free energy of the solid-liquid interface also increase r times. Therefore, the contact angle .theta. when the surface area is increased r times is given by the following formula from Young's formula.

Here, γ _S and γ _SL are the surface free energy of the smooth solid surface and the interfacial energy of the solid-liquid interface, respectively. When this is expressed using the contact angle θ on a smooth surface, Wenzel's formula is obtained.

From this formula, as the surface roughness increases, the contact angle θr becomes smaller than _θ when θ<90°, and conversely increases when θ>90°. That is, by increasing the roughness of the solid surface, the hydrophilic surface becomes more hydrophilic, and the water-repellent surface becomes more water-repellent. It is known that by imparting a microstructure to the surface of titanium oxide, the photo-induced hydrophilization property is improved, and the ability to maintain a superhydrophilic state in a dark place is improved. In addition, photo-induced hydrophilization of thin films laminated with titanium oxide and tungsten oxide as a composite with dissimilar metal oxide photocatalysts can be achieved by photo-induced hydrophilization. A superhydrophilic state can be obtained even under light irradiation conditions that would not cause hydrophilization. The lower end of the conduction band and the upper end of the valence band of tungsten oxide are located energetically deeper than those of titanium oxide. Therefore, when light is irradiated, excited electrons generated in titanium oxide move to the tungsten oxide side, and holes generated in tungsten oxide move to the titanium oxide side. This leads to an improvement in the photocharge separation efficiency of the titanium oxide itself, as well as an increase in the number of holes that can be used on the titanium oxide surface, which promotes the photoinduced hydrophilization reaction. Visible light can also be partially used at 2.8 eV, which leads to high activation. A system in which tungsten oxide is precipitated on the surface of titanium oxide in the form of islands also achieves high activation. In general, the quantum efficiency of the photocatalytic oxidative decomposition reaction is several to several tens of percent, while the photoinduced hydrophilization reaction yields a very low value of less than 0.1%. By providing conditions that are advantageous for the hydrophilization, the quantum efficiency of the oxidative decomposition reaction can be maintained without decreasing even if the number of holes used for photoinduced hydrophilization is doubled.

At a concentration of 80 ppm, the peracetic acid preparation reduced the number of bacteria by more than 5 digits in a short time of 30 seconds, and even at a concentration as low as 10 ppm, a reduction of more than 3 digits was observed in 1 minute. It is produced from acetic acid and hydrogen peroxide in the presence of an acidic catalyst as a peroxide preparation containing , has a rapid bactericidal effect at room temperature, has no toxicity or environmental pollution of decomposed products, and is not decomposed by catalase and has a long-lasting effect. Peroxide preparations have been commercialized in Japan by Kanto Kagaku Co., Ltd.'s Parsan series, etc., and Actril, a low-concentration peracetic acid preparation developed by Medivator Inc. (formerly Mintec) in the United States, requires dilution. PBio Actril, a peracetic acid-based solvent in Japan, is the only EPA (U.S. Environmental Protection Agency)-certified disinfectant that is highly effective against bacterial spores, tuberculosis, viruses, etc., and is low in toxicity and safe to use. can.

Regarding the stability of peracetic acid contained in peracetic acid preparations, according to JECFA and FSANZ, it is rapidly decomposed into water, oxygen and acetic acid in food, and its half-life is several minutes. Even if peracetic acid remains on the food surface and is ingested by humans, it is decomposed in the oral cavity and enters the gastrointestinal tract. Peracetic acid is considered to be enzymatically degraded, and is considered to have no genotoxicity that poses a particular problem for living organisms. In addition, as a result of examining the test results of acute toxicity, repeated dose toxicity and reproductive and developmental toxicity of peracetic acid, peracetic acid was not found to have gastric mucosal irritation, and at least 0 in a 13-week gavage test in rats. No toxic effects were observed at 25 mg/kg body weight/day (as peracetic acid), and no findings were found that could be used to determine carcinogenicity. Therefore, considering the stability of peracetic acid, the mechanism of pharmacokinetics, the results of various toxicity tests, and the actual intake, there is no need to specify ADIs for acetic acid, a decomposition product, as the intake is large from food. Therefore, if the additive "peracetic acid" is used appropriately as an additive, it is considered that there is no safety concern, and it is judged that there is no need to specify ADI.

In addition, peracetic acid preparations are balanced by peracetic acid, acetic acid, and hydrogen peroxide, and the reaction causes continuous peracetic acid, which has a wide range of effects in a short period of time against almost all microorganisms, including bacteria, fungi, and viruses, including spore-forming bacteria. As shown, the inclusion of a chelating agent is required to maintain this equilibrium under the metal ions in the protective agent. In general, chelating agents include hydroxy-carbonate-based organic sequestering agents such as citric acid, glycolic acid, gluconic acid and salts thereof, and amino-carbonate-based organic sequestering agents such as EDTA, acetate, ethylene, diamine, tetra, and triamine. There are hydroxy-aminocarbonates, such as hydroxy, ethylene, diamine, tetraacetic acid, etc., such as toric acetic acid, but organophosphorus-based chelating agents are used in dispersion systems to prevent scale adhesion, etc., and are more acidic than aminocarboxylic acids. It has high water solubility in the region and is also used in the protective agent of the present invention.

The amount of chelating agent (sequestering agent) added varies depending on the amount of metal ions in the protective agent and the type of chelating agent. In the case of Cherest D, manufactured by Cherest Co., Ltd.) and calcium ions, if the total water hardness is 40 ppm (40 mg of calcium carbonate is present in 1 liter), to sequester metal ions with Cherest D, C of Cherest D is used. . V. (Represents the amount of calcium carbonate that can be sequestered by 1 g of chelating agent) is 221 mg CaCO3/g, so the amount to be added is 40/221 = 0.18 g/liter. May vary slightly depending on conditions.

Peracetic acid (PAA) is a liquid with a boiling point of 110°C, a melting point of -0.2°C, a weakly acidic (PK _α of 8.2 at 20°C), colorless, pungent odor, and a minimum of 56.4% PAA with water. An azeotropic mixture (45 mmHg 34°C) is formed, which is relatively stable in solution, gradually decomposing below 20°C, fairly rapidly above 20°C into acetic acid, and rapidly decomposing around 100°C to AcH and PAA. In addition, it is known that the ionic decomposition of PAA is rapidly decomposed by a trace amount of metal ions, etc. In a system without Ach, the PAA decomposition power of metal ions other than Co is too large. However, the apparent degradative power in the presence of AcH is greatly increased, and Mn is found to degrade more than 90% of PAA in 5 minutes. Therefore, peracetic acid (PAA) stabilizers include chelating agents and phosphates, including picolinic acid, quinoline derivatives, pyrophosphates, alkyl esters of pyrophosphate, polyaminocarboxylic acids, rhodan potash, ethylenediaminetetraacetic acid, and the like. A number of formulations have been issued as patents.

For example, among the studies on the extermination of red tide plankton by various chemicals, hydrogen peroxide water is said to be the most practical, but since the specific gravity of hydrogen peroxide water is slightly higher than that of seawater, freshwater areas and sea areas There is a disadvantage that it settles and does not spread even if it is sprayed on the surface, so it was necessary to adjust the specific gravity. Therefore, focusing on the fact that the porous ALC material has a good retention property of hydrogen peroxide solution, an effective diffusion method was devised. 100% of the plankton caused cell destruction. In view of these, the specific gravity of peracetic acid is heavy, but by inserting calcium silicate, which has high liquid absorption, it is also effective in adjusting the specific gravity of sodium peracetate in the protective agent, and the entire protective agent filled in the container. It is required to diffuse evenly and achieve a stable effect.

In addition, hydrogen peroxide, which is also contained in peracetic acid formulations, can disperse titanium oxide powder when mixed with titanium oxide, but it is not possible to completely disperse the precipitate. As a result of mixing up to 25 g of hydrate with 500 ml, dissolution of titanium oxide and tungsten oxide was observed after 2 hours, and citric acid hydrate was adopted as the protective agent in consideration of safety. However, after obtaining a supernatant by mixing citric acid hydrate, it may be filtered to obtain a colorless, transparent and harmless solution in which the photocatalyst effect is maintained by the action of tungsten oxide or molybdenum as a catalyst. However, the presence or absence of filtration is optional, but it is necessary to prevent attenuation of efficacy effects due to filtration, and the degree and method of filtration are also optional.

Furthermore, Fig. 1 shows that the number of viruses decreased during the photocatalytic reaction with only ultraviolet rays and with titanium oxide, but the size of the virus is one order of magnitude smaller than the bacteria, and it is easy for the photocatalyst to kill viruses smaller than the bacteria. However, it may take longer indoors, as it takes 1-2 minutes to decompose the virus with 0.4 mW/cm ² of UV light. From these facts, the photocatalyst solution is constantly activated by using the photocatalytic activation mode, and the protective agent of the present invention can be used without limiting indoor and outdoor places with the same effect as outdoor ultraviolet rays. It shows effectiveness. However, when covering a wide area such as indoor ceilings and walls, a protective agent using visible light responsive tungsten oxide or a metal compound is used.

Ultraviolet rays with a short wavelength and high energy are easily absorbed by objects. At a wavelength of 222 nm, they stop at the stratum corneum with a thickness of about 20 μm on the very surface of the skin, and do not reach the living cells of the human body. While it does not cause inflammation or skin cancer, it can reach inside the virus with a diameter of about 0.1 μm attached to the surface of an object, so it can damage and inactivate genes. However, with UV-A, 50 J/cm2 is required to reduce bacteria and viruses to 1/100, and the UV intensity is about 2.5 mW/ ^cm2 at the strongest, so 50/2.5×10 ^-3 = 5.5 hours at 20,000 sec, and UV-B requires 0.45 J/cm ² to reduce to 1/100. This fluctuates depending on the sunshine hours of the season, and is 25 kJ/m ² /day from July to August, which is 0.18 days, and about 1.6 hours at peak hours, but UV-B is more easily absorbed than UV-A, and in winter it drops to about 1/5, and it is calculated that almost a whole day is required for sterilization and inactivation. Considering these, it takes a considerable amount of time to obtain the effect of sterilization and inactivation only with UV-A or UV-B ultraviolet rays, and for example, ultraviolet irradiation is intermittent, such as for medical instruments. If the case is excluded, the protective agent of the present invention, which obtains the effect of sterilization and inactivation by irradiating the photocatalyst with ultraviolet rays, becomes more effective.

In addition, due to various research and development related to the new coronavirus, some devices have been commercialized that irradiate 222 nm to damage the DNA and ribonucleic acid of bacteria and viruses, and lose their proliferation function by replication. In order to inactivate the virus by 99% with ultraviolet irradiation at 222 nm, it takes 20 seconds at a distance of 0.5 m from the ceiling, 2.4 minutes at a distance of 1.5 m, and 6.7 minutes at a distance of 15 m. However, for practical use, the permissible limit of 222 nm ultraviolet rays must be 22 mJ/cm ² or less within 8 hours per day. However, 222 nm and 254 nm have a difference of 10 times or more in the absorption coefficient of proteins. does not permeate, it is safe for the skin, absorbs 222 nm light to the cornea, does not cause cataracts, and has a corneal transmittance of 0.01% or less, and there are products that output only safe UV rays. being developed. The main purpose of the UV activating device in the protective agent of the present invention is to activate the photocatalyst, and the effects of UV irradiation at the time of application can be obtained even for a short period of time, and the effect on the skin is taken into consideration.

Furthermore, there are various kinds of carbonate species formed by bacteria, even though they are simply called carbonates. There is siderite (FeCO3), which is siderite, and calcium carbonate (CaCO3) includes calcite, aragonite, and vaterite, which have the same chemical formula but different crystal structures. It is said that most of the carbonate rocks existing on the earth are occupied by three types of calcite, aragonite, and dolomite (CaMg(CO3)2), which is a calcium carbonate containing magnesium. Since it has been clarified that the formation of salt species is determined by salinity, temperature, various ion concentrations, etc., these factors will also be considered together with the effectiveness of the photocatalyst solution.

In addition, viruses have nucleic acids with capsids in their protein shells, and the virus is inactivated by destroying part of the protein. It is important to damage the part and reduce the infectivity. The photocatalyst solution is activated by ultraviolet rays and visible light, making it impossible for viruses to adsorb to cells and losing the ability to infect cells to the host. It is also possible to activate it.

Antiviral activities have been evaluated for metal oxides with bacteriophage, and it has been revealed that MoO3, which is molybdenum oxide, has high antiviral activity. Among them, when the antiviral activity of MoO3 was examined for influenza virus and feline calicivirus, which is a substitute for norovirus, it was found that MoO3 had high antiviral activity as when targeting bacteriophage. MoO3 was known to have antibacterial properties, but new knowledge was obtained that it also exhibits high antiviral activity. Although the photoresponsive photocatalyst material was produced by the dipping method, the production method was improved by changing the titanium oxide to the rutile type, etc., and a material combining titanium oxide and molybdenum oxide (hereinafter referred to as Mo/TiO2) was newly produced. , bacteriophage, influenza virus, and feline calicivirus. A low virus infectivity titer and high antiviral activity were observed. These results suggest that Mo/TiO2 exhibits antiviral activity while being responsive to visible light.

Molybdenum is an essential trace element for all species, including humans. It is estimated that the human body contains about 0.1 mg of molybdenum per 1 kg of body weight, and is abundantly distributed in bones, skin, liver, and kidneys. . Molybdenum is used in foods and supplements, and even if it is taken in excess, it is excreted in the urine, so there are no reports of it being harmful to health.

FIG. 5 shows the antiviral activity values of Fe2O3, MnO2, CeO2, MoO3, SnO2, NiO, and ZnO, which are oxides containing metal ions known to have antibacterial activity. Molybdenum oxide (MoO3) has been found to have very high antiviral activity. In addition, since molybdenum oxide has been shown to have high antiviral activity against bacteriophage φ6, it exhibits high antiviral activity against both non-enveloped bacteriophage Qβ and enveloped bacteriophage φ6. Since molybdenum oxide is the one among the seven kinds of metal oxides, the protective agent of the present invention uses molybdenum or sodium molybdate as a photocatalyst material and combines it with titanium oxide to achieve high antibacterial and antiviral properties. You will get activity.

Furthermore, molybdenum oxide exhibits high antiviral activity even in the dark, and its photoirradiation effect, ie, visible light responsiveness, is low. In addition, molybdenum oxide has high antiviral activity against influenza virus and feline calicivirus as well as bacteriophage. In order to use molybdenum oxide, which has antibacterial and antiviral activity, as a visible light-responsive photocatalyst material, as an experiment, titanium oxide powder was immersed in an aqueous solution of sodium molybdate, heated to about 80 ° C., and stirred for 3 hours. 0.001 mg of hydrogen peroxide was mixed with 500 ml of the filtered solution, and antiviral activity was observed even in the dark. In addition, against feline calicivirus and influenza virus, as in the case of bacteriophage Qβ, the results showed higher antiviral activity under light irradiation than under dark conditions. Therefore, molybdenum or sodium molybdate is also used in the protective agent of the present invention, and higher antibacterial and antiviral activity is effective. However, using a photocatalytic mode of activation, molybdenum yields a higher percentage of efficacy, although further details of visible light responsiveness require further investigation. Naturally, it is not necessary to use the photocatalytically active mode when irradiation with sunlight is possible.

Calcium silicate, which is one of the silicon salts, is generally regarded as a safe substance (GRAS substance) in the United States, and is used for the purpose of preventing caking, etc., under good manufacturing practice. % or less, and even in Europe, the upper limit (UL) that does not have a harmful effect on humans cannot be calculated from the current knowledge, but it is 1 per day in terms of silicon. It is concluded that intakes of 20-50 mg/person (60 kg body weight), ie 0.3-0.8 mg/kg body weight/day, do not show adverse effects in humans. Similar to silicon dioxide, calcium silicate forms crystals with a three-dimensional network structure and is highly liquid absorbent. A rubbing effect is obtained, and by forming a protective film, it is possible to prevent the adhesion of bacteria and viruses for a certain period of time.

On the other hand, since nanocellulose is viscous, sticky, and water-soluble, it easily permeates the skin of the hands, and it has a great effect as a moisturizing and protective agent. ing.

In addition, cellulose single nanofibers can be used to prepare a gel, and if the protective agent is a liquid, effects such as improved adhesion are expected by spraying, etc., and when filled in a spray container, it can be used even upside down. Also, the price is overwhelmingly cheap.

The cellulosic polymer constituting the cellulosic polymer fiber is not particularly limited as long as it is a polysaccharide having a β-1,4-glucan structure. Examples include cellulose derived from higher plants, and wood fibers such as cedar. Cellulose/nanocellulose such as natural cellulose fiber (pulp fiber) of (wood pulp of softwood, hardwood, etc.), animal-derived cellulose, bacterial-derived cellulose, chemically synthesized cellulose (regenerated cellulose; including derivatives), Examples include chitin, chitosan, and silk. The cellulose may be high-purity cellulose with a high α-cellulose content, for example, α-cellulose content of about 70 to 100 wt %, depending on the application. The cellulose may be used singly or in combination of two or more. Among cellulosic polymers, preferred are wood fibers (wood pulp of conifers, broad-leaved trees, etc.), seed hair fibers such as cotton linters, and the like. In addition, carboxymethyl cellulose, which is an anionic water-soluble polymer obtained from cellulose as a raw material, can also be used because it has excellent thickening properties, water absorption properties, and water retention properties, but may be used in combination with nanocellulose.

In general, pulp is mostly used for paper, and one of the reasons for this is that pulp is light and maintains a certain strength. Using a commercially available fine powder that is a mixture of the pulp and titanium oxide, if you rub your fingertips together, it will enter the fingerprint, and even if you move it between your fingertips, the fine pulp powder will collide with each other, and the fingertips will be fine particles containing titanium oxide. Since the pulp is so resistant that it does not slip when it dries, the microparticle pulp containing titanium oxide as a protective agent is made by rubbing nanocellulose or a photocatalyst solution into the keratin of the hand skin by rubbing with fingers to form a coating and rubbing action. At the same time, the moisturizing component of nanocellulose is also infiltrated, which is a rubbing method using pulp microparticles. Moreover, when the protective agent is filled in a spray bottle or the like in the form of an aqueous solution, the pulp fine particles floating from the top to the middle are easily sucked in by the spray pump, and are always applied to the skin of the hands, etc. during spraying, ensuring a stable friction effect. It will be obtained as a matter of course. However, the protective agent of the present invention may contain pulp or nanocellulose fibrous coating, but these are non-toxic and harmless. When spraying or applying, shake the container to mix the protective agent well. By using it, the viscosity of the pulp particles increases and it becomes a protective agent with a high rubbing effect.

Another object is to improve the action of cellulase on the rubbing performance of the protective agent, especially the secondary rubbing performance, by adding fine pulp powder. The pulp particles are at least partially broken in compression obtained by mechanical pressure and then in granulated form preferably contain cellulose, in particular shaped as fine particles and containing titanium oxide to stimulate the action of cellulase on rubbing performance. Although fine pulp particles are contained, it is of course suitable that the size of the fine particle pulp particles containing titanium oxide is small.

Since the protective agent of the present invention uses a rubbing method using microparticle pulp containing titanium oxide, the coefficient of friction with human fingers that makes it effective is important, and unlike friction between solids, human fingers have elasticity. Therefore, the friction on the finger surface is affected by the contact area in addition to the vertical load. In [Non-Patent Document 14], experiments such as friction measurement of human fingers are conducted, and the finger surface is sufficiently washed and dried so that the state of the friction surface does not change due to sweat, dirt, etc., and the maximum static friction force is greater than the dynamic friction force under the same vertical load. It was found that the coefficient of friction in the low load region is much larger than that in the high load region, being in the range of approximately 0.5 to 2.5. In addition, it can be confirmed that the coefficient of friction increases as the finger posture θ decreases.Furthermore, the structure of human finger skin is different from that of general skin, and the presence of fingerprints in particular is not seen on other parts of the body. It is peculiar to fingers that cannot be Human fingertips have nails, which increase the rigidity of the fingertips and increase the efficiency of work with the fingers. Since it is thought that the physical characteristics of the finger itself change depending on the measurement direction, the friction coefficient of the finger is considered to be the BW direction (backward), and the opposite direction is the direction in which the contact plate slides from the finger base to the fingertip As a result of examining the difference by measuring in the FW direction (Forward) and in the opposite direction, as shown in [Fig. Regarding the finger posture, it was confirmed that the smaller the posture θ, the larger the friction coefficient. An interesting result of this experiment is that the coefficient of friction in the BW direction is larger than that in the FW direction. However, as the finger posture increased, the disparity appeared clearly.

となる。ここでｓ＝λ_ｓｔは見かけの接触面積に対するせん断強さで、実際に測定可能である。そこで、このせん断強さについては、多くの材料においてせん断力ｓは接触圧力ｐに依存することが知られているが、ここで用いる見かけの接触面積に対するせん断力ｓと平均圧力ｐとの関係は明確でないため、計測システムのＣＣＤカメラによって計測された接触面積を用いて平均圧力ｐは

として求めた。また、接触面における圧力が均一に平均圧力であると仮定して以下の解析を行い人間の指が乾燥アクリル面、水濡れアクリル面で接触したときのｐとｓの測定した結果を［図２］に示したが、近似的にせん断強さは接触圧力に比例しており次の関係が成立することが明らかになった。

ここでｓ_０、αは定数でありαは接触圧力ｐに対するせん断強さｓの増加率ｓ_０は表面力による接触部分（荷重ゼロにおける有限な大きさの接触部分）の単位面積当たりのせん断力である。両者とも指姿勢、摩擦方向によって変化し、一般に乾燥した清浄な指ほど大きくなっている。［数７］のように人間の指についてせん断強さと圧力の関係が線形関係にあるという発見は種々の解析や設計にとって重要である。例えば摩擦係数μの変化が［数７］を基にして簡単にモデル化され、［数５］［数７］を用いて次式を得る。

［数２］より求めたＳ_０、αを用いて［数８］から摩擦係数を計算し、その計算値と実験から得た摩擦係数の比較を［図８］に示したが、接触圧力が増加するにつれて摩擦係数が低下することが［数８］よりわかる。Furthermore, friction analysis of human fingers was performed respectively. Since it is difficult to accurately estimate the true contact area, we proceeded with the analysis based on the apparent contact area obtained from the CCD camera of the experimental system, considered the friction model, and calculated the apparent contact area A and the true contact area A _t But

becomes. Here, s= _λst is the shear strength to the apparent contact area, which can be actually measured. Therefore, regarding this shear strength, it is known that the shear force s depends on the contact pressure p in many materials, but the relationship between the shear force s and the average pressure p for the apparent contact area used here is Since it is not clear, using the contact area measured by the CCD camera of the measurement system, the average pressure p is

I asked as In addition, assuming that the pressure on the contact surface is a uniform average pressure, the following analysis was performed, and the results of measuring p and s when a human finger touched the dry acrylic surface and the wet acrylic surface [Fig. ], it was clarified that the shear strength is approximately proportional to the contact pressure and the following relationship holds.

Here, s ₀ and α are constants, and α is the rate of increase of _shear strength s with respect to contact pressure p. is. Both of them change depending on the finger posture and the direction of friction, and are generally larger for dry and clean fingers. The discovery that the relationship between shear strength and pressure for human fingers is linear as in [Equation 7] is important for various analyzes and designs. For example, the change in friction coefficient μ is easily modeled based on [Equation 7], and the following equation is obtained using [Equation 5] and [Equation 7].

The friction coefficient was calculated from [Equation 8] using S ₀ and α obtained from [Equation 2], and the comparison between the calculated value and the friction coefficient obtained from the experiment is shown in [Fig. [Equation 8] shows that the coefficient of friction decreases as the friction coefficient increases.

ただし、ａ、ｂは荷重によらない定数であり、［数９］より実験値との誤差の最小二乗近似を行った結果を［図９］に示す。これにより人間の指の接触において、ａは６５～１７０、ｂは０．２～０．４の範囲にあることがわかる。［数６］に［数９］を代入すると摩擦力Ｆは次のようになる。

ただし、ｐは接触圧力でＷ／Ａに等しい。よって、摩擦係数μは次のようになる。

したがって摩擦係数μはＷ^ｂ－１に比例する。ここでｓ_０とαは［数８］から得られる定数でありａとｂは［数９］から得られた定数であるので摩擦係数は荷重Ｗのみによって決定される。［数９］の正当性を検証するために、実際の人間の指に関して、横軸にＷｂ－１、縦軸に摩擦係数μをとり、実験値をプロットしたものが［図１０］である。ここで、ｂは［図９］における値をそれぞれ用いた。これより、摩擦係数はほぼＷ^ｂ－１に比例しており近似的に「数９］の関係が成立していることがわかる。In [0078], it was shown that the coefficient of friction can be modeled by the parameters _s0 and α and the pressure p. Therefore, expressing the coefficient of friction as a function of load is useful for motion planning if the coefficient of friction of the fingertip is predicted only by the load applied to the fingertip, and Hertz's analysis is famous for elastic contact. A human finger also has a viscoelastic element, but the shape of the finger is not a perfect sphere and the surface of the finger is not smooth, so the Hertz equation does not necessarily hold. However, as assumed in many types of elastic contact, the contact area A of a human finger is proportional to the power of the load W, and A is expressed by the following equation.

However, a and b are constants that do not depend on the load, and the results of least-squares approximation of the error with the experimental value from [Formula 9] are shown in [Fig. 9]. As a result, it can be seen that a is in the range of 65 to 170 and b is in the range of 0.2 to 0.4 in contact with a human finger. Substituting [Equation 9] into [Equation 6] gives the frictional force F as follows.

However, p is the contact pressure and is equal to W/A. Therefore, the coefficient of friction μ is as follows.

Therefore, the coefficient of friction μ is proportional to W ^b−1 . Here, _s0 and α are constants obtained from [Equation 8], and a and b are constants obtained from [Equation 9], so the friction coefficient is determined only by the load W. In order to verify the validity of [Formula 9], [Fig. 10] is a plot of experimental values for an actual human finger, with Wb-1 on the horizontal axis and the coefficient of friction μ on the vertical axis. Here, the values in FIG. 9 are used for b. From this, it can be seen that the coefficient of friction is approximately proportional to ^Wb-1 , and the relationship of "Equation 9" is approximately established.

Furthermore, as a result of investigating the friction characteristics of human fingers, it was found that the smaller the finger posture angle θ, the larger the friction coefficient, and that there was a tendency that the friction coefficient in the BW direction was larger than that in the FW direction. rice field. The skeleton of human fingers is covered by relatively soft tissue, and there are nails on the back of the fingers. It is believed that this increases the rigidity of the fingertips when compressive stress acts on the fingertips. is larger in the BW direction than in the FW direction, and the range in which the inside of the skin is hardened is also large. As for the finger posture, the greater the posture, the greater the force acting on the nail through the internal tissue of the fingertip. Become. As the tissue hardens, the shear strength increases, and as a result, the frictional force is expected to increase. It is thought that this is because the state changes, but it is also difficult to directly examine the hardness of the internal tissue of the human finger. However, in order to verify this, as a result of experiments using artificial fingers, etc., the friction coefficient in the low load area is about 2 to 3 times larger than that in the high load area, both with and without claws. It was found that the friction characteristics of human fingers show a similar tendency. The maximum value of the coefficient of friction is also a relatively large value of about 2.0, and generally within the range of 0.2 to 2.0. Another significant feature was that the coefficient of friction in the BW direction without claws was extremely small compared to others. Regarding the friction direction, when there is no claw, the FW direction is considerably larger than the BW direction in a wide load range. This tendency appears remarkably in the low load range. Looking at the influence of the claws as a whole, the coefficient of friction in the FW direction is only slightly increased, and there is not much influence. However, in the BW direction, the coefficient of friction is extremely large over a wide range of loads. It can be confirmed that the coefficient of friction in the BW direction is improved to the same level as or more than that in the FW direction. In addition to fingerprints, wrinkles on the palm with a large area are also added, and if the friction speed of the fingers on the palm is increased, or the force of the arm is also added, greater friction can be obtained. A rubbing method using fine particles is effective. As the most notable example, anti-slip fingers used in sports competitions and the like are in the form of powder, and grip maintenance due to their friction affects the fingers, and the magnitude of the coefficient is also known.

In addition, regarding rough hands when frequently using an antiseptic solution, according to the results of verification by [Non-Patent Document 17], the most rough hands were observed around the nails for any disinfectant, followed by between the fingers, the back of the hand, and the fingertips. , It is considered to be a palm, and the epidermis around the nail is soft, and there are slight depressions around the nail half moon and around the nail. It is thought that cracks are more likely to occur, but the protective agent is a low-concentration peroxide preparation, and the wiping effect of the rubbing method using microparticle pulp containing titanium oxide and moisturizing ingredients such as nanocellulose can prevent rough hands.

Nanocellulose used as a protective agent is the basic skeletal substance of all plants, and is obtained by refining cellulose fibers, and is generally said to be a fiber with a diameter of 100 nm or less and an aspect ratio of 100 or more. ing. A part of the cross section of the wood is magnified 1,000 times with an electron microscope and observed as a chip cross section, and further, when the pulp with a width of about 20 μm taken out from the chip is observed at 2,500 times, this pulp is composed of cellulose molecular chains. , microfibrils, and fibrils. In the case of cellulose nanofibers with a width of 10 nm, it refers to a state in which several microfibrils are aggregated. It is a downsizing of 1/1,000 from pulp fibers to cellulose nanofibers, and in electron microscope (SEM) photographs, the surface of pulp fibers is observed, and many fibers made of cellulose nanofibers are gathered. I can see the folds. Carbon nanotubes, a representative nanotechnology material, tend to condense multiple molecules due to van der Waals forces, but in cellulose nanofibers, about 6 x 6 cellulose molecules gather to form nanocellulose with a diameter of 3 to 4 nm. In this case, the bonding between cellulose molecules is mainly due to hydrogen bonding, and the von der Waals force and the adhesive effect due to lignin become effective as the microfibrils and fibrils thicken. In the case of carbon nanotubes, if the dispersed nanotubes are left alone, they stick together and become useless. Along with the technique of loosening and refining the fibers, processing and utilization techniques are also being developed around the world, such as how to orderly arrange the cellulose nanofibers produced, or how to disperse and mix them with other materials. Nanoization is becoming inevitable for various materials that are commonly used, and it is also necessary to consider sodium bicarbonate salt, etc., which is mixed in soap, as a protective agent.

In addition, although the nanocellulose used for the protective agent is not particularly limited, 1.6% and 6% liquids were provided by the National Forest Research Institute and repeated experiments since 2016. Sugino Co., Ltd. An experiment was also conducted using cellulose nanofiber BiNFi-s manufactured by Machine Co., Ltd., and the results were good, with no sedimentation due to rough filtration of titanium dioxide, and rough transparency.

Furthermore, as an example of the component composition of the protective agent, 15% fine pulp particles containing titanium oxide, 25% nanocellulose, 2.5% photocatalytic titanium oxide, and 9% sugar were dissolved in 30% purified water at 70 to 80°C. After a solution was obtained, it was cooled and 1% sodium fatty acid was added and mixed. 41% of the solution is cellulose, and all raw materials are naturally derived protective agents. However, this is just a numerical value setting in an experiment, and it is not limited to these, and is shown as one example. Naturally, when finishing, the values were for making a solution by filtering, and there was an error of about %.

As shown in FIG. 3, titanium oxide, which is a photocatalyst solution, adsorbs a large amount of titanium oxide on cloth fibers such as masks and handkerchiefs. Therefore, the rubbing action becomes effective by applying and spraying the protective agent.

On the other hand, photocatalytic titanium oxide is made of Nippon Soda's titanium oxide coating material Bistreita H ² : anatase type titanium oxide, and the overwhelming majority of photocatalytic titanium oxide coating agents manufactured by Ishihara Sangyo Co., Ltd., visible light It is a responsive photocatalyst, and its derivation is due to mixing the thickening properties of nanocellulose and adding it to fine grain pulp. Moreover, even if you wash your hands or wipe off the water and dry it, the strong acidity of the protective agent will be physically and chemically fixed at the same time, and the photocatalytic activity will react with bacteria and viruses that adhere to your hands and fibers, sterilizing and sterilizing. In addition to being easily removed by the rubbing action due to decomposition, the rubbing effect can be expected to keep the environment and sanitary where new bacteria and viruses are unlikely to adhere and multiply. The present invention continues to be tested due to the need to await extensive clinical trial data.

In addition, the photocatalyst is a non-selective reaction that eventually decomposes carbon dioxide into water regardless of the partner if it is an organic substance. For this reason, the highly hydrophilic photocatalyst nanocellulose detergents and additives that are transitioned and immobilized on laundry clothes, etc. in [Patent Document 7] do not necessarily require a binder when irradiated with light, ultraviolet rays, or visible light. It was discovered that when the photocatalyst permeates, sterilization is generated, and it was possible by not creating the cause of the generation of bacteria. In general, bacteria and viruses are washed away after washing, but depending on the conditions and environment such as bad weather and drying in a humid room, Moraxella osroensis bacteria adhere to and grow on the laundry. Sebum and the like are used as nutrients, and the debris emitted from them emits a bad smell like a rag. As an option to suppress this, the photocatalyst nanocellulose detergent and additives of [Patent Document 7] are mixed into the existing detergent. The method of washing is preferred. However, since bacteria in the washing machine may cause the growth of bacteria even immediately after washing, it is possible to sterilize them by spraying or applying a photocatalyst solution or a protective agent.

また、透過度ｔの逆数（ｌ／ｔ）の常用対数を吸光度Ａ（ａｂｓｏｒｂａｎｃｅ）
Ａ＝－Ｉｏｇｔ＝２－Ｉｏｇｔ吸光度Ａは試料濃度に比例し、これはＢｅｅｒ法則である。吸光度Ａは試料溶液の濃度及び層長に比例すると表現され、これはＬａｍｂｅｒｔ－Ｂｅｅｒの法則でＡ＝Ｒ・Ｃ・ιであり、Ｒは比例定数、Ｃ・ιはそれぞれ濃度、層長を表す。ＣをｍｏＩ／Ｌで表しＲをεと表記、モル吸光係数ｍｏｌａｒａｂｓｏｒｐｔｉｖｉｔｙ Ａ＝ε、ｃ、ι 試料溶液濃度１ｍｏｌ／Ｌのとき吸光度εに相当する事になり、同一測定条件下で物質に固有の値となる。また、ｃを％（ｗ／

これが比吸光度ｓｐｅｃｉｆｉｃａｂｓｏｒｐｔｉｏｎで試料溶液の濃度が１％（ｗ／ｖ）の吸光度に相当する事になる。

この値もまた物質固有の値となり、医薬品の示性値や紫外可視吸光度測定法を用い、上記の２式は測定対象化合物の分子量をＭとし、試料溶液のモル濃度をＸｍｏｌ／Ｌとすると、そのパーセント濃度はＸ、Ｍ／_１０％（ｗ／ｖ）となり

これらを考慮した一例として、例えばブラックライトやＬＥＤライトの光触媒活性様式を付帯させた容器に本発明の保護剤を充填し、外出時の携帯用または保管時や塗布噴霧直前または手肌に塗布噴霧後にブラックライトやＬＥＤライトを照射しても光触媒が活性され、効果も持続させられる。Furthermore, even if a commercially available photocatalyst solution is used as a protective agent by a method of using titanium oxide to touch fibers, paper, plastics, etc., the decomposition reaction of the base material due to the photocatalytic reaction can be delayed or shortened. If time is enough, it will saturate with the concentration required for stain removal and can be prevented. This is a method of penetrating the material and the surface, and in order to penetrate the liquid protective agent into the gaps between the fibers, in addition to LED light and black light, it is also required by calculation formulas for visible light and ultraviolet rays. explain. Visible rays (v) and ultraviolet rays (UV) are waves that travel while repeating electric and magnetic fields like X-rays, microwaves, or radio waves, that is, electromagnetic waves. The difference in color is invisible except for visible light, but it has a wavelength (λ) and a frequency (ν), and the wavelength is expressed in meters (m). Absorption of light from ultraviolet to visible region can be calculated according to the transition. Accordingly, there is UV-visible spectrophotometry. It utilizes the absorption of light associated with electronic transition, and is a method of measuring ultraviolet light and visible light with a wavelength of usually 200 nm to 800 nm. Assuming that light passes through a thick layer of fabric fibers ι, when the intensity of incident light is Io and the intensity of transmitted light is I, the ratio of the two is (I/Io). degree t (transmittance), which is expressed as 100 percent transmission (Percenttransmission) T

Further, the common logarithm of the reciprocal of the transmittance t (l / t) is the absorbance A (absorbance)
A=-Iogt=2-Iogt absorbance A is proportional to sample concentration, which is Beer's law. The absorbance A is expressed as being proportional to the concentration and layer length of the sample solution, which is A = R · C · ι in Lambert-Beer's law, where R is a constant of proportionality, C · ι represents concentration and layer length, respectively. . C is represented by moI/L and R is represented by ε. value. Also, c is % (w/

This is the specific absorbance, which corresponds to the absorbance when the concentration of the sample solution is 1% (w/v).

This value is also a value specific to the substance, and using the characteristic value of pharmaceuticals and the ultraviolet-visible absorbance measurement method, the above two equations assume that the molecular weight of the compound to be measured is M and the molar concentration of the sample solution is X mol / L. Its percent concentration is X, M/ _10% (w/v)

As an example considering these, for example, a container attached with a photocatalytic activity mode of black light or LED light is filled with the protective agent of the present invention, and it is portable when going out, or during storage, just before spraying or spraying on the hands. Even if black light or LED light is applied later, the photocatalyst is activated and the effect is maintained.

Moreover, when the photocatalytic activity mode is added, a container filled with a protective agent having a high transmittance of ultraviolet light is required to enhance the effect of ultraviolet irradiation on the sprayed/coated area. Quartz, which has been widely used as an ultraviolet-transmitting material, transmits ultraviolet rays very well. At present, there is a fluororesin that transmits ultraviolet rays, and it is known to be one of the ultraviolet-transmitting materials that can replace quartz because of its advantages such as no fear of breakage during transportation and resistance to staining. In addition, fluororesin has light transmittance that is different from quartz, which is specular, and because it is a crystalline polymer, it has the property of diffusing and transmitting light. Depending on the shape, it has been discovered that the transmitted light intensity exceeds that of quartz. In [Non-Patent Document 19], a photo-sterilization experiment targeting Bacillus subtilis in a spore-forming state was conducted for a system using fluororesin, and the liquid surface was irradiated with ultraviolet rays through various ultraviolet-transmitting materials used for photo-sterilization. When the light sterilization rate constant is obtained for surface irradiation type sterilizers and circulation type external irradiation type sterilizers that irradiate ultraviolet rays to quartz tubes and fluororesin tubes from the outside, it appears to be a low value due to diffusion permeability. Even if it is, the transmittance is related to the actual transmitted light intensity and is considered to be an index of the sterilization speed. The resin condition has a higher sterilization rate than quartz, and when the irradiation time is replaced with the average residence time and correlated, the error is large in the high sterilization rate region, so 99% of the fluororesin is less time than quartz. I was able to kill the bacteria. Therefore, it is thought that the transmission characteristics of the material have a large effect in the region of high sterilization rate, and it is also reported that the fluororesin tube allows the light (wavelength 365 nm) to pass through the tube at a level equal to or greater than that of the quartz tube due to the diffuse transmission property. Diffusion permeability has a positive effect on the killing rate, and fluororesin can provide almost the same sterilization rate as quartz at low sterilization rates, but in the high sterilization rate range, fluororesin is better. It is also known that the sterilization rate is higher than that made of quartz, and the effect of diffuse transmission is large. From these results, the protective agent container with a photocatalytic activity mode in the present invention uses quartz, fluororesin, etc., and disinfects and viruses using ultraviolet irradiation when filling the protective agent and after application and attachment. It becomes possible to continue the inactivation of , etc. more quickly and effectively. However, the container is not limited to quartz or fluororesin.

A specific example of the photocatalytic activation mode is shown in FIG. A heat insulating material 11 is covered to prevent overheating, and ultraviolet rays 2 can be radiated from the inside by the power source of the ultraviolet irradiation unit 9 at the bottom. The bottle 7 containing protective agent liquid is provided with a protective agent liquid water inlet 6 for discharging the rubbing protective agent 1 , and the protective agent liquid 1 is discharged from the protective agent liquid outlet 3 by a discharge button 5 . A heat insulating material (container protective material) 11 inside the outer case is arranged around the bottle 7 containing the protective agent liquid, and the straight ultraviolet rays 2 of the light irradiation part 9 are applied when the protective agent liquid 1 is sprayed and applied, or on the skin of the hand. After application and rubbing, the photocatalytic activity can be effectively obtained regardless of the environment of use, such as in a dark room, at work, or on the go. As shown in Fig. 12, this device can be turned upside down and the outlet is pushed into the application/spray surface 15, and it can also be used as a pump type. The part is not limited to the battery type, and may be a rechargeable type such as solar or USB, and is not limited. Even in an environment where ultraviolet irradiation cannot be obtained, the protective agent alone may be used, and the external case 8 can be easily attached and detached. Further, the battery unit 10 may be a removable cassette type, and the bottle 7 containing the protective agent for coating and abrasion may be a filling type, or the bottle may be replaced. The photocatalyst activation mode is provided with a light irradiation part for the purpose of activating the photocatalyst. [Fig. 11] to [Fig. 13] show an example of the photocatalyst activation mode, and the shape specification etc. are arbitrary.

Also, the absorption edge due to the bandgap of titanium dioxide (anatase type) is 380 nm, but the absorption center is near 340 nm. The central wavelength of black light is 352 nm, and the central wavelength of ultraviolet LED is 365-375 nm, both of which can be used as excitation light sources. However, since each wavelength distribution is different, as a result of testing with a deodorizing device using a black light and an ultraviolet LED as an excitation light source, the removal rate of 20 ppm of acetaldehyde is in the range of 20 to about 2 ppm. , which is considered to depend on the wavelength distribution of the black light and the ultraviolet LED. That is, even if the peak intensity at 360 nm is about the same, when the integrated intensity at 380 nm or less is compared, the black light has about four times the integrated intensity of the ultraviolet LED. When the odor is highly concentrated, the adsorption of the odor to the photocatalyst proceeds relatively quickly, so the decomposition rate is proportional to the intensity of the ultraviolet rays. From this, it is considered that the black light source has a better removal rate in the high to medium density range, but the removal rate in the low density range (less than several ppm) is different between the black light and the UV LED. I was not able to admit. In that region, the adsorption speed of the malodorous gas to the photocatalyst is remarkably slow, so the removal speed depends on the adsorption speed and does not depend on the amount of ultraviolet rays. However, in a factory environment where several tens of ppm of toluene is the target gas, it is not appropriate to use UV LEDs as excitation light sources, but the regulation standards for substances that pose problems in general living spaces are as low as several ppm. It is in the concentration range, and the use of ultraviolet LEDs is considered effective.

Furthermore, the removal rate of acetaldehyde and hydrogen sulfide due to the difference in photocatalyst temperature can be several times faster than the decomposition at room temperature if the photocatalyst temperature is properly controlled, and it takes a long time to decompose toluene and xylene. However, even in this case, the photocatalyst heating effect is clear, and the difference in the decomposition rate in the low-concentration region is particularly remarkable. From these, photocatalyst heating is considered to be effective in improving the removal speed of many kinds of odors, and malodorous gases are captured on the photocatalyst surface, and the relationship between photocatalyst temperature and removal speed is clear. It also speeds up. That is, when the surface temperature of the photocatalyst rises, the gas temperature in the vicinity of the surface also rises, the molecular motion becomes more intense, and the chances of contacting and being captured by the photocatalyst increase. The trapped gas is rapidly decomposed by a photocatalytic reaction, and the gas trapping power decreases as the temperature of the photocatalyst rises. It is considered that the comprehensive phenomenon of these two actions is shown in the relationship between the photocatalyst temperature and the removal rate.

In addition, the photocatalyst solution allows the nano-sized fine particles of the protective agent to penetrate into bacteria, viruses, etc. when rubbed with fingers, etc., enabling a dramatic rubbing effect. However, although it acts as a smear for bacteria, viruses, etc. when rubbed, abrasion of skin, mucous membranes, etc. is protected by nanocellulose, pulp fine particles, and sugars. It is also known that it has the effect of sterilizing other germs by the action of a photocatalyst.

Furthermore, the toxicity and harmlessness of photocatalysts are already known in detail, and the protective agent is manufactured within that range. It can be said to be a proof of safety that moss and algae that grow thickly are dead, and goldfish and tropical fish are not affected. However, the photocatalyst, which is inferior in ability to process a large amount at once, cannot eliminate excrement of goldfish, etc., and the improvement of water turbidity is not complete. can. On the other hand, photocatalysts are generally fixed objects such as walls and have been effective against solid objects. Therefore, the same effect can be obtained with the protective agent of the present invention.

In addition, photocatalyst solutions represented by titanium oxide are physically a kind of photoconductive substance. Normally, they do not conduct electricity and become conductive when exposed to light. Since the solution is made up of nano-micro particles, it absorbs a large amount and is highly effective. It forms a coating of the protective agent on the skin and fibers that are part of the human body. is continued.

Furthermore, there is no candidate other than a photocatalyst as a safe and harmless sterilization technology that kills bacteria that are resistant to antibiotics. Since then, development into various product fields has progressed, and in that sense, health and medical technology is the beginning of the current application of photocatalysts, and photocatalytic decomposition has been attempted for many compounds such as artificial female hormones used in oral contraceptives. Since it is known that it is possible to completely eliminate female hormone activity, protective agents are also being considered as quasi-drugs.

However, even if it is assumed that the photocatalyst is not effective in a short period of time or is difficult to produce, in addition to the rubbing action of the peracetic acid preparation, as a general practice, washing your hands with water periodically for several minutes to several hours is recommended. However, even if the protective agent is not used each time, the coating effect of the coated photocatalyst is maintained under ultraviolet light and visible light. However, considering the importance of moisturizing and protecting properties, using a protective agent after washing with water will result in moisturizing and protecting the hand skin, as well as making more photocatalysts work on physical and chemical irritation. will also become

When the photocatalyst solution is kneaded into the skin and fibers, it is decomposed by the photocatalytic action. Inhibitors or adjuvants that allow application to textiles are also solved by using known products. In addition, in short-term use, along with the reaction speed and decomposition speed of the photocatalyst, it has a moisturizing and protective structure that prevents rough skin when it comes in contact with nanocellulose, non-hydrophilic pulp particles, and sugars. It is also effective to apply to the skin of the hands. Particularly in winter, the palms and soles of the feet, which do not have pores, tend to develop senile dry skin and are more susceptible to viral and bacterial infections.

On the other hand, the rubbing ability of sugars is related to the affinity of sugars. For example, sugar, which is known to have antibacterial properties, is composed of two types of sucrose, glucose (glucose) and fructose (fructose). Similar ingredients are easy to mix, and this phenomenon occurs because the sugar component is closer to oil than the skin, but it works effectively because it is compatible with water, and there is no need to worry about rough hands. . In addition, sugar has a much smaller molecular weight than cellulose, has eight hydroxyl groups and is highly soluble in water, and has various chemical functions such as giving various derivatives in which a small part in the molecule of the compound is changed. Clinical results have shown that it has excellent antibacterial and antiseptic effects, as well as an action to restore cells. It is possible to use skin moisturizing agents such as steroids, vaseline urea ointment, hyaluronic acid and the like, which are commonly used, but it is preferable to use only the protective agent in consideration of the rubbing effect.

In addition to hand skin, when using a protective agent on the face (excluding the eyes and the area around the eyes) and the human body, algae and seaweed can provide moisturizing and water retention properties in addition to nanocellulose. Among them, Akamoku is one of the seaweeds belonging to brown algae, and a similar species is Shidamoku. It is 5 cm long and has a strong vitality, so it is distributed throughout Japan and overseas, and there are regional differences in the shape of the leaves. Akamoku is characterized by its strong stickiness, and this viscous substance is fucoidan, which is one of the sulfated polysaccharides whose main constituent sugar is fucose, and alginic acid, which is known as a constituent sugar of seaweed. In China, Akamoku has been used as an anti-inflammatory herbal medicine for a long time, and it has been reported that fucoidan has various functions such as antitumor effect, and alginic acid has various functions such as intestinal regulation. For example, mozuku collected in Munakata City, Fukuoka Prefecture, and mozuku from Shima Town, Itoshima Town, Fukuoka Prefecture, and Kume Island, Okinawa Prefecture, which were used for comparison, were freeze-dried and pulverized using a grinder. It is about 500 to 700 mg, and it became clear that 70% to 50% of fucoidan is retained even when compared with the original algae. Furthermore, by examining the processing conditions, we used fucoidan fine powder that retains more fucoidan as a protective agent. , Skin beautifying effects such as elasticity maintenance and moisture absorption, and moisturizing protective ingredients. However, although hypochlorous acid may be used in combination to deodorize seaweeds, the use of hypochlorous acid is, of course, not limited to the purpose of deodorizing. In addition, nanocellulose from seaweeds has been developed and is currently distributed as a commercial product, and it is also a good idea to use this.

Furthermore, Akamoku is a brown algae that has the same formation as kelp, mozuku seaweed, wakame seaweed, and hijiki, and contains a large amount of fucoidan, which is a type of sulfated polysaccharide and a viscous substance. Fucodine has anti-oxidant effect and anti-bacterial effect such as suppressing allergy by inducing apoptosis. Regarding the chemical structure of mozuku fucoidin in particular, in 1996, the University of the Ryukyus Faculty of Agriculture reported that four fucose and one glucuronic acid and two sulfate groups as one unit (molecular weight: about 1,000, consisting of 5 sugars). Therefore, it is possible to contain brown algae as one of the saccharides of the protective agent, and to obtain moisturizing and protection of the hand skin and fabric fibers with adhesiveness using the fucoidin component. However, if a peculiar odor such as algae is generated, consideration should be given to the combined use of perfume, etc.

In addition, considering the use environment, storage environment, and period of use of the protective agent, it may be considered to incorporate a preservative or an antioxidant. Potassium sorbate has the effect of suppressing the generation and growth of bacteria and molds, and is frequently used in foods as an anti-corrosion agent. It is also used as a preservative in toothpaste, shampoo, and cosmetics. Regarding the metabolism and excretion of potassium sorbate, it is taken into the body as sorbic acid, and since sorbic acid is an unsaturated fatty acid, it is finally decomposed into carbon dioxide and water like normal fatty acids and excreted in the urine. It can be used safely even if it is contained in a protective agent because it is considered. Calcium sorbate is a food additive that is widely used in Western countries as a food preservative. It has been evaluated for safety as a substance considered to be a recognized substance), and can be used in the required amount in general foods under the control of Good Manufacturing Practice (GMP). Sorbic acid and its salts have a wide antibacterial spectrum and act bacteriostatically against mold, yeast, and bacteria. It is approved for use as a food, and like potassium sorbate, it can be used as a preservative for protective agents. Preservatives other than sorbic acid include 1,2-hexanediol, a polyhydric alcohol (dihydric alcohol: glycol) that has a refreshing feel and excellent antibacterial properties, and alkane, a type of polyhydric alcohol that has high antibacterial properties. It is also a diol. Glycerin and sorbitol are ineffective, but glycols such as propylene glycol have been found to have an antibacterial effect on Gram-negative bacteria. The antibacterial properties of these glycols are thought to be due to the fact that the glycols dissolve themselves, taking water away from microorganisms, making it impossible for microorganisms to proliferate and killing them. there is In addition, alkanediols have been shown to significantly inhibit the growth of E. coli compared to other polyhydric alcohols, and 1,2-hexanediol has also been shown to suppress the growth of Pseudomonas aeruginosa, Staphylococcus aureus, and black mold. has been shown to have excellent antibacterial properties. Furthermore, it is known that a combination of 1,2-hexanediol and pentylene glycol or caprylyl glycol exhibits synergistic antibacterial properties, and can be used safely as a protective agent or antiseptic without causing skin irritation. . However, its use is optional.

Furthermore, the antioxidant diptyl hydroxytoluene is produced by chemical synthesis from ▲p▼-cresol and ▲iso▼-butylene, and is oil-soluble and has superior stability compared to other antioxidants. Tocopherol, a type of vitamin E and a fat-soluble vitamin, is insoluble in water and soluble in alcohol and oil. Although it is widely used as an antioxidant in food additives, its use in the present invention is considered because it has been pointed out that it is harmful to health. In addition, ascorbic acid (vitamin C), chlorogenic acid, and catechin can also be used as antioxidants for protective agents. However, its use is optional.

A point to consider when using an antioxidant as a protective agent is that ascorbic acids (vitamin C) are often used as antioxidants for water-soluble ingredients for the purpose of nutritional enhancement as vitamins, but on the other hand, Widely used as antioxidants, vitamin C includes L-ascorbic acid and L-sodium ascorbate, which are soluble in water, and L-ascorbyl stearate and L-ascorbyl palmitate, which are easily soluble in oils and fats. However, there is L-ascorbic acid 2-glucoside as a water-soluble vitamin C with good heat stability, and it can be used according to the purpose. Vitamin E of tocopherols (vitamin E) has the effect of preventing the formation of peroxides in the body, and is a vitamin that is easily soluble in oils and fats and has the effect of maintaining the functions of cell membranes and biological membranes. There are α-tocopherol with strong antioxidant effect, δ-tocopherol with strong antioxidant effect, β-tocopherol, γ-tocopherol, etc. Among these suitable for use for antioxidant purposes are d-delta-tocopherols and mixed tocopherols. The specified additive, dl-α-tocopherol, is limited to use for the purpose of preventing oxidation according to the usage standards, but its effect is not as good as that of the above-mentioned two types of existing additives, tocopherols. Furthermore, erythorbic acid is an isomer of ascorbic acid and is a representative antioxidant sometimes called isoascorbic acid, and is widely used in Europe and the United States, but erythorbic acid has no effect as vitamin C. It is said not to exist and is used only for the purpose of preventing oxidation. Its antioxidant activity is similar to that of vitamin Cs. BHA (t-butylhydroxyanisole) and BHT (di-t-butylhydroxytoluene) are typical substances having antioxidant properties obtained by chemical synthesis. Both are derivatives synthesized to enhance the effects of t-(tertiary) butylphenol, which has an antioxidant effect. However, since the timing of implementation of the revised usage standards was not specified, the effectiveness of the usage standards, especially with regard to imported foods, was poor. It can be used for a wide range of products. Salts with ethylenediaminetetraacetic acid as a skeleton are EDTAs, two of which are designated as food additives. It can be used in foods, but in Japan, it is only permitted to be used as a sequestering agent that captures free metal ions in canned and bottled foods and blocks their activity. , in the form of calcium disodium salt. Gallic acid is an existing plant-based additive called boshokushisan or moshokushisan. In Japan, the main raw material is quincunx tannin, which is obtained from quincunx, and in Europe, gallic tannin, which is made from gallic, is the main ingredient. , is similar to the polyphenolic trihydroxybenzoic acid that constitutes gallic acid. Propyl gallate is a designated additive obtained through an esterification reaction between gallic acid and propyl alcohol, and is used as an antioxidant for fats and oils, mainly in Europe and the United States. As other natural antioxidants, rutins, which are glycosides of quercetin, are used as antioxidants because they are resistant to heat and have antioxidant properties. These include "rutin (extract)", "quercetin", "rutin enzyme hydrolyzate", "enzyme-treated rutin (extract)" and "enzyme-treated isoquercitrin", as well as "tea extract". There are also "enzyme-decomposed apple extracts" obtained by decomposing apple fruits with enzymes, but the choice is arbitrary when using these.

In addition, allantoin, which is used as a protective agent, has tissue repair activating action (activating the repair of skin tissue), anti-irritant action, anti-inflammatory and sedative action, and anti-allergic action. It is effective against acne and can be used by people with sensitive skin and babies. Metals such as titanium oxide and tungsten oxide may form peroxides when exposed to air, so the combined use of antioxidants and allantoin provides an anti-allergic inactivation effect. However, the combined use of an antioxidant is optional.

Furthermore, the odor of sweat is generated when sebum and other components contained in sweat are decomposed by bacteria (bacteria) that are indigenous to the skin. Chlorohydroxyaluminum, which acts at a site close to the surface and causes a decrease in perspiration due to the formation of a hydroxide gel containing aluminum in the intraepidermal ducts (sweat ducts) and physical blockage of the intraepidermal sweat ducts. When mixed with a protective agent, it has the double effect of sterilizing the bacteria that cause odors and acting as an astringent, making it possible to prevent underarm odor.

When the protective agent is filtered, it is necessary to have a solution in which each substance is completely dispersed in order to leave the active ingredient in the solution. Effective ingredients are maintained, and high effectiveness can be demonstrated. In addition, if the filtration is performed for a certain period of time, aggregates with a larger particle area will be obtained, so that more stable effective ingredients can be extracted. However, in order to attenuate the effect of the protective agent, it may be considered to increase the amount of the material according to the filtering material, but it is not always necessary to perform the filtration.

In addition, it is said that there are about 570 kinds of viruses isolated from animals, and about two thirds of them have a membrane (envelope) similar to the host cell membrane, and this membrane contains host-derived phospholipids, glycolipids, In addition to complex lipids such as cholesterol, there are virus-specific glycoprotein spikes embedded therein. This spike plays an essential role in the adsorption of the virus to the host and the release of the virus from the host by germination. Essential for expression. On the other hand, the sugar chains on the host cell membrane are extremely diverse and at the same time have extremely high species specificity. have. The mechanism by which viruses exhibit host specificity often reflects the specificity and diversity of host cell membrane sugar chains, and the fact that enveloped viruses recognize and bind to the host cell membrane sugar chains as specific receptors. has become clear. It was also found that even in the case of influenza viruses, for example, where antigen-determining regions are prone to mutation, mutations in the receptor-binding pocket on the spike protein, which is involved in binding to the receptor sugar chain, are less likely to occur. Blocking the receptor-binding pocket with a pseudo-compound means that it may become the seed of an epoch-making antiviral drug that can overcome mutations. Strand-targeted development is said to be very effective. In the protective agent of the present invention, the use of sugar chains for the prevention of viruses and the like that invade through mucous membranes such as wounds of the human body, including hands and skin, is considered. I want to continue development.

On the other hand, in the case of a gel-type protective agent, when filling a spray container, a container with a sponge cap, a container with a roller cap, etc., and removing and decomposing bacteria and viruses that are extremely attached to the skin of the hands, al ether and ether sulfate are used. Even without adding such as, using a solution with a photocatalyst concentration increased by several percent, the rubbing action, moisturizing and protecting power are enhanced. In addition, when fibers such as masks and clothes are gelled, the rubbing action and the rubbing protective film are greatly enhanced, and a large rubbing effect can be obtained.

Furthermore, as a result of spraying or applying the protective agent of the present invention to the nails and soles affected by tinea pedis due to athlete's foot, the tinea pedis on the soles was cured after 3 months, and the athlete's foot that entered the nails was cured after 1 year. It can be visually observed, and when the photocatalytic activity mode is used or when the number of times of application and spraying is frequently used, for example, once every two days or every day, a quick complete cure is conceivable. In addition, when it is applied to the head, itching and dandruff disappear, which is considered to be an improvement in the tinea capitis, which is a dermatomycosis.

In addition, as a result of using a protective agent with a photocatalytic activity pattern other than the human body such as hand skin, image blurring and sound modulation occur. It became possible to watch and listen without any sound modulation, but the modulation can be normalized even if the protective agent is not wiped off.

Furthermore, it is optional to mix the protective agent with a perfume component or a coloring component of the solution.

Although the present invention has been specifically described based on the embodiments, it is needless to say that the present invention is not limited to the above embodiments and can be variously modified without departing from the scope of the invention.

REFERENCE SIGNS LIST 1 rubbing protective agent 2 light beam 3 protective agent liquid discharge port 4 discharge plate 5 discharge button 6 protective agent liquid water absorption pipe 7 protective agent liquid containing bottle 8 outer case 9 light irradiation section 10 power supply section 11 heat insulating (protective) material 12 lighting switch 13 lid (cap)
14 USB charging port 15 Application/spraying surface 16 Pump spring

Claims (12)

one or more photocatalyst liquids and a plurality of supported metals or metal liquids and compounds dispersed in said photocatalyst liquids, silicon and silicon compounds, peracetic acid formulations, a plurality of nanocelluloses, sugars including sugars, algae, pulps, A rubbing protective agent characterized by containing A cylindrical or prismatic illumination and a photocatalytic active mode arranged concentrically with the container filled with the rubbing protective agent,
a linear light source for irradiating activating light concentrically with the rubbing protective agent container; and a heat shielding cover extending along the exterior of the rubbing protective agent-filled container;
The top side of the rubbing protective agent container and the bottom side end of the cylindrical or prismatic lighting are released,
The lighting means for the cylindrical or prismatic lighting is in contact with the end on the lower side, and the rubbing protective agent generating means is in contact with the end on the upper side,
A photocatalytically active mode characterized in that, in operation, said cylindrical or prismatic illumination emits a linear light source through said rubbing protectant container into and around the container. The photocatalyst liquid of the paint protection agent is at least one selected from titanium oxide, tungsten oxide, strontium titanate, zinc oxide, iron oxide, zirconia, zinc sulfide, cadmium sulfide, and mercury sulfide, or a combination of two or more thereof. The rubbing protectant according to claim 1. The supported metal or metal liquid and compound are at least one selected from the group consisting of vanadium, manganese, iron, cobalt, nickel, copper, zinc, niobium, molybdenum, ruthenium, rhodium, palladium, silver, tin, tungsten, platinum and gold. 2. The scuff protectant of claim 1, which is a metal, a compound of said metal, or a combination thereof. The silicon and silicon compounds are at least one or two selected from silicic acid, silicon dioxide, silicates of calcium silicate, magnesium silicate, sodium aluminosilicate, calcium aluminum silicate, zeolite, kaolin, and talc. The rubbing protective agent according to claim 1, which is a combination of the above. The peracetic acid preparation is peracetic acid, hydrogen peroxide, acetic acid, octanoic acid, peroctanoic acid, 1-hydroxyethylidene-1.1-diphosphonic acid, and an equilibrium mixture of water, and at least a combination of two or more. Item 1. The paint protection agent according to item 1. The nanocellulose is a polymer that constitutes a cellulosic polymer fiber, a polysaccharide having a glucan structure, a higher plant-derived cellulose, a natural cellulose fiber, an animal-derived cellulose, a bacterial-derived cellulose, or a chemically synthesized cellulose. 2. The rubbing protective agent according to claim 1, which is a combination of at least one to two or more selected from cellulose/nanocellulose, chitin, chitosan nanocellulose, silk nanocellulose and carboxymethylcellulose. The sugars include cyclodextrin, glucose, fructose, sucrose, maltose, lactose and glycerin, glycol solvents such as dipropylene glycol, polyethylene glycol, polyglycerin and butylene glycol, polyhydric alcohols such as xylitol and maltitol, chondroitin sulfate and Polysaccharides such as hyaluronic acid, proteins such as collagen, sterol esters such as hydroxydistearate, organic acid salts such as sodium lactate, and diglycerol adducts, which are one or more combinations Item 1. The paint protection agent according to item 1. The pulp is wood pulp, plant pulp, grass, straw, rice, bamboo, hemp, fruit, waste paper pulp raw material, non-wood pulp, waste paper pulp raw material, mechanical pulp, chemical pulp manufacturing method from different grain sizes. 2. The rubbing protective agent according to claim 1, which is a combination of one to two or more. Cylindrical or prismatic illumination for use in the photocatalytically active mode of claim 2 includes, but is not limited to, ultraviolet UV-A, UV-B, UV-C and visible ultraviolet wavelengths. 10. The rub protectant of claims 1 and 3-9, wherein the rub protectant composition is liquid, gel, paste, granule, solidified. The rubbing protective film and the rubbing method according to any one of claims 1 to 11, wherein the rubbing protective agent composition is used for sterilization, antibacterial, antiviral, sterilization, deodorizing, antifungal, antiallergic, moisturizing and water retention, quick drying, and pain relief. .

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