JP2022022923A - Paste protection material - Google Patents

Abstract

To provide a paste protection material, which contains photocatalytic solution, copper ion, copper aqueous solution, nanocellulose, pulp and saccharides or seaweeds or algae and which exerts a photocatalytic effect and an application effect of bacteria and viruses such as skin and fibers by copper, simultaneously, prevention of skin damage by virtue of moisturizing and protection of skin of hands, and sustained application effect.SOLUTION: There is provided an application protection material that uses an application method that utilizes interfacial tension of friction with non-hydrophilic pulp fine powder, with which photocatalyst solution enters a gap between skin of hands and fibers, which exerts an application effect of bacteria and viruses due to photocatalytic activity of the ultraviolet/visible light reaction bactericidal/antibacterial effect due to copper aqueous solution, simultaneously, and application effect by keeping an environment where adhesion and growth of bacteria are difficult to occur and sanitation due to moisturizing and protection and quick-drying of skin of hands by virtue of nanocellulose, pulp and saccharides or seaweeds or algae.SELECTED DRAWING: Figure 2

Description

The present invention uses photocatalytic active rubbing (sterilization, antibacterial, antivirus, sterilization, deodorization, antifungal), antibacterial use of copper ions and copper aqueous solution, and moisturizing, protection, and quick-drying of nanocellulose, etc. Regarding protective materials.

There are many substances used as antibacterial agents and disinfectants, such as alcohol and hypochlorite, but among them, photocatalysts are various without using harmful chemicals, just by exposing them to sunlight or visible light. It is used as a key to environmental purification because it causes chemical reactions such as decomposition of harmful organic substances and can be widely applied in the environmental field such as water purification, air purification, deodorization, antibacterial, antivirus, antifungal, and antifouling. ing. The most used photocatalyst is titanium oxide, which is a safe and non-toxic substance that is also used in toothpaste and cosmetics and is also recognized as a food additive. However, it is a very stable and peculiar substance, and since it only works as a catalyst (photocatalyst) and does not change itself, in principle, if there is light, the effect can be used semi-permanently, and light with high energy that is harmful to living organisms. The reaction proceeds with near-ultraviolet rays on the relatively long wavelength side contained in LEDs and fluorescent lamps, and water treatment, air purification, deodorizing VOC treatment, antibacterial, antifungal, antiviral, self-cleaning / prevention It can be widely applied to prevent stains and slime, and has many advantages such as low cost and excellent durability.

In addition, when titanium oxide is exposed to light, active oxygen is generated, and in particular, OH radicals have much stronger oxidizing power than chlorine, hypochlorite, hydrogen peroxide, ozone, etc., which are widely used for disinfection and sterilization. In addition to converting to non-toxic substances such as carbon dioxide, it destroys coenzymes such as coenzyme A in the cells of bacteria, enzymes that act on the respiratory system, cancer cells, etc., and decomposes organic substances, decomposition of toxins produced by bacteria and mold, It can also decompose viruses and exert antibacterial and antiviral effects to stop the growth of bacteria and molds and the adhesion of viruses. By these actions, almost all harmful organic substances such as various harmful chemical substances and chemical substances in the air such as malodorous substances, bacteria and viruses adhering to fibers and human body are easily decomposed by irradiation with light. It can be detoxified.

Furthermore, although copper ions are also shown in [Non-Patent Document 10], they have been widely used in daily life as antibacterial, antifouling agents, and bactericides, and today they are supported on titanium oxide or tungsten oxide to respond to visible light. It is known to be useful as a material for type photocatalysts.

Japanese Patent No. 27833339 Japanese Patent No. 2517874 Japanese Patent No. 6576996 Japanese Patent No. 6184108 Japanese Unexamined Patent Publication No. 2002-308712 Japanese Unexamined Patent Publication No. 2014-11356 Japanese Patent Application No. 2020-46968 Japanese Unexamined Patent Publication No. 2016-10724

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 タンニンの化学 最近の研究 西岡五夫 化学と生物Ｖｏｌ２４、Ｎｏ．７ 木本性植物の組織培養によるタンニン生産と生合成 谷口抄子、波多野力、矢崎一史 木材学会誌 Ｖｏｌ．５２、Ｎｏ．２ｐ．６７－７６ 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 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

Pulp Properties and Paper Strength Jujo Paper Industries Co., Ltd. Research Institute Kyouichi Oku Ingredients and utilization of tropical forests (2) Seisuke Ohara Tropical Forestry No39 1997 Chemistry of Tannins Recent Studies Goo Nishioka Chemistry and Biology Vol24, No. 7 Tannin production and biosynthesis by tissue culture of woody plants Shoko Taniguchi, Riki Hatano, Kazushi Yazaki Journal of the Wood Society Vol. 52, No. 2p. 67-76 Photocatalyst application technology Kazuhito Hashimoto July 25, 2007 Tokyo Tosho Co., Ltd. All about photocatalysts Akira Fujishima November 22, 2017 Diamond Antibacterial and bactericidal action process of copper ion solution based on antibacterial drug susceptibility test results Tsuneo Ishida Journal of Japanese Society of Microbial Ecology Vol. 31, No. 2, 45-46 2016 Molecular Biology of Cells I Meet for the First Time Akio Ito Iwanami Shoten Co., Ltd. August 29, 2006

The problem that the invention is trying to solve

However, the photocatalytic solutions and non-photocatalytic solutions shown in Patent Documents 1 to 6 are generally used for walls and floors assuming a substrate, for residential use, industrial use, etc., and there is room for improvement in photocatalysts assuming hand skin and fibers. In addition, the effect of the photocatalyst using titanium oxide, tungsten oxide, etc. is affected by the irradiation amount of ultraviolet rays and visible light. Since titanium oxide exhibits strong oxidative decomposition and bactericidal power, it adheres to the skin of the hands and prevents the growth of indigenous bacteria from the outside, and the indigenous bacteria that protect from ultraviolet rays and create healthy skin (good). In addition to decomposing and sterilizing indigenous bacteria), if the target substance does not come to the surface, it cannot cause reactions such as decomposition, and it decomposes almost all harmful organic substances by photocatalytic action. It was said that it was impossible to apply it to fibers that would be sterilized. Furthermore, the photocatalyst does not produce bactericidal, antibacterial, and antiviral effects unless exposed to light, and active oxygen such as OH radicals has a short life due to light irradiation, and the antibacterial effect is achieved if bacteria do not come near titanium oxide. Since it is not exhibited, if titanium oxide is buried in a carrier or binder, it is difficult for light to hit and bacteria do not easily approach, and the antibacterial effect is low, so it is possible to coat the fibers and hands with a titanium oxide photocatalyst. It is indispensable. The photocatalytic reaction has the disadvantage that it cannot cause a reaction such as decomposition unless the target substance comes to the surface, and the target substance is attracted by adsorption and decomposed by the photocatalyst. Although it has been hybridized, it has the disadvantage that the reaction does not occur when the photocatalyst is behind the activated carbon because the activated carbon does not transmit light. Further, as shown in [Non-Patent Document 2], tungsten oxide is known as a visible light responsive photocatalyst that expresses photocatalytic activity under visible light, and is self-reduced by electrons excited by light irradiation to be tungsten. Since the photocatalytic activity decreases as the valence of the ion changes from hexavalent to pentavalent, it is difficult to completely decompose the volatile organic compound, and the high activation of tungsten oxide causes the problem. Tungsten oxide carrying platinum or palladium has been produced, and attempts have been made to completely decompose volatile organic compounds, but the cost increase due to the noble metal for high activation becomes a problem. In addition, many general disinfectants and antibacterial agents have a pungent odor, and chlorine-based and alcohols also have a dehydrating effect, so if used frequently, they deprive both sebum and water on the skin surface. It results in degreasing, which tends to cause rough hands, leads to the growth of pathogens, and becomes a hotbed for bacterial growth. Further, although the moisturizing property can be maintained by applying the hand skin cream, there is also a problem that the bactericidal, antibacterial and antiviral effects are weakened.

In view of the above problems, the subject of the present invention is to apply ultraviolet rays and visible light to a photocatalyst solution having bactericidal, antibacterial, antiviral, sterilizing, deodorizing, and antifungal effects in order to cope with the usage environment of consumers. In addition, copper ions and copper aqueous solution that maintain the effect regardless of the environment in which it is used, nanocellulose with conductive moisturizing and protective effects and pulp and saccharides or seaweeds and algae are blended to create gaps in the skin and fibers. It exists on the surface because the peelability of the photocatalyst that penetrates into the skin and the intermolecular force acts on the inside (hand skin, fiber side / subsequent bulk side) and the surface side (hereinafter surface), and the molecular density on the bulk side is overwhelmingly high. It is a rubbing using pulp fine powder due to interfacial tension, which is one of the surfactants that is always drawn into the bulk side. In addition to copper ions and aqueous copper solutions that provide antibacterial and bactericidal effects, nanocellulose and non-hydrophilic pulp are used to accelerate the drying time of the skin by rubbing it, thereby moisturizing and protecting the skin after rubbing, as well as sterilizing and antibacterial.・ Anti-virus, sterilization, deodorization, and anti-mold effect are maintained normally, and in addition to preventing rough skin, sterilization, antibacterial, anti-virus, sterilization, deodorization, and anti-mold effect are also maintained by applying or spraying on fibers. Provide materials.

Means to solve problems

Therefore, in order to solve the above problems, the present invention uses a rubbing method using non-hydrophilic pulp fine powder rubbing mixed with hydrophilic vegetable nanocellulose, and a super-hydrophilic photocatalyst solution is applied to the gaps of the skin. Environment and hygiene where bacteria and viruses that enter and adhere to the skin, etc. are exfoliated and decomposed by photocatalytic activity, and are easily removed by the killing action of bacteria and viruses by sterilization and decomposition. Sterilization, antibacterial, anti-virus, sterilization, deodorization, anti-mold (hereinafter referred to as "rubbing action"), and even in an environment where it is difficult to obtain their activities, the antibacterial and bactericidal effects of copper ion water and copper aqueous solution, as well as tasteless and odorless Safe and hydrophilic vegetable nanocellulose and pulp, sugar, seaweed, algae moisturize and protect the hand skin and quick-drying hand skin rubbing protective material (hereinafter referred to as rubbing protective material) and fiber rubbing action The purpose is a cloth fiber rubbing protective material (hereinafter referred to as rubbing protective material) for sterilization, antibacterial, antivirus, sterilization, deodorization, and antifungal (hereinafter referred to as rubbing processing).

As the titanium oxide used for the photocatalytic solution, natural anatase-type titanium oxide (hereinafter referred to as photocatalytic solution) or brookite-type titanium oxide (hereinafter referred to as photocatalytic solution) having a band cap of 3.2 eV and a wavelength equivalent of about 388 nm and having high photocatalytic activity is used. The photocatalytic 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 can not only decompose and remove stains on the surface, but also inactivate bacteria including Moraxella, viruses, filamentous fungi, cancer cells, etc. The application to the fields of medicine, medical treatment, and sanitary materials focusing on the anti-microbial properties of titanium oxide, which is not limited to specific bacteria, is also being actively carried out. Since this effect utilizes a photocatalytic reaction, the basic concept of coating is the same as that for self-cleaning applications that mainly utilize decomposition activity, but as shown in [Non-Patent Document 1], the photocatalyst is sterilized. It is known that antibacterial and antiviral properties are possible, and titanium oxide has strong characteristics against nitric acid and chromium, and can be specialized in oxidative rot and forming a thin film in the gaps of the skin. As a result, it shows a sufficient effect, and at the same time, the energy of the surface tension that enters the gaps of the adhered dirt is added, and it is possible to sterilize and exfoliate and decompose bacteria and viruses and eliminate unnecessary substances, so that a strong effect can be obtained. Become.

In addition, since sunlight contains only 3 to 4% of ultraviolet rays and fluorescent lamps contain only a small amount of ultraviolet rays, it works with visible light in order to efficiently use the photocatalyst for indoor applications. A photocatalyst is indispensable, and various devices such as an oxygen defect type and a nitrogen-doped type have been devised as a photocatalyst that works with visible light, and it is used as one of the photocatalyst solutions used in the rubbing protective material of the present invention. Not limited to.

The titanium oxide used in the present invention is natural anatase-type titanium oxide or brookite-type titanium oxide having high photocatalytic activity.

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

The nanocellulose used in the present invention is a cellulosic polymer fiber having an average fiber diameter (D) of 3 nm to 100 nm and a moisturizing solution, and a weight ratio of cellulosic polymer fiber: moisturizing solution = 1: 1 to 1:20. However, the weight ratio is not limited.

In the nanocellulose used in the present invention, the polymers constituting the cellulosic polymer fiber are polysaccharides having a glucan structure, cellulose derived from higher plants, natural cellulose fiber, cellulose derived from animals, cellulose derived from bacteria, and chemicals. At least one to two or more kinds selected from cellulose / nanocellulose, chitin, and chitosan composed of cellulose synthesized in the above, but not limited to.

The rub protection agent of the present invention is, for example, micro-sized fine powder of paper pulp separated and extracted from cellulose fibers, cyclodextrin, glucose, fructose, sucrose, maltose, lactose and glycerin, dipropylene glycol, polyethylene glycol (for example, number). Average molecular weight 120 to 20000), glycolic solvents such as polyglycerin (for example, number average molecular weight 120 to 20000) and butylene glycol, polyhydric alcohols such as xylitol / martitol, polysaccharides such as chondroitin sulfate / hyaluronic acid, Examples thereof include proteins such as collagen, sterol esters such as hydroxydistearate, organic acid salts such as sodium lactate, and diglycerin adducts, and one or a combination of two or more of these may be used. .. Among these, polyhydric alcohols and nanocellulose, which has strong hydrophilicity to the skin, are contained in micro-sized pulp to prevent the moisturizer from locally infiltrating only the sprayed area, and when the hands are rubbed together. It is preferable to spread the moisturizer throughout, and one or more selected from them is preferable.

The seaweed / algae used in the present invention is, for example, at least one kind of powder or liquid of Sargassum horneri or mozuku, but is not limited.

The non-photocatalyst solution to be mixed with the rubbing protective material of the present invention is not limited to one or more such as titanium phosphate, titania phosphate, titanium oxide, divalent metal and tetravalent metal phosphate. Further, a non-photocatalyst solution that is generally manufactured and sold may be used, and is not limited thereto.

The titanium oxide and tungsten oxide used in the rubbing protective material of the present invention may be a photocatalytic solution generally manufactured and sold, and may be one or more, but is not limited.

The rubbing protective material of the present invention is not limited to one or more of titanium oxide, tungsten oxide, strontium titanate, zinc oxide, iron oxide, zirconia, zinc sulfide, cadmium sulfide, mercury sulfide and the like. Further, the photocatalyst solution that is generally manufactured and sold may be used, and is not limited thereto.

The phosphoric acids used in the rub protection material of the present invention are phosphate and calcium phosphate, but phosphoric acids in a photocatalyst solution generally manufactured and sold may be used and are not limited.

The rubbing protective material of the present invention may be applied or sprayed to a human body other than the hand skin, for example, the heel of the foot, the oral cavity, etc., and is not limited to the site of use. However, when it is used in the oral cavity other than the hair and the eyeball, the content of the photocatalyst is preferably 0.004% or less.

The fibers used by applying or spraying the rubbing protective material of the present invention include wood and natural fibers such as plant fibers (cellulose polymer), animal fibers (protein polymers), mineral fibers and chemical fibers such as inorganic fibers, and purified fibers. Fiber (natural polymer), regenerated fiber (natural polymer), semi-synthetic fiber (semi-synthetic polymer), synthetic fiber (synthetic polymer) (hereinafter referred to as fiber) material, and products and products manufactured from them. Yes, but not limited to them.

Examples of the use of the object to which the rubbing protective material of the present invention is applied or sprayed include oral care products such as toothbrushes and interdental brushes and metals such as keys and coins, paper products such as banknotes, newspapers and stationery. Tableware, such as chopsticks and cups, housing-related items, such as door knobs, toilets, bathrooms, bedding, and audio, such as CDs and DVDs, but are not limited thereto. As one of those examples, after applying a rubbing protective material to the disc surface of a CD or DVD in which image blurring or sound modulation occurs, it is possible to view the image or sound without modulation by wiping it off. became.

Furthermore, as shown in [Non-Patent Document 11], unicellular organisms that increase by asexual reproduction repeat infinite proliferation unless there is some kind of trauma that can be said to be an accident, but oxidative decomposition of organic matter by a photocatalyst has no selectivity for decomposition targets. Is well known, and it is naturally required that viruses with or without envelopes be effective regardless of their type. For viruses such as influenza and norovirus, activated oxygen species generated by photocatalytic action suppress the virus activity by oxidatively decomposing the envelope and capsid, which are the outer membranes of the virus. Furthermore, since it has been reported in experiments and the like that the antiviral action occurs on the surface of the photocatalyst and the inactivating action is obtained for the virus that comes into contact with the surface of the photocatalyst in the air, the photocatalyst of the present invention and the nanocellulose rubbing protective material By using, the rubbing action becomes possible.

In addition, as an antibacterial reaction on the bacterial cell wall of copper ions, bacterial cells show high affinity for Cu2 + in the antibacterial reaction on the gram-negative bacterial cell wall and outer membrane, and most of Cu2 + binds to amino acid residues of cell surface proteins. In addition to binding to the outer membrane protein, Cu2 + forms a copper-protein complex and inhibits protein synthesis by binding to the lactamase enzyme. Cu2 + reacts with functional groups with high electron density such as sulfur, nitrogen, and oxygen on the surface layer of bacterial cells to form salts and copper complexes with low solubility. In particular, since enzymes containing -SH groups are present in the respiratory system enzymes, Cu2 + inactivates these -SH groups by oxidizing them and damages cells.

Moreover, as the biosynthesis of the outer membrane major protein and the outer membrane permeation of Cu2 +, the outer membrane major lipoprotein formation is degraded by the first enzyme of signal peptide cleavage by the lipoprotein signal peptidase and by the signal peptide peptidase (protease IV). Degradation of the signal peptide promoted and cleaved by the second enzyme of the above is essential for cells, and it is considered that inhibition of this degrading enzyme causes a bactericidal action of cells. It is considered that Cu2 + is difficult to pass through the Lipid A passage of lipopolysaccharide LPS, so that it is difficult to pass passively through the outer membrane of E. coli. The outer membrane acts as a permeation barrier for relatively large molecules, and when a substance permeates the phospholipid bilayer of the outer membrane, a pollin protein that actively transports it acts to select a metal cation in Escherichia coli. Are OppD, NmpC, and protein P, and even if copper ions form a copper-binding protein on the outer membrane, the formation of the outer membrane is not disrupted. On the other hand, since the amount of copper ions transported to the periplasmic space and PGN layer of Escherichia coli by active transport is considered to be relatively large, a large amount of copper ions are accumulated in the outer membrane and the periplasmic space, and as a result, copper ions are accumulated. Will be heavily spent on the synthetic degradation of the adventitia, the production of copper proteins and the reactions of PGN formation and degradation.

In addition, copper ions and aqueous copper solutions exist as molecular (non-dissociated) and ionic substances, and these ionic substances cannot permeate the phospholipids that make up the cells of microorganisms, whereas they are molecular. The substance permeates the inside of the cell and stops the activity of the gene by breaking the chemical bonds such as enzyme proteins and DNA in the cell of the microorganism, and as a result, exhibits a strong bactericidal effect. The molecular type has a weak instantaneous bactericidal activity, but on the other hand, it exhibits stable bactericidal activity even in an environment where organic substances are present, and this bactericidal activity is maintained for a long period of time, even in an environment where dirt is present around it. Sterilization becomes possible by long-term contact with the target microorganisms.

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 mixed with a photocatalyst solution and used, but as the allowable concentration of the mixed substance, this value is for the case where the substance is present alone in the air, and is exposed to two or more substances. In such cases, it should not be judged only by the permissible concentration of each substance, and if there is no proof that the addition does not hold in reality, the toxicity of two or more substances Is assumed to be added, and it is shown that it is appropriate to judge that the exposure exceeds the permissible concentration when the value of I calculated by the following equation exceeds 1.

In this case, Ci indicates the average exposure concentration of each component, and Ti indicates the allowable concentration of each component. However, the standard for the allowable concentration of harmful substances is recommended by the Japan Society for Occupational Health, with the aim of being used as a guide for preventing health problems of workers due to environmental causes in the workplace.

In addition, copper ionized water and copper aqueous solution can stably maintain the bactericidal effect with strong bactericidal power, and even in a dirty environment where many organic substances are present, the bactericidal effect is continuously exerted, and it is difficult to sterilize. Non-resistant bacteria (heat-resistant bacteria whose resistance increases by forming buds and drug-resistant bacteria for which antibiotics are no longer effective), fungi such as mold and yeast, and viruses (including non-enveloped virus) A revitalizing effect can be expected.

Further, the nm size to μm size fine particle pulp used in the present invention absorbs and mixes liquefied hydrophilic nanocellulose and superhydrophilic photocatalytic solution by taking advantage of the property of being incompatible with non-hydrophilic water. It is well infiltrated in the state, but when applied or sprayed, the fine particles of the pulp are released from the hydrophilic component and act as the original non-hydrophilic pulp fine particles, preventing liquid dripping and when using the skin. A rubbing method is used in which the fine particle pulp is dried while absorbing the water content of the rubbing action of the photocatalyst solution by rubbing with the fingers. That is, non-hydrophilic pulp is a carrier for adsorbing bacteria and viruses that are desired to be decomposed and destroyed, and plays an important role in separating and destroying it by rubbing.

The invention's effect

The rubbing protective material of the present invention is a general disinfectant or disinfectant / antibacterial agent with a pungent odor, and rough hands caused by degreasing that deprives both skin oil and water on the skin surface, which also leads to the growth of pathogenic bacteria. , A super-hydrophilic photocatalyst solution that sterilizes and decomposes bacteria and viruses with strong oxidizing power without using chlorine-based alcohols, which are highly likely to be a hotbed for bacterial growth, was used for the skin and fabric fibers. In this case, a non-hydrophilic pulp fine powder rubbing method is used, and the photocatalyst solution enters the gaps between the skin and fibers, and the bacteria and viruses that adhere to the skin and fibers due to the photocatalyst activity are sterilized and decomposed. Hydrophilic, tasteless, odorless and safe vegetable nanocellulose and non-hydrophilic pulp, sugar or seaweed It is a hand skin rubbing protective material that can obtain the moisturizing / protecting effect and quick-drying property of the hand skin by the same kind and algae, and a fiber rubbing protective material that rubs the fibers. However, indigenous bacteria that always live in humans and prevent the growth of invading bacteria from the outside and good indigenous bacteria that protect healthy skin from ultraviolet rays prevent the growth of bad indigenous bacteria if they are healthy and are the source of infection. However, since infection may occur when the resistance is reduced, even if they are killed by photocatalytic activity, the rubbing protective material that can obtain both rubbing action and moisturizing / protecting action at the same time is related to physical condition. It works without any problems, which enables safer and more stable use.

Titanium oxide, which is one of the photocatalytic solutions used in the present invention, is a harmless component, but it is a perfect measure to prevent health problems, etc. against airborne fine powder at production sites and factories. As a matter of course, there are no reports of accidents, and the rubbing protective material can be safely used for infiltration of the skin of the hands into the skin membrane, indoor space, liquid application such as fiber application, and spraying.

Furthermore, in [Non-Patent Document 3], the virus inactivation by photocatalytic reaction of titanium oxide non-woven fabric was also confirmed to be effective in some development experiments, and a definitive report is under consideration. However, the liquefied rubbing protective material of the present invention is applied or sprayed on the surface of clothing, masks, etc., and the rubbing effect is transition-fixed by adhering it to fingers, etc., and by photocatalytic action. It can be expected to suppress bacteria and viruses.

In addition, copper ionized water and an aqueous solution of copper, which is a copper oxide, are mixed in the photocatalyst solution because antibacterial and bactericidal power can be obtained regardless of the environment in which they are used, such as ultraviolet rays and visible light that promote activation of the photocatalyst solution. By using it together, the bactericidal and antibacterial action of copper ionized water and copper aqueous solution can be obtained even in an environment where the activity of the photocatalyst cannot be obtained.

Furthermore, it is known that the photocatalytic activity of tungsten oxide alone is extremely low, and it is known that it is useful as a visible light responsive photocatalytic material by using a copper compound or copper ion as a catalytic activity accelerator. Can also be an effective visible light responsive photocatalytic material, especially in combination with copper compounds. A method for combining a copper compound and tungsten oxide is shown in [Patent Document 8]. For example, CuO powder is mixed in an amount of about 1 to 5% by mass with tungsten oxide powder, or copper is mixed with tungsten oxide powder. A polar solvent solution containing a divalent salt (copper chloride, copper acetate, copper sulfate, copper nitrate, etc.) is added, mixed, dried, and then fired at a temperature of about 500 to 600 ° C. to form copper ions on the surface of tungsten oxide. There is a method of carrying it. As described above, supporting a copper compound also serves as a catalytic activator for tungsten oxide. However, in the present invention, copper ionized water and a copper aqueous solution are contained, and other than the catalytic activity of titanium oxide and tungsten oxide, it is shown in [0026]. As described above, antibacterial and antivirus by copper ionized water and copper aqueous solution became possible.

In addition, nm-sized to μm-sized fine particle pulp that takes advantage of the non-hydrophilicity that is a characteristic of pulp is infiltrated in the liquid when mixed with liquefied hydrophilic nanocellulose or super-hydrophilic photocatalyst solution. It prevents dripping, and the fine particles of the pulp are released from the hydrophilic component by application or spraying, and when the rubbing protective material attached to the hand skin is rubbed with the fingers, the non-hydrophilic fine particle pulp is coated with the photocatalyst solution component and becomes a photocatalyst solution. Since it is not necessary to wipe off the rubbing protective material with a fiber such as a handkerchief or a towel by the rubbing method of absorbing and drying the rubbing action of the above, it can be used anywhere in terms of hygiene. Of course, since the pulp fine particles are nm size to μm size, the pulp components cannot be visible even if they are rubbed together, but non-hydrophilic pulp adsorbs bacteria and viruses that want to be decomposed and destroyed. It becomes an antibacterial and anti-virus by separating and destroying it by rubbing the skin and fibers.

It is a figure which showed the antiviral effect by a photocatalytic reaction. It is a figure which showed the mechanism of virus inactivation by a photocatalytic reaction. It is a figure which showed the state which the photocatalytic titanium oxide adhered to the space of a fiber, and the state which the pulp particle adhered to a fiber. It is a figure which showed the mechanism which kills Escherichia coli with a photocatalyst.

It is already known that a photocatalyst acts by irradiation with ultraviolet rays from sunlight, and the reaction speed of the photocatalyst is light intensity × absorption intensity × reaction efficiency. At present, as shown in [Patent Document 6], various developments have been made even for the visible light responsive type, and the photocatalytic action is recognized. As one of the photocatalytic materials among them, tungsten oxide is known as a visible responsive photocatalyst that expresses photocatalytic activity by visible light, but it is self-reduced by electrons excited by light irradiation. As the valence of tungsten ions changes from hexavalent to pentavalent, the photocatalytic activity decreases, which makes it difficult to completely decompose volatile organic compounds. As a method for highly activating tungsten oxide, as described in [Non-Patent Document 2], considering the effect of the addition of plant ash produced from plants on the decomposition performance of volatile organic compounds of tungsten oxide, basil as plant ash. As a result of a photocatalytic activity experiment using acetaldehyde after burning the leaves and mixing them with tungsten oxide powder, we succeeded in complete decomposition of acetaldehyde 4 hours after irradiation with visible light, which was difficult with tungsten oxide alone, and added basil ash. When the amount was optimized, 2.5 wt% was the most active, and as a result of powder X-ray diffraction of the main component of basil ash to clarify the reason, mainly Ca. Since it is (OH) ₂ , MgO, and KHCO ₃ , as a result of adding each to tungsten oxide, MgO has low activity, both Ca (OH) ₂ and KHCO ₃ have high activity, and acetaldehyde has been completely decomposed. , KHCO ₃ or Ca (OH) ₂ did not show high activation, demonstrating the need for both components. Therefore, it is presumed that Ca (OH) ₂ and KHCO ₃ contained in the plant ash base-treated the surface of tungsten oxide to form a thin layer such as calcium tungstate or potassium tungstate, which led to an improvement in photocatalytic activity. From the verification report, we used tungsten oxide with vegetable ash added to the rubbing protective material to further activate the photocatalytic effect. However, the plants used for the added plant ash are under consideration in experiments with basil leaves and southern leaves, and the type of plant ash is not limited.

Further, as shown in [Non-Patent Document 8], a material has been developed in which the rubbing effect of a photocatalyst is effective even with visible light in a room. The sizes of bacteria and viruses that cause infectious diseases are 1 to 10 μm for bacteria and 0.02 to 0.2 μm for viruses, and there is a big difference. Bacteria are unicellular microorganisms that self-proliferate, and viruses have a simple structure of nucleic acids and a membrane that encloses them, as well as fibrous substances called surface fibers that are mainly composed of glycoproteins such as mimivirus. It parasitizes other organisms (rental dormitories) including it and self-propagates. Hemaglutinin (HA), a protein on the surface of these viruses, proliferates in the body by repeatedly adsorbing, invading, unshelling, synthesizing, maturing, and releasing into human body (host) cells. Since the protein is denatured, it cannot be adsorbed and does not invade the human body (host) and proliferate nucleic acid. Therefore, at this stage, the virus is inactivated (infectious state) by the photocatalytic reaction. 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 contained therein, and finally completely decomposes the organic matter derived from the virus. In addition to this, the strong oxidative decomposition power of the photocatalyst not only inactivates bacteria, but also completely decomposes them as organic substances, even for bacteria that are 10 times larger than viruses. For example, when the inactivation effect of a photocatalytic reaction on drug-resistant bacteria was investigated, the results decreased to near the detection limit within 10 minutes to 2 hours, and the results were obtained by a visible light responsive photocatalyst. , Showed the importance of utilizing photocatalysts in indoor environments where sunlight does not reach. As described above, the reaction mechanism of the photocatalyst is different from other eradication / antibacterial / antiviral agents, and as in the case of Escherichia coli shown in FIG. As a result, it leads to difficulty in forming resistant bacteria. Therefore, the coating protective material of the present invention using a photocatalytic solution is effective against the rubbing action and is a photocatalytic solution on the skin by nanocellulose, pulp and saccharides. Enables vapor deposition and moisturizing protection.

In addition, the virus droplets may adhere to the floor indoors and outdoors and be infected by the soles of the feet and shoes. The powder retains its antibacterial properties semi-permanently against the floor material, so that it exhibits sterility against viruses without losing its sterility. As a photocatalyst, it is already widely used in tiles, walls, and glass of houses, and it has an antifouling effect against bacteria-derived stains. However, the number of bacteria and the amount of ammonia are suppressed and maintained by 90% or more, and there is a rubbing effect. For the photocatalytic glass, in addition to the organic matter decomposition activity using copper oxide, it shows visible light responsiveness and high antiviral property. .. In this way, the photocatalytic action of the photocatalyst is recognized even in the indoor space, and the photocatalytic activity can be obtained by spraying or applying the photocatalytic protective material not only to the skin of the hands but also to the walls and bedding in the room. Bedding.

In addition, the particle shape of titanium oxide is made into a golden flat sugar type, etc., and then apatite, which is a substance constituting bones and teeth and has excellent biocompatibility and has no photocatalytic activity, is attached to the surface like a golden flat sugar vine. In this gold-flat sugar type particle, titanium oxide particles are immersed in a pseudo-body fluid having a composition similar to that of human body fluid, and by keeping the temperature close to the body temperature, apatite is naturally formed so that bones and teeth are formed on the surface of titanium oxide. By using the photocatalytic solution produced and prepared in, the rubbing protective material can be used even in an environment of visible light.

While general sterilizing / antibacterial agents and bactericidal agents release medicinal components by elution to prevent or kill the growth of bacteria, photocatalytic reactions occur on the surface, and the larger the surface area, the more efficient it is. A highly activated titanium photocatalyst of ultrafine particles with a small particle size and a large surface area has also been developed, focusing on the improvement of the photocatalyst. As a result, a rubbing action can be obtained by efficiently decomposing the chemical substances that come into contact with it.

In addition, the highly reactive electrophilic addition reaction (oxidation reaction that robs electrons) can instantly obtain a high bactericidal effect in a clean environment such as a laboratory or laboratory, but there are many organic substances in actual sites. In an environment with severe stains, organic substances may react quickly and the bactericidal activity may be lost. As a result, the bactericidal effect against various microorganisms may not be sufficiently exerted or the bactericidal treatment may not be obtained. It is useful to use copper ionized water or an aqueous solution of copper, which has a long-term bactericidal activity rather than a momentary bactericidal activity, because it may cause an infectious disease due to a secondary infection.

Furthermore, FIG. 1 shows a decrease in the virus during the photocatalytic reaction with only ultraviolet light and titanium oxide, but the size of the virus is an order of magnitude smaller than that of the bacterium, and it is easy for the photocatalyst to kill the virus smaller than the bacterium. However, since it takes 1 to 2 minutes to decompose the virus with ultraviolet rays of 0.4 mW / cm ² , it may take more time indoors. For these reasons, by using titanium oxide, tungsten oxide, and phosphoric acids as the photocatalyst solution, it becomes an auxiliary role that is required to have the same effect as ultraviolet rays even in indoor visible light, and the rubbing protective material is used in indoor and outdoor places. Can be used without limitation.

In addition, various compounds such as toluene, xylene, ethylbenzene, formaldehyde, acetaldehyde, and ethyl acetate are examples of VOCs that volatilize relatively easily in air at room temperature, and these are used as raw materials and additives for solvent or plastic synthesis. It is a typical environmental chemical substance related to various industrial activities and daily life, and the regulated value is 300 μg to 3000 μg per 1 m ³ . The effect of the photocatalyst under this condition is that 300 μg / m ³ has a concentration of 2 ppm, for example, when calculated with formaldehyde, the molecular weight is 30 g per mole, and assuming an 8 tatami room (30 m ³ ), formaldehyde is in 30 m ³ . At 2 ppm, the number of particles is 10 to the 21st power. The reaction formula for decomposition is HCHO + H ₂ O + 4h ⁺ → CO ₂ + 4H ⁺ , and 4 holes (light) are required for formaldehyde to decompose into carbon dioxide, and the efficiency is 30%. When applied to the reaction formula, it is 10 to the 22nd power of light that can decompose 2ppm formaldehyde in the air of 8 tatami mats. In the case of indoor light only, the number of lights is 1 μW / cm ² , and the number of lights is 10 to the 16th power per 1 m ³ 4 per second. From these figures, the time required for decomposition is ^{10 22/10 17} = 105 seconds, which is about 1 day, but the above was calculated using formaldehyde in the room. Furthermore, when applied to the calculation formula with toluene, C ₆ H ₅ CH ₃ + 14H ₂ O + 36h ⁺ → 7CO ₂ + 36H ⁺ , the efficiency of the photocatalytic reaction is 1/10 times that of formaldehyde, and the number of light required for decomposition is 30. Although it doubles, if the ultraviolet rays from the window are included, formaldehyde can be decomposed into photocatalysts in 20 minutes and toluene in 10 hours. Considering these, the light in the room alone is not effective, but it enters from the outside. Creating an environment where the coming ultraviolet rays can be used is also a consideration.

この時、環境水中にカルシウムイオンが存在すると、炭酸カルシウムが沈殿する。

また，Ｂａｃｉｌｌｕｓ ｓｐｈａｅｒｉｃｕｓのような尿素分解菌は、尿素をアンモニアと炭酸に分解する。

その際に炭酸イオンが生じ、Ｈ２ＣＯ３⇔ＨＣＯ３^－＋Ｈ＋
環境水中にカルシウムイオンが存在した場合、炭酸カルシウムを沈殿させることが知られている。

タンパクやアミノ酸を分解することにより、アンモニアを生産するバクテリアも同じように炭酸カルシウムを沈殿させることがあり、硫酸還元菌も以下の反応により、炭酸カルシウムを沈殿させることが報告されている。

Now that cyanobacteria and the like are prevalent, the mechanism by which bacteria form carbonates is known, although not completely in some species, such as green sulfur bacteria and red sulfur. Photosynthetic bacteria such as bacteria and cyanobacteria consume carbon dioxide and perform photosynthesis. At that time, if bicarbonate ion contained in environmental water is used as a carbon source, OH- is generated and the pH rises, but HCO3 ^- → CO2 + OH- ^, each of which is shown in the formula below.
When this OH- further reacts with bicarbonate ion, carbonate ion is generated.

At this time, if calcium ions are present in the environmental water, calcium carbonate precipitates.

In addition, urea-degrading bacteria such as Bacillus phaericus decompose urea into ammonia and carbonic acid.

At that time, carbonate ions are generated, and ^{H2CO3⇔HCO3-} + H +
It is known that calcium carbonate is precipitated when calcium ions are present in the environmental water.

It has been reported that bacteria that produce ammonia may also precipitate calcium carbonate by decomposing proteins and amino acids, and sulfate-reducing bacteria also precipitate calcium carbonate by the following reaction.

In addition, there are various types of carbonates formed by bacteria, even if they are called carbonates. For example, calcium carbonate (CaCO3), which is calcite, magnesium carbonate (MgCO3), which is used as an abrasive and anti-slip, and so on. There are sidelite (FeCO3), which is a rhombic iron ore, and calcium carbonate (CaCO3) also includes calcite (calcite), aragonite (calcite), and vatelite, which have the same chemical formula but different crystal structures. It is said that most of the carbonate rocks existing on the earth are composed of calcite, aragonite, and dolomite (CaMg (CO3) 2), which is a calcium carbonate containing magnesium, and which carbonic acid is inorganic in the environment. Since it has been clarified that whether or not a salt species is formed is determined by the salt content, temperature, various ion concentrations, etc., these can also be used together with the effectiveness of the photocatalyst solution.

Furthermore, copper reacts with water to generate active oxygen molecular species with strong oxidizing power, and although there are strengths and weaknesses in antibacterial performance depending on the bacterial species, it decomposes molecules such as bacteria, and as an antibacterial effect demonstrated in antibacterial tests. In addition to Legionella, cryptospolidium, and O-157, viruses that come into contact with copper also inactivate their infectivity. In addition, copper is contained in the human body in an amount of 70 to 100 mg, which is an essential nutritional component for health and is safe enough to be added to powdered milk of newborns. Therefore, the copper ionized water or copper aqueous solution used in the present invention is used. It is harmless even if a rubbing protective agent containing copper is used on the human body, and antibacterial and antiviral effects can be obtained. -Has a deodorizing effect and can be used efficiently and safely.

In addition, the virus has a nucleic acid having a capsid in the shell of the protein, but since the virus is inactivated by destroying a part of the protein, it is one of the virus membrane proteins due to the strong oxidizing and reducing power of the photocatalyst. It is important to damage the area and reduce its infectivity. The photocatalytic solution is activated by ultraviolet rays or visible light, which makes it impossible for the virus to be adsorbed to the cells and loses the ability to infect the cells to the host. It is also possible to activate it.

Furthermore, by mixing tungsten oxide and phosphoric acids with the photocatalytic solution of the rubbing protective material, the number of fluorescent light sources and the like increases, but considering the environment in which it is used, copper ion water and copper aqueous solution have antibacterial and antiviral effects. It does not necessarily require a strong light source. However, when a non-photocatalyst solution is used, there is no need for a light source, and the effect is similar to that of a photocatalyst.

On the other hand, lignin in wood is usually one of the main components occupying 20 to 35% of woody biomass, and is chemically a compound having an aromatic nucleus (benzene ring) bonded to it and becomes huge. The abundance is large, and it is said to be the second most abundant organic compound on the ground. The word lignin has its origin in the Latin word lignum, which means wood, and has the meaning of "wooden element" as the component that makes wood woody. When lignin is removed from wood, it loses its physical properties as wood and is a fiber. The paper pulp remains, which is a process called liquefaction performed in the paper industry. The remaining lignin from which the pulp has been removed is incinerated and used as a heat source. It is difficult to remove the degree of cooking of pulp, that is, the content of lignin, and it is recognized that the highest value of strength exists in an appropriate amount, and lignin binds to cellulose or hemicellulose to some extent to form an intermediate layer or a primary layer. It is made of hemicellulose with a fibrous structure such as. Therefore, when the amount of lignin is large, the swelling of highly hydrophilic hemicellulose is hindered, and even if the hemicellulose is beaten, neither fibrillation nor plasticity progresses, so that the fiber bond is weak. It is well known in the paper manufacturing industry that when lignin in pulp is removed without disintegrating cellulose or hemicellulose, the strength increases as the lignin content decreases, as in the case of delignin due to chlorine dioxide or the like. ..

In addition, nanocellulose is milky and viscous, and because it has an emulsion-like role and is also water-soluble, it easily infiltrates the skin of the hands and has a great effect as a moisturizing / protective material. It is also accepted in the test. Moreover, the compatibility of wood-derived nanocellulose with pulp is very good and effective.

Furthermore, gels can be prepared by using cellulose single nanofibers, and if the rubbing protective material is a liquid, it is expected to have the effect of improving adhesion by spraying, etc., and if it is filled in a spray container, it can be used even if it is turned upside down. It is effective and overwhelmingly cheap in terms of price.

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, and for example, cellulosic derived from higher plants, for example, wood fiber such as cedar. Natural cellulose fibers (pulp fibers) such as (wood pulp such as coniferous trees and broadleaf trees), cellulose derived from animals, cellulose derived from bacteria, cellulose nanocellulose such as chemically synthesized cellulose (regenerated cellulose; including derivatives), Examples include chitin and chitosan. The cellulose may be high-purity cellulose having a high α-cellulose content, for example, an α-cellulose content of about 70 to 100 wt%, depending on the intended use. The cellulose may be used alone or in combination of two or more, and among the cellulosic polymers, wood fibers (wood pulp such as conifers and hardwoods) and seed hair fibers such as cotton linters are preferable.

Microfibrillation of raw material fibers can be performed by conventional methods such as beating and homogenizing the raw material fibers, and nanocellulose is used to make the cellulose fibers finer to the width of the nm order. Cellulose microfibrils can be loosened into fiber units of one to several tens.

In addition, the general use of pulp is often on paper, which can be said to be one reason that the pulp is light and can maintain a certain strength. When the pulp is made into fine powder and rubbed with the fingertips, it enters the fingerprint and even if the fingertips are moved with each other, the differentials of the pulp fine powder collide with each other, and the fingertips have resistance enough to prevent slipping. For fine pulp, nanocellulose or a photocatalyst solution is rubbed against the keratin of the skin by rubbing the fingers, and a film is applied to perform the rubbing action, and at the same time, the moisturizing component of nanocellulose is also infiltrated as a rubbing method using pulp fine particles. Moreover, when the rubbing protective material is filled in a spray bottle or the like in the form of an aqueous solution, the pulp fine particles floating from the upper part to the middle part are easily sucked by the spray pump, and are always applied to the hand skin at the time of spraying to have a friction effect. It will be obtained stably.

Further, by adding the pulp fine powder, the action of cellulase on the rubbing performance of the rubbing protective material, particularly the secondary rubbing performance, is improved. The pulp particles are at least partially broken by compression obtained by mechanical pressure, then preferably in a granulated form, preferably containing cellulose, formed as a particularly microscopic substance, to stimulate the action of cellulase on the rubbing performance. However, as a matter of course, it is suitable that the size of the pulp particles is small, and the pulp particles of the rubbing protective material should be μm or less.

Nanocellulose used as a protective material for rubbing is a basic skeletal substance of all plants, and is obtained by refining cellulose fibers. Generally, it is said that the size of the fibers is 100 nm or less and the aspect ratio is 100 or more. It has been. 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 when the pulp with a width of about 20 μm taken out from the chip is observed at 2,500 times, this pulp is a cellulose molecular chain. In the case of cellulose nanofibers having a structure hierarchically constructed with microfibrils and fibrils and having a width of 10 nm, it refers to a state in which several microfibrils are aggregated. It is a 1/1000 downsizing from pulp fibers to cellulose nanofibers, and in the electron microscope (SEM) photograph, the surface of the pulp fibers is observed, and many fibers made up of cellulose nanofibers are gathered together. I understand the folds. In carbon nanotubes, which are typical nanotech materials, multiple fibers are condensed by van der Waals force, but in cellulose nanofibers, about 6 × 6 cellulose molecules gather to form nanocellulose with a diameter of 3 to 4 nm. In the case, the bonds between cellulose molecules are mainly due to hydrogen bonds, and as the thickness increases from microfibrils to fibrils, the van der Waals force and the adhesive effect of lignin become effective. In the case of carbon nanotubes, if the dispersed nanotubes are left alone, they will stick to each other and become unusable, but in the case of cellulose nanofibers, even if they are defibrated and placed in water, they will not adhere immediately. Processing and utilization technology has been developed all over the world on how to regularly arrange cellulose nanofibers formed together with the technology for loosening and refining fibers, or how to disperse and mix them with other materials. Nano-ization is inevitable for various materials that are generally used, and it is also necessary to consider baking soda salt and the like mixed in soap as the rubbing protective material.

Wood consists of 50% carbon, 6% hydrogen, and 44% enzyme, and consists of three main components: cellulose / hemicellulose, which is a polysaccharide such as glucose, and lignin, which has a benzene ring and has a hydrophobic and complicated structure. Cellulose microfibrils, which occupy about 50% or more of the main component, further aggregate to form a bundle of fibrils, forming a plant fiber having a width of 0.02 to 0.04 mm and a length of several mm. The plant fibers are firmly adhered to each other by lignin, and the fibers forming the plant fiber aggregate are pulp, which is a raw material for paper. Plant fibers have a structure like a minute pipe with a hollow center, and water absorbed from the roots is sent through this pipe to the leaves at the tip of the tree against gravity, absorbs carbon dioxide, photosynthesizes, and releases oxygen. However, the cell wall of the tree is a cellulose microfibril unit or an assembly thereof due to the hydrophobicity of lignin and the cellulose microfibrils which are high-strength nanofibers such as reinforcing bars, and the amorphous hemicellulose component which fills the gap between the cellulose microfibrils and lignin. It is a plant-derived nanomaterial separated and dispersed to a width of several tens of nm or less as a body. In addition to paper products, cellulose is also used in foods, cosmetics and pharmaceuticals, and is widely used as a molding agent for tablets containing active ingredients to disintegrate in the body.

In addition, various pretreatment methods for pulp and cellulose fibers and many excellent properties have been found, and with the development of nanotechnology, they are attracting attention as nanomaterials derived from biomass. Rod-shaped or spindle-shaped cellulose nanocrystals (CNC or nanocrystalline cellulose NCC) with a length of 150 nm or less and fibrous cellulose nanofibers (or cellulose nanofibril CNF, or nanofibrillated cellulose) containing micron-level lengths. It is roughly divided into NFC).

The outline of the treatment conditions for the finely divided fibers and microfibrillated cellulose obtained by treating the aqueous dispersion of wood pulp is as follows: raw material slurry concentration 4 to 7%, orifice diameter 0.4 to 6 mm, treatment pressure 34,450. The fiber diameter is ~ 55,120 kPa (oriental passage line speed is about 750 km / h) and the number of times of passage through the orifice is 1 to 80 times. By this treatment, wood pulp having a fiber diameter of 6 to 100 μm and a fiber length of 1 to 4 mm is made finer, and the fiber diameter is 0. MFCs with a fiber length of 02 to 0.06 μm (20 to 60 nm) and a fiber length of several μm (thousands of nm) can be obtained, but it is known that it depends on the degree of fibrillation of cellulose. It has been reported that the effect of increasing the air permeability becomes greater as the cellulose is fibrillated.

The nanocellulose used for the rubbing protective material is not particularly limited, but 1.6% and 6% liquids were provided by the National Forest Research Institute, and experiments were repeated from 2016 as examples.

Further, as an example of the composition of the components of the rubbing protective material, 15% of pulp particles, 25% of nanocellulose, 2.5% of photocatalytic titanium oxide, and 9% of sugar were dissolved in 30% of purified water at 70 to 80 ° C. After the 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 rubbing protective materials. However, it is only an experimental numerical setting, and is not limited to these, and is shown as one of the examples. Of course, at the time of finishing, it is a numerical value for making a solution by filtering, and an error of about% occurs.

As shown in FIG. 3, for fabric fibers such as masks and handkerchiefs, titanium oxide, which is a photocatalytic solution, has a horrifying surface with irregularities and a large surface area, and a large amount of adsorption, rather than a dense and smooth surface with a small surface precision. Therefore, the rubbing action becomes effective by applying and spraying the rubbing protective material.

On the other hand, the photocatalytic titanium oxide is made of Vistrateer H2: anatase ^- type titanium oxide, which is a titanium oxide coating material manufactured by Nippon Soda, and is the photocatalyst of the overwhelming majority of coating agents manufactured by Ishihara Sangyo Co., Ltd. Is to mix the thickening of nanocellulose. Moreover, the strong acidity of the rubbing protective material is physically and chemically immobilized at the same time regardless of whether it is hand-washed or wiped off with water, and the photocatalytic activity causes bacteria and viruses adhering to the skin and fibers to react and sterilize. -In addition to being easily removed by the rubbing action of decomposition, it can be expected to have a rubbing effect that keeps the environment and hygiene where new bacteria and viruses are less likely to adhere and multiply. The present invention is in the process of being tested because it is necessary to wait for a large amount of clinical trial data.

In addition, if the photocatalyst is an organic substance, it is a non-selective reaction that eventually decomposes carbon dioxide into water regardless of the partner. For this reason, for example, highly hydrophilic photocatalytic nanocellulose detergents and additives that have been transitioned to and immobilized on laundry clothes of [Patent Document 7] do not necessarily require a binder when irradiated with light, ultraviolet rays, or visible light. It was found that when the photocatalyst permeates, bactericidal activity is generated, and it is possible by not creating the cause of the outbreak of bacteria. Generally, germs 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 osloensis bacteria adhere to and multiply on the laundry, and then water and moisture The photocatalyst nanocellulose detergent and additives of [Patent Document 7] are one option to suppress the odor of so-called rags, which is produced by using sebum as a nutrient to produce something like feces. Is preferably mixed with a ready-made detergent and washed. However, since germs in the washing machine may cause the growth of germs even immediately after washing, they can be sterilized by spraying or applying a photocatalyst solution or a rubbing protective material.

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

Further, even if a commercially available photocatalytic solution known as a method of using titanium oxide in contact with fibers, paper, plastics, etc. as a rubbing protective material is used, the decomposition reaction of the base material due to the photocatalytic reaction is delayed or If it takes only a short time, it will be saturated with the concentration required for removing stains and can be prevented. This is a method of infiltrating the inside and surface of the material, and in order to allow the liquid rubbing protective material to enter the gaps between the fibers, we will also explain that it is possible to calculate visible light and ultraviolet rays in addition to LED lights. .. Visible light visibie (v) and ultraviolet Ultraviolet (UV) light are waves that travel while repeating electric and magnetic fields like X-rays, microwaves, or radio waves, that is, electromagnetic waves. Although no color difference can be seen except in visible light, it has a wavelength wavenght (λ) and a frequency fluoride (ν), and the unit is expressed in meters (m) depending on the wavelength, and the substance is an electron in relation to its chemical structure. It can be calculated that the visible light is absorbed from the ultraviolet rays according to the transition. Thereby, there is an ultraviolet-visible absorbance measurement method. It utilizes the absorption of light accompanying electronic transitions, and is a method for measuring light ultraviolet rays and visible light having a wavelength of usually 200 nm to 800 nm. Assuming that the light shown in FIG. 10 passes through a layer of thick fabric fiber ι, the intensity of the incident light is Io and the intensity of the transmitted light is I, and the ratio of the two is (I). / Io) is the transmittance t, and this is the 100% transmittance T.

Further, the common logarithm of the reciprocal (l / t) of the transmittance t is the absorbance A (absorbance) A = -Iogt = 2-Iog. The absorbance A is proportional to the sample concentration, which is Beer's law. Absorbance A is expressed as being proportional to the concentration and layer length of the sample solution, which is A = RC ・ ι according to Lambert-Beer's law, R is a proportionality constant, and C ・ ι is the concentration and layer length, respectively. .. C is expressed as moI / L, R is expressed as ε, and the molar extinction coefficient molarabsorbitivity A = ε, c, ι corresponds to the absorbance ε when the sample solution concentration is 1 mol / L, which is unique to the substance under the same measurement conditions. It becomes a value. Also, c is% (w /

This corresponds to the absorbance of the sample solution having a concentration of 1% (w / v) in the specific absorbance specific support.

This value is also a value peculiar to the substance, and using the indication value of the drug 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 Xmol / L. The percent concentration is X, M / _10% (w / v).

In addition, when titanium oxide is irradiated with ultraviolet rays, radicals having strong oxidizing power are generated, and the effect of oxidizing / decomposing organic compounds (for example, dirt / malodorous gas) and rubbing inorganic compounds (for example, NOx / NH ₃ ) is exhibited. Therefore, it is being applied to environmental purification. Although it can exhibit excellent photocatalytic activity under sunlight irradiation, the amount of ultraviolet rays contained in the light source of incandescent lamps, fluorescent lamps, etc. is as small as about 4%, and it is possible to exhibit sufficient photocatalytic activity with such a light source. Can not. However, as is known today for apatite-coated titanium dioxide, in addition to visible light-responsive tungsten oxide and phosphoric acids, copper ionized water and copper aqueous solution can be used to prevent harmful organic substances, odors and molds even in the absence of light. It is also possible to decompose substances such as viruses and bacteria and perform a rubbing action.

Furthermore, when titanium oxide is irradiated with ultraviolet light, two types of reactions, a "photo-induced decomposition reaction" and a "photo-induced hydrophilization reaction", proceed on the surface thereof. These photocatalytic reactions proceed from the place where the electrons constituting titanium oxide are excited, and since the anatase-type titanium oxide bandgap is 3.2 eV, it is irradiated with ultraviolet light having a wavelength of 380 nm or less. Then, the electrons are excited to the conductor, and holes (holes, h ⁺ ), which are shells of electrons, are generated in the valence band. The generated holes and electrons can be efficiently diffused into titanium oxide, and the photocatalytic reaction proceeds together with oxygen and water existing in the reaction place such as air or water. The feature of this photocatalytic reaction is that it is irradiated with light that can excite titanium oxide, even if it is faint light. In the case of dirt adhering to cloth or the like, or for the purpose of promoting the effect in a short time of a few minutes of rubbing, holes / electron pairs are continuously generated. Molecules adsorbed on the surface of titanium oxide undergo oxidative decomposition by these continuously generated electrons and holes, and the stains intended for NOx decomposition are oxidized by the antifouling effect aiming at the antifouling effect by utilizing this photoinduced decomposition reaction. Since it is disassembled, it does not get dirty. In this way, the titanium oxide photocatalyst, which can decompose stains and has a great effect on keeping the appearance clean, not only has a wide antibacterial spectrum against bacteria, but also has a very wide range against other microorganisms. This is thought to be because titanium oxide itself is not an antibacterial agent. While other antibacterial agents themselves have the effect of killing bacteria and suppressing their growth, in the case of titanium oxide, titanium oxide itself is not an antibacterial agent and is produced by photoexcitation. An electron-hole pair, or an active species derived from it, attacks the bacterium and imparts antibacterial activity. Titanium oxide itself is a photocatalyst and is considered to be a factor with a wide range of antimicrobial activity. It was also found that the photocatalytic reaction and the antibacterial effect of copper and silver ions are synergistically obtained today in order to obtain the antibacterial effect even under weak ultraviolet light such as indoor light. Therefore, an antibacterial effect can be obtained against copper and silver resistant bacteria even under weak light, which is also one of the characteristics of the antibacterial effect. Furthermore, since the decomposition of organic matter from holes and electron pairs generated by photoexcitation is the driving force of the antibacterial effect, if light is irradiated even after sterilization, the decomposition of organic matter continues and the sterilized dead bacteria are decomposed. go. As described above, the antibacterial effect of the titanium oxide photocatalytic reaction has characteristics that other antibacterial agents do not have, and as an example, it has been commercialized as an air purifier for air purification.

Titanium oxide has the same characteristics as titanium oxide, but has a bandgap energy of about 2.8 eV (about 460 nm), so it is expected to be a visible light responsive photocatalyst. It is inferior in oxidizing ability because it is more base than. Therefore, the surface activity is improved by surface modification with noble metals and other semiconductors, alloying with various metals, and improvement of photocatalytic properties by nanotube structure, etc., and the photocatalytic properties of tungsten oxide, which has the potential to be useful as a photocatalyst, are improved. An efficient photocatalyst is obtained by using an oxide surface modification with a small amount of copper as a co-catalyst.

Further, in the rubbing protective material, nano-sized fine particles sneak into bacteria, viruses, etc. when rubbing fingers or the like with a photocatalytic solution, enabling a dramatic rubbing action. However, although it acts as a rubbing agent for bacteria and viruses during rubbing, wear on the skin and mucous membranes 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 details of the toxicity and harmlessness of the photocatalyst are already known, and the rubbing protective material is manufactured within that range. It can be said that the safety is proved that the moss and algae that thrive in the area are killed and do not affect goldfish and tropical fish. On the other hand, photocatalysts are generally fixed objects such as walls and have been considered to be effective for solid objects. Therefore, the same effect can be obtained with the rubbing protective material of the present invention.

A photocatalytic solution typified by titanium oxide is physically a kind of photocatalytic substance. Normally, when it is exposed to light without conducting electricity, it becomes conductive and absorbs light to become a catalyst. Since the solution is nano-micro particles, the amount of adsorption is large and the effect is great, and a coating of the rubbing protective material is formed on the skin and fibers that are part of the human body. The coating action continues.

Furthermore, there is no candidate other than photocatalyst as a safe and harmless sterilization technology that kills bacteria that antibiotics do not work on, and photocatalysts have been tried in many hospital operating rooms and their effects have been demonstrated. Since then, development into various product fields has progressed, and in that sense, health care technology is the beginning of the application of current photocatalysts, and photocatalytic decomposition of many compounds such as artificial female hormones used for oral contraceptives has been attempted. Since it is known that female hormone activity can be completely reduced to zero, we also consider non-medicinal products as a protective material for rubbing.

However, even assuming that the photocatalyst is ineffective or difficult to achieve in a short time, it is a general practice to wash the hands with water regularly for several minutes to several hours, but use a rubbing protective material. The rubbing effect of the coated photocatalyst is maintained even if it is not used each time. However, considering the importance of moisturizing and protecting, using a rubbing protective material after washing with water will result in moisturizing and protecting the skin of the hands, as well as using more photocatalyst to exert physical and chemical stimuli. It also becomes.

When the photocatalytic solution is kneaded into the hands and fibers, it is decomposed by the photocatalytic action, so it was avoided to apply the hands and fibers other than the substrate. Preventive agents or auxiliary agents that can be used for fibers are also solved by using known products. In addition, when used for a short period of time, in addition to the reaction rate and decomposition rate of the photocatalyst, the moisturizing and protective structure that prevents rough skin when contacting the hands with nanocellulose, non-hydrophilic pulp fine particles and sugars, etc. Is also added, so it is possible to apply it to the skin.

On the other hand, the rubbing ability of saccharides is related to the affinity of saccharides. For example, sugar whose antibacterial properties are known is composed of sucrose, which is two types of glucose (glucose) and fructose (fructose), and the main components are carbon and hydrogen, and the main components are carbon, hydrogen, and oxygen, which are oil components. Since similar ingredients are easily mixed, the sugar component is closer to oil than the skin, so this phenomenon occurs, but it works effectively because it is compatible with water, and there is no worry of rough hands. .. In addition, sugar has a much smaller molecular weight than cellulose, has eight hydroxyl groups, dissolves well in water, and has various chemical functions such as giving various derivatives with altered small parts in the molecule of the compound. Since clinical results have shown that it has excellent antibacterial and antiseptic effects and cell recovery effects, it can be expected to play a role in assisting the photocatalyst's rubbing effect in places where visible light illuminance is extremely low by mixing it with a rubbing protective material.

Sargassum horneri is one of the seaweeds belonging to brown algae, and similar species include Sargassum horneri. Since it is 5 cm and has strong vitality, it is distributed all over Japan and overseas, and the shape of leaves varies from region to region. Akamoku is characterized by its strong stickiness, and this viscous substance is fucoidan, which is one of the sulfate 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 Chinese herbal medicine for a long time, but 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, as a result of freezing and drying mozuku from Shima-cho and Itoshima-cho, Fukuoka, and Kumejima, Okinawa, which were compared with Akamoku collected in Munakata City, Fukuoka Prefecture, the amount of fucoidan in Akamoku was about. It is about 500 to 700 mg, and it has been clarified that it retains fucoidan by 70% to 50% even when compared with the original algae. By further examining the processing conditions, the fucoidan fine powder that retains more fucoidan is used as the rubbing protective material, and in addition to the rubbing action, the water retention and elasticity of the skin are used as an auxiliary or substitute for nanocellulose and pulp. It has a skin-beautifying effect such as maintenance and hygroscopicity, and is a moisturizing protective ingredient. However, hypochlorous acid may be used in combination as a deodorant for seaweeds, but of course, hypochlorous acid is not limited to being used for the purpose of deodorization.

Furthermore, when the sample of Akamoku was heat-treated, the general ingredients (moisture / ash, protein, fat, carbohydrate) were not significantly different from those of the original algae of Akamoku, and are listed in the 5th edition of the Japanese Food Ingredients Table. It was found that the composition is similar to that of other general components of brown algae, and the reason why it is rich in carbohydrates is that alginic acid and fucoidan, which are dietary fibers, are considered to be the main components, so it is a fine powder. In the case of chemical processing, there is no problem in using it as a rubbing protective material even if it is heat-treated by drying or the like. In addition, since it is also useful as a source of minerals, it is considered to be a stable material including its effectiveness, and at the same time, its viscosity is used to prevent dripping of the rubbing protective material filled in the spray spray container. It also becomes.

In addition, as a result of the hot water extract extraction experiment, the seaweed of the kelp genus contains water-soluble argin in 1% or less of Akamoku, 4% in true kelp, and 9% in Hosome kelp. The purified fucoidan content (hereinafter referred to as fucoidan) was not roughly affected, and as a result of analyzing its constituents, uronic acid and sulfate roots were contained in addition to fucoidan, and the fucoidan content was 10% or more in brown algae. The highest price is 44.5% of Akamoku. In addition, uronic acid and sulfate roots are contained even if the mixed alginic acid is completely removed by purification, and when looking at the fucoidan, uronic acid, and sulfate roots considered as constituents in terms of molar ratio, only fucoidan is a constituent sugar. In fucoidan sulfate, the molar ratio of fucoidan to sulfate root may be considered to be 1: 2, and in the case of more than this, it is necessary to have a constituent sugar other than fucoidan. Therefore, there are four types of examples showing a molar ratio of sulfuric acid of 2 or less, including Akamoku, which are considered to be fucoidan sulfate, but most of the others are reported to be polysaccharides composed of fucoidan and other monosaccharides. There is. In view of these, as a matter of course, seaweed containing brown algae has no problem in composition even if it is heat-treated, and can be a raw material whose safety has been confirmed, and has shown its effectiveness as a rubbing protective material.

Furthermore, Akamoku is a brown alga with the same formation as kelp, mozuku seaweed, wakame seaweed, hijiki seaweed, etc., and contains a large amount of fucoidan, which is a type of sulfated polysaccharide and is a viscous substance. This fucoidan has antioxidative action and antibacterial action such as suppressing allergies due to induction of apoptosis. In particular, the chemical structure of fucoidan was reported by the Ryukyu University Faculty of Agriculture Group in 1996, and four fucose and one glucuronic acid. It is said that it has a repeating structure with a structure consisting of two sulfate groups as one unit (having a molecular weight of about 1,000 and five sugars), and the high molecular weight mozuku fucoidan is a polysaccharide having a molecular weight of about 10,000 or more. Therefore, it is possible to contain brown algae as one of the saccharides of the rubbing protective material and to obtain moisturizing and protection of the skin and cloth fibers by the adhesiveness using the fucoidan component.

In addition, the antiviral effect of the photocatalyst can be expected to have an effect on viruses in general, but it does not guarantee the effect on all viruses or specific viruses, or the preventive or therapeutic effect on diseases. However, since it has been reported in many experiments that the inactivation of airborne infectious viruses such as influenza using a photocatalyst in an air purifier is likely to be an effective means in a closed space, as an example. Protective material for human hands, toes, heels, oral cavity, masks for fibers, clothing, bedding, curtains, shoe insoles, toothbrushes, interdental brushes, oral care products such as toothpicks, door knobs, lighting equipment, split chopsticks By spraying or applying to wood and fibers such as cooking utensils and ornaments, it can be expected to suppress and prevent the action of bacteria and viruses by photocatalytic action.

On the other hand, in the case of a gel-like rubbing protective material, it is filled in a spray container, a container with a sponge cap, a container with a roller cap, etc. Even if ether or the like is not added, a solution in which the concentration of the photocatalyst is increased by several percent is used, and the rubbing action and the moisturizing / protecting power are further enhanced. In addition, by making the fiber into a gel, the rubbing action is greatly improved and a lot of rubbing effect can be obtained.

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

Claims (3)

A rubbing protective material for hand skin that is applied or sprayed on the surface of the fingers to fix the nanocellulose solution in a thin film by the activity of the photocatalytic solution, the antibacterial activity of copper ionized water and the copper aqueous solution, and the friction drying of the fingers.
With the nanocellulose solution of the photocatalytic component that improves the smearability of the finger surface, the copper ionized water and the copper aqueous solution, and the component that improves the moisturizing property and protective quick-drying property of the finger surface and promotes fixation on the thin film. can be,
The photocatalyst is a liquid or powder of an ultraviolet and visible light responsive photocatalyst or a non-photocatalyst, and the copper ionized water and the copper aqueous solution may be a liquid or powder, and the nanocellulose solution is a nanocellulose whose main material is wood. , Pulp, sugar, at least one of algae liquids or powders, characterized by liquefying, gelling, pasting, solidifying and mixing them with a distilled water-soluble liquid at 100 ° C or higher. Rubbing protective material for. It is a fiber coating protective material for fixing the nanocellulose solution in a thin film by coating or spraying on the fiber surface and fixing the nanocellulose solution in a thin film by the activity of the photocatalytic solution, the antibacterial activity of copper ionized water and the copper aqueous solution, and the friction drying of the fingers.
The photocatalyst component that improves the rubbing property of the fiber surface, the copper ionized water and the copper aqueous solution that improve the antibacterial property of the fiber surface, and the moisturizing property and protective quick-drying property of the fiber surface are improved to promote fixing on the thin film. It is the nanocellulose solution of the contained component, and is
The photocatalyst is a liquid or powder of an ultraviolet and visible light responsive photocatalyst or a non-photocatalyst, the copper ionized water and the copper aqueous solution may be a liquid or a powder, and the nanocellulose solution is nanocellulose mainly made of wood. Fiber coating protection, which is at least one of a liquid or powder of pulp or saccharide, and is liquefied, gelled, pasted, solidified and mixed with a distilled water-soluble solution at 100 ° C. or higher. Material. A rubbing protective material that is applied and sprayed on the surface of fingers or fibers to fix the activity of photocatalytic solutions, the antibacterial activity of copper ion water and copper aqueous solution, and chloric acid water and the nanocellulose solution in a thin film.
The photocatalytic component that improves the rubbing property of the finger or fiber surface, the copper ionized water and copper aqueous solution that maintain and improve the antibacterial property of the fiber surface, and the thin film that improves the moisturizing property and protective quick-drying property of the finger or fiber surface. The nanocellulose solution is a component containing promotion of fixation above. The photocatalyst component is a solution or powder of at least one ultraviolet and visible light type photocatalyst of titanium oxide, tungsten oxide, and phosphoric acids.
The nanocellulose solution is at least one of nanocellulose made mainly of wood and liquid or powder of pulp, sugar, seaweed, algae, and hypochlorite, and is water-soluble in distillation at 100 ° C. or higher. A rubbing protective material characterized by being liquefied, gelled, pasted, solidified and mixed with a liquid.

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