JP2006169208A - Supported ultrafine silver particle having excellent antibacterial property - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method and a material for the production of a safe, strong and quick-acting supported antibacterial silver. <P>SOLUTION: A silver salt solution is applied to the surface of a carrier such as natural or synthetic fiber, glass, ceramic, metal oxide and sintered metal oxide and the solution is reduced with an active hydrogen reducing agent or by the irradiation with ultraviolet rays having a wavelength of ≤400 nm to form ultrafine silver particles having excellent antibacterial property and supported on the surface of the carrier. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention provides a strong and rapid antibacterial silver carrier that is harmless to humans and animals due to the physical properties of fine silver powder, by reducing and supporting silver fine particles on the surface of the carrier, More specifically, the silver ion crystal grains that are quantitatively adsorbed by the action of electronegativity distributed on the surface of the carrier molecule are reduced in situ, and the resulting ultrafine primary particles of silver are optimal for their launch. The conditions were determined from the control of the non-stoichiometric coordination phenomenon of oxygen atoms in the silver oxide particles, and the particle size control on the picometer to nanometer scale on the surface of the support was successful. Non-patent document 7 is cited as to what is antibacterial.

Furthermore, as a principle of supporting the fine silver particles, it is generated using the instantaneous electron-nuclearity breakdown phenomenon between the electronegativity distributed on the surface of the carrier molecule and the extranuclear electrons of oxygen atoms during deoxidation of the silver oxide particles. It was found that the silver fine particles and the negatively charged charged portion on the surface of the carrier were strongly attracted and supported in situ.

Silver ion grains that are quantitatively adsorbed from the above actions are chemically reduced in situ, and the ultrafine primary particles of silver that are produced are adsorbed and supported on the spot, thereby providing a highly durable silver antibacterial function. At the same time, it has become possible to provide an extremely excellent antibacterial carrier that is further enhanced by physical properties that conform to the quantum size effect of the silver fine particles.

Conventionally, it is widely known that metal ions such as silver, copper and zinc have an antibacterial action against microorganisms such as bacteria, and many antibacterial agents and antibacterial treatment techniques utilizing these have been developed. Unlike other precious metals, silver has been closely related to the human diet as a high-grade western tableware and dental filler, and its safety (non-toxicity) has been demonstrated.

In addition to the excellent antibacterial action of silver, as a guarantee to support safety, Non-Patent Document 1, which is well-known as a world-renowned academic book, is cited, but it is used for sterilization of drinking water in civilized advanced countries such as the United States. . The safety and excellent antibacterial properties of silver include examples in which silver is an antibacterial agent or antibacterial treatment technology, and silver does not allow other metal antibacterial agents and drug antibacterial agents to follow.

If we examine about 600 patent documents from the last 10 years that propose silver antibacterial functional ingredients, we can find out the characteristics of two broad categories in the form. Patent document classification 1 includes a method of using only silver in a metal state and a method of supporting silver ions on the inorganic salt crystals by exchanging silver ions with cations of insoluble inorganic salt crystals. As a classification 2, there is a method using an antibacterial / antifungal agent containing other metals or metal ions such as silver, copper and zinc.
Patent literature classification 1
JP 2003-212707 A JP 2004-161632 A JP 2002-293705 A JP 2000-198708 A Japanese Patent Laid-Open No. 11-5744 JP-A-11-57729 JP-A-11-222494, JP 11-292534 A JP-A-11-322525 Japanese Patent Laid-Open No. 9-175819 JP-A-10-45410 JP-A-6-166514 JP-A-5-294808 JP-A-11-26304 JP 7-247111 A JP 2000-198708 A JP-A-11-222494 Japanese Patent Laid-Open No. 9-175819 JP-A-6-166514 JP-A-5-294808 JP-A-11-26304 Japanese Patent Laid-Open No. 7-247111 Patent Document Classification 2 JP 2003-206210 A JP-A-11-347537 Japanese Patent Laid-Open No. 9-100116 JP-A-7-53319 JP-A-5-155725 JP-A-11-192492 JP-A-10-139609 JP-A-7-97302 JP-A-6-87715 JP-A-5-229911 JP-A-5-345703 JP-A-7-97302 JP-A-6-87715 CRC Handbook of Chemistry and Physics: 68th Edition (1987-1988, CRC PRESS, Inc. Boca Raton Florida) International Society for 1969 Hybrid Microelectronics Symposium Noboru Kubota Electronic Materials Research Laboratories (STANDER HLA for three days, September 29th, 30th and October 1st) Applied Physics Vol. 39, No. 9 (May 25, 1970) “Regarding the control of particle size of silver powder by precipitation method” Kubota Nori Noboru Kubota: Research on Pd-Ag thick film circuits and their devices (Doctoral dissertation, March 24, 1972, Osaka University) Electronic Materials July 2001 issue "Conductive Adhesive" Kubota Nori Science chronology 2003 edition Maruzen Co., Ltd. Student 59 (page 859) Nerve and muscle electrolyte concentration and resting potential Kojien (Iwanami Shoten version 1998) “What is antibacterial?” National Life Center “Takashi Eye” 131, June 1997

As mentioned above, there are many proposals that use the antibacterial properties of silver, but most proposals use the conventional rule of thumb antibacterial action as a criterion for evaluation. There are no examples that make an effective evaluation. For the selection of antibacterial agents that are indispensable for the design of antibacterial agents, such as the function, efficiency, and hygiene safety, The proposal has a problem in that various characteristics cannot be clarified in general.

The eye of the present invention has the advantage that it can contribute to the conservation of the global environment by experimentally confirming that the antibacterial action of silver is powerful and quick in order to promote the research and research pursuing the efficiency of the antibacterial function. In view of this, the issue was to use only metallic silver alone to ensure high safety. Non-patent document 1 as cited document.

The problems common to all previous proposals are not clearly defined regarding the speed of antibacterial action and the strength and weakness of the antibacterial action, and there is no clear definition of terms used to express the antibacterial efficiency qualitatively and quantitatively. Definitions of terms associated with the introduction and utilization of the social life intended by the present invention must be prepared in advance. What is antibacterial is defined and used in the description of this specification.

Since the meaning of antibacterial has a wide range of use of “against bacteria”, the term of antibacterial action needs to have a specific meaning and the following terms are defined. "Sterilization" means killing microorganisms, "Sterilization" means killing or removing all microorganisms present in the object. "Sterilization" means removing microorganisms from the object by means such as washing. “Bacteria” refers to suppressing the growth of microorganisms. For example, the description is made with expressions such as bactericidal antibacterial action, bactericidal antibacterial action, or bacteriostatic antibacterial action. To make sure that the situation is clear.

It is also necessary to sort out the problems considered to require improvement from Patent Document Category 1 and Patent Document Category 2 exemplified above, and to make them problems. Are taken together. The opinion of the present invention will be specifically described based on the proposal of Patent Document 1. The evaluation point of the proposal is the idea that metal silver powder particles are supported on a solid surface as an antibacterial agent, but the chemical reduction process for forming metal silver fine particles and the surface of titanium oxide particles support the silver particles. There is a problem with the conditions

That is, the silver fine particles according to the present invention capable of maximizing the antibacterial activity are considered to generate a standing high-speed electric field pulse on the surface of the silver particles from excitation due to the quantum size effect as described in another section. It is proved by the observation experiment under the microscope that not only the particle size is fine but also the fastest instantaneous bactericidal effect that the cells are destroyed at a high speed by the high-speed electric field pulse. Compared with the above, the particle generation process has the following problems, the antibacterial action efficiency remains at a general level, and the efficacy of silver cannot be exhibited.

The proposal proposes the use of silver powder obtained by simply chemically reducing an aqueous solution of a silver complex salt. In this method, however, the structure of the silver powder particles produced by reduction is essentially the same as the obtained reduced silver powder. In addition, the antibacterial effect is only a bacteriostatic antibacterial effect exhibited by ordinary silver particles, and there is no description of the strength or action speed of the antibacterial effect in Patent Document 1, and no specific explanation of the antibacterial effect is found. It is assumed that the level of antibacterial action expressed in general silver fine particles is the same. The specific contents will clarify the technical problems described below.

In this proposal, an antibacterial and antifungal powder is produced by supporting fine silver particles of nanometer size obtained by reducing silver complex salt in water on the surface of titanium oxide powder particles coexisting in the aqueous solution of silver complex salt. There is a proposal for a method of manufacturing. It is generally well known that when metallic silver particles are precipitated from silver salt and silver complex aqueous solution by chemical reduction, the state of the resulting silver particles gradually changes due to the influence of the silver ion concentration that decreases as the silver precipitates. Yes. The reduction reaction rate changes with the change in the silver ion concentration, and the thermodynamic quantities of the reaction system fluctuate all at once, making it impossible to control the various states of the silver particles that are produced to a constant level. .

It must be pointed out that it is almost impossible to produce nanometer-sized fine silver powder in a uniformly dispersed state without agglomeration, and that the method described in the proposal is almost impossible. Absent. Next, as a problem of the method of supporting fine silver particles on the surface of titanium oxide fine particles, when silver fine particles are supported on the surface of another substance at the same time as reduction formation, the matching of the interface potential required for the support and the stability It is thought that the situation is very difficult in the chemical reduction system of silver which is difficult to secure. The enthalpy of reduction of silver ions is not constant because it is controlled by the ionic product of the reducing system, but is much smaller than other zinc, copper and the like. Therefore, when the titanium oxide particles are in a hydrated state by being wet with reducing water, it is considered that there is almost no force for adsorbing silver particles in the vicinity of the oxygen atom of titanium oxide having a relatively low electronegativity. Therefore, it is considered that the interfacial strength of the supported particles cannot be expected unless the silver particles are very fine and the lattice energy is significantly reduced by the quantum size effect. As an example, Patent Document 2, Patent Document 3, Patent Document 4, Patent Document 5, Patent Document 6, Patent Document 7, Patent Document 8, Patent Document 9, Patent Document 10, Patent Document 11, Patent Document 12, Patent Document 13, Patent Document 14, and Patent Document 15 are disclosed.

It is essential to take measures to adapt to the physical properties of the reduced silver particles and the surface of the support, both of which are stable, and the results achieved by chance depending on conventional trial and error are dangerous. In the silver-supported titanium oxide powder prepared by a compliant method, the phenomenon that the silver powder falls off from the surface of the carrier particles in the washing process is predicted, and it is considered that there is much room for improvement in this proposal.

When Patent Document 2 and Patent Document 3 are verified, both attempt to utilize the antibacterial function of metallic silver in the state of silver colloid. The former is a silver colloid dispersion itself, and the latter is a silver colloid as an inorganic substance. It is a proposal to use what is carried on each as an antibacterial agent. Both proposals seem to have chosen silver colloids as a means of obtaining fine silver particles in a stable state, but silver colloids are compared to colloids of other metals (such as gold and platinum). It is easily affected by fluctuations in ionic charge from the dispersion medium, and easily coagulates, so it seems difficult to put it into practical use for a long time in a stable colloid state. The suggestion to be supported on the particles is that coagulation coarsening occurs in the particles due to the rapid collapse of the double electric layer accompanying the stabilization of the energy of the adsorption system. As mentioned, it is suggested by the properties related to the physical properties of silver colloid.

Silver colloid is a kind of lyophobic colloid, a hydrocolloid with water as a dispersion medium, and also a negative colloid in which the particles are negatively charged. The cause of the charge is either cation or anion from the solution. Because the particles are positively or negatively charged and ions of opposite sign are attracted to it, creating an electrical double layer around the particles, and the opposing charges attract each other, Through this, the particles are attracted by the water molecules and kept away from the water, and since they all have the same polarity of charge, they do not repel each other and settle.

Since the charge of colloidal particles is affected by the action of a very small amount of electrolyte present in the solution, the colloidal solution becomes unstable due to the influence of changes in the electrolyte concentration, ionization voltage, etc. Aggregation of colloids such as precipitation occurs. Silver colloids have a particularly low aqueous solution stability compared to others and are prone to coagulation. Therefore, when used as an antibacterial agent, it is necessary to take special measures for stabilizing the colloid. Also, when colloid is supported on a carrier, it is necessary to coagulate the colloidal particles immediately before the support, and the particles are agglomerated due to the aggregation of the particles at this time, and the antibacterial efficiency of the support is reduced. There is a risk that the significance of using the colloidal silver colloid will be halved. In other words, the statement that silver is supported on an inorganic material in a colloidal state seems to be an error.

Various methods for the continuous use of the antibacterial action of silver using silver ion or silver complex ion exchanged with the cation in the inorganic composite crystal compound in the method in the patent literature using the antibacterial property of silver I have a suggestion. As the inorganic composite crystal compound, a composite ion crystal that is insoluble in water is generally selected, but a characteristic crystal is selected for each proposal. For example, there are a large number of disclosures in a method of using a composite crystal compound containing calcium ions as cations in a crystal. Representative examples include Patent Document 16, Patent Document 17, Patent Document 18, Patent Document 19, and Patent Document 20. Patent Document 21, Patent Document 22, and the like. A problem common to all the proposals is that silver ions or silver complex ions are substituted and supported based on the principle of ion exchange with cations of other ion crystals. Silver ions in each carrier crystal are The anion is paired with a strong energy based on the electrostatic attraction between the ions, so it can be easily detached from the crystal even if another anion comes in contact with the outside. In particular, since most of the complex ion crystals used in the proposal are insoluble in water, all of the constituent anions of the crystals are difficult to dissociate. That is, water-insoluble ionic crystals are composed of anions that cannot be dissociated.

For the above reasons, since the proposed silver ion elution amount is very small, the antibacterial agent consumption is low and the sustainability is long, but the antibacterial effect is considered weak and slow. In addition, when silver and other antibacterial metal components other than silver, such as copper and zinc, are substituted at the same time, since the metals are eluted in descending order of their ionization potential, silver remains in the crystal until the end. As a result, the problem that the antibacterial property of silver becomes difficult to be used also occurs. Therefore, it is considered that the proposed antibacterial agent can only be expected to be as effective as a bacteriostatic antibacterial effect, and can be judged to be far from the immediate bactericidal antibacterial effect targeted by the present invention.

Patent Literature 23, Patent Literature 24, Patent Literature 25, Patent Literature 26, Patent Literature 27, and Patent Literature 28 accepted in Patent Literature Classification 2 contain other metals such as silver, copper, zinc, or ions of the metals. As a proposal regarding antibacterial / antifungal agents, etc., it is recognized that the antibacterial / antifungal function of silver and the function of other metals are regarded as the same, but it is basically different from the object of the present invention. For example, an antibacterial agent or antibacterial method characterized by selecting at least one metal component from the group consisting of silver, copper, zinc, tin, titanium, selenium, etc., even if silver is selected There is no difference in the effect of selecting other metals individually in each, and they all have the same result and technical contradiction.

Patent Document 32 proposes an antibacterial agent containing chromium, lead, arsenic, cobalt, cadmium, etc., which is strictly prohibited as a cause of pollution and environmental pollution, as an antibacterial component, and is provided for public use. Must be said to be out of the question. Patent Document 29 proposes that silver and copper are mixed in equal amounts as nitrates and supported on powder, but depending on the chemical conditions of the environment, there is a high possibility that copper ions will flow out and contaminate the surroundings. As such, there is no particular recognition to avoid danger.

In the case of ion crystals such as zeolite formed by replacing silver ions with cations in the crystal, or silver complex salt crystals in which silver is coordinated as complex ions, silver ions as a member of the crystal are negative ions coming from the surrounding environment. If there is an ion, it can be paired with the ion and eluted out of the crystal quickly and easily. There are also proposals to use silver ions present in a part of ionic crystals as antibacterial agents, such as zeolites in which silver ions are introduced into crystals by ion exchange or substitution, and complex salt crystals in which silver complex ions are substituted. When an agent is exposed to a global environment containing various chemical components, anions having the possibility of pairing with silver ions present in those environments, such as nitrate ions, sulfate ions, chloride ions, etc. When contacted with an antibacterial agent, the silver ions in the crystal elute very easily, causing the antibacterial agent to be consumed and reduced in efficacy, eliminating the biggest problem when using silver as an antibacterial agent in the form of ions. Not.

As a means to alleviate the loss due to elution of silver ions, a means for appropriately coating the surface of the antibacterial agent from various materials and methods has been proposed as a measure for improving the durability of the antibacterial agent often found in the conventional proposals. However, this method leads to a decrease in the efficiency of silver antibacterial action, leaving a problem for the future. Metallic silver has been widely used in daily life since ancient times, and there is no record of toxicity problems. However, some silver compounds are designated as deleterious substances, such as silver nitrate. Then, it is determined by the nature of the anion paired with silver. Silver is an organic and inorganic compound, and when water-soluble compounds are taken orally, silver ions react with gastric acid and are excreted as water-insoluble silver chloride, so do not consume a large amount of silver ion solution. It is known that there is almost no harm. Furthermore, metallic silver does not immediately combine and dissolve when it encounters an anion that can be a counter ion of silver. Even with strong acid anions such as nitrate radicals, the oxidation of nitric acid first produces silver oxide, and then it reacts with nitrate radical ions to form silver nitrate for the first time. Safety is clear.

Taking a bird's-eye view of the entire technology, research on the antibacterial properties of silver was preceded by trial and error from the viewpoint of general public health. There is no consistent theory about the antibacterial action of silver, and there are few established theories based on scientific evidence. In order to elucidate the antibacterial action of silver, it is important for the present inventors to consider the metal physical properties of silver that occupy its mechanism of action, and to observe and analyze the phenomenon when the antibacterial action of silver appears. The following antibacterial action experiment was conducted based on the view that is essential for elucidating the principle of silver antibacterial action. Non-patent document 2, Non-patent document 3, and Non-patent document 5 are cited for the metal physical properties of silver.

First, a fine powder of the silver fine particle carrier of the present invention (described in Example 1- (7)) was dispersed in water to prepare a sample. One drop of this sample is dropped on the center part of the slide glass set in the optical microscope, covered lightly with a cover glass from the top, and fixed at a fixed interval so that the sample can flow while freely wetting the gap between both glass plates. A test piece was obtained. As a bacterial culture solution, a culture solution of protozoa (Balantidium caviae) parasitic on the cecum of guinea pigs was used. The state in which a large number of protozoa actively migrated in the culture solution could be clearly confirmed under a microscope (400 times magnification). Take about 1 drop of the above bacterial culture in a spoid and apply it to the edge of the cover glass of the test piece. While keeping the protozoa in a state that allows migration to the inside of the liquid phase of the sample, a microscopic observation and visual recording video Was taken. The results were as follows.

When the protozoa migrates into the aqueous dispersion sample of the silver fine particle carrier of the present invention and enters and contacts the sample system, the ciliary movement stops immediately after several rotational movements and dies. During that time, it can be expressed as an immediate bactericidal antibacterial effect within a few seconds, and after ciliary movement is stopped, the cell membrane of the cells is physically destroyed and the protoplasm inside can be clearly observed, and its bactericidal action is positive. It can be said that the situation is suitable for expressing as dramatic. The main reason why the present inventors selected the protozoa as the target for the antibacterial efficiency test is that the size of the protozoa is relatively large, such as several micrometers, which can be easily observed with an optical microscope of about 400 times, However, the cell wall of the protozoa has low chemical permeability and resistance to chlorine is low in E. coli. It is known to be about 600,000 times stronger. Therefore, the ability to instantly sterilize even protozoa at a level where no sterilizing effect can be expected at the chlorine concentration of water treatment can be regarded as one of the ideal targets for antibacterial efficiency required for future antibacterial agents. The recorded video of the experiment is prepared for disclosure if necessary.

It has been demonstrated in another experiment that Escherichia coli has the effect of killing the sample of the present invention almost instantaneously at the same time as contact. It has been found that the mechanism of killing in time is the large energy that gives a sudden potential change (Non-patent Document 6) to the cell membrane surface of the microorganism in contact. Among metals, silver has unique physical properties as a noble metal, but considering the above-mentioned rapid phenomenon of antibacterial action, it should be compared with a slow action that inhibits mere daily reactions like the conventional antibacterial effect. A remarkable effect was obtained.

The inventors of the present invention have developed an antibacterial action mechanism of silver and silver ions in a technical area that has not been known about the antibacterial properties of silver, starting with suggestions from the results of silver physical properties research conducted in the past. From the experience of research and development, the present invention has been completed. From experimental observations of the present invention, it has been found that the influence of the quantum size effect exhibited by the small crystal system of silver has the strongest and quickest antibacterial action, which has led to the rapid promotion of the present invention. The result of the research on the physical properties of silver is a part of the contents described in Non-Patent Document 4, and the electrical properties of the Pd-Ag thick film resistance element, such as the electrical resistance, resistance temperature coefficient, current noise, etc. Quantum size effects such as grain size, lattice defects, defect density, etc. of particles and palladium powder particles [Phenomenon in which thermodynamic quantities (lattice energy, melting point, ionization potential, etc.) deviate significantly from normal physical properties in small systems] I know that there is a phenomenon that the absolute value changes greatly. The quantum size effect is an effect of increasing the surface energy caused by the crystal lattice asymmetry of fine particles. However, if there is a region of physical phenomena in the antibacterial action mechanism, the quantum size effect is naturally applied to the antibacterial action. It was expected to have an effect, and an experimental study was conducted based on this recognition.

As a result of the examination, the present invention was advanced while arranging basic matters that were insufficiently examined in the interpretation of the action mechanism for the conventional antibacterial agents and trying to find and correct errors. First of all, from the aspect of single-cell microorganisms and the mechanism of metabolic activity, when dealing with conventional ideas, single-cell microorganisms such as bacteria carry out metabolic activities necessary for life support in one cell, but the metabolic energy of each microorganism is extremely high I found out that it was small and many people gathered to affect the surroundings. The only thing that protects the cells of microorganisms is the cell membrane. Although it consists of a semipermeable membrane, it has selective permeability, not just a semipermeable membrane, and uses specific energy in the intracellular metabolism to make specific ions into a concentration gradient. Actively transports counteracting and maintains the homeostasis that is the basis of life. Even if it regulates the movement of ions according to changes in the surrounding environment and always keeps the potential difference between the inside and outside of the cell membrane (Non-patent Document 6) constant, a high potential far exceeding the potential adjustable by the cell is When applied from the outside, the function of the membrane was inhibited and the cells died, and I realized that the control of this function was ultimately considered as an electrical signal.

The movement form of microorganisms showing some motility moves by moving flagella and cilia as seen in the protozoan experiment, but its scientific composition is known to be a protein of the same kind as animal muscle fibers. In normal animals, it is thought that contraction of muscle fibers occurs when two types of proteins, actin and myosin, which overlap each other in layers are slipped. The regulation of muscle contraction and relaxation is based on the movement of calcium ions, but the movement of calcium ions is controlled by electrical signals transmitted by nerves. Therefore, it can be seen that the motor function of single-cell microorganisms such as protozoa is ultimately controlled by electrical signals. From the above, the metabolic energy necessary for maintaining the life of single-cell microorganisms is extremely small, and the instruction necessary for maintaining the order of life-supporting activities cannot be denied the nature of being dependent on weak electrical signals. Can it be said that there are many errors in the conventional antibacterial technical idea?

An outline of the results of detailed examination of the electrical properties of the cell membrane of single-cell microorganisms will be described. Biological cells are each wrapped in a cell membrane, and have the property that there is a difference in potential (polarization) between the inside and outside of the membrane. The potential difference between the inside and outside of the membrane when the cell is inactive is called resting potential, which is expressed by the potential of the inner surface when the cell membrane surface potential is 0, and always takes a negative value. In response to slight changes in the external environment, the ion permeability of the membrane is adjusted to maintain a resting potential, but when a stimulus exceeding a certain threshold is applied to the cell, the ion permeability of the membrane changes rapidly and the action potential (action) potential) occurs. The process of changing the membrane potential consists of the disappearance of the potential difference (depolarization)-> polarity reversal (overshoot)-> return to the resting potential (repolarization) again, and the electrical waveform as a whole becomes a spike wave within 5 microseconds. . The difference (amplitude) between the resting potential and action potential varies depending on the cell type, but nerve and muscle cells are particularly prominent, and the electrical properties of the cell membrane are extremely important for the cells to maintain normal life activity. An unrelated external electrical stimulus that plays a role causes not only a little disruption and damage to the cell membrane, but if the electrical stimulus becomes excessive, it causes the cell to die immediately. These are not found in the proposals related to the conventional antibacterial mechanism, and there is no invention that deals with the order destruction related to the membrane potential of the cell membrane of microorganisms.

For reference, the resting potential of mammalian skeletal muscle fibers is −70 to −90 mV, the threshold membrane potential is −50 to −60 mV, the action potential is +40 to +50 mV, and the amplitude is about 110 to 140 mV. is there. Cell membranes of microorganisms such as bacteria have similar properties, suggesting a mechanism that plays an important role in various life activities such as nutritional activities and danger avoidance, adapting to changes in the external environment. In addition, the flagellar and cilia constituent proteins possessed by some bacteria and protozoa are proteins of the same type as muscle fibers of higher animals, suggesting that they move by a mechanism similar to that of higher animals.

The antibacterial action of the silver fine particle support of the present invention is based on the results of the antibacterial experiment on the protozoa and Escherichia coli and the antibacterial effect of applying an external voltage on the cell membrane potential of the single cell microorganism. Has been determined to be an antibacterial effect due to electrical energy resulting from the physical properties of the silver fine particles. Therefore, regarding the physical properties of the silver fine particles of the silver fine particle carrier, the physical properties of silver considered to directly contribute to the antibacterial effect were identified, and the quantum size effect of the properties was considered.

The quantum size effect is quoted in the above description, but is defined here again. When the size (size) of a solid sample becomes as small as the de Broglie wavelength of conduction electrons and holes in the material, the thermodynamic quantities and transport coefficients of the material change depending on the size. Appearing is called the quantum size effect. The present inventors have focused on the redox potential as the physical property of silver that most directly affects the antibacterial properties of silver. It is believed that the extreme increase of the redox potential pulse energy, especially due to the quantum size effect, is the biggest factor in the immediate bactericidal antibacterial effect. Although steady-state measurement of the redox potential is possible, actual measurement of pulses excited by the quantum size effect and theoretical deduction are technically difficult, but they are included in the scope of understanding as a concept. It is done.

The antibacterial effect of silver that disrupts the cell membrane potential of unicellular microorganisms and leads to destruction of the cell membrane is thought to be due to the following mechanism. The pulsed electric field of the oxidation-reduction cycle having the active region in the vicinity of the surface of the silver fine particles excited by the quantum size effect can be regarded as a cell membrane destruction effect when applied to the cell membrane of a single cell microorganism. In this case, the transmission of electrical pulses is considered to be due to ionic conduction in the aqueous electrolyte solution. Therefore, even if the antibacterial silver fine particles are not in direct contact, all microorganisms present in the electric field region above the cell membrane breakdown threshold voltage are sterilized. Suffers an effect.

Silver is a metal that exhibits remarkably different physical properties from other metals even in a normal state that does not consider the excited state due to the quantum size effect. Silver is a kind of noble metal, together with gold, platinum, etc., and most of it is produced in the state of metal elements, but this is because elements called noble metals are generally much lower in chemical potential than other metal elements. Rather than producing a compound that is stable when combined with an element, it is characterized by the physical property of being more stable in the state of a metal. The antibacterial action of silver is considered to be a characteristic attributed to the original physical properties of silver, but the grounds are inferred from the results of the present invention and are not deduced from the physical properties of silver. Among the usual metal physical properties (bulk physical properties) of silver, the findings of the present inventor regarding the items related to the electronic properties of silver obtained through the knowledge about the antibacterial mechanism of silver according to the present invention were described. This eliminates some errors in the antibacterial properties of silver, and at the same time has the effect of developing and developing the technology.

Physical property values that do not include the quantum size effect of silver with the disturbance of cell membrane potential of single-cell microorganisms as the mechanism of antibacterial action include ionization energy (7.58 cV), electron affinity (1.0 eV), redox potential (Ag + / Ag, 0.799V) and the spectral reflectance of the metal surface 5.5% (315 nm) 8.9% (320 nm). As an index of energy consumed for the entry / exit of electrons in the oxidation-reduction reaction of silver, there are ionization energy and electron affinity. Looking at the numerical value of silver, it is thought that silver has a smaller energy disparity in the exchange of electrons than metals such as copper and zinc, and that a redox reaction is in a kind of resonance state and a macro equilibrium is established. However, when viewed microscopically, it is thought that it is violently fluctuating repeatedly under the influence of environmental conditions such as light, heat, and movement of the dissociation equilibrium of the electrolyte. As a result, when observed from outside the system, a unique phenomenon that cannot be seen in other metals observed only in silver appears. As for the oxidation-reduction potential of silver, the above value obtained by measuring the potential difference with the hydrogen electrode in a steady state is commonly used, but the wave amplitude of the surface electric field potential in the electrolyte solution of fine silver powder is about twice the above value. It can be seen that a pulse wave of 1500 mV (about 1000 Hz) is generated. This is a high voltage corresponding to a voltage about 17 times the cell membrane static potential of 90 mV of a single-cell microorganism, and since it is applied as an alternating voltage, the impact received by the cells is more than expected. In the near ultraviolet region (315 to 320 nm), there is absorption of light reaching an absorbance of 90% or more, and in the case of fine particles, plasmons are observed as excitation light. In particular, it is known that silver fine particles supported on a ferroelectric substance have an antibacterial effect enhanced by an excitation phenomenon comparable to the quantum size effect. These silvers exhibit various phenomena different from ordinary metals due to the physical properties based on a unique atomic structure. Next, the most important behavior of silver for understanding the effect of silver in the present invention will be described.

The most important attributes of the physical properties of silver that have created the features of the present invention are the reaction with oxygen and the specificity of the silver oxide. Although there is much room for debate in terms of the reaction mechanism, this case has been sufficiently confirmed as a phenomenological theory and has already become a common sense in the field of industrial technology. Silver dissolves a large amount of oxygen at a melting point or higher, but since it is an alloy of only a liquid phase, dissolved oxygen is released during cooling and solidification, and the solidified solid silver has a remarkably foamed spongy structure. Therefore, silver dissolution takes place in a vacuum. It is considered that the affinity between silver and oxygen is not due to the sharing of outer electrons, but is in a unique binding state close to a metal bond. Therefore, the electron covalent bond with oxygen found in general metals does not exist in silver. Chemically synthesized silver oxide is precisely a non-stoichiometric oxide, which decomposes immediately upon application of light irradiation, heating, strong impact, etc., releases oxygen and is reduced to silver. These properties are the opposite of those of general metals. Since silver has a positive electron affinity property value of 1.0 eV, it has an energy value of 1.0 eV (96.490 kJ / mol) when Ag + ions are reduced to metal by obtaining the electron e. It can be seen that-is released. The following can be inferred from the above facts.

Among silver, silver ions, silver complex ions, inorganic silver salt compounds, inorganic silver complex compounds, organic silver compounds, and the like, the state in which free energy is the lowest and stable is metallic silver. Silver ions, complex ions, and compounds all have higher thermodynamic free energy than silver, and are trying to release energy (thermodynamic work) out of the system (Gibbs concept of free energy). This is the reason why silver is almost noble as a noble metal, but unlike other noble metals, there is a certain amount of Ag + (cation) due to the action of water in the atmosphere. ing. This silver ion is thought to be generated by a mechanism similar to the hydration phenomenon with atmospheric moisture, but the generation mechanism is still unclear because the formation of ions is extremely small and it is difficult to confirm 0H- of the counter ion. Not. In general metals, there is an oxide or hydroxide film on the surface in the atmosphere, so the mechanism of the hydration reaction can be explained clearly. However, in the case of silver, there is almost no oxide film, so it is questioned. ing.

Next, it will be explained that the specificity of the silver oxide is one of the important features of the present invention. As silver oxides, Ag ₂ O, Ag ₂ O ₃ , AgO and the like are known. From the point of view of chemical bonding theory, it occupies the end of the electrochemical series and lacks reactivity, but in order to react with oxygen, it is first necessary for the electrons to leave the metal and then ionize. In the case of silver, the ionization energy is relatively high (7.58 eV) and the heat of sublimation is large (melting point 962 ° C.), the reactivity is low. Partially offset by the large energy gained. Therefore, the silver oxidation reaction is significantly affected by the energy of hydration by water in the reaction system. It was discovered that the binding energy of silver and oxygen can be controlled within a certain range by controlling the hydration energy of silver ions. As a result, the coordination number of oxygen bonded to silver can be changed, and the crystal structure, lattice defect density, and redox potential of the silver oxide particles that form the base of the fine silver particles that are generated can be changed to some extent. Became. Since the silver oxide obtained by the above control is in an unstable state, it is difficult to take out and analyze it in the middle, but it is generally about Ag _{1.1 to 2.0} O _{0.8 to 1.0} . Non-stoichiometric silver oxide in range. The silver fine particles that are finally produced have their modes determined by controlling the charge distribution and electronegativity on the surface of the support, but the function of immediate bactericidal antibacterial properties is reliably maintained.

The antibacterial silver fine particle carrier of the present invention is characterized by a carrier that stably supports silver fine particles whose physical properties of silver fine particles supported on a carrier are activated by a quantum size effect and whose antibacterial function is remarkably amplified. As a specific method for giving a quantum size effect, a chemical reduction method for silver particles is important, and in the present invention, the following method is used. Further, the activated antibacterial silver fine particles of the present invention are reduced and deposited at a position utilizing the influence of the surface charge (electronegativity) of the carrier. In the conventional method of producing only silver particles alone, it is difficult to control and produce fine particles.

The first embodiment relates to carrier selection and surface cleaning treatment. As the carrier of the present invention, a material selected from polymer resin, natural gauze or synthetic fiber, glass, ceramics, metal oxide and metal oxide sintered body (including ceramics) can be used. Regarding the shape of the carrier, powder, fiber, porous, rod-like, plate-like, or any other shape member can be used. The carrier must have a clean surface. Dirt and deposits must be thoroughly cleaned by washing or other methods. This is because the surface of the carrier used serves as a reaction vessel when fine silver particles are reduced and precipitated, and therefore the presence of foreign substances may impair the effects of the present invention.

Although the surface of the carrier depends on the shape, degreasing cleaning with alcohol is the most standard and effective. Detergents, surfactants, etc. may be affected by monomolecular films due to adsorption and should be avoided because they may affect the quantum size effect of the silver particles. After degreasing and cleaning, it is necessary to perform sufficient pure water cleaning. The cleaning treatment of the carrier surface has an important influence on the effect of the present invention. The washed carrier is stored in dry air or dry nitrogen gas until the next step.

The second embodiment is a step of applying a silver salt solution to the surface of the carrier. As the silver salt, one kind is selected from an ammoniacal silver nitrate solution, a silver sulfate aqueous solution and a silver nitrate aqueous solution, but no significant difference in the antibacterial effect of the silver fine particles produced by reduction is recognized. Any of them can express the characteristic effects of the present invention, but depending on the type of material to be supported, there is a slight difference in the form of silver supported, so an appropriate silver salt was tested depending on the material and shape of the carrier. It is preferable to select them. According to the knowledge of the inventors, ammoniacal silver nitrate is suitable for supporting inorganic substances such as glass, ceramics, and ceramics, and aqueous solutions of silver nitrate and silver sulfate are suitable for supporting organic resins, natural and synthetic fibers, respectively.

The ion concentration (Ag @ +, mol / l) of the silver salt applied to the carrier is suitably in the range of 0.1 to 0.001. When the concentration of silver is too high, the particles are likely to aggregate and the quantum size effect is hardly imparted, resulting in a decrease in antibacterial action. Antibacterial functions tend to be higher when the concentration of silver is dilute. The silver salt is applied to the carrier by an appropriate method such as dipping or spraying depending on the shape and size of the carrier, but the next drying step is extremely important. Special care should be taken if improper treatment in the drying process significantly affects the antibacterial effect.

The silver salt aqueous solution applied to the carrier is kept at room temperature (20 + −3 ° C.) for several minutes to 10 minutes to establish an equilibrium state between the surface charge and hydrated ions. During this period, the silver salt aqueous solution must be stored in a sealed container so that the water does not evaporate. This is referred to as interfacial charge equilibrium aging between the silver salt and the carrier surface, and is the main control item of the present invention.

When the above aging is completed, the moisture of the silver salt aqueous solution, which is important next, is removed. This step is not mere drying, but removes water from the ionic crystals to remove hydration energy, and causes the fine crystals of the silver salt to orient at the support potential sites of the carrier. It is well known that an ionic crystal such as a silver salt is in a state where the polarization of ion pairs is suppressed due to the strong influence of hydration energy in the state of an aqueous solution. Therefore, the surface charge of the carrier formed by the difference in the type and density of atoms present on the surface of the carrier and the hydrated silver salt ions are not in a completely oriented state, but both tend to be gradually oriented during the aging period. It seems to have taken the position. Therefore, when water in the silver salt solution is removed, the dehydrated silver salt ion crystal is strongly and rapidly adsorbed and fixed at the potential site having the counter charge of the soot carrier in the vicinity thereof. As a result, the silver salt crystal supporting site is first set at a place where the energy is most stable.

Removal of water from the silver salt aqueous solution applied to the carrier is performed by the following method. The carrier is dried in a light-shielded drier at a temperature of 20-30 ° C. and a relative humidity of 10-20% RH. Vacuum drying is preferable if possible, but there is a danger of silver salt crystals peeling off the surface of the support due to rapid vacuum drying. After drying slowly using a dryer to remove some water, the remaining moisture is vacuum dried. It is preferable to remove by. The more completely the moisture is removed, the more the silver salt crystal counterion is released from the binding of hydration energy and the fixation to the carrier becomes stronger, and the antibacterial function of the fine silver particles produced in the subsequent process is also improved. In addition, the service life of the support is extended.

The main skeleton of the antibacterial silver fine particle carrier of the present invention is completed through the above steps. That is, a completely dried silver salt fine crystal is firmly supported by electrostatic adsorption on a portion having a relatively high electronegativity on the surface of the carrier. Although the crystal structure of the silver ion crystal electrostatically adsorbed on the surface of the carrier has not yet been clarified, it was coordinated on the surface of the carrier, not in the form of a single ion crystal, according to the analysis of the electron diffraction pattern. Patterns other than ionic bonds are observed, and it seems that they are deeply related to the atoms on the surface of the carrier. In particular, silver sulfate has a diffraction pattern that can be interpreted as a peculiar multidentate coordination. In any case, the behavior of the silver ion crystal on the support surface is important for elucidating the support mechanism of the silver fine particle support, and at the same time estimating the practicality such as durability and reliability of the silver support. But it is important.

In the next step, fine silver salt crystals supported on the surface of the support are treated with an aqueous alkali hydroxide solution to change into silver oxide particles. As the alkali hydroxide used here, any one kind of alkali hydroxide can be selected from caustic soda, caustic potash, lithium hydroxide and calcium hydroxide. That is, no matter which alkali hydroxide is selected and the above treatment is performed, all the non-stoichiometric oxides are produced, and the antibacterial silver fine particle carrier produced by the final reduction in the next step. These silver particles are all found to be in an excited state of the quantum size effect, which is one of the features of the present invention.

There are many choices of alkali hydroxides that can be used here, but the degree of freedom is wide. However, calcium hydroxide also has a drawback that it easily absorbs carbon dioxide and precipitates calcium carbonate. Caustic soda, caustic potash or lithium hydroxide can be used without any difference. The treatment conditions with alkali hydroxide are as follows. When selecting caustic soda or caustic potash, use 1/10 to 1/40 normal aqueous solutions, respectively. When lithium hydroxide or calcium hydroxide is selected, a 1/40 to 1/50 normal aqueous solution is used. The treatment temperature is 20 + -3 degrees C. The carrier is immersed in the treatment liquid. The treatment time is 5 to 10 minutes. During the treatment, the treatment solution is gently agitated so that the treatment liquid is evenly distributed. The carrier after the treatment is washed with pure water as follows.

The carrier is immersed in pure water and gently agitated for cleaning. The pure water is changed until the cleaning liquid is not discolored with the phenolphthalene indicator, and the cleaning liquid is repeatedly washed and dried in a stream of dry nitrogen gas or clean dry air. The humidity of the air used for drying is preferably about 10% RH or less, but it is preferable to exclude all other impure components. In particular, carbon dioxide, nitrogen oxides, sulfur oxides, hydrogen sulfide, and hydrogen halides may have a very detrimental effect on the characteristics of the fine silver oxide particles of the support in this processing step. Measures to eliminate are necessary. In that sense, it is preferable and economical to use nitrogen gas for semiconductor production in this drying process.

The carrier after drying is subjected to a reduction treatment by the following method. There are roughly two types of reduction treatment methods, one of which is a chemical reduction method and the other of which is a physical reduction method. The chemical reduction method is convenient when the number of supports to be reduced is large, and the cost required for the treatment is relatively low. Among active hydrogen-based reducing agents, among formic acid, formaldehyde, acetaldehyde, ascorbic acid and hydroquinone. From the above, any one type can be selected and used. Even if any reducing agent is selected, there is no difference in the effect of the present invention, but the three reducing agents, formic acid, formaldehyde and acetaldehyde, generate carbon monoxide upon reaction with silver oxide. That risk measure is necessary. In addition, ascorbic acid and hydroquinone do not have the same danger as the former, but the aqueous solution is easily oxidized automatically, so that it is difficult to store and manage the liquid and has a relatively high cost. The physical reduction method is costly and time-consuming in terms of equipment and processing efficiency compared to the chemical method, and is economically disadvantageous. However, it does not require a treatment such as washing after the reduction treatment, and as an antibacterial silver fine particle carrier. Slightly excellent in durability because there is little contamination in the process.

The processing method by the chemical reduction method will be described. An operation of extracting oxygen atoms of fine silver oxide particles supported on the support with care so as not to change the atomic arrangement of the non-stoichiometric oxide is performed. In order to prevent silver atom migration due to reaction heat, the concentration of the reducing agent is a large excess (1/10 mol / l) of the required reaction amount, and the reaction temperature is set to 20 + −3 ° C. All the active hydrogen-based reducing agents are adjusted to 1/10 mol / l aqueous solution. The active hydrogen concentration of the reducing agent is evaluated and managed as needed by the oxidation-reduction titration method of general chemical analysis. Since the amount of the reducing agent is so large that it does not become a problem compared to the amount of oxygen of the fine silver oxide particles supported on the carrier, there is no special consideration for the amount of reducing agent used during the reduction treatment. unnecessary. It can be sufficiently covered with consideration to the extent of using a reducing agent solution in an amount that allows the carrier to be sufficiently immersed. However, since only the concentration of the reducing agent solution is related to the heat of reaction, it needs to be evaluated accurately. The time for immersing the carrier in the reducing agent solution is 3 to 5 minutes at a temperature of 20 + -3 degrees C. In the meantime, the gentle stirring is the same as in the case of the treatment with the alkali solution. The carrier that has been treated with the reducing agent is immediately washed with pure water. At this time, it is necessary to immediately wash the carrier after the reduction treatment. If the carrier after the reduction treatment is left in the atmosphere, the residue of the reducing agent is oxidized and adsorbed on the active surface of the fine silver particles, so that the antibacterial action may be reduced. Therefore, it is preferable to provide equipment for carrying out the present invention after the reducing agent treatment.

Next, the physical reduction method is described. This method is a method for producing an antibacterial silver fine particle support by physically reducing fine silver oxide particles supported on a support by ultraviolet irradiation. This method is superior to the chemical reduction method described above in that it is easy to operate and requires almost no consumables such as chemicals. However, it is difficult to control ultraviolet radiation energy, process efficiency, quality control, etc. However, there is a problem that it is not yet fully developed. Therefore, the method at the experimental production level is now described. As described above, silver has a very large absorption band in the near ultraviolet region near 300 nm. When the silver fine particles are excited by the quantum size effect, this absorption band gradually shifts to the visible light region and finally reaches around 550 nm. Although reduction (oxygen release) is also performed by irradiating light with a wavelength corresponding to the peak of each absorption band, low-pressure ultraviolet lamps are used because irradiation in the high-energy ultraviolet region has higher reduction efficiency. . Therefore, using a commercially available low-pressure ultraviolet lamp (150 W / 100 V: wavelength 400 nm or less peak: 185 nm), the surface of the carrier is irradiated with ultraviolet rays for 10 minutes at a distance of 30 cm from the lamp. When the above UV lamp is used, the UV irradiation time required for the reduction in the production of the antibacterial silver fine particle carrier requires some adjustment depending on the type of carrier and the properties of the fine silver particles. As a rough guide, it is about 8 to 10 minutes. The antibacterial silver fine particle carrier produced by using this physical reduction method can be immediately used for the intended antibacterial agent without being washed or otherwise required after the reduction operation is completed.

Example 1: Example using polymer resin as carrier, Transparent film (0.1 mm x 20 cm x 20 cm) of polyethylene terephthalate resin (PET) was selected from general-purpose resins as the carrier of the present invention. In the following description of the implementation process of the present invention, the PET film and that during processing will be simply referred to as “substrate” or “carrier”.

(1) Cleaning and drying of the PET substrate: 150 ml of absolute ethanol (first grade reagent) is placed in a 300 ml container, the substrate is immersed in it, and the substrate is rocked using tweezers in the liquid. And washed. Next, the base material was accommodated in another container having a capacity of 300 ml, and 300 ml of pure water (electric conductivity of 1 micro S or less) was added thereto for washing. This washing with pure water was repeated three times. After washing, the substrate was placed in a fully automatic dehumidification storage (D-BOX, manufactured by Sampleratec) and dried in a nitrogen gas stream (flow rate 100 ml / min) for 12 hours.

(2) Silver salt coating and aging: 100 ml of silver nitrate aqueous solution (concentration: 0.05 mol / l) is accommodated in a 300 ml capacity container, and the temperature of the liquid is 21 degrees C (set temperature range: 20 + -3 degrees C). Held on. Next, the dried base material was immersed in an aqueous silver nitrate solution in a container and immersed for 5 minutes while gently stirring with tweezers. During this time, care was taken so that the surface of the substrate did not come out above the liquid level. After completion of the immersion, the substrate is pulled up and the liquid droplets are attached to the surface, and another container (with a capacity of about 500 ml having a dish-like shape inside) is kept at a temperature of 20 + -3 ° C and the humidity is almost saturated. The container was placed in a separate container and filled with pure water, and the substrate surface was kept dry for 10 minutes for aging.

(3) Water removal (energy control of hydrated ions): A drier (i-BOX Auto, manufactured by Sampla Tech, Inc.) in which the base material after the aging operation has been maintained at a temperature of 25 + -5 degrees C and a humidity of 10% RH or less ) And dried for 12 hours to remove moisture.

(4) Alkaline treatment and washing: 150 ml of aqueous caustic soda (concentration 1/30 mol / l) was placed in a 300 ml container, and the temperature was maintained at 21 ° C. (set temperature range: 20 + −3 ° C.). The substrate was immersed in this with tweezers and subjected to alkali treatment for 7 minutes while gently rocking. The base material pulled up from the alkali treatment liquid was immediately washed with pure water to remove the adhering alkali liquid. In the washing method, about 200 ml of pure water (temperature is room temperature 20 + -5 degrees C) was accommodated in a container having a capacity of 300 ml, and the substrate was immersed and swung in this for about 2 minutes. Each time of washing, the pure water was changed and washed 5 times. After the third washing, one drop of a 2% alcohol solution of phenolphthalene was added to the washing water after each washing, and the washing was finished after confirming that the washing liquid did not turn reddish purple. When the cleaning liquid is colored reddish purple, it indicates that alkali remains, so it is necessary to increase the number of cleanings, but this is not necessary in this embodiment.

(5) Drying: The substrate after the washing was immediately stored in a shading dryer. The shading dryer was dried for 1 hour in a nitrogen gas stream (flow rate 300 ml / min) using a separate facility similar to the fully automatic dehumidifying storage (D-BOX) described in the above section (1). In addition, since the said drying process needs to be light-shielded, the black light-shielding film was affixed on the transparent part of the front door of a dryer.

(6) Chemical reduction treatment, washing and drying: In a container with a capacity of 300 ml, 150 ml of an aqueous formaldehyde solution (formalin) [concentration: 1/10 mol / l] is stored, and the temperature is 20 degrees C (temperature control range + -3 degrees) C). The dried substrate was dipped in this using tweezers and reduced for 4 minutes while gently rocking. After the treatment, the substrate was pulled up and immediately washed and dried. Next, the base material was accommodated in a container having a capacity of 500 ml, and 300 ml of pure water (electrical conductivity of 1 microsecond or less) was added to the container to wash the base material for about 1 minute. Similarly, the pure water was changed, and the washing was further repeated 3 times, for a total of 4 times for 4 minutes. The final wash water electrical conductivity was 0.85 microS. The completion of washing was based on the electric conductivity of washing water being less than 1 micro S.

(7) Antibacterial function test and test result: The problem to be solved by the present invention is to provide an antibacterial agent capable of exerting a safe, powerful and quick immediate bactericidal antibacterial action for a long period of time when a relatively small amount of silver is used. There is to do. At present, there is no test method to test the antibacterial mechanism of antibacterial agents that meet the relevant issues. Therefore, the present inventors have devised a unique antibacterial test method capable of most simply verifying the goal of the present invention based on the opinions of hygienists and veterinarians, and led the present invention to completion. The outline of the inspection test method will be described below. All antibacterial function tests of the antibacterial silver fine particle carrier of the present invention were conducted by the following test methods. The unicellular microorganisms used for the test were protozoa highly resistant to chemical antibacterial agents as test samples. In the actual test, Balantidium caviae, a kind of protozoa that is relatively easy to obtain and culture and relatively low in toxicity, was used. Example 1 The antibacterial action efficiency of an antibacterial silver fine particle support using PET as a carrier was 17.5 seconds.

In the antibacterial function test determination and evaluation method, in the field of view of the test microscope, a mechanism for visually confirming the invasion of protozoa was formed in the field of view of the antibacterial agent sample to be tested, and observations until the bacteria died were recorded. Normal protozoa always swim violently, and there is no break. When the action of the antibacterial agent is applied, the movement becomes dull or changes to an irregular movement such as rotation, and then the movement stops, the bacterial body deforms and expands, eventually destroying the cell membrane and causing the protoplasm It flowed out of the cell membrane tear. These changes in the situation can be easily observed with a 400 × optical microscope.

Example 2: Example using polymer resin as carrier, As a carrier of the present invention, a polyamideimide resin (Kapton) orange transparent film (0.1 mm × 15 cm × 15 cm) was selected and used.

(1) Cleaning and drying of base material: 150 ml of absolute ethanol (first grade reagent) is contained in a 300 ml capacity container, and the base material is immersed in it and washed while rocking the base material using tweezers in the liquid. did. Next, the base material was accommodated in another container having a capacity of 300 ml, and 300 ml of pure water (electric conductivity of 1 micro S or less) was added thereto for washing. This washing with pure water was repeated three times. After completion of the cleaning, the base material was housed in a fully automatic dehumidification storage (D-BOX, manufactured by Sampleratec) and dried in a nitrogen gas stream (flow rate 150 ml / min) for 6 hours.

(2) Silver coating and aging: 100 ml of an aqueous silver sulfate solution (concentration: 0.05 mol / l) is contained in a 300 ml capacity container, and the temperature of the liquid is kept at 20 degrees C (set temperature range + -3 degrees C). did. Next, the dried base material was immersed in an aqueous silver sulfate solution in the container, and immersed for 5 minutes while gently stirring with tweezers. During this time, care was taken so that the surface of the substrate did not come out above the liquid level. After completion of immersion, the substrate is pulled up and the liquid droplets are attached to the surface, and the temperature is 20 + -3 degrees C. The humidity is kept almost saturated. And was aged with the substrate surface kept dry for 10 minutes.

(3) Water removal (energy control of hydrated ions): A drier (i-BOX Auto, manufactured by Sampla Tech, Inc.) in which the base material after the aging operation has been maintained at a temperature of 25 + -5 degrees C and a humidity of 10% RH or less ) And dried for 10 hours to remove moisture.

(4) Alkaline treatment and washing: 150 ml of an aqueous caustic potash solution (concentration 1/30 mol / l) was placed in a 300 ml capacity container, and the temperature was maintained at 20 ° C. (set temperature range + −3 ° C.). The substrate was immersed in this using tweezers and subjected to alkali treatment for 7 minutes while gently rocking. The base material pulled up from the alkaline treatment liquid was immediately washed with pure water to remove the adhered alkaline liquid. In the washing method, about 200 ml of pure water (temperature is room temperature 20 + -5 degrees C) was accommodated in a container having a capacity of 300 ml, and the substrate was immersed and swung in this for about 2 minutes. Each time of washing, the pure water was changed and washed 5 times. After the third washing, one drop of a 2% alcohol solution of phenolphthalene was added to the washing water after each washing, and the washing was finished after confirming that the washing liquid did not turn reddish purple. When the cleaning liquid is colored reddish purple, it indicates that alkali remains, so it is necessary to increase the number of cleanings, but this is not necessary in this embodiment.

(5) Drying: The substrate after the washing was immediately stored in a light-shielding dryer. The shading dryer was dried for 1 hour in a nitrogen gas stream (flow rate 300 ml / min) using a separate facility similar to the fully automatic dehumidifying storage (D-BOX) described in the above section (1). In addition, since the said drying process needs light shielding, the black light shielding film was affixed on the transparent part of the front door of a dryer.

(6) Chemical reduction treatment, washing and drying: 200 ml of acetaldehyde aqueous solution [concentration: 1/10 mol / l] is accommodated in a 300 ml capacity container, and the temperature is adjusted to 20 degrees C (temperature control range + -3 degrees C). did. Next, the dried substrate was immersed using tweezers and subjected to a reduction treatment for 4 minutes while gently rocking. After the treatment, the substrate was pulled up and immediately washed as follows. The substrate was housed in a 500 ml capacity container, and 300 ml of pure water (electric conductivity 1 micro S or less) was added to the container, and the substrate was washed for about 1 minute while rocking. Similarly, the pure water was changed, and the washing was further repeated three times, for a total of four times for 4 minutes. The final wash water electrical conductivity was 0.65 microS. The completion of washing was based on the electric conductivity of washing water being less than 1 micro S.

(7) Antibacterial function test and test results: The following is the same as Example 1- (7), but Example 2 The antibacterial action efficiency of the antibacterial silver fine particle carrier using Kapton film as a carrier was 4.3 seconds. It was.

Example 3: Example of carrying on natural and synthetic fibers, cotton cloth (Japanese pharmacy method gauze) (width 30 cm x length 30 cm) was used as the carrier of the present invention.

(1) Cleaning and drying of the base material: 150 ml of absolute ethanol (first grade reagent) is placed in a 300 ml capacity container, and the base material is folded in four and immersed therein, and the base material is shaken using submerged tweezers. Washed while moving. Next, the base material was accommodated in another container having a capacity of 300 ml, and 300 ml of pure water (electric conductivity of 1 micro S or less) was added thereto for washing. This washing with pure water was repeated four times. After the completion of washing, the base material was housed in a fully automatic dehumidification storage (D-BOX, manufactured by Sampleratech) and dried in a nitrogen gas stream (flow rate 150 ml / min) for 6 hours.

(2) Silver salt coating and aging: 200 ml of silver nitrate aqueous solution (concentration: 0.02 mol / l) is contained in a 300 ml capacity container, and the temperature of the liquid is kept at 20 degrees C (set temperature range + -3 degrees C). did. Next, the dried substrate was immersed in an aqueous silver nitrate solution in the container, and immersed for 5 minutes while gently stirring with tweezers. During this time, care was taken so that the surface of the substrate did not come out above the liquid level. After completion of the immersion, the base material is pulled up, the excess droplets are lightly squeezed and spread again, and another container (with a capacity of about 500 ml in which the temperature is kept at 20 + -3 degrees C and humidity is almost saturated) The container was placed in a separate container and filled with pure water, and kept for 10 minutes in an airtight state so that the surface of the base material was not dried.

(3) Moisture removal (energy control of hydrated ions): a drier (i-BOX Auto, manufactured by Sampleratech) in which the base material after the aging operation is maintained at a temperature of 25 + -5 ° C and a humidity of 10% RH or less And dried for 10 hours to remove moisture.

(4) Alkali treatment and washing: 200 ml of a lithium hydroxide aqueous solution (concentration 1/30 mol / l) was placed in a 300 ml container, and the temperature was kept at 20 ° C. (set temperature range + −3 ° C.). The substrate was immersed in this using tweezers, and subjected to alkali treatment for 5 minutes while gently rocking. The base material pulled up from the alkaline treatment liquid was immediately washed with pure water to remove the adhered alkaline liquid. In the cleaning method, about 250 ml of pure water (temperature is room temperature 20 + -5 degrees C) was accommodated in a container having a capacity of 300 ml, and the substrate was immersed and swung in this for about 2 minutes. Each time of washing, the pure water was changed and washed 7 times. After the fifth wash, one drop of a 2% alcohol solution of phenolphthalene was added to the wash water after each wash to confirm that the wash liquid did not turn reddish purple and the wash was terminated. When the cleaning liquid is colored reddish purple, it indicates that alkali remains, so it is necessary to increase the number of cleanings, but this is not necessary in this embodiment.

(5) Drying: The substrate after the washing was immediately stored in a light-shielding dryer. The light-shielding dryer was dried for 4 hours in a nitrogen gas stream (flow rate 300 ml / min) using a separate facility similar to the fully automatic dehumidification storage box (D-BOX) described in the above step (1). In addition, since the said drying process needs light shielding, the black light shielding film was affixed on the transparent part of the front door of a dryer.

(6) Chemical reduction treatment, washing and drying: 200 ml of formic acid aqueous solution (concentration: 1/10 mol / l) was placed in a 300 ml capacity container, and the temperature was adjusted to 20 ° C. (temperature control range + −3 ° C.). . Next, the dried substrate was immersed using tweezers and subjected to a reduction treatment for 4 minutes while gently rocking. After the treatment, the substrate was pulled up and immediately washed as follows. The substrate was housed in a 500 ml capacity container, and 300 ml of pure water (electric conductivity 1 micro S or less) was added to the container, and the substrate was washed for about 1 minute while rocking. Similarly, the pure water was replaced and the washing was repeated three more times, for a total of 6 times for 6 minutes. The final wash water electrical conductivity was 0.8 microS. The completion of washing was based on the electric conductivity of washing water being less than 1 micro S.

(7) Antibacterial function test and test results: The following is the same as in Example 1- (7), but the antibacterial silver microparticle carrying body using Example 3 Japanese Pharmacopoeia gauze carrier has an antibacterial action efficiency of 3.0 seconds. Met.

Example 4: Example supported on natural and synthetic fibers, Tetoron woven fabric (width 30 cm x length 30 cm) was used as the carrier of the present invention.

(1) Cleaning and drying of the base material: 250 ml of absolute ethanol (first grade reagent) is placed in a 300 ml capacity container, and the base material is folded in four and immersed in the container, and the base material is shaken using submerged tweezers. Washed while moving. Next, the base material was lightly squeezed and accommodated in another 300 ml capacity container, and 300 ml of pure water (electric conductivity 1 micro S or less) was added thereto and washed. This washing with pure water was repeated four times. After washing, the substrate was stored in a fully automatic dehumidifying storage (D-BOX, manufactured by Sampleratec) and dried in a nitrogen gas stream (flow rate 150 ml / min) for 6 hours.

(2) Silver salt coating and aging: 200 ml of silver sulfate aqueous solution (concentration: 0.02 mol / l) is contained in a 300 ml capacity container, and the temperature of the liquid is 20 degrees C (set temperature range + -3 degrees C). Retained. Next, the dried substrate was immersed in an aqueous silver sulfate solution in a container, and immersed for 5 minutes while gently stirring with tweezers. During this time, care was taken so that the surface of the substrate did not come out above the liquid level. After completion of the immersion, the base material is pulled up, the excess droplets are lightly squeezed and spread again, and another container (with a capacity of about 500 ml in which the temperature is kept at 20 + -3 degrees C and humidity is almost saturated) The container was placed in a separate container and filled with pure water, and kept for 10 minutes in an airtight state so that the surface of the base material was not dried.

(3) Moisture removal (energy control of hydrated ions): a drier (i-BOX Auto, manufactured by Sampleratech) in which the base material after the aging operation is maintained at a temperature of 25 + -5 ° C and a humidity of 10% RH or less And dried for 10 hours to remove moisture.

(4) Alkali treatment and washing: 200 ml of an aqueous caustic soda solution (concentration 1/30 mol / l) was placed in a 300 ml capacity container, and the temperature was maintained at 20 ° C. (set temperature range + −3 ° C.). The substrate was immersed in this using tweezers, and subjected to alkali treatment for 5 minutes while gently rocking. The base material pulled up from the alkaline treatment liquid was immediately washed with pure water to remove the adhered alkaline liquid. In the cleaning method, about 250 ml of pure water (temperature is room temperature 20 + -5 degrees C) was accommodated in a 300 ml capacity container, and the substrate was immersed and swung in this for about 2 minutes. Each time of washing, the pure water was changed and washed 7 times. After the fifth wash, one drop of a 2% alcohol solution of phenolphthalene was added to the wash water after each wash to confirm that the wash liquid did not turn reddish purple and the wash was terminated. When the cleaning liquid is colored reddish purple, it indicates that alkali remains, so it is necessary to increase the number of cleanings, but this is not necessary in this embodiment.

(5) Drying: The substrate after the washing was immediately stored in a light-shielding dryer. The shading dryer was dried for 4 hours in a nitrogen gas stream (flow rate 300 ml / min) using a separate facility in the same manner as the fully automatic dehumidification storage box (D-BOX) described in the above step (1). In addition, since the said drying process needs light shielding, the black light shielding film was affixed on the transparent part of the front door of a dryer.

(6) Chemical reduction treatment, washing and drying: 200 ml of ascorbic acid aqueous solution (concentration: 1/10 mol / l) is contained in a 300 ml capacity container, and the temperature is 20 degrees C (temperature control range: 20 + -3 degrees C). Adjusted. Next, the dried substrate was dipped using tweezers and reduced for 4 minutes while gently rocking. After the treatment, the substrate was pulled up and immediately washed as follows. The substrate was housed in a 500 ml capacity container, and 300 ml of pure water (electric conductivity 1 micro S or less) was added to the container, and the substrate was washed for about 1 minute while rocking. Similarly, the pure water was replaced and the washing was repeated three more times, for a total of 6 times for 6 minutes. The final wash water had an electrical conductivity of 0.7 microS. The completion of washing was based on the electric conductivity of washing water being less than 1 micro S.

(7) Antibacterial function test and test results: The following is the same as Example 1- (7), but the antibacterial silver fine particle carrier using Tetron fabric as a carrier in Example 4 has an antibacterial action efficiency of 3.6 seconds. there were.

Example 5: An example using ceramics and glass as a carrier, and a titania (titanium oxide) ceramic plate (0.5 mm × 30 cm × 30 cm) selected from ceramics which are metal oxide sintered bodies as a carrier of the present invention.

(1) Cleaning and drying of the substrate: 150 ml of absolute ethanol (first grade reagent) is placed in a 300 ml container, and the substrate is immersed in it, while the substrate is rocked using tweezers in the liquid. Washed. Next, the base material was accommodated in another container having a capacity of 300 ml, and 300 ml of pure water (electric conductivity of 1 micro S or less) was added thereto for washing. This washing with pure water was repeated three times. After the completion of washing, the base material was housed in a fully automatic dehumidification storage (D-BOX, manufactured by Sampleratec) and dried in a nitrogen gas stream (flow rate 100 ml / min) for 5 hours.

(2) Silver salt coating and aging: 100 ml of silver sulfate aqueous solution (concentration: 0.02 mol / l) is contained in a 300 ml capacity container, and the temperature of the liquid is 20 degrees C (set temperature range + -3 degrees C). Retained. Next, the dried base material was immersed in an aqueous silver sulfate solution in the container, and immersed for 5 minutes while gently stirring with tweezers. During this time, care was taken so that the surface of the substrate did not come out above the liquid level. After completion of immersion, the substrate is pulled up and the liquid droplets are attached to the surface, and the temperature is 20 + -3 degrees C. The humidity is kept almost saturated. And was aged with the substrate surface kept dry for 10 minutes.

(3) Moisture removal (energy control of hydrated ions): a drier (i-BOX Auto, manufactured by Sampleratech) in which the base material after the aging operation is maintained at a temperature of 25 + -5 ° C and a humidity of 10% RH or less And dried for 10 hours to remove moisture.

(4) Alkali treatment and washing: 150 ml of a lithium hydroxide aqueous solution (concentration: 1/40 mol / l) was placed in a 300 ml capacity container, and the temperature was maintained at 20 ° C. (set temperature range + −3 ° C.). An alkali treatment was performed for 5 minutes while the substrate was immersed in this with tweezers and gently rocked. The base material pulled up from the alkaline treatment liquid was immediately washed with pure water to remove the adhered alkaline liquid. In the washing method, about 200 ml of pure water (temperature is room temperature 20 + -5 degrees C) was accommodated in a container having a capacity of 300 ml, and the substrate was immersed and swung in this for about 2 minutes. Each time of washing, the pure water was changed and washed 5 times. After the third washing, one drop of a 2% alcohol solution of phenolphthalene was added to the washing water after each washing, and the washing was finished after confirming that the washing liquid did not turn reddish purple. When the cleaning liquid is colored reddish purple, it indicates that alkali remains, so it is necessary to increase the number of cleanings, but this is not necessary in this embodiment.

(5) Drying: The substrate after the washing was immediately stored in a light-shielding dryer. The shading dryer was dried for 1 hour in a nitrogen gas stream (flow rate 300 ml / min) using a separate facility similar to the fully automatic dehumidifying storage (D-BOX) described in the above section (1). In addition, since the said drying process needs light shielding, the black light shielding film was affixed on the transparent part of the front door of a dryer.

(6) Chemical reduction treatment, cleaning and drying: 150 ml of formaldehyde aqueous solution (formalin concentration: 1/10 mol / l) is contained in a 300 ml capacity container, and the temperature is set to 20 ° C. (temperature control range + −3 ° C.) did. Next, the dried substrate was dipped using tweezers and reduced for 4 minutes while gently rocking. After the treatment, the substrate was pulled up and immediately washed and dried. The substrate was housed in a 500 ml capacity container, and 300 ml of pure water (electric conductivity 1 micro S or less) was added to the container, and the substrate was washed for about 1 minute while rocking. Similarly, the pure water was changed and the washing was repeated three more times, for a total of four times for 4 minutes. The final wash water had an electrical conductivity of 0.4 microS. The completion of washing was based on the electric conductivity of washing water being less than 1 micro S.

(7) Antibacterial function test and test results: The following is the same as Example 1- (7), but the antibacterial silver microparticle carrying body using Example 5 titania as a carrier had an antibacterial action efficiency of 2.7 seconds. .

Example 6: Example using ceramic and glass as carrier, Pyrex (registered trademark) plate (0.5 mm × 30 cm × 30 cm), which is heat-resistant glass, was selected and used as the carrier of the present invention.

(1) Cleaning and drying of the substrate: 150 ml of absolute ethanol (first grade reagent) is placed in a 300 ml container, and the substrate is immersed in it, while the substrate is rocked using tweezers in the liquid. Washed. Next, the base material was accommodated in another container having a capacity of 300 ml, and 300 ml of pure water (electric conductivity of 1 micro S or less) was added thereto for washing. This washing with pure water was repeated three times. After washing, the base material was housed in a fully automatic dehumidification storage (D-BOX, manufactured by Sampleratec) and dried in a nitrogen gas stream (flow rate 100 ml / min) for 5 hours.

(2) Silver salt coating and aging: Ammonia silver nitrate solution (concentration: 0.03 mol / l) 100 ml is contained in a 300 ml capacity container, and the temperature of the liquid is 20 degrees C (set temperature range + -3 degrees C). Retained. Next, the dried substrate was immersed in an ammoniacal silver nitrate solution in a container and immersed for 5 minutes while gently stirring with tweezers. During this time, care was taken so that the surface of the substrate did not come out above the liquid level. After completion of immersion, the substrate is pulled up and the liquid droplets are attached to the surface, and the temperature is 20 + -3 degrees C. The humidity is kept almost saturated. And was aged with the substrate surface kept dry for 10 minutes.

(3) Moisture removal (energy control of hydrated ions): a drier (i-BOX Auto, manufactured by Sampleratech) in which the base material after the aging operation is maintained at a temperature of 25 + -5 ° C and a humidity of 10% RH or less And dried for 5 hours to remove moisture.

(4) Alkali treatment and washing: 150 ml of an aqueous caustic potash solution (concentration: 1/40 mol / l) was placed in a 300 ml container, and the temperature was maintained at 20 ° C. (set temperature range + −3 ° C.). An alkali treatment was performed for 5 minutes while the substrate was immersed in this with tweezers and gently rocked. The base material pulled up from the alkaline treatment liquid was immediately washed with pure water to remove the adhered alkaline liquid. In the washing method, about 200 ml of pure water (temperature is room temperature 20 + -5 degrees C) was accommodated in a container having a capacity of 300 ml, and the substrate was immersed and swung in this for about 2 minutes. Each time of washing, the pure water was changed and washed 5 times. After the third washing, one drop of a 2% alcohol solution of phenolphthalene was added to the washing water after each washing, and the washing was finished after confirming that the washing liquid did not turn reddish purple. When the cleaning liquid is colored reddish purple, it indicates that alkali remains, so it is necessary to increase the number of cleanings, but this is not necessary in this embodiment.

(5) Drying: The substrate after the washing was immediately stored in a light-shielding dryer. The shading dryer was dried for 1 hour in a nitrogen gas stream (flow rate 300 ml / min) using a separate facility similar to the fully automatic dehumidifying storage (D-BOX) described in the above section (1). In addition, since the said drying process needs light shielding, the black light shielding film was affixed on the transparent part of the front door of a dryer.

(6) Reduction treatment by ultraviolet irradiation: A mercury lamp (150 W / 100 VAC, λ = 185 nm) and a power supply device manufactured by Toshiba were prepared as ultraviolet sources. The distance from the substrate surface was kept at 20 cm, and the position of the lamp was fixed so that the substrate surface was irradiated with ultraviolet rays at a right angle. Since the substrate was supported on both sides, UV irradiation was performed twice on each side. The irradiation time was 10 minutes on each side for a total of 20 minutes. Thus, the antibacterial silver fine particle carrier of the present invention having Vyrex as a carrier was produced by a reduction method by ultraviolet irradiation.

(7) Antibacterial function test and test results: The following is the same as Example 1- (7), but Example 6 has an antibacterial silver fine particle support using Pyrex (registered trademark) glass as the carrier, and the antibacterial action efficiency is 3 0.0 seconds.

Example 7: Example using porcelain as carrier, alumina ceramics (0.5 mm x 50 cm x 50 cm) were selected from general-purpose porcelain and used as the carrier of the present invention.

(1) Cleaning and drying of the substrate: 150 ml of absolute ethanol (first grade reagent) is placed in a 300 ml container, and the substrate is immersed in it, while the substrate is rocked using tweezers in the liquid. Washed. Next, the base material was accommodated in another container having a capacity of 300 ml, and 300 ml of pure water (electric conductivity of 1 micro S or less) was added thereto for washing. This washing with pure water was repeated three times. After completion of the cleaning, the base material was housed in a fully automatic dehumidification storage (D-BOX, manufactured by Sampleratec) and dried in a nitrogen gas stream (flow rate 100 ml / min) for 5 hours.

(2) Silver salt coating and aging: 100 ml of silver nitrate aqueous solution (concentration: 0.02 mol / l) is contained in a 300 ml capacity container, and the temperature of the liquid is kept at 20 degrees C (set temperature range + -3 degrees C). did. Next, the dried substrate was immersed in an aqueous silver nitrate solution in a container and immersed for 5 minutes while gently stirring with tweezers. During this time, care was taken so that the surface of the substrate did not come out above the liquid level. After completion of immersion, the substrate is pulled up and the liquid droplets are attached to the surface, and the temperature is 20 + -3 degrees C. The humidity is kept almost saturated. And was aged with the substrate surface kept dry for 10 minutes.

(3) Moisture removal (energy control of hydrated ions): a drier (i-BOX Auto, manufactured by Sampleratech) in which the base material after the aging operation is maintained at a temperature of 25 + -5 ° C and a humidity of 10% RH or less And dried for 12 hours to remove moisture.

(4) Alkali treatment and washing: 200 ml of an aqueous calcium hydroxide solution (concentration 1/50 mol / l) was placed in a 300 ml container, and the temperature was maintained at 20 ° C. (set temperature range + −3 ° C.). The substrate was immersed in this with tweezers and subjected to alkali treatment for 7 minutes while gently rocking. The base material pulled up from the alkaline treatment liquid was immediately washed with pure water to remove the adhered alkaline liquid. In the washing method, about 200 ml of pure water (temperature is room temperature 20 + -5 degrees C) was accommodated in a container having a capacity of 300 ml, and the substrate was immersed and swung in this for about 2 minutes. Each time of washing, the pure water was changed and washed 5 times. After the third wash, one drop of a 2% alcohol solution of phenolphthalene was added to the wash water after each wash, and it was confirmed that the wash liquid did not turn reddish purple, and the wash was completed. When the cleaning liquid is colored reddish purple, it indicates that alkali remains, so it is necessary to increase the number of cleanings, but this is not necessary in this embodiment.

(5) Drying: The substrate after the washing was immediately stored in a light-shielding dryer. The shading dryer was dried in a nitrogen gas stream (flow rate 150 ml / minl) for 3 hours using a separate facility similar to the fully automatic dehumidification storage (D-BOX) described in the above step (1). In addition, since the said drying process needs light shielding, the black light shielding film was affixed on the transparent part of the front door of a dryer.

(6) Chemical reduction treatment, washing and drying: 150 ml of acetaldehyde aqueous solution (concentration: 1/20 mol / l) is accommodated in a 300 ml capacity container, and the temperature is set to 20 degrees C (temperature control range + -3 degrees C). did. Next, the dried substrate was dipped using tweezers and reduced for 5 minutes while gently rocking. After the treatment, the substrate was pulled up and immediately washed and dried. The substrate was housed in a 500 ml capacity container, and 300 ml of pure water (electric conductivity 1 micro S or less) was added to the container, and the substrate was washed for about 1 minute while rocking. Similarly, the pure water was changed, and the washing was further repeated 3 times, for a total of 4 times for 4 minutes. The final wash water had an electrical conductivity of 0.7 microS. The completion of washing was based on the electric conductivity of washing water being less than 1 micro S.

(7) Antibacterial function test and test results: The following is the same as Example 1- (7), but the antibacterial silver microparticle carrying body using alumina porcelain as the carrier of Example 7 has an antibacterial action efficiency of 5.5 seconds. there were.

The invention of claim 1 is an antibacterial silver fine particle carrier, wherein a silver salt solution is applied to the surface of the carrier, water is removed, and then silver oxide particles are generated on the surface of the carrier by alkaline solution treatment. Since it has the feature of reducing treatment from active hydrogen-based reducing agent or ultraviolet irradiation with a wavelength of 400 nanometers or less, there are a large number of carriers used by industries dealing with this field, so it has a great market effect as a synergistic added value by providing materials It has the immediacy to produce.

The invention of claim 2 is the antibacterial silver fine particle carrier according to claim 1, wherein the carrier is a polymer resin, natural gauze or synthetic fiber, glass, ceramics, metal oxide and metal oxide sintered body. It is characterized in that it is at least one carrier selected from the group consisting of the above materials, and therefore, it is possible to supply materials that produce a large market effect with synergistic added value to the above materials and to provide a manufacturing method. I have.

The invention of claim 3 is the antibacterial silver fine particle carrier according to claim 1, wherein the silver salt solution is at least one silver selected from the group consisting of an ammoniacal silver nitrate solution, a silver sulfate aqueous solution, and a silver nitrate aqueous solution. Since it is a salt solution, it has the immediacy of supplying materials and providing manufacturing methods that produce a great market effect with the above materials with synergistic added value.

The invention of claim 4 is the antibacterial silver fine particle carrier according to claim 1, wherein the alkaline solution is at least one selected from the group consisting of aqueous solutions of caustic soda, caustic potash, lithium hydroxide, and calcium hydroxide. Since it is an alkaline solution, it has the immediacy of supplying the material and providing the manufacturing method that produce a great market effect with the above-mentioned materials with synergistic added value.

The invention of claim 5 is the antibacterial silver fine particle carrier according to claim 1, wherein the active hydrogen reducing agent is at least one selected from the group consisting of formic acid, formaldehyde, acetaldehyde, ascorbic acid and hydroquinone. Since it is a hydrogen-based reducing agent, it has the immediacy of supplying a material and providing a manufacturing method that produce a great market effect with a synergistic added value to the above materials.

Claims (5)

After applying a silver salt solution to the surface of the carrier and removing water, this is immersed in an alkaline solution to produce silver oxide particles, which are then activated by an active hydrogen reducing agent or by irradiation with ultraviolet light having a wavelength of 400 nm or less. An antibacterial silver fine particle carrier characterized by producing and carrying silver fine particles having excellent antibacterial properties on the surface of the carrier by reduction treatment. The carrier is at least one carrier selected from the group consisting of natural or synthetic fibers such as polymer resins and gauze, glass, ceramics, metal oxides, and metal oxide sintered bodies. The antibacterial silver fine particle carrier according to 1. The antibacterial silver fine particle carrier according to claim 1, wherein the silver salt solution is at least one silver salt solution selected from the group consisting of an ammoniacal silver nitrate solution, a silver sulfate aqueous solution, and a silver nitrate aqueous solution. . The antibacterial silver fine particle carrier according to claim 1, wherein the alkaline solution is at least one alkaline solution selected from the group consisting of aqueous solutions of caustic soda, caustic potash, lithium hydroxide, and calcium hydroxide. . The antibacterial silver fine particles according to claim 1, wherein the active hydrogen reducing agent is at least one active hydrogen reducing agent selected from the group consisting of formic acid, formaldehyde, acetaldehyde, ascorbic acid, and hydroquinone. Carrier.