JP4980855B2 - Cosmetics - Google Patents

Description

  The present invention relates to a cosmetic containing honey, β-glucan, and an antibacterial composition.

  Conventionally, cosmetics represented by moisturizers, beauty liquids, facial cleansing foams and the like have been used by many people, and various types are provided mainly for products targeting women.

  Among these cosmetics, cosmetics containing honey are capable of producing an excellent moisturizing effect, and are high in safety because they are raw materials derived from foods, and have gained high popularity.

  On the other hand, β-glucan is one of physiologically active substances that have been attracting attention in recent years. This β-glucan is a polysaccharide isolated from yeast and basidiomycetes (mushrooms), and is considered to contribute to the improvement of human immunity.

Therefore, by adding β-glucan to a cosmetic containing honey, the skin surface can be moisturized, and the immunity on the skin inner surface can be activated to improve skin quality (for example, , See Patent Document 1).
JP 2005-206573 A

  However, it is difficult to maintain the quality of the conventional cosmetic containing honey and β-glucan while preventing microbial contamination and spoilage over a long period (for example, 3 months).

  In other words, since honey is the nectar of flowers collected by insects, it may contain bacteria and so on, and honey in the undiluted state contains saccharides at high concentrations, so that microbial growth However, when diluted to make cosmetics, the activity of microorganisms becomes active, which may cause corruption.

  Further, β-glucan generally used industrially is often separated from yeasts and basidiomycetes, and is a microorganism-derived polysaccharide, which may cause microbial contamination of cosmetics.

  Therefore, as described in Patent Document 1, a method of preventing cosmetics from being contaminated with microorganisms or decaying by adding an antibacterial agent such as parabens, benzoic acids or silver ions can be considered.

  However, parabens and benzoic acids may be irritating when cosmetics are applied to the hand skin, and may cause rashes or rashes depending on the user.

  Therefore, it seems that it is preferable to use silver ions that can prevent microbial contamination and spoilage at a relatively low concentration and are harmless to the human body.

  However, silver ions in aqueous solvents lack dispersion stability and tend to aggregate over time. Aggregated silver ions rapidly lose antiseptic and antibacterial effects, resulting in cosmetic quality over a long period of time. It was difficult to hold.

  The present invention has been made in view of such circumstances, and for a long time, it contains honey and β-glucan, and contains an antibacterial composition derived from silver having long-term dispersion stability. To provide cosmetics capable of maintaining quality.

  In order to solve the above conventional problems, the cosmetic according to the present invention is a cosmetic containing honey, β-glucan, and an antibacterial composition, wherein the antibacterial composition comprises collagen and its After adding a silver salt solution and a catalyst to the aqueous solution of the polypeptide compound obtained by hydrolysis and reacting it, the α amino group of the polypeptide compound is reduced by irradiating it with ultraviolet light having a wavelength of 400 nm or less. At the same time, the fine silver particles were deposited on the nitrogen atoms of the α-amino group by electrostatic adsorption.

The following points are also characteristic.
(1) The collagen and the polypeptide compound obtained by hydrolysis thereof have a molecular weight in the range of 130,000 to 2,000 and are water-soluble.
(2) The silver solution is at least one silver salt solution selected from the group consisting of an ammoniacal silver nitrate aqueous solution, a silver nitrate aqueous solution, and a silver sulfate aqueous solution.
(3) The catalyst is at least one aqueous solution selected from the group consisting of aqueous solutions of lithium hydroxide, calcium hydroxide, sodium hydroxide, and potassium hydroxide.
(4) The light source used for reduction by ultraviolet irradiation is one or two selected from natural sunlight, a high-pressure or low-pressure xenon gas discharge tube, a high-pressure or low-pressure mercury lamp, or a light source group having equivalent ultraviolet radiation. Use more than seeds.

  In invention of Claim 1, it is cosmetics containing a honey, (beta) -glucan, and an antibacterial composition, Comprising: The said antibacterial composition is a polypeptide compound obtained by collagen and its hydrolysis. After adding a silver salt solution and a catalyst to the aqueous solution and reacting them, fine silver particles are precipitated in the vicinity of the α-amino group of the polypeptide compound by reducing it by irradiating ultraviolet rays having a wavelength of 400 nm or less. At the same time, since the fine silver particles are supported on the nitrogen atoms of the α-amino group by electrostatic adsorption, they contain honey and β-glucan that are likely to rot when used as cosmetics. Therefore, it is possible to provide a cosmetic that can prevent microbial contamination and spoilage and that does not cause harm to the human body due to antibacterial components.

  In the invention described in claim 2, since the collagen and the polypeptide compound obtained by hydrolysis thereof have a molecular weight in the range of 130,000 to 2,000 and are water-soluble, an antibacterial composition in cosmetics The dispersion stability of the product can be further improved, and aggregation can be prevented to prevent microbial contamination and spoilage for a long time.

  In the invention according to claim 3, since the silver solution is at least one silver salt solution selected from the group consisting of an aqueous ammoniacal silver nitrate solution, an aqueous silver nitrate solution, and an aqueous silver sulfate solution, microbial contamination and decay are prevented. It can be set as the cosmetics containing many antibacterial compositions with high effect.

  In the invention according to claim 4, since the catalyst is at least one aqueous solution selected from the group consisting of aqueous solutions of lithium hydroxide, calcium hydroxide, sodium hydroxide, and potassium hydroxide, The production efficiency of the antibacterial composition can be improved, and a cosmetic containing a large amount of the antibacterial composition having a high effect of preventing microbial contamination and spoilage can be obtained.

  In the invention according to claim 5, the light source used for the reduction by ultraviolet irradiation is natural sunlight, a high-pressure or low-pressure xenon gas discharge tube, a high-pressure or low-pressure mercury lamp, or a light source group having ultraviolet radiation equivalent to them. Since it is decided to use one kind or two or more kinds selected, it is possible to improve the production efficiency of the antibacterial composition and to make a cosmetic containing a lot of antibacterial compositions having a high effect of preventing microbial contamination and spoilage. be able to.

  The present invention is a cosmetic comprising honey, β-glucan, and an antibacterial composition, wherein the antibacterial composition is a silver salt solution in an aqueous solution of a polypeptide compound obtained by collagen and hydrolysis thereof. In addition, the fine silver particles are precipitated in the vicinity of the α-amino group of the polypeptide compound at the same time as the reduction by irradiating it with ultraviolet light having a wavelength of 400 nm or less. The present invention provides a cosmetic characterized in that silver particles are supported on nitrogen atoms of an α-amino group by electrostatic adsorption.

  In other words, it is a cosmetic that contains honey with a high moisturizing effect and β-glucan with a high immunostimulatory effect, and as a antibacterial agent, fine silver particles are electrostatically adsorbed on the nitrogen atoms of the α-amino group. By using the antibacterial composition thus prepared, a cosmetic that is safe to the hand skin and can prevent microbial contamination and decay over a long period of time is provided.

  Here, it is preferable to use one or a mixture of two or more honey-derived, clover-derived, acacia-derived, and camellia-derived honey.

  By using these honeys, it is possible to effectively prevent the honey from solidifying or agglomerating the honey components, and the antibacterial composition is agglomerated using the agglomerated honey components as a core to prevent microbial contamination. Attenuation of the anti-corruption effect can be prevented.

β-glucan is not particularly limited and cannot be derived from black yeast. Please write something else. Those which can be used and are derived from black yeast are preferred.

  In addition, as a feature of the present invention, the antibacterial agent reacts by adding a silver salt solution and a catalyst to an aqueous solution of a polypeptide compound obtained by collagen and hydrolysis thereof, and then irradiating it with ultraviolet rays having a wavelength of 400 nm or less. By carrying out reduction, fine silver particles are precipitated in the vicinity of the α-amino group of the polypeptide compound, and at the same time, the anti-bacterial composition comprising the fine silver particles supported on the nitrogen atom of the α-amino group by electrostatic adsorption I am using things.

  Hereinafter, this antibacterial composition will be specifically described.

  The antibacterial composition used in the present embodiment is an antibacterial composition that is harmless to humans and is environmentally friendly, in which fine silver particles are supported on a water-soluble or hydrophilic component derived from a natural polymer. Specifically, it can also be said to be an antibacterial composition comprising silver or fine particles carried on collagen or a polypeptide compound molecule obtained by hydrolysis of collagen.

  In general, a composition having antibacterial properties using silver is conventionally supported by silver or other metals containing silver as ions in a crystal such as zeolite, and silver or the like is partially supported on a part of the ionic crystal. Many antibacterial agents or those supported on an inorganic solid surface have been proposed.

  However, in these proposals, the range of use is limited by the form of the carrier. For example, (1) It cannot be mixed or diluted as an aqueous solution. (2) Depending on the type of metal or anion other than silver, there is a drawback that it is toxic and its use in the human body or natural environment is restricted.

  In addition, among conventional silver-based liquid antibacterial materials, there is an example (for example, see Japanese Patent Application Laid-Open No. 2004-99450) that dares to fear that silver is eluted into water, but bacteria and fungi are known. The design that keeps the reproductive water away and reduces the probability of contact with the antibacterial component impairs the antibacterial function of silver.

  In the research related to the previous invention (see Japanese Patent Application No. 2004-367074), the present inventors discovered that the antibacterial property of silver is based on the physical properties of fine silver particles, and applied the novel antibacterial silver fine particles to which this is applied. Invented the body. In particular, in the present invention, it has been found that the silver antibacterial property is further remarkably increased because the silver fine particles are significantly excited by the quantum size effect. Discovered the fact that by producing and supporting ultrafine silver particles on the surface of the carrier, it was found to exhibit significantly stronger and faster bactericidal antibacterial properties than conventional silver antibacterial agents. A solid antibacterial silver carrier was proposed.

  In the above proposal, the thermodynamic quantities due to the quantum size effect greatly deviate from the bulk value and are significantly excited by controlling the order of atomic arrangement of silver fine grain crystals discontinuously and creating a lattice asymmetric state. It will be in the state. As a result, it was discovered that the antibacterial property of silver was further increased, and succeeded in supporting the fine silver particles produced by applying this principle on the surface of the carrier. In the above proposal, it is disclosed that fine silver particles of several nanometer scale are supported on the surface of a solid support by electrostatic adsorption. Further, as a principle of supporting the fine silver particles, it has been disclosed as a research result that the van der Waals force due to the electrostatic adsorption between the electronegativity distributed on the surface of the carrier molecule and the positive charge of the fine silver particles is disclosed. ing. The details of the background art are as already described in Patent Document 2.

  As described above, the unique metal physical properties of silver are optimal as antibacterial functional agents, but most of the proposed ones including the prior patents of the present inventors (Japanese Patent Application No. 2004-367074) are It is a form that is insoluble in water or difficult to disperse in water, and is not necessarily an effective form with respect to moisture, which is one of the major factors in the growth conditions of bacteria and fungi.

  Moreover, in the method of supporting silver on a solid surface, although the fine particle is formed and the quantum size effect is enhanced, the mobility of the silver fine particle itself is restricted by the carrier, so that it contacts with bacteria. It became a factor that hindered the opportunity.

  Therefore, the antibacterial composition used in the present embodiment is a solution to such a conventional problem, and the movement of silver by imparting water solubility while maintaining the quantum size effect of the silver fine particles. It increases the degree and realizes an immediate bactericidal antibacterial function.

  The antibacterial composition used here is an electronegative functional group (peptide group) of an organic polymer micelle capable of adopting a water-soluble or hydrophilic gel state from fine silver particles according to the invention of the prior application (see Japanese Patent Application No. 2004-367074). The water-soluble antibacterial composition is intended to be provided by supporting the water-soluble polymer micelle with an antibacterial effect equivalent to that of the prior invention. In the present invention, since a peptide compound derived from collagen is used as a carrier, it is one of the features that it has extremely high safety especially for ecosystems.

  In particular, the antibacterial composition according to the present embodiment is made in view of the above prior art, particularly the proposal of the prior application made by the present inventors, and the fine silver particles based on the prior application are obtained. , Providing a powerful antibacterial composition that is water-soluble and safe and harmless by supporting it by electrostatic adsorption on the electronegative groups of water-soluble polymer micelles rather than the insoluble solid carrier in the previous application It becomes possible to do.

  The silver salt solution used at the time of preparing the antibacterial composition according to this embodiment may be at least one silver salt solution selected from the group consisting of an ammoniacal silver nitrate aqueous solution, a silver nitrate aqueous solution, and a silver sulfate aqueous solution.

  By using these silver salt solutions, fine silver particles can be efficiently precipitated.

  Moreover, the catalyst used at the time of preparation of an antibacterial composition is good also as at least 1 type of aqueous solution selected from the group which consists of each aqueous solution of lithium hydroxide, calcium hydroxide, sodium hydroxide, and potassium hydroxide.

  By using these aqueous solutions, fine silver particles can be efficiently precipitated.

  Furthermore, in the preparation of the antibacterial composition according to the present embodiment, natural light, a high-pressure or low-pressure xenon gas discharge tube, a high-pressure or low-pressure mercury lamp, or equivalent ultraviolet radiation is used as a light source used for reduction by ultraviolet irradiation. You may make it use 1 type, or 2 or more types selected from the light source group which has an ability.

  By using these light sources, fine silver particles can be efficiently precipitated.

  Hereinafter, the antibacterial composition according to the present embodiment will be further described based on experimental results and the like.

  As stated in the prior application proposal (Japanese Patent Application No. 2004-367074), the overall research on the antibacterial properties of silver was preceded by trial and error from the viewpoint of general public health. It is pointed out that the search for the principle, such as the action mechanism of the agent, is insufficient. In particular, the antibacterial action of silver is misleading and there are few established theories based on scientific grounds.

  In order to verify the effects of the present invention and to elucidate the antibacterial action of silver, the present inventors consider that the metal physical properties of silver occupying the mechanism of action are important, and the antibacterial action of silver The following antibacterial action experiment was carried out with the view that the observation and analysis of the phenomenon of the occurrence of selenium was essential for the elucidation of the principle of silver antibacterial action.

  The antibacterial composition (water-soluble strong antibacterial agent in which silver fine particles are supported on collagen micelles) used in this embodiment was diluted 1000 times with ion-exchanged water to prepare a sample. A drop of this sample is dropped on the center of a slide glass set in an 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 an optical microscope (400 times magnification).

  Take about 1 drop of the above bacterial culture solution as a dropper and apply it to the edge of the cover glass of the test piece. While keeping the protozoa migrating inside the liquid phase of the sample, the microscope observation and visual field video recording Went. The results were as follows.

  As soon as the protozoa migrated into the dilute aqueous solution of the antibacterial composition enters the sample system, the ciliary movement stops after several rotations and is killed. In the meantime, it is only a few seconds. The expression of immediate bactericidal antibacterial effect was most appropriate.

  In addition, after the ciliary movement is stopped, the cell membrane of the cells is physically destroyed, and the protoplasm inside is clearly observed, and its bactericidal action is suitable for being expressed as truly dramatic. It was a situation.

  The main reason why the present inventors selected the protozoa as a target for the antibacterial efficiency test is as follows. In other words, protozoa are relatively large, a few micrometers in size, can be easily observed with an optical microscope of about 400 times, and movement by flagella is active. There is an advantage that it can be easily confirmed visually. The cell walls of protozoa are said to have low chemical permeability and 600,000 times stronger resistance to chlorine than E. coli. Therefore, since it is a protozoan that cannot be expected to have a bactericidal effect at all in the chlorine concentration of water treatment, the bactericidal ability to instantly kill these is considered as one of the ideal targets of antibacterial efficiency required for future antibacterial agents. Can be tricked.

  The video recording of the experiment is ready to be disclosed if necessary.

  Furthermore, other experiments have demonstrated that the above-described sample of the present invention against Escherichia coli has an almost instantaneous killing effect upon contact. As described above, the mechanism by which the antibacterial composition (silver fine particle carrier) used in the present embodiment kills single-cell microorganisms in an extremely short time is a large energy that gives a rapid potential change to the cell membrane surface of the microorganism in contact. It is thought that there is. Among metals, silver is a metal with unique physical properties as a noble metal, and the antibacterial effect mentioned above is also considered as a slow phenomenon that only inhibits the living reaction like the conventional antibacterial effect, considering its rapid phenomenon. Is a remarkable effect that does not need to be compared.

  As a result of the examination, the basic matters that were insufficiently examined in the interpretation of the action mechanism for the conventional antibacterial agents were arranged, and the present invention was promoted while trying to find and correct errors.

  First, we will consider the aspects of single-cell microorganisms and the mechanism of metabolic activity, and deal 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 individual microorganisms is extremely small, and a large number gather to affect the surroundings.

  The only thing that protects microbial cells is the cell membrane, which is almost defenseless. The cell membrane is a semipermeable membrane, but it is not a simple semipermeable membrane. It has selective permeability and uses the energy obtained by intracellular substance metabolism to actively transport specific ions against the concentration gradient (active tr). -Anport) is known. As a result, homeostasis, which is the basis of life, can be maintained.

  However, single-cell microorganisms also regulate ion movement according to changes in the surrounding environment, and always try to keep the potential difference inside and outside the cell membrane constant. When applied from, the function of the membrane is inhibited and the cells die, and it can be seen that the control of this function is ultimately based on electrical signals.

  In addition, as shown in the protozoan experiment, some microorganisms exhibiting motility move by moving flagella and cilia, but their scientific composition is known to be the same type of protein as animal muscle fibers. ing. In general animals, it is thought that contraction of muscle fibers occurs when two types of proteins called actin and myosin, which overlap each other in layers, slip.

  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 functions of single-cell microorganisms such as protozoa are finally controlled by electrical signals.

  From the above, it can be seen that the metabolic energy necessary for maintaining the life of single-cell microorganisms is extremely small, and the instructions necessary for maintaining the order of life-supporting activities depend on weak electrical signals.

  Also in these points, it is understood that many errors exist in the conventional antibacterial technical idea.

  Next, an outline of the results of detailed examination of the electrical properties of the cell membrane of a unicellular microorganism will be described. Biological cells are each encased in a cell membrane. Cell membranes 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 a resting potential, which is expressed as 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 the resting potential, but when a stimulus exceeding a certain threshold is applied to the cell, the ion permeability of the membrane changes at a stretch, An action potential is generated.

  The change process of the membrane potential consists of the disappearance of the potential difference (depolarization), the reversal of polarity (overshoot), and the return to the resting potential (repolarization) again, and the electrical waveform as a whole becomes a spike wave within 5 msec. . The difference (amplitude) between the resting potential and the action potential differs depending on the cell type, but is particularly remarkable in nerve and muscle cells. Although the electrical properties of cell membranes have an important role in maintaining normal life activity of cells, irrelevant electrical stimuli from outside cause considerable disruption and damage to cell membranes. Excessive electrical acupuncture causes cells to die immediately.

  As described above, no proposals related to the conventional antibacterial mechanism have any inventions aimed at 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 that they play an important role in various life activities such as nutritional activities and danger avoidance by adapting to changes in the external environment.

  Moreover, 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 are moving by the same mechanism as higher animals.

  Based on the antibacterial experiment results against protozoa and Escherichia coli of an aqueous solution of the antibacterial composition (silver fine particle-supported collagen) used in this embodiment, and the knowledge and suggestion regarding the antibacterial effect of external voltage application on the cell membrane potential of the single cell microorganism The antibacterial effect of the antibacterial composition 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 antibacterial composition (silver fine particle carrier) used in the present embodiment, the physical properties of silver considered to directly contribute to the antibacterial effect are specified, and the quantum size effect of the characteristics is determined. Consider.

  The quantum size effect has already been described in the prior patent application, but since it is an important concept common to the present invention, it will be described in detail again.

  When the size of a solid sample is reduced to about the de Broglie wavelength of conduction electrons and holes in the material, changes that affect the thermodynamic quantities and transport coefficient of the material appear. This 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. In particular, the extreme increase in the pulse energy of the redox potential due to the quantum size effect is believed to be the biggest factor in the immediate bactericidal antibacterial effect. Although steady-state measurement of the redox potential is possible, it is technically difficult to actually measure a pulse excited by the quantum size effect, or to calculate by theoretic deduction. It is understood.

  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.

  Silver fine particles excited by the quantum size effect are considered to be a cell membrane destruction effect by applying a pulse electric field of a redox cycle having an active region in the vicinity of the surface to the cell membrane of a single cell microorganism. In this case, the electrical pulse transmission is considered to be due to ionic conduction in the electrolyte aqueous solution. All suffer from bactericidal action.

  Even in a normal state that does not consider the excited state due to the quantum size effect, silver is a metal that exhibits physical properties that are significantly different from those of other metals. Silver is a kind of precious metal together with gold, platinum, etc., and most of it is produced in the state of metallic elements. This is because an element called a precious metal is generally much lower in chemical potential than other metal elements, and is more stable when present in the metal state than it combines with other elements to form a more stable compound. This is due to the physical property.

  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 silver metal physical properties (bulk physical properties), through the knowledge about the antibacterial mechanism of silver according to the present invention, the inventor's findings regarding the items related to the electronic properties of silver obtained are described, and the conventional silver It eliminates some errors in antibacterial properties and provides reference for the development and development of the technology.

  As a physical property value of silver that does not include the quantum size effect, the disturbance of the cell membrane potential of single-cell microorganisms is the mechanism of antibacterial action, (1) ionization energy (7.58 eV), (2) electron affinity (1.0 eV), (3) Redox potential (Ag + / Ag, 0.799 V) and (4) Spectral reflectance of metal surface [5.5% (315 nm) 8.9% (320 nm)].

  There are ionization energy and electron affinity as an index of energy spent in and out of electrons in the redox reaction of silver. 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 the redox reaction is in a kind of resonance state and a macro equilibrium is established. The

  However, from a microscopic viewpoint, it is thought that it is violently shaken repeatedly under the influence of environmental conditions such as light, heat, and movement of dissociation equilibrium of electrolyte. As a result, when observed from the outside of 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-mentioned numerical value obtained by measuring the potential difference from 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-mentioned numerical 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 is applied as an alternating voltage, so the impact received by the cells is more than expected.

  In order to express the physical properties of the fine silver particles described above as an antibacterial functional material, it is important to increase the probability of contact with bacteria, and the fine silver particles are contained in an aqueous solution that is the environment where bacteria and fungi are most likely to grow. The water-soluble antibacterial functional material in which particles are present evenly has the most remarkable immediate bactericidal antibacterial effect. The effect is obvious from the above-mentioned experiment, but will be described in detail in each example.

  The antibacterial composition used in the present embodiment is characterized in that fine silver particles activated by a quantum size effect are supported on water-soluble polymer micelles. The method for activating the antibacterial properties of the fine silver particles by the quantum size effect is based on the principle described in detail in the specification of the prior application by the present inventors. In addition, the development of a water-soluble support component is an essential condition for realizing the water-solubility characteristic of the present invention. To that end, how to overcome the principle contradiction of supporting solid metal particles on liquid molecules A concrete measure to solve the problem is necessary.

  Therefore, the preparation process of the antibacterial composition used in the present embodiment will be described below.

  First, selection of a water-soluble carrier that carries silver particles will be described. In particular, this water-soluble carrier can overcome the above-mentioned principle problems by selecting collagen and collagen-derived polypeptide compounds (polymer micelles).

  Collagen is a kind of simple protein that is insoluble in ordinary solvents. It is a general term for proteins that maintain the structure of the body such as skin, bones, tendons, and tightened tissues. It is a 180-nm rod-shaped molecule, and three peptide chains have a special helical structure called a collagen helix. When this is hydrolyzed by hot water treatment, a water-soluble protein generally called gelatin is obtained. Depending on the type of collagen, hydrothermal treatment conditions, etc., various types of gelatin having different properties and molecular weights can be obtained. The molecular weight of gelatin is estimated to be 15,000-250,000 or 20,000-70,000. The use of gelatin having a molecular weight of 130,000 to 2,000 as an optimal water-soluble carrier for the practice of the present invention is optimal as an antibacterial composition for all applications. As gelatin, what is marketed as a foodstuff or confectionery material can be used, for example.

  As described above, collagen is a high-molecular substance having a peptide chain as a connecting structure, and gelatin is a similar high-molecular substance except that the molecular weight is small. Therefore, collagen and gelatin are chemically the same component, and the extraction method is slightly different. The peptide bond is cleaved to generate an α-amino group and an α-carboxyl group, and a coordination bond is generated between the free electron of the nitrogen atom of the α-amino group and the silver ion. However, this bond is extremely unstable, judging from the unique physical properties of silver atoms, and the evidence shows that silver easily undergoes reductive aggregation. In general, the coordination bond of silver is weaker than the copper and gold of the same family as judged from the binding energy, and it is well known that many silver compounds are easily decomposed by light and heat and reduced to metallic silver. This is a characteristic not found in other elements.

  The fine silver particles are supported on collagen micelles by using nitrogen atoms of α-amino groups formed by cleavage of peptide bonds of the collagen by hydrolysis as sites. As described above, the silver atoms once oriented by coordination bonds collide and agglomerate with neighboring particles while sequentially solving the coordination by releasing energy by thermal motion. When the size of the aggregated particles reaches several nanometers, a positive charge accumulates on the particle surface, but at the charged site formed around the α-amino group on the surface of the collagen micelle having an electronegativity value corresponding to the size of the positive charge. Sucked. Here, the support by the van der Waals force using electrostatic attraction as a joining mechanism is completed.

  Here, the water-soluble polymer micelle means a microcrystalline particle constituting a polymer substance. A micelle is a basic unit of a crystal of a polymer fiber structure, and is considered to be a basic unit of a polymer crystal that becomes a carrier of fine silver particles according to the present invention, and adopts this name. However, a recent study reveals a folded structure (folded structure of molecular chains forming a plate crystal, which is a unit of polymer crystal), in the microcrystalline particles constituting the unit crystal plate (lamella) of the polymer substance. It has been. The usage of micelles means a basic unit of crystal of a high-molecular substance only in the present invention, and refers to a polymer having a molecular weight of at least 10,000. Therefore, the micelle which is water-soluble is in a state of gel dispersion different from the aqueous solution of a general low molecular compound. Charges of specific molecular parts that do not exist in an aqueous solution can be unevenly distributed and are stable, and unique properties that are not found in general aqueous electrolyte solutions are observed. Due to this specificity, fine silver particles can be supported stably and strongly with the charge of a specific portion of the polymer as a support site.

  Next, the selection and addition process of the silver salt solution added to support the fine silver particles on the carrier will be described.

  As the silver salt, one kind is selected from an ammoniacal silver nitrate aqueous solution, a silver nitrate aqueous solution and a silver sulfate aqueous solution, but no remarkable difference is observed in the antibacterial effect of the fine silver particles produced by reduction. Any of them can exhibit the characteristic effects of the present invention, but it is preferable to select an appropriate silver salt by testing depending on the material and properties of the carrier. According to the knowledge of the inventors, the aqueous ammoniacal silver nitrate solution and the aqueous silver nitrate solution are suitable for loading on a relatively high molecular weight collagen or gelatin having a molecular weight of 100,000 or more, and are the most versatile silver salt solutions. The aqueous silver sulfate solution is suitable for supporting collagen or gelatin having a molecular weight of several thousand to less than 100,000.

  The concentration (Ag @ + mol / l) of the silver salt aqueous solution used for loading is suitably in the range of 0.1 to 0.001. If the silver ion concentration is too high, the generated silver particles tend to aggregate, and the quantum size effect of the fine silver particles is reduced, so that the antibacterial effect tends to be reduced. When the silver ion concentration is set to a lower value, a result superior in antibacterial effect is obtained.

  Next, the selection and addition process of the catalyst added after the addition process of the silver salt solution will be described.

  As the catalyst, one type is selected from each of lithium hydroxide, calcium hydroxide, sodium hydroxide and potassium hydroxide aqueous solutions, and all of them are markedly different in the antibacterial effect of the fine silver particles produced by reduction. It is not allowed. The catalyst is used as a catalyst for temporarily substituting the silver ion of the aqueous silver salt solution previously added to the aqueous solution of the carrier with the hydrogen of the α carboxyl group generated by the cleavage of the peptide bond of the carrier. .

  The catalyst is preferably selected by testing an appropriate catalyst according to the type of carrier and molecular weight. Since calcium hydroxide has a relatively low solubility in water, it is suitable for loading on a relatively low molecular weight collagen having a molecular weight of less than 10,000. Lithium hydroxide is effective for application to high molecular weight (100,000 or more) collagen. Sodium hydroxide and potassium hydroxide are common catalysts that are effective when used for collagen in the entire molecular weight region. Therefore, when selecting collagen, a trial loading trial using sodium hydroxide or potassium hydroxide as the first supported catalyst is recommended.

  As the aqueous solution concentration of the catalyst to be added, an aqueous solution containing an amount of the catalyst component corresponding to 2 to 5% by weight with respect to the collagen used as the carrier is used. Since the solubility in water varies depending on the type of catalyst component, the concentration of the aqueous catalyst solution can be selected as appropriate, but it is preferably 10% by weight or less. In particular, when choosing strong alkaline lithium hydroxide, potassium hydroxide and sodium hydroxide, it is recommended to use each in an aqueous solution of less than 10% by weight.

  Next, the supported reaction system that has completed the chemical reaction is irradiated with ultraviolet rays, and silver ions bonded to the α-amino group and α-carboxyl group in the system by coordination or substitution are photoreduced in situ, A process for supporting fine silver particles, in which fine silver particles are generated and at the same time electrostatically adsorbed to the negative electric field region around the α-amino group, will be described.

  This process is the most important and characteristic process of the present invention. Although the operation is relatively simple, the supporting mechanism and its significance are extremely precise and large.

  Any light source can be used as long as it is a light source including a near ultraviolet region having a wavelength of 400 nm or less. It is preferable to use a mercury lamp that radiates ultraviolet rays intensively, a xenon gas discharge tube, or a luminaire having an ultraviolet emission capability equivalent to or higher than those. As a result of conducting an experiment with sunlight, the inventors should select a time zone from 11:00 am to 2:00 pm in fine weather, and should be sufficiently satisfied as a result of testing a sample irradiated with sunlight for 30 minutes. It was confirmed that a reduction result was obtained.

  Confirmation of the photoreduction process by ultraviolet irradiation is a method of comparing the difference between absorption at a specific wavelength near 300 nm of a sample before ultraviolet irradiation and absorption at the same wavelength after ultraviolet irradiation reduction treatment using an ultraviolet absorption spectrum meter. Is in principle appropriate. However, since collagen derived from natural products has large variations in molecular weight, types of impurities, and contents thereof, measurement by an ultraviolet absorption spectrum is difficult. Therefore, a method using a colorimeter is recommended as a simple method for checking and managing the photoreduction process.

  Confirmation of the photoreduction process by a colorimeter is made by measuring and comparing the specific transmittance of light having a wavelength of 430 to 540 nm before and after the photoreduction process, and if the difference is 5% or more, the completion of the reduction can be confirmed. This method is simple but has practical convenience and is industrially effective.

  As described above, the antibacterial composition used in the present embodiment increases the mobility of silver by imparting water solubility while maintaining the quantum size effect of the silver fine particles by the above-described manufacturing method, and instant sterilization. Antibacterial function can be realized.

  Hereinafter, the cosmetic according to this embodiment in which the antibacterial composition is dispersed will be specifically described.

[Preparation of antibacterial composition]
First, a general-purpose antibacterial agent in which silver fine particles were supported on a collagen polypeptide was produced as an antibacterial composition.
(1) Gelatin type R manufactured by Nippi Co., Ltd. was used as the carrier of the present invention. 100 grams of gelatin was placed in a 500 ml round bottom flask, 200 ml of water was added, and the gelatin was completely dissolved while heating and stirring at 50 ° C.
(2) Next, 70 ml of 0.5% aqueous silver nitrate solution was added to the gelatin solution, and the reaction was stirred for 30 minutes while maintaining the temperature at 60 ± 2.0 ° C.
(3) To this, 100 ml of a 5.0% potassium hydroxide aqueous solution was added and stirred for 2.5 hours while maintaining the above temperature.
(4) Next, heating was stopped and the reaction solution was cooled to room temperature. During this time, stirring was continued. When this step was completed, about 5 ml of a part of the reaction solution was previously collected in a colorimetric tube (A) for colorimeter.
(5) Transfer the reaction liquid to a flat stainless steel vat (30 x 21 x 5 cm), hold it horizontally, and irradiate it with ultraviolet rays for 10 minutes from the center of the reaction liquid surface at a vertical distance of 30 cm directly below. went. About 5 ml of a part of the reaction solution was collected and stored in the colorimetric tube (B). The ultraviolet light source device used for the photoreduction is a stabilized xenon lamp 75W and a dedicated constant current power source C2576 manufactured by Hamamatsu Photonics.
(6) In order to confirm the photoreduction step, the colorimetric samples collected and stored in advance in the above step (4) and step (5) were compared for light transmittance at a wavelength of 430 nm to confirm the reduction reaction. At that time, the colorimetric tube (A) / colorimetric tube (B) transmission ratio was 25%, and it was confirmed that the reduction was sufficiently performed. The colorimeter used was Photo Uni5 manufactured by ATAGO Corporation.

[Cosmetics preparation and stability test]
Next, a cosmetic was prepared. Here, for the convenience of the test, as the simplest cosmetic liquid, a raw material honey, a 0.4% β-glucan solution, and an antibacterial composition solution containing an antibacterial composition at a concentration of 160 ppm were blended.

First, a test was conducted to determine the optimum mixing ratio of honey and 0.4% β-glucan solution. The samples used are as follows.
(Sample A) A cosmetic solution prepared by mixing 90 parts by weight of honey and 10 parts by weight of 0.4% β-glucan solution.
(Sample B) A cosmetic solution prepared by mixing 80 parts by weight of honey and 20 parts by weight of 0.4% β-glucan solution.
(Sample C) A cosmetic solution prepared by mixing 70 parts by weight of honey and 30 parts by weight of 0.4% β-glucan solution.

  200 mL of these samples A to C were prepared and allowed to stand at room temperature for 48 hours to confirm mixing stability. The results are shown in Table 1.

表１にも示すように、サンプルＡ及びサンプルＢは48時間経過後も均一に混合された状態を保っていたため、美容液として適していることが示された。しかしながら、サンプルＣは、48時間経過した時点で蜂蜜と水分とが若干分離しており、均一混合型の美容液としては不向きであるものと考えられた。ただし、このサンプルＣも、例えば油水混合型のドレッシングの如く、振ってから使用する美容液とすれば効果に問題はないものと考えられ、抗菌性組成物の添加対象として何等障害となるものではない。

As shown in Table 1, since Sample A and Sample B were kept in a uniformly mixed state even after 48 hours, it was shown that they were suitable as cosmetic liquids. However, in sample C, honey and moisture were slightly separated after 48 hours, and it was considered that the sample C was unsuitable as a uniform mixed type cosmetic liquid. However, this sample C is also considered to have no problem in effect if it is used as a cosmetic liquid to be used after shaking, such as an oil / water mixing type dressing, and is not an obstacle to the addition of the antibacterial composition. Absent.

  However, here, based on the above results, the cosmetic liquid is of a uniform mixing type and contains 10% of 0.4% β-glucan solution.

Next, on the basis of sample A, the antibacterial composition according to the present embodiment was added to prepare a beauty essence, and the antibacterial composition in the same essence and the ability to inhibit microbial growth were examined. . The samples used are as follows.
(Sample A) A cosmetic solution prepared by mixing 90 parts by weight of honey and 10 parts by weight of 0.4% β-glucan solution.
(Sample D) A cosmetic liquid in which 90 parts by weight of honey, 10 parts by weight of a 0.4% β-glucan solution, and an antibacterial composition are mixed to adjust the final concentration of the antibacterial composition to 0.16 ppm.
(Sample E) A cosmetic solution in which 90 parts by weight of honey, 10 parts by weight of a 0.4% β-glucan solution, and an antibacterial composition are mixed to adjust the final concentration of the antibacterial composition to 8 ppm.
(Sample F) A cosmetic liquid in which 90 parts by weight of honey, 10 parts by weight of a 0.4% β-glucan solution, and an antibacterial composition are mixed to adjust the final concentration of the antibacterial composition to 10 ppm.

  200 mL of these samples A, D, E, and F were prepared and allowed to stand at room temperature for half a year to examine whether or not microorganisms were propagated. The results are shown in Table 2.

表２にも示すように、サンプルＡは抗菌性組成物を添加してないため、半年経過した時点で腐敗しており、蜂蜜とβグルカンとの混合物が腐敗しやすいものであることが示唆された。

As shown in Table 2, since the antibacterial composition was not added to Sample A, it decayed when half a year passed, suggesting that the mixture of honey and β-glucan is likely to decay. It was.

  On the other hand, in Sample D, Sample E, and Sample F to which the antibacterial composition according to this embodiment was added, the propagation of microorganisms was not confirmed even after half a year.

  This indicates that the antibacterial composition according to the present embodiment has long-term dispersion stability and can maintain the quality for a long period of six months.

  In addition, it should be noted that the antibacterial composition according to the present embodiment maintained long-term dispersion stability even at a low concentration of 0.16 ppm, and was able to maintain quality for a long period of six months.

  By the way, sample E and sample F contain 8 ppm and 10 ppm of the antibacterial composition, respectively, so no decay was observed, but even if the test was continued after half a year, there was no microorganism between samples E and F. There was no significant difference in the reproductive inhibition effect.

  Therefore, even if 8 ppm or more of the antibacterial composition according to the present embodiment is added, there is no particular problem as a cosmetic. However, considering the manufacturing cost, the concentration of the antibacterial composition is limited to about 8 ppm. Seems good.

  As described above, the cosmetic according to the present invention is a cosmetic containing honey, β-glucan, and an antibacterial composition, and the antibacterial composition is obtained by collagen and hydrolysis thereof. After adding a silver salt solution and a catalyst to an aqueous solution of the polypeptide compound to be reacted, and reducing it by irradiating it with ultraviolet light having a wavelength of 400 nm or less, the polypeptide compound is finely adjacent to the α-amino group of the polypeptide compound. At the same time as the silver particles are precipitated, the fine silver particles are supported by electrostatic adsorption on the nitrogen atoms of the α-amino group, so that it contains honey and β-glucan that are easily spoiled when used as cosmetics. However, it is possible to prevent cosmetic contamination and rot for a long time, and to make a cosmetic that does not cause harm to the human body due to antibacterial components.

  Finally, the description of each embodiment described above is an example of the present invention, and the present invention is not limited to the above-described embodiment. For this reason, it is a matter of course that various modifications can be made in accordance with the design and the like as long as they do not depart from the technical idea according to the present invention other than the embodiments described above.

Claims (5)

A cosmetic comprising honey, β-glucan, and an antibacterial composition,
The antibacterial composition is prepared by adding a silver salt solution and a catalyst to an aqueous solution of a collagen compound and a polypeptide compound obtained by hydrolysis thereof, and then performing a reduction by irradiating with an ultraviolet ray having a wavelength of 400 nm or less. Thus, a fine silver particle is precipitated in the vicinity of the α-amino group of the polypeptide compound, and at the same time, the fine silver particle is supported on a nitrogen atom of the α-amino group by electrostatic adsorption.   The cosmetic according to claim 1, wherein the collagen and a polypeptide compound obtained by hydrolysis thereof have a molecular weight in the range of 130,000 to 2,000 and are water-soluble.   The cosmetic according to claim 1, wherein the silver solution is at least one silver salt solution selected from the group consisting of an aqueous ammoniacal silver nitrate solution, a silver nitrate aqueous solution, and a silver sulfate aqueous solution.   The cosmetic according to claim 1, wherein the catalyst is at least one aqueous solution selected from the group consisting of aqueous solutions of lithium hydroxide, calcium hydroxide, sodium hydroxide, and potassium hydroxide. .   The light source used for the reduction by ultraviolet irradiation is one or more selected from natural sunlight, a high-pressure or low-pressure xenon gas discharge tube, a high-pressure or low-pressure mercury lamp, or a light source group having equivalent ultraviolet radiation. The cosmetic according to claim 1, wherein the cosmetic is used.